About GPO   |   Newsroom/Media   |   Congressional Relations   |   Inspector General   |   Careers   |   Contact   |   askGPO   |   Help  
 
Home   |   Customers   |   Vendors   |   Libraries  

The Electronic Code of Federal Regulations (e-CFR) is a regularly updated, unofficial editorial compilation of CFR material and Federal Register amendments produced by the National Archives and Records Administration's Office of the Federal Register (OFR) and the Government Printing Office.

Parallel Table of Authorities and Rules for the Code of Federal Regulations and the United States Code
Text | PDF

Find, review, and submit comments on Federal rules that are open for comment and published in the Federal Register using Regulations.gov.

Purchase individual CFR titles from the U.S. Government Online Bookstore.

Find issues of the CFR (including issues prior to 1996) at a local Federal depository library.

[2]
 
 

Electronic Code of Federal Regulations

e-CFR Data is current as of November 25, 2014

Title 40Chapter ISubchapter CPart 63 → Subpart HHHHHHH


Title 40: Protection of Environment
PART 63—NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS FOR SOURCE CATEGORIES (CONTINUED)


Subpart HHHHHHH—National Emission Standards for Hazardous Air Pollutant Emissions for Polyvinyl Chloride and Copolymers Production


Contents

What This Subpart Covers

§63.11860   What is the purpose of this subpart?
§63.11865   Am I subject to the requirements in this subpart?
§63.11870   What is the affected source of this subpart?
§63.11871   What is the relationship to 40 CFR part 61, subpart F?
§63.11872   What is the relationship to other subparts in this part?
§63.11875   When must I comply with this subpart?

Emission Limits, Operating Limits and Work Practice Standards

§63.11880   What emission limits, operating limits and standards must I meet?

General Compliance Requirements

§63.11885   What parts of the General Provisions apply to me?
§63.11890   What are my additional general requirements for complying with this subpart?
§63.11895   How do I assert an affirmative defense for exceedance of emission standard during malfunction?
§63.11896   What am I required to do if I make a process change at my affected source?

Testing and Compliance Requirements

§63.11900   By what date must I conduct initial performance testing and monitoring, establish any applicable operating limits and demonstrate initial compliance with my emission limits and work practice standards?
§63.11905   When must I conduct subsequent performance testing and monitoring to demonstrate continuous compliance?
§63.11910   What are my initial and continuous compliance requirements for storage vessels?
§63.11915   What are my compliance requirements for equipment leaks?
§63.11920   What are my initial and continuous compliance requirements for heat exchange systems?
§63.11925   What are my initial and continuous compliance requirements for process vents?
§63.11930   What requirements must I meet for closed vent systems?
§63.11935   What CEMS and CPMS requirements must I meet to demonstrate initial and continuous compliance with the emission standards for process vents?
§63.11940   What continuous monitoring requirements must I meet for control devices required to install CPMS to meet the emission limits for process vents?
§63.11945   What performance testing requirements must I meet for process vents?
§63.11950   What emissions calculations must I use for an emission profile?
§63.11955   What are my initial and continuous compliance requirements for other emission sources?
§63.11956   What are my compliance requirements for ambient monitoring?
§63.11960   What are my initial and continuous compliance requirements for stripped resin?
§63.11965   What are my general compliance requirements for wastewater?
§63.11970   What are my initial compliance requirements for process wastewater?
§63.11975   What are my continuous compliance requirements for process wastewater?
§63.11980   What are the test methods and calculation procedures for process wastewater?

Notifications, Reports and Records

§63.11985   What notifications and reports must I submit and when?
§63.11990   What records must I keep?
§63.11995   In what form and how long must I keep my records?
§63.12000   Who implements and enforces this subpart?

Definitions

§63.12005   What definitions apply to this subpart?
§§63.12006-63.12099   [Reserved]
Table 1 to Subpart HHHHHHH of Part 63—Emission Limits and Standards for Existing Affected Sources
Table 2 to Subpart HHHHHHH of Part 63—Emission Limits and Standards for New Affected Sources
Table 3 to Subpart HHHHHHH of Part 63—Summary of Control Requirements for Storage Vessels at New and Existing Sources
Table 4 to Subpart HHHHHHH of Part 63—Applicability of the General Provisions to Part 63
Table 5 to Subpart HHHHHHH of Part 63—Operating Parameters, Operating Limits and Data Monitoring, Recording and Compliance Frequencies for Process Vents
Table 6 to Subpart HHHHHHH of Part 63—Toxic Equivalency Factors
Table 7 to Subpart HHHHHHH of Part 63—Calibration and Accuracy Requirements for Continuous Parameter Monitoring Systems
Table 8 to Subpart HHHHHHH of Part 63—Methods and Procedures for Conducting Performance Tests for Process Vents
Table 9 to Subpart HHHHHHH of Part 63—Procedures for Conducting Sampling of Stripped Resin and Process Wastewater
Table 10 to Subpart HHHHHHH of Part 63—HAP Subject to the Resin and Process Wastewater Provisions at New and Existing Sources
Appendix A to Part 63—Test Methods Pollutant Measurement Methods From Various Waste Media
Appendix B to Part 63—Sources Defined for Early Reduction Provisions
Appendix C to Part 63—Determination of the Fraction Biodegraded (Fbio) in a Biological Treatment Unit
Appendix D to Part 63—Alternative Validation Procedure for EPA Waste and Wastewater Methods
Appendix E to Part 63—Monitoring Procedure for Nonthoroughly Mixed Open Biological Treatment Systems at Kraft Pulp Mills Under Unsafe Sampling Conditions

Source: 77 FR 22906, Apr. 17, 2012, unless otherwise noted.

What This Subpart Covers

§63.11860   What is the purpose of this subpart?

This subpart establishes national emission standards for hazardous air pollutants emitted from the production of polyvinyl chloride and copolymers at major sources. This subpart also establishes requirements to demonstrate initial and continuous compliance with the emission standards.

§63.11865   Am I subject to the requirements in this subpart?

You are subject to the requirements in this subpart if you own or operate one or more polyvinyl chloride and copolymers production process units (PVCPU) as defined in §63.12005 that are located at, or are part of, a major source of hazardous air pollutants (HAP) emissions as defined in §63.2. The requirements of this subpart do not apply to research and development facilities, as defined in section 112(c)(7) of the Clean Air Act, or to chemical manufacturing process units, as defined in §63.101, that produce vinyl chloride monomer or other raw materials used in the production of polyvinyl chloride and copolymers.

§63.11870   What is the affected source of this subpart?

(a) This subpart applies to each polyvinyl chloride and copolymers production affected source.

(b) The polyvinyl chloride and copolymers production affected source is the facility wide collection of PVCPU, storage vessels, heat exchange systems, surge control vessels, wastewater and process wastewater treatment systems that are associated with producing polyvinyl chloride and copolymers.

(c) An existing affected source is one for which construction was commenced on or before May 20, 2011, at a major source.

(d) A new affected source is one for which construction is commenced after May 20, 2011, at a major source.

(e) If components of an existing affected source are replaced such that the replacement meets the definition of reconstruction in §63.2 and the reconstruction commenced after May 20, 2011, then the existing affected source becomes a reconstructed source and is subject to the relevant standards for a new affected source. The reconstructed source must comply with the requirements for a new affected source upon initial startup of the reconstructed source or by April 17, 2012, whichever is later.

§63.11871   What is the relationship to 40 CFR part 61, subpart F?

After the applicable compliance date specified in §63.11875(a), (b) or (c), an affected source that is also subject to the provisions of 40 CFR part 61, subpart F, is required to comply with the provisions of this subpart and no longer has to comply with 40 CFR part 61, subpart F.

§63.11872   What is the relationship to other subparts in this part?

After the applicable compliance date specified in §63.11875(a), (b) or (c), an affected source that is also subject to the provisions of other subparts in 40 CFR part 60 or this part is required to comply with this subpart and any other applicable subparts in 40 CFR part 60 or this part.

§63.11875   When must I comply with this subpart?

(a) If you own or operate an existing affected source, you must achieve compliance with the applicable provisions in this subpart no later than April 17, 2015. On or after April 17, 2015, any such existing affected source is no longer subject to the provisions of 40 CFR part 61, subpart F.

(b) If you start up a new affected source on or before April 17, 2012, you must achieve compliance with the provisions of this subpart no later than April 17, 2012. On or after April 17, 2012, any such new affected source is not subject to the provisions of 40 CFR part 61, subpart F.

(c) If you start up a new affected source after April 17, 2012, you must achieve compliance with the provisions of this subpart upon startup of your affected source. Upon startup, any such new affected source is not subject to the provisions of 40 CFR part 61, subpart F.

(d) You must meet the notification requirements in §§63.9 and 63.11985 according to the dates specified in those sections. Some of the notifications must be submitted before you are required to comply with the emission limits and standards in this subpart.

Emission Limits, Operating Limits and Work Practice Standards

§63.11880   What emission limits, operating limits and standards must I meet?

(a) You must comply with each emission limit and standard specified in Table 1 to this subpart that applies to your existing affected source, and you must comply with each emission limit and standard specified in Table 2 to this subpart that applies to your new affected source.

(b) You must establish an operating limit for each operating parameter required to be monitored in §63.11925, and you must establish each operating limit as an operating range, minimum operating level or maximum operating level. You must comply with each established operating limit.

(c) You must comply with the emission limits and standards specified in §§63.11910 through 63.11980 that apply to your affected source.

General Compliance Requirements

§63.11885   What parts of the General Provisions apply to me?

Table 4 to this subpart specifies which parts of the General Provisions in subpart A of this part apply to you.

§63.11890   What are my additional general requirements for complying with this subpart?

(a) The emission limits, operating limits and work practice standards specified in this subpart apply at all times, including periods of startup, shutdown or malfunction.

(b) At all times, you must operate and maintain your affected source, including associated air pollution control components and monitoring system components, in a manner consistent with safety and good air pollution control practices for minimizing emissions. Determination of whether acceptable operation and maintenance procedures are being used will be based on information available to the Administrator, which may include, but is not limited to, monitoring results, review of operation and maintenance procedures, review of operation and maintenance records, and inspection of the source.

(c) You must install, calibrate, maintain, and operate all monitoring system components according to §§63.8, 63.11935(b) and (c), and paragraphs (c)(1) and (2) of this section.

(1) Except for periods of monitoring system malfunctions, repairs associated with monitoring system malfunctions and required monitoring system quality assurance or quality control activities (including, as applicable, calibration checks and required zero and span adjustments), you must operate the continuous monitoring system at all times the affected source is operating. A monitoring system malfunction is any sudden, infrequent, not reasonably preventable failure of the monitoring system to provide data. Monitoring system failures that are caused in part by poor maintenance or careless operation are not malfunctions. You are required to complete monitoring system repairs in response to monitoring system malfunctions and to return the monitoring system to operation as expeditiously as practicable.

(2) You may not use data recorded during monitoring system malfunctions, repairs associated with monitoring system malfunctions, or required monitoring system quality assurance or control activities in calculations used to report emissions or operating levels. You must use all the data collected during all other required data collection periods in assessing the operation of the control device and associated control system. You must report any periods for which the monitoring system failed to collect required data.

(d) A deviation means any of the cases listed in paragraphs (d)(1) through (7) of this section.

(1) Any instance in which an affected source subject to this subpart, or an owner or operator of such a source, fails to meet any requirement or obligation established by this subpart, including, but not limited to, any emission limit, operating limit or work practice standard.

(2) When a performance test indicates that emissions of a pollutant in Table 1 or 2 to this subpart are exceeding the emission standard for the pollutant specified in Table 1 or 2 to this subpart.

(3) When a 3-hour block average from a continuous emissions monitor, as required by §63.11925(c)(1) through (3), exceeds an emission limit in Table 1 or 2 to this subpart.

(4) When the average value of a monitored operating parameter, based on the data averaging period for compliance specified in Table 5 to this subpart, does not meet the operating limit established in §63.11880(b).

(5) When an affected source discharges directly to the atmosphere from any of the sources specified in paragraphs (d)(5)(i) through (iv) of this section.

(i) A pressure relief device, as defined in §63.12005.

(ii) A bypass, as defined in §63.12005.

(iii) A closed vent system in vacuum service.

(iv) A closure device on a pressure vessel.

(6) Any instance in which the affected source subject to this subpart, or an owner or operator of such a source, fails to meet any term or condition specified in paragraph (d)(6)(i) or (ii) of this section.

(i) Any term or condition that is adopted to implement an applicable requirement in this subpart.

(ii) Any term or condition relating to compliance with this subpart that is included in the operating permit for any affected source required to obtain such a permit.

(7) Any failure to collect required data, except for periods of monitoring system malfunctions, repairs associated with monitoring system malfunctions, and required monitoring system quality assurance or quality control activities (including, as applicable, calibration checks and required zero and span adjustments).

§63.11895   How do I assert an affirmative defense for exceedance of emission standard during malfunction?

In response to an action to enforce the standards set forth in §63.11880, you may assert an affirmative defense to a claim for civil penalties for violations of such standards that are caused by malfunction, as defined at 40 CFR 63.2. Appropriate penalties may be assessed, however, if you fail to meet your burden of proving all of the requirements in the affirmative defense. The affirmative defense shall not be available for claims for injunctive relief.

(a) Evidence. To establish the affirmative defense in any action to enforce such a standard, you must timely meet the notification requirements in paragraph (b) of this section, and must prove by a preponderance of evidence that:

(1) The violation:

(i) Was caused by a sudden, infrequent, and unavoidable failure of air pollution control and monitoring equipment, process equipment, or a process to operate in a normal or usual manner.

(ii) Could not have been prevented through careful planning, proper design or better operation and maintenance practices.

(iii) Did not stem from any activity or event that could have been foreseen and avoided, or planned for.

(iv) Were not part of a recurring pattern indicative of inadequate design, operation or maintenance.

(2) Repairs were made as expeditiously as possible when violation occurred. Off-shift and overtime labor were used, to the extent practicable to make these repairs.

(3) The frequency, amount and duration of the violation (including any bypass) were minimized to the maximum extent practicable.

(4) If the violation resulted from a bypass of control equipment or a process, then the bypass was unavoidable to prevent loss of life, personal injury, or severe property damage.

(5) All possible steps were taken to minimize the impact of the violations on ambient air quality, the environment and human health.

(6) All emissions monitoring and control systems were kept in operation if at all possible, consistent with safety and good air pollution control practices.

(7) All of the actions in response to the violations were documented by properly signed, contemporaneous operating logs.

(8) At all times, the affected source was operated in a manner consistent with good practices for minimizing emissions.

(9) A written root cause analysis has been prepared, the purpose of which is to determine, correct, and eliminate the primary causes of the malfunction and the violations resulting from the malfunction event at issue. The analysis shall also specify, using best monitoring methods and engineering judgment, the amount of excess emissions that were the result of the malfunction.

(b) Report. The owner or operator seeking to assert an affirmative defense shall submit a written report to the Administrator in the compliance report required by §63.11985(b) with all necessary supporting documentation, that it has met the requirements set forth in this section.

§63.11896   What am I required to do if I make a process change at my affected source?

If you make a process change to an existing affected source that does not meet the criteria to become a new affected source in §63.11870(d), you must comply with the requirements in paragraph (a) of this section and the testing and reporting requirements in paragraphs (c) and (d) of this section. If you make a process change to a new affected source, you must comply with the requirements in paragraph (b) of this section and the testing and reporting requirements in paragraphs (c) and (d) of this section. Refer to §63.12005 for the definition of process changes.

(a) You must demonstrate that the changed process unit or component of the affected facility is in compliance with the applicable requirements for an existing affected source. You must demonstrate initial compliance with the emission limits and establish any applicable operating limits in §63.11880 within 180 days of the date of start-up of the changed process unit or component of the affected facility. You must demonstrate compliance with any applicable work practice standards upon startup of the changed process unit or component of the affected facility.

(b) You must demonstrate that all changed emission points are in compliance with the applicable requirements for a new affected source. You must demonstrate initial compliance with the emission limits and establish any applicable operating limits in §63.11880 within 180 days of the date of startup of the changed process unit or component of the affected facility. You must demonstrate compliance with any applicable work practice standards upon startup of the changed process unit or component of the affected facility.

(c) For process changes, you must demonstrate continuous compliance with your emission limits and standards, operating limits, and work practice standards according to the procedures and frequency in §§63.11910 through 63.11980.

(d) For process changes, you must submit the report specified in §63.11985(b)(4)(iii).

Testing and Compliance Requirements

§63.11900   By what date must I conduct initial performance testing and monitoring, establish any applicable operating limits and demonstrate initial compliance with my emission limits and work practice standards?

(a) For existing affected sources, you must establish any applicable operating limits required in §63.11880 and demonstrate initial compliance with the emission limits and standards specified in Tables 1 and 3 to this subpart, as applicable, no later than 180 days after the compliance date specified in §63.11875 and according to the applicable provisions in §63.7(a)(2).

(b) For existing affected sources, you must demonstrate initial compliance with any applicable work practice standards required in §63.11880 no later than the compliance date specified in §63.11875 and according to the applicable provisions in §63.7(a)(2).

(c) For new or reconstructed affected sources, you must establish any applicable operating limits required in §63.11880, and demonstrate initial compliance with the emission limits and standards specified in Tables 2 and 3 to this subpart, as applicable, no later than 180 days after the effective date of publication of the final rule in the Federal Register or within 180 days after startup of the source, whichever is later, according to §63.7(a)(2)(ix).

(d) For new and reconstructed affected sources, you must demonstrate initial compliance with any applicable work practice standards required in §63.11880 no later than the startup date of the affected source or the effective date of publication of the final rule in the Federal Register, whichever is later, and according to the applicable provisions in §63.7(a)(2).

(e) If you demonstrate initial compliance using a performance test and a force majeure is about to occur, occurs, or has occurred for which you intend to assert a claim of force majeure, then you must follow the procedures in §63.7(a)(4).

§63.11905   When must I conduct subsequent performance testing and monitoring to demonstrate continuous compliance?

Following the date of your initial demonstration of compliance in §63.11900, you must conduct subsequent performance testing and monitoring to demonstrate continuous compliance with your emission limits, operating limits, and work practice standards according to the procedures and frequency in §§63.11910 through 63.11980. If you make a process change as specified in §63.11896, such that a different emission limit or operating parameter limit applies, you must conduct a performance test according to §63.11896.

§63.11910   What are my initial and continuous compliance requirements for storage vessels?

You must comply with the requirements specified in Table 3 to this subpart for each storage vessel in HAP service.

(a) For each fixed roof storage vessel used to comply with the requirements specified in Table 3 to this subpart, you must meet the requirements in paragraphs (a)(1) through (4) of this section. If you elect to use a fixed roof storage vessel vented to a closed vent system and control device, the closed vent system and control device must meet the requirements in §§63.11925 through 63.11950.

(1) Design requirements. (i) The fixed roof must be installed in a manner such that there are no visible cracks, holes, gaps, or other open spaces between roof section joints or between the interface of the roof edge and the tank wall.

(ii) Each opening in the fixed roof must be equipped with a closure device designed to operate such that when the closure device is secured in the closed position there are no visible cracks, holes, gaps, or other open spaces in the closure device or between the perimeter of the opening and the closure device.

(2) Operating requirements. (i) Except as specified in paragraph (a)(2)(ii) of this section, the fixed roof must be installed with each closure device secured in the closed position.

(ii) Opening of closure devices or removal of the fixed roof is allowed under conditions specified in paragraphs (a)(2)(ii)(A) and (B) of this section.

(A) A closure device may be opened or the roof may be removed when needed to provide access.

(B) A conservation vent that vents to the atmosphere is allowed during normal operations to maintain the tank internal operating pressure within tank design specifications. Normal operating conditions that may require these devices to open are during those times when the internal pressure of the storage vessel is outside the internal pressure operating range for the storage vessel as a result of loading or unloading operations or diurnal ambient temperature fluctuations.

(iii) During periods of planned routine maintenance of a control device, operate the storage vessel in accordance with paragraphs (a)(2)(iii)(A) and (B) of this section. You must keep the records specified in §63.11990(b)(6).

(A) Do not add material to the storage vessel during periods of planned routine maintenance.

(B) Limit periods of planned routine maintenance for each control device to no more than 360 hours per year (hr/yr).

(3) Inspection and monitoring requirements. (i) Visually inspect the fixed roof and its closure devices for defects initially and at least once per calendar year except as specified in paragraph (a)(3)(ii) of this section. Defects include, but are not limited to, visible cracks, holes, or gaps in the roof sections or between the roof and the wall of the storage vessel; broken, cracked or otherwise damaged seals, or gaskets on closure devices; and broken or missing hatches, access covers, caps or other closure devices.

(ii) The inspection requirement specified in paragraph (a)(3)(i) of this section does not apply to parts of the fixed roof that you determine are unsafe to inspect because operating personnel would be exposed to an imminent or potential danger as a consequence of complying with paragraph (a)(3)(i) of this section, provided you comply with the requirements specified in paragraphs (a)(3)(ii)(A) and (B) of this section.

(A) You prepare and maintain at the plant site written documentation that identifies all parts of the fixed roof that are unsafe to inspect and explains why such parts are unsafe to inspect.

(B) You develop and implement a written plan and schedule to conduct inspections the next time alternative storage capacity becomes available and the storage vessel can be emptied or temporarily removed from service, as necessary, to complete the inspection. The required inspections must be performed as frequently as practicable but do not need to be performed more than once per calendar year. You must maintain a copy of the written plan and schedule at the plant site.

(4) Repair requirements. (i) Complete repair of a defect as soon as possible, but no later than 45 days after detection. You must comply with the requirements in this paragraph (a)(4)(i) except as provided in paragraph (a)(4)(ii) of this section.

(ii) Repair of a defect may be delayed beyond 45 days if you determine that repair of the defect requires emptying or temporary removal from service of the storage vessel and no alternative storage capacity is available at the site to accept the removed material. In this case, repair the defect the next time alternative storage capacity becomes available and the storage vessel can be emptied or temporarily removed from service.

(b) If you elect to use an internal floating roof storage vessel or external floating roof storage vessel to comply with the requirements specified in Table 3 to this subpart, you must meet all requirements of §§63.1060 through 63.1067 of subpart WW of this part for internal floating roof storage vessels or external floating roof storage vessels, as applicable.

(c) For each pressure vessel used to comply with the requirements specified in Table 3 to this subpart, you must meet the requirements in paragraphs (c)(1) through (4) of this section.

(1) Whenever the pressure vessel is in hazardous air pollutants (HAP) service, you must operate the pressure vessel as a closed system that does not vent to the atmosphere, e.g., during filling, emptying and purging. The vent stream during filling, emptying and purging must meet the requirements of §63.11925(a) and (b).

(2) Each opening in the pressure vessel must be equipped with a closure device designed to operate such that when the closure device is secured in the closed position there are no visible cracks, holes, gaps or other open spaces in the closure device or between the perimeter of the opening and the closure device.

(3) All potential leak interfaces must be monitored annually for leaks using the procedures specified in §63.11915 and you may adjust for background concentration. You must comply with the recordkeeping provisions specified in §63.11990(b)(4) and the reporting provisions specified in §63.11985(a)(1), (b)(1), and (b)(10).

(4) Pressure vessel closure devices must not discharge to the atmosphere. Any such release (e.g., leak) constitutes a violation of this rule. You must submit to the Administrator as part of your compliance report the information specified in §63.11985(b)(10). This report is required even if you elect to follow the procedures specified in §63.11895 to establish an affirmative defense.

§63.11915   What are my compliance requirements for equipment leaks?

For equipment in HAP service (as defined in §63.12005), you must comply with the requirements in paragraphs (a) through (c) of this section.

(a) Requirement for certain equipment in subpart UU of this part. You must comply with §§63.1020 through 63.1025, 63.1027, 63.1029 through 63.1032, and 63.1034 through 63.1039 of subpart UU of this part.

(b) Requirements for pumps, compressors, and agitators. You must meet the requirements of paragraphs (b)(1) and (2) of this section. For each type of equipment specified in paragraphs (b)(1) and (2) of this section, you must also meet the requirements of paragraph (a) of this section.

(1) Rotating pumps. HAP emissions from seals on all rotating pumps in HAP service are to be minimized by either installing sealless pumps, pumps with double mechanical seals or equivalent equipment, or by complying with the requirements of 40 CFR part 63, subpart UU for rotating pumps. If double mechanical seals are used, emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the pump; by complying with §63.11925(a) and (b); or equivalent equipment or procedures approved by the Administrator.

(2) Reciprocating pumps, rotating compressors, reciprocating compressors and agitators. HAP emissions from seals on all reciprocating pumps, rotating compressors, reciprocating compressors and agitators in HAP service are to be minimized by either installing double mechanical seals or equivalent equipment, or by complying with the requirements of 40 CFR part 63, subpart UU for reciprocating pumps, rotating compressors, reciprocating compressors and/or agitators. If double mechanical seals are used, HAP emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the pump; by complying with §63.11925(a) and (b); or equivalent equipment or procedures approved by the Administrator.

(c) Requirements for pressure relief devices. For pressure relief devices in HAP service, as defined in §63.12005, you must meet the requirements of this paragraph (c) and paragraph (a) of this section, you must comply with the recordkeeping provisions in §63.11990(c), and you must comply with the reporting provisions in §§63.11985(a)(2), (b)(2) and (c)(7).

(1) For pressure relief devices in HAP service that discharge directly to the atmosphere without first meeting the process vent emission limits in Table 1 or 2 to this subpart by routing the discharge to a closed vent system and control device designed and operated in accordance with the requirements in §§63.11925 through 63.11950, you must install, maintain, and operate release indicators as specified in paragraphs (c)(1)(i) and (ii) of this section. Any release to the atmosphere without meeting the process vent emission limits in Table 1 or 2 to this subpart, constitutes a violation of this rule. You must submit the report specified in §63.11985(c)(7), as described in paragraph (c)(1)(iii) of this section.

(i) A release indicator must be properly installed on each pressure relief device in such a way that it will indicate when an emission release has occurred.

(ii) Each indicator must be equipped with an alert system that will notify an operator immediately and automatically when the pressure relief device is open. The alert must be located such that the signal is detected and recognized easily by an operator.

(iii) For any instance that the release indicator indicates that a pressure relief device is open, you must notify operators that a pressure release has occurred, and, within 10 days of the release, you must submit to the Administrator the report specified in §63.11985(c)(7). This report is required even if you elect to follow the procedures specified in §63.11895 to establish an affirmative defense.

(2) For pressure relief devices in HAP service that discharge directly to a closed vent system and control device designed and operated in accordance with the requirements in §§63.11925 through 63.11950, and are required to meet process vent emission limits in Table 1 or 2 to this subpart. Any release to the atmosphere without meeting the process vent emission limits in Table 1 or 2 to this subpart, constitutes a violation of this rule. You must notify operators that a pressure release has occurred, and, within 10 days of the release, you must submit to the Administrator the report specified in §63.11985(c)(7). This report is required even if you elect to follow the procedures specified in §63.11895(b) to establish an affirmative defense.

§63.11920   What are my initial and continuous compliance requirements for heat exchange systems?

(a) Except as provided in paragraph (b) of this section, you must perform monitoring to identify leaks of volatile organic compounds from each heat exchange system in HAP service subject to the requirements of this subpart according to the procedures in paragraphs (a)(1) through (4) of this section.

(1) Monitoring locations for closed-loop recirculation heat exchange systems. For each closed loop recirculating heat exchange system, you must collect and analyze a sample from the location(s) described in either paragraph (a)(1)(i) or (ii) of this section.

(i) Each cooling tower return line prior to exposure to air for each heat exchange system in HAP service.

(ii) Selected heat exchanger exit line(s) so that each heat exchanger or group of heat exchangers within a heat exchange system is covered by the selected monitoring location(s).

(2) Monitoring locations for once-through heat exchange systems. For each once-through heat exchange system, you must collect and analyze a sample from the location(s) described in paragraph (a)(2)(i) of this section. You may also elect to collect and analyze an additional sample from the location(s) described in paragraph (a)(2)(ii) of this section.

(i) Selected heat exchanger exit line(s) so that each heat exchanger or group of heat exchangers in HAP service within a heat exchange system is covered by the selected monitoring location(s).

(ii) The inlet water feed line for a once-through heat exchange system prior to any heat exchanger. If multiple heat exchange systems use the same water feed (i.e., inlet water from the same primary water source), you may monitor at one representative location and use the monitoring results for that sampling location for all heat exchange systems that use that same water feed.

(3) Monitoring method. You must determine the total strippable volatile organic compounds concentration or vinyl chloride concentration at each monitoring location using one of the analytical methods specified in paragraphs (a)(3)(i) through (iii) of this section.

(i) Determine the total strippable volatile organic compounds concentration (in parts per million by volume) as methane from the air stripping testing system using Modified El Paso Method (incorporated by reference, see §63.14) using a flame ionization detector analyzer.

(ii) Determine the total strippable volatile organic compounds concentration (in parts per billion by weight) in the cooling water using Method 624 at 40 CFR part 136, appendix A. The target list of compounds shall be generated based on a pre-survey sample and analysis by gas chromatography/mass spectrometry and process knowledge to include all compounds that can potentially leak into the cooling water. If Method 624 of part 136, appendix A is not applicable for all compounds that can potentially leak into the cooling water for a given heat exchange system, you cannot use this monitoring method for that heat exchange system.

(iii) Determine the vinyl chloride concentration (in parts per billion by weight) in the cooling water using Method 107 at 40 CFR part 61, appendix A.

(4) Monitoring frequency. You must determine the total strippable volatile organic compounds or vinyl chloride concentration at each monitoring location at the frequencies specified in paragraphs (a)(4)(i) and (ii) of this section.

(i) For heat exchange systems for which you have not delayed repair of any leaks, monitor at least monthly. You may elect to monitor more frequently than the minimum frequency specified in this paragraph.

(ii) If you elect to monitor the inlet water feed line for a once-through heat exchange system as provided in paragraph (a)(2)(ii) of this section, you must monitor the inlet water feed line at the same frequency used to monitor the heat exchange exit line(s), as required in paragraph (a)(2)(i) of this section.

(b) A heat exchange system is not subject to the monitoring requirements in paragraph (a) of this section if it meets any one of the criteria in paragraphs (b)(1) through (3) of this section.

(1) All heat exchangers that are in HAP service within the heat exchange system operate with the minimum pressure on the cooling water side at least 35 kilopascals greater than the maximum pressure on the process side.

(2) The heat exchange system does not contain any heat exchangers that are in HAP service.

(3) The heat exchange system has a maximum cooling water flow rate of 10 gallons per minute or less.

(c) The leak action levels for both existing and new sources are specified in paragraphs (c)(1) through (3) of this section.

(1) If you elect to monitor your heat exchange system by using the monitoring method specified in paragraph (a)(3)(i) of this section, then the leak action level is a total strippable volatile organic compounds concentration (as methane) in the stripping gas of 3.9 parts per million by volume.

(2) If you elect to monitor your heat exchange system by using the monitoring method specified in paragraph (a)(3)(ii) of this section, then the leak action level is a total strippable volatile organic compounds concentration in the cooling water of 50 parts per billion by weight.

(3) If you elect to monitor your heat exchange system by using the monitoring method specified in paragraph (a)(3)(iii) of this section, then the leak action level is a vinyl chloride concentration in the cooling water of 50 parts per billion by weight.

(d) A leak is defined as specified in paragraph (d)(1) or (2) of this section, as applicable.

(1) For once-through heat exchange systems for which you monitor the inlet water feed, as described in paragraph (a)(2)(ii) of this section, a leak is detected if the difference in the measurement value of the sample taken from a location specified in paragraph (a)(2)(i) of this section and the measurement value of the corresponding sample taken from the location specified in paragraph (a)(2)(ii) of this section equals or exceeds the leak action level.

(2) For all other heat exchange systems, a leak is detected if a measurement value taken according to the requirements in paragraph (a) of this section equals or exceeds the leak action level.

(e) If a leak is detected, you must repair the leak to reduce the measured concentration to below the applicable action level as soon as practicable, but no later than 45 days after identifying the leak, except as specified in paragraphs (f) and (g) of this section. Repair includes re-monitoring as specified in paragraph (a) of this section to verify that the measured concentration is below the applicable action level. Actions that you can take to achieve repair include but are not limited to:

(1) Physical modifications to the leaking heat exchanger, such as welding the leak or replacing a tube;

(2) Blocking the leaking tube within the heat exchanger;

(3) Changing the pressure so that water flows into the process fluid;

(4) Replacing the heat exchanger or heat exchanger bundle; or

(5) Isolating, bypassing or otherwise removing the leaking heat exchanger from service until it is otherwise repaired.

(f) If you detect a leak when monitoring a cooling tower return line or heat exchanger exit line under paragraph (a) of this section, you may conduct additional monitoring following the requirements in paragraph (a) of this section to further isolate each heat exchanger or group of heat exchangers in HAP service within the heat exchange system for which the leak was detected. If you do not detect any leaks when conducting additional monitoring for each heat exchanger or group of heat exchangers, the heat exchange system is excluded from repair requirements in paragraph (e) of this section.

(g) The delay of repair action level is defined as either a total strippable volatile organic compounds concentration (as methane) in the stripping gas of 39 parts per million by volume or a total strippable volatile organic compounds concentration in the cooling water of 500 parts per billion by weight or a vinyl chloride concentration in the cooling water of 500 parts per billion by weight. While you remain below the repair action level, you may delay the repair of a leaking heat exchanger only if one of the conditions in paragraphs (g)(1) or (2) of this section is met. If you exceed the repair action level you must repair according to paragraph (e) of this section. You must determine if a delay of repair is necessary as soon as practicable, but no later than 45 days after first identifying the leak.

(1) If the repair is technically infeasible without a shutdown and the total strippable volatile organic compounds or vinyl chloride concentration is initially and remains less than the delay of repair action level for all monitoring periods during the delay of repair, you may delay repair until the next scheduled shutdown of the heat exchange system. If, during subsequent monitoring, the total strippable volatile organic compounds or vinyl chloride concentration is equal to or greater than the delay of repair action level, you must repair the leak within 30 days of the monitoring event in which the total strippable volatile organic compounds or vinyl chloride concentration was equal to or exceeded the delay of repair action level.

(2) If the necessary equipment, parts, or personnel are not available and the total strippable volatile organic compounds or vinyl chloride concentration is initially and remains less than the delay of repair action level for all monitoring periods during the delay of repair, you may delay the repair for a maximum of 120 days from the day the leak was first identified. You must demonstrate that the necessary equipment, parts or personnel were not available. If, during subsequent monthly monitoring, the total strippable volatile organic compounds or vinyl chloride concentration is equal to or greater than the delay of repair action level, you must repair the leak within 30 days of the monitoring event in which the leak was equal to or exceeded the total strippable volatile organic compounds or vinyl chloride delay of repair action level.

(h) To delay the repair under paragraph (g) of this section, you must record the information in paragraphs (h)(1) through (4) of this section.

(1) The reason(s) for delaying repair.

(2) A schedule for completing the repair as soon as practical.

(3) The date and concentration of the leak as first identified and the results of all subsequent monitoring events during the delay of repair.

(4) An estimate of the potential emissions from the leaking heat exchange system following the procedures in paragraphs (h)(4)(i) and (ii) of this section.

(i) Determine the total strippable volatile organic compounds or vinyl chloride concentration in the cooling water, in parts per billion by weight. If the Modified El Paso Method is used, calculate the total strippable volatile organic compounds concentration in the cooling water using equation 7-1 from Modified El Paso Method (incorporated by reference, see §63.14) and the total strippable volatile organic compounds concentration measured in the stripped air.

(ii) Calculate the emissions for the leaking heat exchange system by multiplying the volatile organic compounds or vinyl chloride concentration in the cooling water, ppbw, by the flow rate of the cooling water at the selected monitoring location and by the expected duration of the delay according to Equation 1 of this section. The flow rate may be based on direct measurement, pump curves, heat balance calculations or other engineering methods.

eCFR graphic er17ap12.000.gif

View or download PDF

Where:

EL = Emissions from leaking heat exchange system, pounds of volatile organic compounds or vinyl chloride.

CVC = Actual measured concentration of total strippable volatile organic compounds or vinyl chloride measured in the cooling water, parts per billion by weight (ppbw).

VCW = Total volumetric flow rate of cooling water, gallons per minute (gpm).

ρCW = Density of cooling water, pounds per gallon (lb/gal).

Ddelay = Expected duration of the repair delay, days.

§63.11925   What are my initial and continuous compliance requirements for process vents?

Each process vent must meet the requirements of paragraphs (a) through (h) of this section.

(a) Emission limits. Each process vent must meet the emission limits in Table 1 or 2 to this subpart prior to the vent stream being exposed to the atmosphere. The emission limits in Table 1 or 2 to this subpart apply at all times. The emission limits in Table 1 or 2 to this subpart must not be met through dilution.

(b) Closed vent systems and control devices. Each batch process vent, continuous process vent and miscellaneous vent that is in HAP service must be routed through a closed vent system to a control device. All gas streams routed to the closed vent system and control device must be for a process purpose and not for the purpose of diluting the process vent to meet the emission limits in Table 1 or 2 to this subpart. Each control device used to comply with paragraph (a) of this section must meet the requirements of §§63.11925 and 63.11940, and all closed vent systems must meet the requirements in §63.11930. You must not use a flare to comply with the emission limits in Table 1 or 2 to this subpart.

(c) General monitoring requirements. Except as provided in paragraphs (c)(1) through (3) of this section, for each control device used to comply with the process vent emission limit specified in Table 1 or 2 to this subpart, you must install and operate a continuous parameter monitoring system (CPMS) to monitor each operating parameter specified in §63.11940(a) through (h) to comply with your operating limit(s) required in §63.11880(b).

(1) Hydrogen chloride continuous emission monitoring system (CEMS). In lieu of establishing operating limits in §63.11880(b) and using CPMS to comply with the operating limits, as specified in §63.11940(a) through (h), upon promulgation of a performance specification for hydrogen chloride CEMS, new and existing sources have the option to install a hydrogen chloride CEMS to demonstrate initial and continuous compliance with the hydrogen chloride emission limit for process vents, as specified in paragraphs (d) and (e) of this section.

(2) Dioxin/furan CEMS. In lieu of establishing operating limits in §63.11880(b) and using CPMS to comply with the operating limits as specified in §63.11940(a) through (h), upon promulgation of a performance specification for dioxin/furan CEMS, new and existing sources have the option to install a dioxin/furan CEMS to demonstrate initial and continuous compliance with the dioxins/furan emission limit for process vents, as specified in paragraphs (d) and (e) of this section.

(3) Total hydrocarbon CEMS. In lieu of establishing operating limits in §63.11880(b) and using CPMS to comply with the operating limits as specified in §63.11940(a) through (h), new and existing affected sources have the option to install a total hydrocarbon CEMS to demonstrate initial and continuous compliance with the total hydrocarbons or total organic HAP emission limit for process vents, as specified in paragraphs (d) and (e) of this section.

(d) Initial compliance. To demonstrate initial compliance with the emission limits in Table 1 or 2 to this subpart, you must comply with paragraphs (d)(1) through (5) of this section.

(1) You must conduct an initial inspection as specified in §63.11930(d) for each closed vent system.

(2) For each CEMS and CPMS required or that you elect to use as specified in paragraph (c) of this section, you must prepare the quality control program and site-specific performance evaluation test plan as specified in §63.11935(b) and site-specific monitoring plan specified in §63.11935(c), respectively.

(3) For each CEMS and CPMS required or that you elect to use as specified in paragraph (c) of this section, you must install, operate, and maintain the CEMS and CPMS as specified in §§63.11935(b) and (c), respectively, and you must conduct an initial site-specific performance evaluation test according to your site-specific monitoring plan and §§63.11935(b)(3) and (c)(4), respectively.

(4) For each emission limit for which you use a CEMS to demonstrate compliance, you must meet the requirements specified in §63.11890(c), and you must demonstrate initial compliance with the emission limits in Table 1 or 2 to this subpart based on 3-hour block averages of CEMS data collected at the minimum frequency specified in §63.11935(b)(2) and calculated using the data reduction method specified in §63.11935(e). For a CEMS used on a batch operation, you may use a data averaging period based on an operating block in lieu of the 3-hour averaging period.

(5) For each emission limit in Table 1 or 2 for which you do not use a CEMS to demonstrate compliance, you must meet the requirements of paragraphs (d)(5)(i) and (ii) of this section.

(i) You must conduct an initial performance test according to the requirements in §63.11945 to demonstrate compliance with the total hydrocarbons or total organic HAP emission limit, vinyl chloride emission limit, hydrogen chloride emission limit, and dioxin/furan emission limit in Table 1 or 2 to this subpart.

(ii) During the performance test specified in paragraph (d)(5)(i) of this section, for each CPMS installed and operated as specified in paragraph (c) of this section, you must establish an operating limit as the operating parameter range, minimum operating parameter level, or maximum operating parameter level specified in §63.11935(d). You must meet the requirements specified in §63.11890(c). Each operating limit must be based on the data averaging period for compliance specified in Table 5 to this subpart using data collected at the minimum frequency specified in §63.11935(c)(2) and calculated using the data reduction method specified in §63.11935(e). For a CPMS used on a batch operation, you may use a data averaging period based on an operating block in lieu of the averaging period specified in Table 5 to this subpart.

(e) Continuous compliance. To demonstrate continuous compliance with the emission limits in Table 1 or 2 to this subpart for each process vent, you must comply with paragraphs (e)(1) through (5) of this section.

(1) You must meet the requirements in §63.11930 for each closed vent system.

(2) You must operate and maintain each CEMS and CPMS required in paragraph (c) of this section as specified in §63.11935(b) and (c), respectively.

(3) For each emission limit for which you use a CEMS to demonstrate compliance, you must meet the requirements in paragraphs (e)(3)(i) and (ii) of this section.

(i) You must conduct a periodic site-specific CEMS performance evaluation test according to your quality control program and site-specific performance evaluation test plan specified in §63.11935(b)(1).

(ii) You must demonstrate continuous compliance with the emission limits in Table 1 or 2 to this subpart based on 3-hour block averages of CEMS data collected at the minimum frequency specified in §63.11935(b)(2), and calculated using the data reduction method specified in §63.11935(e). You must meet the requirements specified in §63.11890(c). For a CEMS used on a batch operation, you may use a data averaging period based on an operating block in lieu of the 3-hour averaging period.

(4) For each emission limit for which you do not use a CEMS to demonstrate compliance, you must meet the requirements of paragraphs (e)(4)(i) and (ii) of this section.

(i) You must conduct a performance test once every 5 years according to the requirements in §63.11945 for each pollutant in Table 1 or 2 to this subpart.

(ii) For each CPMS operated and maintained as specified in paragraph (e)(2) of this section, you must meet the requirements specified in paragraphs (e)(4)(ii)(A) through (C) of this section.

(A) You must conduct periodic site-specific CPMS performance evaluation tests according to your site-specific monitoring plan and §63.11935(c).

(B) For each control device being monitored, you must continuously collect CPMS data consistent with §63.11890(c) and your site-specific monitoring plan. You must continuously determine the average value of each monitored operating parameter based on the data collection and reduction methods specified in §§63.11935(c)(2) and 63.11935(e), and the applicable data averaging period for compliance specified in Table 5 to this subpart for all periods the process is operating. For a CPMS used on a batch operation, you may use a data averaging period based on an operating block in lieu of the averaging periods specified in Table 5 to this subpart.

(C) You must demonstrate continuous compliance with each operating limit established in paragraph (d)(5)(ii) of this section using these average values calculated in paragraph (e)(4)(ii)(B) of this section.

(5) Each closed vent system and control device used to comply with an emission limit in Table 1 or 2 to this subpart must be operated at all times when emissions are vented to, or collected by, these systems or devices.

(f) To demonstrate compliance with the dioxin/furan toxic equivalency emission limit specified in Table 1 or 2 to this subpart, you must determine dioxin/furan toxic equivalency as specified in paragraphs (f)(1) through (3) of this section.

(1) Measure the concentration of each dioxin/furan (tetra-through octachlorinated) congener emitted using Method 23 at 40 CFR part 60, appendix A-7.

(2) For each dioxin/furan (tetra-through octachlorinated) congener measured in accordance with paragraph (f)(1) of this section, multiply the congener concentration by its corresponding toxic equivalency factor specified in Table 6 to this subpart.

(3) Sum the products calculated in accordance with paragraph (f)(2) of this section to obtain the total concentration of dioxins/furans emitted in terms of toxic equivalency.

(g) Emission profile. You must characterize each process vent by developing an emissions profile for each contributing continuous process vent, miscellaneous vent and batch process vent according to paragraphs (g)(1) through (3) of this section.

(1) For batch process vents, the emissions profile must:

(i) Describe the characteristics of the batch process vent under worst-case conditions.

(ii) Determine emissions per episode and batch process vent emissions according to the procedures specified in §63.11950.

(2) For continuous process vents, the flow rate and concentration must be determined according to paragraphs (g)(2)(i) through (iii) or according to paragraph (g)(2)(iv):

(i)(A) Method 1 or 1A of 40 CFR part 60, appendix A-1, as appropriate, shall be used for selection of the sampling site. The sampling site shall be after the last recovery device (if any recovery devices are present) but prior to being combined with any other continuous process vent, batch process vent, or miscellaneous vent, prior to the inlet of any control device that is present and prior to release to the atmosphere.

(B) No traverse site selection method is needed for vents smaller than 0.10 meter in diameter.

(ii) The gas volumetric flow rate shall be determined using Method 2, 2A, 2C or 2D of 40 CFR part 60, appendix A-1, as appropriate.

(iii) (A) Method 18 of 40 CFR part 60, appendix A-6 or Method 25A of 40 CFR part 60, appendix A-7 shall be used to measure concentration; alternatively, any other method or data that has been validated according to the protocol in Method 301 of appendix A of this part may be used.

(B) Where Method 18 of 40 CFR part 60, appendix A-6 is used, the following procedures shall be used to calculate parts per million by volume concentration:

(1) The minimum sampling time for each run shall be 1 hour in which either an integrated sample or four grab samples shall be taken. If grab sampling is used, then the samples shall be taken at approximately equal intervals in time, such as 15-minute intervals during the run.

(2) The concentration of either total organic compounds (TOC) (minus methane and ethane) or organic HAP shall be calculated according to paragraph (g)(2)(iii)(B)(2)(i) or (g)(2)(iii)(B)(2)(ii) of this section as applicable.

(i) The TOC concentration (CTOC) is the sum of the concentrations of the individual components and shall be computed for each run using Equation 1 of this section:

eCFR graphic er17ap12.001.gif

View or download PDF

Where:

CTOC = Concentration of TOC (minus methane and ethane), dry basis, parts per million by volume.

Cji = Concentration of sample component j of the sample i, dry basis, parts per million by volume.

n = Number of components in the sample.

x = Number of samples in the sample run.

(ii) The total organic HAP concentration (CHAP) shall be computed according to Equation 1 of this section except that only the organic HAP species shall be summed. The list of organic HAP is provided in Table 2 to subpart F of this part.

(C) Where Method 25A of 40 CFR part 60, appendix A-7 is used, the following procedures shall be used to calculate parts per million by volume TOC concentration:

(1) Method 25A of 40 CFR part 60, appendix A-7, shall be used only if a single organic HAP compound is greater than 50 percent of total organic HAP, by volume, in the vent stream.

(2) The vent stream composition may be determined by either process knowledge, test data collected using an appropriate EPA method, or a method or data validated according to the protocol in Method 301 of appendix A of this part. Examples of information that could constitute process knowledge include calculations based on material balances, process stoichiometry, or previous test results provided the results are still relevant to the current vent stream conditions.

(3) The organic HAP used as the calibration gas for Method 25A of 40 CFR part 60, appendix A-7 shall be the single organic HAP compound present at greater than 50 percent of the total organic HAP by volume.

(4) The span value for Method 25A of 40 CFR part 60, appendix A-7 shall be 50 parts per million by volume.

(5) Use of Method 25A of 40 CFR part 60, appendix A-7 is acceptable if the response from the high-level calibration gas is at least 20 times the standard deviation of the response from the zero calibration gas when the instrument is zeroed on the most sensitive scale.

(iv) Engineering assessment including, but not limited to, the following:

(A) Previous test results provided the tests are representative of current operating practices at the process unit.

(B) Bench-scale or pilot-scale test data representative of the process under representative operating conditions.

(C) Maximum flow rate, TOC emission rate, organic HAP emission rate, or net heating value limit specified or implied within a permit limit applicable to the process vent.

(D) Design analysis based on accepted chemical engineering principles, measurable process parameters, or physical or chemical laws or properties. Examples of analytical methods include, but are not limited to:

(1) Use of material balances based on process stoichiometry to estimate maximum organic HAP concentrations,

(2) Estimation of maximum flow rate based on physical equipment design such as pump or blower capacities,

(3) Estimation of TOC or organic HAP concentrations based on saturation conditions,

(4) Estimation of maximum expected net heating value based on the vent stream concentration of each organic compound or, alternatively, as if all TOC in the vent stream were the compound with the highest heating value.

(E) All data, assumptions, and procedures used in the engineering assessment shall be documented.

(3) For miscellaneous process vents the emissions profile must be determined according to paragraph (g)(2)(iv) of this section.

(h) Process changes. Except for temporary shutdowns for maintenance activities, if you make a process change such that, as a result of that change, you are subject to a different process vent limit in Table 1 or 2 to this subpart, then you must meet the requirements of §63.11896.

§63.11930   What requirements must I meet for closed vent systems?

(a) General. To route emissions from process vents subject to the emission limits in Table 1 or 2 to this subpart to a control device, you must use a closed vent system and meet the requirements of this section and all provisions referenced in this section. However, if you operate and maintain your closed vent system in vacuum service as defined in §63.12005, you must meet the requirements in paragraph (h) of this section and are not required to meet the requirements in paragraphs (a) through (g) of this section.

(b) Collection of emissions. Each closed vent system must be designed and operated to collect the HAP vapors from each continuous process vent, miscellaneous process vent and batch process vent, and to route the collected vapors to a control device.

(c) Bypass. For each closed vent system that contains a bypass as defined in §63.12005 (e.g., diverting a vent stream away from the control device), you must not discharge to the atmosphere through the bypass. Any such release constitutes a violation of this rule. The use of any bypass diverted to the atmosphere during a performance test invalidates the performance test. You must comply with the provisions of either paragraph (c)(1) or (2) of this section for each closed vent system that contains a bypass that could divert a vent stream to the atmosphere.

(1) Bypass flow indicator. Install, maintain, and operate a flow indicator as specified in paragraphs (c)(1)(i) through (iv) of this section.

(i) The flow indicator must be properly installed at the entrance to any bypass.

(ii) The flow indicator must be equipped with an alarm system that will alert an operator immediately, and automatically when flow is detected in the bypass. The alarm must be located such that the alert is detected and recognized easily by an operator.

(iii) If the alarm is triggered, you must immediately initiate procedures to identify the cause of the alarm. If any closed vent system has discharged to the atmosphere through a vent or bypass, you must initiate procedures to stop the bypass discharge.

(iv) For any instances where the flow indicator alarm is triggered, you must submit to the Administrator as part of your compliance report, the information specified in §63.11985(b)(9) and (10). This report is required even if you elect to follow the procedures specified in §63.11895 to establish an affirmative defense and submit the reports specified in §63.11985(b)(11).

(2) Bypass valve configuration. Secure the bypass valve in the non-diverting position with a car-seal or a lock-and-key type configuration.

(i) You must visually inspect the seal or closure mechanism at least once every month to verify that the valve is maintained in the non-diverting position, and the vent stream is not diverted through the bypass. A broken seal or closure mechanism or a diverted valve constitutes a violation from the emission limits in Table 1 or 2 to this subpart. You must maintain the records specified in paragraph (g)(1)(ii) of this section.

(ii) For each seal or closure mechanism, you must comply with either paragraph (c)(2)(ii)(A) or (B) of this section.

(A) For each instance that you change the bypass valve to the diverting position, you must submit to the Administrator as part of your compliance report, the information specified in §63.11985(b)(9) and (10). This report is required even if you elect to follow the procedures specified in §63.11895 to establish an affirmative defense and submit the reports specified in §63.11985(b)(11).

(B) You must install, maintain, and operate a bypass flow indicator as specified in paragraphs (c)(1)(i) and (ii) of this section and you must meet the requirements in paragraph (c)(1)(iii) and (iv) of this section for each instance that the flow indicator alarm is triggered.

(d) Closed vent system inspection and monitoring requirements. Except as provided in paragraph (d)(3) of this section, you must inspect each closed vent system as specified in paragraph (d)(1) or (2) of this section.

(1) Hard-piping inspection. If the closed vent system is constructed of hard-piping, you must comply with the requirements specified in paragraphs (d)(1)(i) and (ii) of this section.

(i) Conduct an initial inspection according to the procedures in paragraph (e) of this section.

(ii) Conduct annual inspections for visible, audible, or olfactory indications of leaks.

(2) Ductwork inspection. If the closed vent system is constructed of ductwork, you must conduct initial and annual inspections according to the procedures in paragraph (e) of this section.

(3) Equipment that is unsafe to inspect. You may designate any parts of the closed vent system as unsafe to inspect if you determine that personnel would be exposed to an immediate danger as a consequence of complying with the initial and annual closed vent system inspection requirements of this subpart.

(e) Closed vent system inspection procedures. Except as provided in paragraph (e)(4) of this section, you must comply with all provisions of paragraphs (e)(1) through (3) of this section.

(1) General. Inspections must be performed during periods when HAP is being collected by or vented through the closed vent system. A leak is indicated by an instrument reading greater than 500 parts per million by volume above background or by visual inspection.

(2) Inspection procedures. Each closed vent system subject to this paragraph (e)(2) must be inspected according to the procedures specified in paragraphs (e)(2)(i) through (vii) of this section.

(i) Inspections must be conducted in accordance with Method 21 at 40 CFR part 60, appendix A-7, except as otherwise specified in this section.

(ii) Except as provided in paragraph (e)(2)(iii) of this section, the detection instrument must meet the performance criteria of Method 21 at 40 CFR part 60, appendix A-7, except the instrument response factor criteria in section 8.1.1.2 of Method 21 must be for the representative composition of the process fluid and not of each individual volatile organic compound in the stream. For process streams that contain nitrogen, air, water or other inerts that are not organic HAP or volatile organic compound, the representative stream response factor must be determined on an inert-free basis. You may determine the response factor at any concentration for which you will monitor for leaks.

(iii) If no instrument is available at the plant site that will meet the performance criteria of Method 21 at 40 CFR part 60, appendix A-7 specified in paragraph (e)(2)(ii) of this section, the instrument readings may be adjusted by multiplying by the representative response factor of the process fluid, calculated on an inert-free basis as described in paragraph (e)(2)(ii) of this section.

(iv) The detection instrument must be calibrated before use on each day of its use by the procedures specified in Method 21 at 40 CFR part 60, appendix A-7.

(v) Calibration gases must be as specified in paragraphs (e)(2)(v)(A) through (D) of this section.

(A) Zero air (less than 10 parts per million by volume hydrocarbon in air).

(B) Mixtures of methane in air at a concentration less than 10,000 parts per million by volume. A calibration gas other than methane in air may be used if the instrument does not respond to methane or if the instrument does not meet the performance criteria specified in paragraph (e)(2)(ii) of this section. In such cases, the calibration gas may be a mixture of one or more of the compounds to be measured in air.

(C) If the detection instrument's design allows for multiple calibration scales, then the lower scale must be calibrated with a calibration gas that is no higher than 2,500 parts per million by volume.

(D) Perform a calibration drift assessment, at a minimum, at the end of each monitoring day. Check the instrument using the same calibration gas(es) that were used to calibrate the instrument before use. Follow the procedures specified in Method 21 at 40 CFR part 60, appendix A-7, section 10.1, except do not adjust the meter readout to correspond to the calibration gas value. Record the instrument reading for each scale used as specified in paragraph (g)(4) of this section. Divide these readings by the initial calibration values for each scale and multiply by 100 to express the calibration drift as a percentage. If any calibration drift assessment shows a negative drift of more than 10 percent from the initial calibration value, then all equipment monitored since the last calibration with instrument readings below the appropriate leak definition and above the leak definition multiplied by the value specified in paragraph (e)(2)(v)(D)(1) of this section must be re-monitored. If any calibration drift assessment shows a positive drift of more than 10 percent from the initial calibration value, then, at your discretion, all equipment since the last calibration with instrument readings above the appropriate leak definition and below the leak definition multiplied by the value specified in paragraph (e)(2)(v)(D)(2) of this section may be re-monitored.

(1) 100 minus the percent of negative drift, divided by 100.

(2) 100 plus the percent of positive drift, divided by 100.

(vi) You may elect to adjust or not adjust instrument readings for background. If you elect not to adjust readings for background, all such instrument readings must be compared directly to 500 parts per million by volume to determine whether there is a leak. If you elect to adjust instrument readings for background, you must measure background concentration using the procedures in this section. You must subtract the background reading from the maximum concentration indicated by the instrument.

(vii) If you elect to adjust for background, the arithmetic difference between the maximum concentration indicated by the instrument and the background level must be compared with 500 parts per million by volume for determining whether there is a leak.

(3) Instrument probe. The instrument probe must be traversed around all potential leak interfaces as described in Method 21 at 40 CFR part 60, appendix A-7.

(4) Unsafe-to-inspect written plan requirements. For equipment designated as unsafe to inspect according to the provisions of paragraph (d)(3) of this section, you must maintain and follow a written plan that requires inspecting the equipment as frequently as practical during safe-to-inspect times, but not more frequently than the annual inspection schedule otherwise applicable. You must still repair unsafe-to-inspect equipment according to the procedures in paragraph (f) of this section if a leak is detected.

(f) Closed vent system leak repair provisions. The provisions of this paragraph (f) apply to closed vent systems collecting HAP from an affected source.

(1) Leak repair general for hard-piping. If there are visible, audible, or olfactory indications of leaks at the time of the annual visual inspections required by paragraph (d)(1)(ii) of this section, you must follow the procedure specified in either paragraph (f)(1)(i) or (ii) of this section.

(i) You must eliminate the leak.

(ii) You must monitor the equipment according to the procedures in paragraph (e) of this section and comply with the leak repair provisions in paragraph (f)(2) of this section.

(2) Leak repair schedule. Leaks must be repaired as soon as practical, except as provided in paragraph (f)(3) of this section.

(i) A first attempt at repair must be made no later than 5 days after the leak is detected.

(ii) Except as provided in paragraph (f)(3) of this section, repairs must be completed no later than 15 days after the leak is detected or at the beginning of the next introduction of vapors to the system, whichever is later.

(3) Delay of repair. Delay of repair of a closed vent system for which leaks have been detected is allowed if repair within 15 days after a leak is detected is technically infeasible or unsafe without a closed vent system shutdown or if you determine that emissions resulting from immediate repair would be greater than the emissions likely to result from delay of repair. Repair of such equipment must be completed as soon as practical, but not later than the end of the next closed vent system shutdown.

(g) Closed vent system records. For closed vent systems, you must record the information specified in paragraphs (g)(1) through (5) of this section, as applicable.

(1) Bypass records. For each closed vent system that contains a bypass that could divert a vent stream away from the control device and to the atmosphere, or cause air intrusion into the control device, you must keep a record of the information specified in either paragraph (g)(1)(i) or (ii) of this section, as applicable.

(i) You must maintain records of any alarms triggered because flow was detected in the bypass, including the date and time the alarm was triggered, the duration of the flow in the bypass, as well as records of the times of all periods when the vent stream is diverted from the control device or the flow indicator is not operating.

(ii) Where a seal mechanism is used to comply with paragraph (c)(2) of this section, hourly records of flow are not required. In such cases, you must record that the monthly visual inspection of the seals or closure mechanisms has been done, and must record the occurrence of all periods when the seal mechanism is broken, the bypass valve position has changed, or the key for a lock-and-key type lock has been checked out, and records of any car-seal that has been broken.

(2) Inspection records. For each instrumental or visual inspection conducted in accordance with paragraph (d)(1) or (2) of this section for closed vent systems collecting HAP from an affected source during which no leaks are detected, you must record that the inspection was performed, the date of the inspection, and a statement that no leaks were detected.

(3) Leak records. When a leak is detected from a closed vent system collecting HAP from an affected source, the information specified in paragraphs (g)(3)(i) through (vi) of this section must be recorded and kept for 5 years.

(i) The instrument and the equipment identification number and the operator name, initials, or identification number.

(ii) The date the leak was detected and the date of the first attempt to repair the leak.

(iii) The date of successful repair of the leak.

(iv) The maximum instrument reading measured by the procedures in paragraph (e) of this section after the leak is successfully repaired.

(v) Repair delayed and the reason for the delay if a leak is not repaired within 15 days after discovery of the leak. You may develop a written procedure that identifies the conditions that justify a delay of repair. In such cases, reasons for delay of repair may be documented by citing the relevant sections of the written procedure.

(vi) Copies of the compliance reports as specified in §63.11985(b)(9), if records are not maintained on a computerized database capable of generating summary reports from the records.

(4) Instrument calibration records. You must maintain records of the information specified in paragraphs (g)(4)(i) through (vi) of this section for monitoring instrument calibrations conducted according to sections 8.1.2 and 10 of Method 21 at 40 CFR part 60, appendix A-7, and paragraph (e) of this section.

(i) Date of calibration and initials of operator performing the calibration.

(ii) Calibration gas cylinder identification, certification date, and certified concentration.

(iii) Instrument scale(s) used.

(iv) A description of any corrective action taken if the meter readout could not be adjusted to correspond to the calibration gas value in accordance with section 10.1 of Method 21 at 40 CFR part 60, appendix A-7.

(v) Results of each calibration drift assessment required by paragraph (e)(2)(v)(D) of this section (i.e., instrument reading for calibration at end of the monitoring day and the calculated percent difference from the initial calibration value).

(vi) If you make your own calibration gas, a description of the procedure used.

(5) Unsafe-to-inspect records. If you designate equipment as unsafe-to-inspect as specified in paragraph (d)(3) of this section, you must keep the records specified in paragraph (g)(5)(i) and (ii) of this section.

(i) You must maintain the identity of unsafe-to-inspect equipment as specified in paragraph (d)(3) of this section.

(ii) You must keep a written plan for inspecting unsafe-to-inspect equipment as required by paragraph (e)(4) of this section and record all activities performed according to the written plan.

(h) Closed vent systems in vacuum service. If you operate and maintain a closed vent system in vacuum service as defined in §63.12005, you must comply with the requirements in paragraphs (h)(1) through (3) of this section, and you are not required to comply with any other provisions of this section. Any incidence where a closed vent system designed to be in vacuum service is operating and not in vacuum service constitutes a violation of this rule, unless the closed vent system is meeting the requirements in paragraphs (a) through (g) of this section for closed vent systems that are not in vacuum service. Any such incidence during a performance test invalidates the performance test.

(1) In vacuum service alarm. You must install, maintain, and operate a pressure gauge and alarm system that will alert an operator immediately and automatically when the pressure is such that the closed vent system no longer meets the definition of in vacuum service as defined in §63.12005. The alarm must be located such that the alert is detected and recognized easily by an operator.

(2) In vacuum service alarm procedures. If the alarm is triggered for a closed vent system operating in vacuum service as specified in paragraph (h)(1) of this section, you must immediately initiate procedures to identify the cause of the alarm. If the closed vent system is not in vacuum service, you must initiate procedures to get the closed vent system back in vacuum service as defined in §63.12005, or you must immediately comply with the requirements in paragraphs (a) through (g) of this section for closed vent systems that are not in vacuum service.

(3) In vacuum service alarm records and reports. For any incidences where a closed vent system designed to be in vacuum service is not in vacuum service, you must submit to the Administrator as part of your compliance report, the information specified in §63.11985(b)(10). This report is required even if you elect to follow the procedures specified in §63.11895 to establish an affirmative defense and submit the reports specified in §63.11985(b)(11).

§63.11935   What CEMS and CPMS requirements must I meet to demonstrate initial and continuous compliance with the emission standards for process vents?

(a) General requirements for CEMS and CPMS. You must meet the requirements in paragraph (b) of this section for each CEMS specified in §63.11925(c) used to demonstrate compliance with the emission limits for process vents in Table 1 or 2 to this subpart. You must meet the CPMS requirements in paragraph (c) of this section and establish your operating limits in paragraph (d) of this section for each operating parameter specified in Table 5 to this subpart for each process vent control device specified in §63.11925(b) that is used to comply with the emission limits for process vents in Table 1 or 2 to this subpart, except that flow indicators specified in §63.11940(a) are not subject to the requirements of this section.

(b) CEMS. You must install, operate, and maintain each CEMS according to paragraphs (b)(1) through (7) of this section and continuously monitor emissions.

(1) You must prepare your quality control program and site-specific performance evaluation test plan, as specified in §63.8(d) and (e). You must submit your performance evaluation test plan to the Administrator for approval, as specified in §63.8(e)(3).

(2) The monitoring equipment must be capable of providing a continuous record, recording data at least once every 15 minutes.

(3) You must conduct initial and periodic site-specific performance evaluations and any required tests of each CEMS according to your quality control program and site-specific performance evaluation test plan prepared as specified in §63.8(d) and (e).

(4) If supplemental gases are added to the control device, you must correct the measured concentrations in accordance with §63.11945(d)(3).

(5) You must operate and maintain the CEMS in continuous operation according to the quality control program and performance evaluation test plan. CEMS must record data at least once every 15 minutes.

(6) CEMS must meet the minimum accuracy and calibration frequency requirements specified in the performance specifications specified in paragraphs (b)(6)(i) and (ii) of this section, as applicable.

(i) A hydrogen chloride or dioxin/furan CEMS must meet the requirements of the promulgated performance specification for the CEMS.

(ii) A total hydrocarbon CEMS must meet the requirements of 40 CFR Part 60, Appendix B, performance specification 8A.

(7) Before commencing or ceasing use of a CEMS system, you must notify the Administrator as specified in paragraphs (b)(7)(i) and (ii) of this section.

(i) You must notify the Administrator 1 month before starting use of the continuous emissions monitoring system.

(ii) You must notify the Administrator 1 month before stopping use of the continuous emissions monitoring system, in which case you must also conduct a performance test within 60 days of ceasing operation of the system.

(c) CPMS. You must install, maintain, and operate each CPMS as specified in paragraphs (c)(1) through (6) of this section and continuously monitor operating parameters.

(1) As part of your quality control program and site-specific performance evaluation test plan prepared as specified in §63.8(d) and (e), you must prepare a site-specific monitoring plan that addresses the monitoring system design, data collection, and the quality assurance and quality control elements specified in paragraphs (c)(1)(i) through (v) of this section and §63.8(d). You are not required to submit the plan for approval unless requested by the Administrator. You may request approval of monitoring system quality assurance and quality control procedure alternatives to those specified in paragraphs (c)(1)(i) through (v) of this section in your site-specific monitoring plan.

(i) The performance criteria and design specifications for the monitoring system equipment, including the sample interface, detector signal analyzer, and data acquisition and calculations.

(ii) Sampling interface (e.g., thermocouple) location such that the monitoring system will provide representative measurements.

(iii) Equipment performance checks, calibrations, or other audit procedures.

(iv) Ongoing operation and maintenance procedures in accordance with provisions in §63.8(c)(1) and (3).

(v) Ongoing reporting and recordkeeping procedures in accordance with provisions in §63.10(c), (e)(1) and (e)(2)(i).

(2) The monitoring equipment must be capable of providing a continuous record, recording data at least once every 15 minutes.

(3) You must install, operate, and maintain each CPMS according to the procedures and requirements in your site-specific monitoring plan.

(4) You must conduct an initial and periodic site-specific performance evaluation tests of each CPMS according to your site-specific monitoring plan.

(5) All CPMS must meet the specific parameter (e.g., minimum accuracy and calibration frequency) requirements specified in §63.11940 and Table 7 to this subpart.

(6) Monitoring equipment for temperature, pressure, volumetric flow rate, mass flow rate and conductivity must be capable of measuring the appropriate parameter over a range that extends at least 20 percent beyond the normal expected operating range of values for that parameter. The data recording system associated with affected CPMS must have a resolution that is equal to or better than one-half of the required system accuracy.

(d) Establish operating limit. For each operating parameter that must be monitored in §63.11925(c) for process vent control devices, you must establish an operating limit as specified in paragraphs (d)(1) through (4) of this section. You must establish each operating limit as an operating parameter range, minimum operating parameter level, or maximum operating parameter level as specified in Table 7 to this subpart. Where this subpart does not specify which format to use for your operating limit (e.g., operating range or minimum operating level), you must determine which format is best to establish proper operation of the control device such that you are meeting the emission limits specified in Table 1 or 2 to this subpart.

(1) For process vent control devices, the operating limit established for each monitored parameter specified in §63.11940 must be based on the operating parameter values recorded during any performance test conducted to demonstrate compliance as required by §63.11925(d)(4) and (e)(4) and may be supplemented by engineering assessments and/or manufacturer's recommendations. You are not required to conduct performance tests over the entire range of allowed operating parameter values. The established operating limit must represent the conditions for which the control device is meeting the emission limits specified in Table 1 or 2 to this subpart.

(2) You must include as part of the notification of compliance status or the operating permit application or amendment, the information in paragraphs (d)(2)(i) through (iv) of this section, as applicable, for each process vent control device requiring operating limits.

(i) Descriptions of monitoring devices, monitoring frequencies and operating scenarios.

(ii) The established operating limit of the monitored parameter(s).

(iii) The rationale for the established operating limit, including any data and calculations used to develop the operating limit and a description of why the operating limit indicates proper operation of the control device.

(iv) The rationale used to determine which format to use for your operating limit (e.g., operating range, minimum operating level or maximum operating level), where this subpart does not specify which format to use.

(3) For batch processes, you may establish operating limits for individual batch emission episodes, including each distinct episode of process vent emissions or each individual type of batch process that generates wastewater, if applicable. You must provide rationale in a batch precompliance report as specified in §63.11985(c)(2) instead of the notification of compliance status for the established operating limit. You must include any data and calculations used to develop the operating limits and a description of why each operating limit indicates proper operation of the control device during the specific batch emission episode.

(4) If you elect to establish separate operating limits for different batch emission episodes within a batch process as specified in paragraph (d)(3) of this section, you must maintain daily records indicating each point at which you change from one operating limit to another, even if the monitoring duration for an operating limit is less than 15 minutes. You must maintain a daily record according to §63.11990(e)(4)(i).

(e) Reduction of CPMS and CEMS data. You must reduce CEMS and CPMS data to 1-hour averages according to §63.8(g) to compute the average values for demonstrating compliance specified in §§63.11925(e)(3)(ii), 63.11925(e)(4)(ii)(B), and 63.11960(c)(2) for CEMS and CPMS, as applicable.

§63.11940   What continuous monitoring requirements must I meet for control devices required to install CPMS to meet the emission limits for process vents?

As required in §63.11925(c), you must install and operate the applicable CPMS specified in paragraphs (a) through (g) of this section for each control device you use to comply with the emission limits for process vents in Table 1 or 2 to this subpart. You must monitor, record, and calculate CPMS data averages as specified in Table 7 to this subpart. Paragraph (h) of this section provides an option to propose alternative monitoring parameters or procedures.

(a) Flow indicator. If flow to a control device could be intermittent, you must install, calibrate, and operate a flow indicator at the inlet or outlet of the control device to identify periods of no flow.

(b) Thermal oxidizer monitoring. If you are using a thermal oxidizer to meet an emission limit in Table 1 or 2 to this subpart and you are required to use CPMS as specified in §63.11925(c), you must equip the thermal oxidizer with the monitoring equipment specified in paragraphs (b)(1) through (3) of this section, as applicable.

(1) If a thermal oxidizer other than a catalytic thermal oxidizer is used, you must install a temperature monitoring device in the fire box or in the ductwork immediately downstream of the fire box in a position before any substantial heat exchange occurs.

(2) Except as provided in paragraph (b)(3) of this section, where a catalytic thermal oxidizer is used, you must install temperature monitoring devices in the gas stream immediately before and after the catalyst bed. You must monitor the temperature differential across the catalyst bed.

(3) Instead of complying with paragraph (b)(2) of this section, and if the temperature differential between the inlet and outlet of the catalytic thermal oxidizer during normal operating conditions is less than 10 degrees Celsius (18 degrees Fahrenheit), you may elect to monitor the inlet temperature and conduct catalyst checks as specified in paragraphs (b)(3)(i) and (ii) of this section.

(i) You must conduct annual sampling and analysis of the catalyst activity (i.e., conversion efficiency) following the manufacturer's or catalyst supplier's recommended procedures. If problems are found during the catalyst activity test, you must replace the catalyst bed or take other corrective action consistent with the manufacturer's recommendations within 15 days or by the next time any process vent stream is collected by the control device, whichever is sooner.

(ii) You must conduct annual internal inspections of the catalyst bed to check for fouling, plugging, or mechanical breakdown. You must also inspect the bed for channeling, abrasion, and settling. If problems are found during the annual internal inspection of the catalyst, you must replace the catalyst bed or take other corrective action consistent with the manufacturer's recommendations within 15 days or by the next time any process vent stream is collected by the control device, whichever is later. If the catalyst bed is replaced and is not of like or better kind and quality as the old catalyst then you must conduct a new performance test according to §63.11945 to determine destruction efficiency. If a catalyst bed is replaced and the replacement catalyst is of like or better kind and quality as the old catalyst, then a new performance test to determine destruction efficiency is not required.

(c) Absorber and acid gas scrubber monitoring. If you are using an absorber or acid gas scrubber to meet an emission limit in Table 1 or 2 to this subpart and you are required to use CPMS as specified in §63.11925(c), you must install the monitoring equipment specified in paragraphs (c)(1) through (3) of this section.

(1) Install and operate the monitoring equipment as specified in either paragraph (c)(1)(i) or (ii) of this section.

(i) A flow meter to monitor the absorber or acid gas scrubber influent liquid flow.

(ii) A flow meter to monitor the absorber or acid gas scrubber influent liquid flow and the gas stream flow using one of the procedures specified in paragraphs (c)(1)(ii)(A), (B), or (C) of this section. You must monitor the liquid-to-gas ratio determined by dividing the flow rate of the absorber or acid gas scrubber influent by the gas flow rate. The units of measure must be consistent with those used to calculate this ratio during the performance test.

(A) Determine gas stream flow using the design blower capacity, with appropriate adjustments for pressure drop.

(B) Measure the gas stream flow at the absorber or acid gas scrubber inlet.

(C) If you have previously determined compliance for a scrubber that requires a determination of the liquid-to-gas ratio, you may use the results of that test provided the test conditions are representative of current operation.

(2) Install and operate the monitoring equipment as specified in either paragraph (c)(2)(i), (ii), or (iii) of this section.

(i) Install and operate pressure gauges at the inlet and outlet of the absorber or acid gas scrubber to monitor the pressure drop through the absorber or acid gas scrubber.

(ii) If the difference in the inlet gas stream temperature and the inlet liquid stream temperature is greater than 38 degrees Celsius, you may install and operate a temperature monitoring device at the scrubber gas stream exit.

(iii) If the difference between the specific gravity of the scrubber effluent scrubbing fluid and specific gravity of the scrubber inlet scrubbing fluid is greater than or equal to 0.02 specific gravity units, you may install and operate a specific gravity monitoring device on the inlet and outlet of the scrubber.

(3) If the scrubbing liquid is a reactant (e.g., lime, ammonia hydroxide), you must install and operate one of the devices listed in either paragraph (c)(3)(i), (ii) or (iii) of this section.

(i) A pH monitoring device to monitor the pH of the scrubber liquid effluent.

(ii) A caustic strength monitoring device to monitor the caustic strength of the scrubber liquid effluent.

(iii) A conductivity monitoring device to monitor the conductivity of the scrubber liquid effluent.

(d) Regenerative adsorber monitoring. If you are using a regenerative adsorber to meet an emission limit in Table 1 or 2 to this subpart and you are required to use CPMS as specified in §63.11925(c), you must install and operate the applicable monitoring equipment listed in paragraphs (d)(1) through (5) of this section, and comply with the requirements in paragraphs (d)(6) and (7) of this section. If the adsorption system water is wastewater as defined in §63.12005, then it is subject to the requirements of §63.11965.

(1) For non-vacuum regeneration systems, an integrating regeneration stream flow monitoring device having an accuracy of ±10 percent, capable of recording the total regeneration stream mass for each regeneration cycle. For non-vacuum regeneration systems, an integrating regeneration stream flow monitoring device capable of continuously recording the total regeneration stream mass flow for each regeneration cycle.

(2) For non-vacuum regeneration systems, an adsorber bed temperature monitoring device, capable of continuously recording the adsorber bed temperature after each regeneration and within 15 minutes of completing any temperature regulation (cooling or warming to bring bed temperature closer to vent gas temperature) portion of the regeneration cycle.

(3) For non-vacuum and non-steam regeneration systems, an adsorber bed temperature monitoring device capable of continuously recording the bed temperature during regeneration, except during any temperature regulating (cooling or warming to bring bed temperature closer to vent gas temperature) portion of the regeneration cycle.

(4) For a vacuum regeneration system, a pressure transmitter installed in the vacuum pump suction line capable of continuously recording the vacuum level for each minute during regeneration. You must establish a minimum target and a length of time at which the vacuum must be below the minimum target during regeneration.

(5) A device capable of monitoring the regeneration frequency (i.e., operating time since last regeneration) and duration.

(6) You must perform a verification of the adsorber during each day of operation. The verification must be through visual observation or through an automated alarm or shutdown system that monitors and records system operational parameters. The verification must verify that the adsorber is operating with proper valve sequencing and cycle time.

(7) You must conduct weekly measurements of the carbon bed outlet volatile organic compounds concentration over the last 5 minutes of an adsorption cycle for each carbon bed. For regeneration cycles longer than 1 week, you must perform the measurement over the last 5 minutes of each adsorption cycle for each carbon bed. The outlet concentration of volatile organic compounds must be measured using a portable analyzer, in accordance with Method 21 at 40 CFR part 60, appendix A-7, for open-ended lines. Alternatively, outlet concentration of HAP(s) may be measured using chromatographic analysis using Method 18 at 40 CFR part 60, appendix A-6.

(e) Non-regenerative adsorber monitoring. If you are using a non-regenerative adsorber, or canister type system that is sent off site for regeneration or disposal, to meet an emission limit in Table 1 or 2 to this subpart and you are required to use CPMS as specified in §63.11925(c), you must install a system of dual adsorber units in series and conduct the monitoring and bed replacement as specified in paragraphs (e)(1) through (4) of this section.

(1) Establish the average adsorber bed life by conducting daily monitoring of the outlet volatile organic compound or HAP concentration, as specified in this paragraph (e)(1), of the first adsorber bed in series until breakthrough occurs for the first three adsorber bed change-outs. The outlet concentration of volatile organic compounds must be measured using a portable analyzer, in accordance with Method 21 at 40 CFR part 60, appendix A-7, for open-ended lines. Alternatively, outlet concentration of HAP may be measured using chromatographic analysis using Method 18 at 40 CFR part 60, appendix A-6. Breakthrough of the bed is defined as the time when the level of HAP detected is at the highest concentration allowed to be discharged from the adsorber system.

(2) Once the average life of the bed is determined, conduct ongoing monitoring as specified in paragraphs (e)(2)(i) through (iii) of this section.

(i) Except as provided in paragraphs (e)(2)(ii) and (iii) of this section, conduct daily monitoring of the adsorber bed outlet volatile organic compound or HAP concentration, as specified in paragraph (e)(1) of this section.

(ii) You may conduct monthly monitoring if the adsorbent has more than 2 months of life remaining, as determined by the average primary adsorber bed life, established in paragraph (e)(1) of this section, and the date the adsorbent was last replaced.

(iii) You may conduct weekly monitoring if the adsorbent has more than 2 weeks of life remaining, as determined by the average primary adsorber bed life, established in paragraph (e)(1) of this section, and the date the adsorbent was last replaced.

(3) The first adsorber in series must be replaced immediately when breakthrough is detected between the first and second adsorber. The original second adsorber (or a fresh canister) will become the new first adsorber and a fresh adsorber will become the second adsorber. For purposes of this paragraph (e)(3), “immediately” means within 8 hours of the detection of a breakthrough for adsorbers of 55 gallons or less, and within 24 hours of the detection of a breakthrough for adsorbers greater than 55 gallons.

(4) In lieu of replacing the first adsorber immediately, you may elect to monitor the outlet of the second canister beginning on the day the breakthrough between the first and second canister is identified and each day thereafter. This daily monitoring must continue until the first canister is replaced. If the constituent being monitored is detected at the outlet of the second canister during this period of daily monitoring, both canisters must be replaced within 8 hours of the time of detection of volatile organic compounds or HAP at 90 percent of the allowed level (90 percent of breakthrough definition).

(f) Condenser monitoring. If you are using a condenser to meet an emission limit in Table 1 or 2 to this subpart and you are required to use CPMS as specified in §63.11925(c), you must install and operate a condenser exit gas temperature monitoring device.

(g) Other control devices. If you use a control device other than those listed in this subpart to comply with an emission limit in Table 1 or 2 to this subpart and you are required to use CPMS as specified in §63.11925(c), you must comply with the requirements as specified in paragraphs (g)(1) and (2) of this section.

(1) Submit a description of the planned monitoring, recordkeeping, and reporting procedures. The Administrator will approve, deny or modify the proposed monitoring, reporting and recordkeeping requirements as part of the review of the plan or through the review of the permit application or by other appropriate means.

(2) You must establish operating limits for monitored parameters that are approved by the Administrator. To establish the operating limit, the information required in §63.11935(d) must be submitted in the notification of compliance status report specified in §63.11985(a).

(h) Alternatives to monitoring requirements. (1) You may request approval to use alternatives to the continuous operating parameter monitoring listed in this section, as specified in §§63.11985(c)(4) and 63.8.

(2) You may request approval to monitor a different parameter than those established in §63.11935(d) or to set unique monitoring parameters, as specified in §§63.11985(c)(5) and 63.8. Until permission to use an alternative monitoring parameter has been granted by the Administrator, you remain subject to the requirements of this subpart.

§63.11945   What performance testing requirements must I meet for process vents?

(a) General. For each control device used to meet the emission limits for process vents in Table 1 or 2 to this subpart, you must conduct the initial and periodic performance tests required in §63.11925(d) and (e) and as specified in §63.11896 using the applicable test methods and procedures specified in Table 8 to this subpart and paragraphs (b) through (d) of this section.

(b) Process operating conditions. You must conduct performance tests under the conditions specified in paragraphs (b)(1) through (3) of this section, as applicable. Upon request, the owner or operator shall make available to the Administrator such records as may be necessary to determine the conditions of performance tests. In all cases, a site-specific plan must be submitted to the Administrator for approval prior to testing in accordance with §63.7(c). The test plan must include the emission profiles described in §63.11925(g).

(1) Continuous process vents. For continuous process vents, you must conduct all performance tests at maximum representative operating conditions for the process. For continuous compliance, you must conduct subsequent performance tests within the range of operating limit(s) that were established for the control device during the initial or subsequent performance tests specified in §63.11925(d) and (e). If an operating limit is a range, then you must conduct subsequent performance tests within the range of maximum or minimum operating limits for the control device, which result in highest emissions (i.e., lowest emission reduction).

(2) Batch process operations. Testing must be conducted at absolute worst-case conditions or hypothetical worst-case conditions as specified in paragraph (c) of this section.

(3) Combination of both continuous and batch unit operations. You must conduct performance tests when the batch process vents are operating at absolute worst-case conditions or hypothetical worst-case conditions, as specified in paragraphs (c)(1) and (2) of this section, and at maximum representative operating conditions for the process. For continuous compliance, you must operate the control device as close as possible to your operating limit(s) for the control device established during the initial or subsequent performance tests specified in §63.11925 (d) and (e). If an operating limit is a range, then you must operate the control device as close as possible to the maximum or minimum operating limit for the control device, whichever results in higher emissions (i.e., lower emission reduction), unless the Administrator specifies or approves alternate operating conditions.

(c) Batch worst-case conditions. The absolute worst-case conditions for batch process operations must be characterized by the criteria presented in paragraph (c)(1) of this section. The hypothetical worst-case conditions for batch process operations must be characterized by the criteria presented in paragraph (c)(2) of this section.

(1) Absolute worst-case conditions. For batch process operations, absolute worst-case conditions are defined by the criteria presented in paragraph (c)(1)(i) of this section if the maximum load is the most challenging condition for the control device. Otherwise, absolute worst-case conditions are defined by the conditions in paragraph (c)(1)(ii) of this section. You must consider all relevant factors, including load and compound-specific characteristics in defining absolute worst-case conditions.

(i) A 1-hour period of time in which the inlet to the control device contains the highest HAP mass loading rate, in pounds per hour, capable of being vented to the control device. An emission profile as described in §63.11925(g) must be used to identify the 1-hour period of maximum HAP loading.

(ii) The period of time when the HAP loading or stream composition (including non-HAP) is most challenging for the control device. These conditions include, but are not limited to the following:

(A) Periods when the stream contains the highest combined organic load, in pounds per hour, described by the emission profiles in §63.11925(g).

(B) Periods when the streams contain HAP constituents that approach limits of solubility for scrubbing media.

(C) Periods when the streams contain HAP constituents that approach limits of adsorptivity for adsorption systems.

(2) Hypothetical worst-case conditions. For batch process operations, hypothetical worst-case conditions are simulated test conditions that, at a minimum, contain the highest hourly HAP load of emissions that would be predicted to be vented to the control device based on the emissions profiles described in paragraphs (c)(3)(ii) or (iii) of this section.

(3) Emission profile. For batch process operations, you must develop an emission profile for the vent to the control device that describes the characteristics of the vent stream at the inlet to the control device under worst-case conditions. The emission profile must be developed based on any one of the procedures described in paragraphs (c)(3)(i) through (iii) of this section.

(i) Emission profile by process. The emission profile must consider all batch emission episodes that could contribute to the vent stack for a period of time that is sufficient to include all processes venting to the stack and must consider production scheduling. The profile must describe the HAP load to the device that equals the highest sum of emissions from the episodes that can vent to the control device in any given hour. Emissions per episode must be calculated using the procedures specified in §63.11950. Emissions per episode must be divided by the duration of the episode only if the duration of the episode is longer than 1 hour.

(ii) Emission profile by equipment. The emission profile must consist of emissions that meet or exceed the highest emissions, in pounds per hour that would be expected under actual processing conditions. The profile must describe equipment configurations used to generate the emission events, volatility of materials processed in the equipment, and the rationale used to identify and characterize the emission events. The emissions may be based on using a compound more volatile than compounds actually used in the process(es), and the emissions may be generated from all equipment in the process(es) or only selected equipment.

(iii) Emission profile by capture and control device limitation. The emission profile must consider the capture and control system limitations and the highest emissions, in pounds per hour that can be routed to the control device, based on maximum flow rate and concentrations possible because of limitations on conveyance and control equipment (e.g., fans and lower explosive level alarms).

(d) Concentration correction calculation. If a combustion device is the control device and supplemental combustion air is used to combust the emissions, the concentration of total hydrocarbons, total organic HAP, vinyl chloride, and hydrogen chloride must be corrected as specified in paragraph (d)(1) or (2) of this section. If a control device other than a combustion device is used to comply with an outlet concentration emission limit for batch process vents, you must correct the actual concentration for supplemental gases as specified in paragraph (d)(3) of this section.

(1) Determine the concentration of total hydrocarbons, total organic HAP, vinyl chloride, or hydrogen chloride corrected to 3-percent oxygen (Cc) using Equation 1 of this section.

eCFR graphic er17ap12.002.gif

View or download PDF

Where:

Cc = Concentration of total hydrocarbons, total organic HAP, vinyl chloride, or hydrogen chloride corrected to 3-percent oxygen, dry basis, parts per million by volume.

Cm = Concentration of total hydrocarbons, total organic HAP, vinyl chloride, or hydrogen chloride, dry basis, parts per million by volume.

%O2d = Concentration of oxygen, dry basis, percentage by volume.

(2) To determine the oxygen concentration, you must use the emission rate correction factor (or excess air), integrated sampling and analysis procedures of Method 3, 3A, or 3B at 40 CFR part 60, appendix A-2, or ANSI/ASME PTC 19.10-1981 (incorporated by reference, see §63.14).

(3) Correct the measured concentration for supplemental gases using Equation 2 of this section. Process knowledge and representative operating data may be used to determine the fraction of the total flow due to supplemental gas.

eCFR graphic er17ap12.003.gif

View or download PDF

Where:

Ca = Corrected outlet concentration of HAP, dry basis, parts per million by volume (ppmv).

Cm = Actual concentration of HAP measured at control device outlet, dry basis, ppmv.

Qa = Total volumetric flow rate of all gas streams vented to the control device, except supplemental gases.

Qs = total volumetric flow rate of supplemental gases.

§63.11950   What emissions calculations must I use for an emission profile?

When developing your emission profiles for batch process vents as required in §63.11925(g), except as specified in paragraph (i) of this section, you must calculate emissions from episodes caused by vapor displacement, purging a partially filled vessel, heating, depressurization, vacuum operations, gas evolution, air drying, or empty vessel purging, using the applicable procedures in paragraphs (a) through (h) of this section.

(a) Vapor displacement. You must calculate emissions from vapor displacement due to transfer of material using Equation 1 of this section.

eCFR graphic er17ap12.004.gif

View or download PDF

(Eq. 1)

Where:

E = Mass of HAP emitted.

V = Volume of gas displaced from the vessel.

R = Ideal gas law constant.

T = Temperature of the vessel vapor space; absolute.

Pi = Partial pressure of the individual HAP.

MWi = Molecular weight of the individual HAP.

n = Number of HAP compounds in the emission stream.

i = Identifier for a HAP compound.

(b) Gas sweep of a partially filled vessel. You must calculate emissions from purging a partially filled vessel using Equation 2 of this section. The pressure of the vessel vapor space may be set equal to 760 millimeters of mercury (mmHg). You must multiply the HAP partial pressure in Equation 2 of this section by a HAP-specific saturation factor determined in accordance with Equations 3 through 5 of this section. Solve Equation 3 of this section iteratively beginning with saturation factors (in the right-hand side of the equation) of 1.0 for each condensable compound. Stop iterating when the calculated saturation factors for all compounds are the same to two significant figures for subsequent iterations. Note that for multi-component emission streams, saturation factors must be calculated for all condensable compounds, not just the HAP.

eCFR graphic er17ap12.005.gif

View or download PDF

(Eq. 2)

Where:

E = Mass of HAP emitted.

V = Purge flow rate of the noncondensable gas at the temperature and pressure of the vessel vapor space.

R = Ideal gas law constant.

T = Temperature of the vessel vapor space; absolute.

Pi = Partial pressure of the individual HAP at saturated conditions.

Pj = Partial pressure of individual condensable compounds (including HAP) at saturated conditions.

PT = Pressure of the vessel vapor space.

MWi = Molecular weight of the individual HAP.

t = Time of purge.

n = Number of HAP compounds in the emission stream.

i = Identifier for a HAP compound.

j = Identifier for a condensable compound.

m = Number of condensable compounds (including HAP) in the emission stream.

eCFR graphic er17ap12.006.gif

View or download PDF

Where:

Si = Saturation factor for individual condensable compounds.

Pi = Partial pressure of individual condensable compounds at saturated conditions.

PT = Pressure of the vessel vapor space.

A = Surface area of liquid.

V = Purge flow rate of the noncondensable gas.

Visat = Volumetric flow rate of individual condensable compounds at saturated vapor pressure.

Ki = Mass transfer coefficient of individual condensable compounds in the emission stream.

Ko = Mass transfer coefficient of reference compound (e.g., 0.83 cm/s for water).

Mo = Molecular weight of reference compound (e.g., 18.02 for water).

Mi = Molecular weight of individual condensable compounds in the emission stream.

n = Number of condensable compounds in the emission stream.

(c) Heating. You must calculate emissions caused by the heating of a vessel to a temperature lower than the boiling point using the procedures in paragraph (c)(1) of this section. If the contents of a vessel are heated to the boiling point, you must calculate emissions using the procedures in paragraph (c)(2) of this section.

(1) If the final temperature to which the vessel contents are heated is lower than the boiling point of the HAP in the vessel, you must calculate the mass of HAP emitted per episode using Equation 6 of this section. The average gas space molar volume during the heating process is calculated using Equation 7 of this section. The difference in the number of moles of condensable in the vessel headspace between the initial and final temperatures is calculated using Equation 8 of this section.

eCFR graphic er17ap12.007.gif

View or download PDF

(Eq. 6)

Where:

E = Mass of HAP vapor displaced from the vessel being heated.

Navg = Average gas space molar volume during the heating process.

PT = Total pressure in the vessel.

Pi,1 = Partial pressure of the individual HAP compounds at initial temperature (T1).

Pi,2 = Partial pressure of the individual HAP compounds at final temperature (T2).

MWHAP = Average molecular weight of the HAP compounds calculated using Equation 13 of this section.

ni,1 = Number of moles of condensable in the vessel headspace at initial temperature (T1).

ni,2 = Number of moles of condensable in the vessel headspace at final temperature (T2).

n = Number of HAP compounds in the emission stream.

ln = Natural logarithm.

eCFR graphic er17ap12.008.gif

View or download PDF

(Eq. 7)

Where:

Navg = Average gas space molar volume during the heating process.

V = Volume of free space in vessel.

PT = Total pressure in the vessel.

R = Ideal gas law constant.

T1 = Initial temperature of the vessel.

T2 = Final temperature of the vessel.

eCFR graphic er17ap12.009.gif

View or download PDF

Where:

V = Volume of free space in vessel.

R = Ideal gas law constant.

T1 = Initial temperature in the vessel.

T2 = Final temperature in the vessel.

Pi,1 = Partial pressure of the individual HAP compounds at T1.

Pi,2 = Partial pressure of the individual HAP compounds at T2.

n = Number of HAP compounds in the emission stream.

(2) If the final temperature to which the vessel contents are heated is at the boiling point or higher, you must calculate emissions using the procedure in paragraphs (c)(2)(i) and (ii) of this section.

(i) To calculate the emissions from heating to the boiling point use Equations 9, 10 and 11 of this section. (Note that Pa2 = 0 in the calculation of Δη in Equation 10 of this section.)

eCFR graphic er17ap12.010.gif

View or download PDF

Where:

E = Mass of HAP emitted.

Δη = The number of moles of noncondensable displaced from the vessel, as calculated using Equation 10 of this section.

PT = Pressure in the receiver.

Pi = Partial pressure of the individual HAP determined at the exit temperature of the condenser or at the conditions of the dedicated receiver.

Pj = Partial pressure of the individual condensable (including HAP) determined at the exit temperature of the condenser or at the conditions of the dedicated receiver.

n = Number of HAP compounds in the emission stream.

i = Identifier for a HAP compound.

j = Identifier for a condensable compound.

MWHAP = The average molecular weight of HAP in vapor exiting the dedicated receiver, as calculated using Equation 11 of this section with partial pressures determined at the exit temperature and exit pressure conditions of the condenser or at the conditions of the dedicated receiver.

m = Number of condensable compounds (including HAP) in the emission stream.

eCFR graphic er17ap12.011.gif

View or download PDF

eCFR graphic er17ap12.012.gif

View or download PDF

Where:

Δη = Number of moles of noncondensable gas displaced from the vessel.

V = Volume of free space in the vessel.

R = Ideal gas law constant.

T1 = Initial temperature of vessel contents, absolute.

T2 = Final temperature of vessel contents, absolute.

Pan = Partial pressure of noncondensable gas in the vessel headspace at initial (n=1) and final (n=2) temperature.

MWHAP = The average molecular weight of HAP in vapor exiting the dedicated receiver.

(Pi)Tn = Partial pressure of each HAP in the vessel headspace at initial (T1) and final (T2) temperature of the receiver.

MWi = Molecular weight of the individual HAP.

n = Number of HAP compounds in the emission stream.

i = Identifier for a HAP compound.

(ii) While boiling, the vessel must be operated with a properly operated process condenser. An initial demonstration that a process condenser is properly operated must be conducted during the boiling operation and documented in the notification of compliance status report described in §63.11985(a). You must either measure the liquid temperature in the receiver or the temperature of the gas stream exiting the condenser and show it is less than the boiling or bubble point of the HAP in the vessel; or perform a material balance around the vessel and condenser and show that at least 99 percent of the recovered HAP vaporized while boiling is condensed. This demonstration is not required if the process condenser is followed by a condenser acting as a control device or if the control device is monitored using a CEMS.

(d) Depressurization. You must calculate emissions from depressurization using Equation 12 of this section.

eCFR graphic er17ap12.013.gif

View or download PDF

Where:

E = Emissions.

V = Free volume in vessel being depressurized.

R = Ideal gas law constant.

T = Temperature of the vessel, absolute.

P1 = Initial pressure in the vessel.

P2 = Final pressure in the vessel.

Pj = Partial pressure of the individual condensable compounds (including HAP).

MWi = Molecular weight of the individual HAP compounds.

n = Number of HAP compounds in the emission stream.

m = Number of condensable compounds (including HAP) in the emission stream.

i = Identifier for a HAP compound.

j = Identifier for a condensable compound.

ln = Natural logarithm.

(e) Vacuum systems. You must calculate emissions from vacuum systems using Equation 13 of this section if the air leakage rate is known or can be approximated. The receiving vessel is part of the vacuum system for purposes of this subpart.

eCFR graphic er17ap12.014.gif

View or download PDF

Where:

E = Mass of HAP emitted.

PT = Absolute pressure of receiving vessel or ejector outlet conditions, if there is no receiver.

Pi = Partial pressure of the HAP at the receiver temperature or the ejector outlet conditions.

Pj = Partial pressure of condensable (including HAP) at the receiver temperature or the ejector outlet conditions.

La = Total air leak rate in the system, mass/time.

MWnc = Molecular weight of noncondensable gas.

t = Time of vacuum operation.

MWi = Molecular weight of the individual HAP in the emission stream, with HAP partial pressures calculated at the temperature of the receiver or ejector outlet, as appropriate.

(f) Gas evolution. You must calculate emissions from gas evolution using Equation 13 in paragraph (e) of this section with mass flow rate of gas evolution, Wg, substituted for La.

(g) Air drying. You must calculate emissions from air drying using Equation 14 of this section:

eCFR graphic er17ap12.015.gif

View or download PDF

Where:

E = Mass of HAP emitted.

B = Mass of dry solids.

PS1 = HAP in material entering dryer, weight percent.

PS2 = HAP in material exiting dryer, weight percent.

(h) Empty vessel purging. You must calculate emissions from empty vessel purging using Equation 15 of this section (Note: The term e-Ft/v can be assumed to be 0):

eCFR graphic er17ap12.016.gif

View or download PDF

Where:

V = Volume of empty vessel.

R = Ideal gas law constant.

T = Temperature of the vessel vapor space; absolute.

Pi = Partial pressure of the individual HAP at the beginning of the purge.

MWi = Molecular weight of the individual HAP.

F = Flow rate of the purge gas.

t = Duration of the purge.

n = Number of HAP compounds in the emission stream.

i = Identifier for a HAP compound.

(i) Engineering assessments. You must conduct an engineering assessment to calculate HAP emissions or emission episodes from each process vent that are not due to vapor displacement, partially filled vessel purging, heating, depressurization, vacuum operations, gas evolution, air drying or empty vessel purging. An engineering assessment may also be used to support a finding that the emissions estimation equations in this section are inappropriate. All data, assumptions and procedures used in the engineering assessment must be documented, are subject to preapproval by the Administrator, and must be reported in the batch precompliance report. An engineering assessment should include, but is not limited to, the items listed in paragraphs (i)(1) through (4) of this section.

(1) Previous test results provided the tests are representative of current operating practices at the process unit.

(2) Bench-scale or pilot-scale test data representative of the process under representative operating conditions.

(3) Maximum flow rate, HAP emission rate, concentration, or other relevant parameter specified or implied within a permit limit applicable to the process vent.

(4) Design analysis based on accepted chemical engineering principles, measurable process parameters, or physical or chemical laws or properties. Examples of analytical methods include, but are not limited to the following:

(i) Use of material balances based on process stoichiometry to estimate maximum organic HAP concentrations.

(ii) Estimation of maximum flow rate based on physical equipment design such as pump or blower capacities.

(iii) Estimation of HAP concentrations based on saturation conditions.

§63.11955   What are my initial and continuous compliance requirements for other emission sources?

(a) Before opening any process component (including pre-polymerization reactors used in the manufacture of bulk resins) for any reason, the quantity of vinyl chloride must be reduced to an amount that occupies a volume of no more than 2.0 percent of the component's or equipment's containment volume, or 25 gallons, whichever is larger, at standard temperature and pressure.

(b) Before opening a polymerization reactor for any reason, the quantity of vinyl chloride is not to exceed 0.04 pounds per ton of PVC product, with the product determined on a dry solids basis.

(c) Any gas or vapor HAP removed from a process component in accordance with paragraphs (a) and (b) of this section must be vented to a closed vent system and control device meeting the requirements of §§63.11925 through 63.11950.

(d) Each gasholder in vinyl chloride service must meet the requirements of paragraphs (d)(1) through (3) of this section.

(1) Each gasholder must be vented to a closed vent system and control device meeting the requirements of §§63.11925 through 63.11950.

(2) Each gasholder must operate with one or more of the following installed on the water seal to reduce emissions:

(i) Floating balls;

(ii) Hollow floating disks;

(iii) Oil layer; and/or

(iv) Floating mats.

(3) Each gasholder must have established operating procedures that include provisions for ensuring that the requirements of paragraph (d)(2) of this section are met at all times except during periods of maintenance or repair. The standard operating procedures must be developed and implemented and made available to the Administrator upon request.

§63.11956   What are my compliance requirements for ambient monitoring?

You must operate a reliable and accurate vinyl chloride monitoring system for detection of major leaks and identification of the general area of the affected source where a leak is located. A vinyl chloride monitoring system means a device which obtains air samples from one or more points on a continuous sequential basis and analyzes the samples with gas chromatography or, if you assume that all hydrocarbons measured are vinyl chloride, analyzes the samples with infrared spectrophotometry, flame ion detection, or an equivalent or alternative method. You must operate the vinyl chloride monitoring system according to a program that you develop for your affected source. You must submit a description of the program to the Administrator within 45 days of your compliance date, unless a waiver of compliance is granted by the Administrator, or the program has been approved and the Administrator does not request a review of the program. Approval of a program will be granted by the Administrator provided the Administrator finds:

(a) The location and number of points to be monitored and the frequency of monitoring provided for in the program are acceptable when they are compared with the number of pieces of equipment in vinyl chloride service and size and physical layout of the affected source.

(b) It contains a definition of leak which is acceptable when compared with the background concentrations of vinyl chloride in the areas of the plant to be monitored by the vinyl chloride monitoring system. Measurements of background concentrations of vinyl chloride in the areas of the plant to be monitored by the vinyl chloride monitoring system are to be included with the description of the program. The definition of leak for a given plant may vary among the different areas within the plant and is also to change over time as background concentrations in the plant are reduced.

(c) It contains an acceptable plan of action to be taken when a leak is detected.

(d) It provides for an acceptable calibration and maintenance schedule for the vinyl chloride monitoring system and portable hydrocarbon detector. For the vinyl chloride monitoring system, a daily span check must be conducted with a concentration of vinyl chloride equal to the concentration defined as a leak according to paragraph (b) of this section. The calibration must be done with either:

(1) A calibration gas mixture prepared from the gases specified in sections 7.2.1 and 7.2.2 of Method 106 at 40 CFR part 61, appendix B, and in accordance with section 10.1 of Method 106, or

(2) A calibration gas cylinder standard containing the appropriate concentration of vinyl chloride. The gas composition of the calibration gas cylinder standard must have been certified by the manufacturer. The manufacturer must have recommended a maximum shelf life for each cylinder so that the concentration does not change greater than ±5 percent from the certified value. The date of gas cylinder preparation, certified vinyl chloride concentration, and recommended maximum shelf life must have been affixed to the cylinder before shipment from the manufacturer to the buyer. If a gas chromatograph is used as the vinyl chloride monitoring system, these gas mixtures may be directly used to prepare a chromatograph calibration curve as described in Sections 8.1 and 9.2 of Method 106. The requirements in Sections 7.2.3.1 and 7.2.3.2 of Method 106 for certification of cylinder standards and for establishment and verification of calibration standards are to be followed.

§63.11960   What are my initial and continuous compliance requirements for stripped resin?

(a) Emission limits. You must meet the applicable vinyl chloride and total non-vinyl chloride organic HAP emission limits for stripped resin specified in Table 1 or 2 to this subpart.

(b) Determination of total non-vinyl chloride organic HAP. You must develop a facility-specific list of HAP that are expected to be present in each grade of resin produced by your PVCPU. This list must be continuously updated and must be available for inspection by the Administrator. This list must include the identification of each grade of resin produced, each HAP expected to be present in that grade of resin, and the CAS number for each HAP.

(1) For the purposes of demonstrating initial and continuous compliance as required in paragraphs (c) and (d) of this section, you must meet the requirements specified in paragraphs (b)(1)(i) and (b)(1)(ii) of this section.

(i) You must analyze each resin sample for all Table 10 HAP using the test methods specified in paragraph (e) of this section.

(ii) You must also analyze each resin sample for any HAP that are not a Table 10 HAP but are expected to be present in that resin sample based on your facility-specific list of HAP using the appropriate test method specified in paragraph (e) of this section.

(2) [Reserved]

(c) Demonstration of initial compliance. You must demonstrate initial compliance for each resin stripper or for each group of resin strippers used to process the same resin type.

(1) You must conduct an initial performance test for the resin stripper, measuring the concentration of vinyl chloride and total non-vinyl chloride organic HAP in the stripped resin at the outlet of each resin stripper as specified in paragraphs (c)(1)(i) through (iv) of this section.

(i) Use the test method(s) and procedures specified in paragraph (e) of this section.

(ii) Collect samples when the PVCPU is producing the resin grade of which you manufacture the most, based on the total mass per resin grade of a given resin type produced in the 12 months preceding the sampling event.

(iii) For continuous processes, during a 24-hour sampling period, for each resin grade produced, collect 1 grab sample at intervals of 8 hours or per grade of PVC produced, whichever is more frequent. Each sample must be taken as the resin flows out of the stripper.

(iv) For batch processes, during a 24-hour sampling period, for each batch of each resin grade produced, collect 1 grab sample for each batch. Each sample must be taken immediately following the completion of the stripping operation.

(2) Demonstrate initial compliance with the vinyl chloride and total non-vinyl chloride organic HAP emission limits in Table 1 or 2 to this subpart as specified in paragraphs (c)(2)(i) and (ii) of this section.

(i) Calculate the 24-hour arithmetic average vinyl chloride and total non-vinyl chloride organic HAP concentrations for each stripper for each resin grade produced during the 24-hour sampling period, using the vinyl chloride and non vinyl-chloride HAP concentrations measured for the grab samples collected as specified in paragraph (c)(1)(iii) and (iv) of this section and using the calculation procedure specified in paragraph (f) of this section to determine the total non-vinyl chloride organic HAP concentration of each sample.

(ii) Demonstrate compliance with the vinyl chloride and total non-vinyl chloride organic HAP emission limits in Table 1 or 2 to this subpart based on the 24-hour arithmetic average concentrations calculated in either paragraph (c)(2)(ii)(A) or (B) of this section.

(A) If more than one resin grade was produced during the 24-hour sampling period, use Equation 1 of this section to calculate the 24-hour grade weighted arithmetic average vinyl chloride and total non-vinyl chloride organic HAP concentrations for each stripper, or for each group of strippers used to process the same type of resin, using the 24-hour average vinyl chloride and total non-vinyl chloride organic HAP concentrations calculated in paragraph (c)(2)(i) of this section and the mass of each resin grade produced during the 24-hour sampling period.

eCFR graphic er17ap12.017.gif

View or download PDF

Where:

AT = 24-hour average concentration of resin type T, parts per million by weight (dry basis).

PGi = Production of resin grade Gi, pounds.

CGi = 24-hour average concentration of vinyl chloride or total non-vinyl chloride organic HAP in resin grade Gi, ppmw.

QT = Total production of resin type T over the 24-hour sampling period, pounds.

(B) If only one resin grade was produced during the 24-hour sampling event, use the 24-hour arithmetic average vinyl chloride and total non-vinyl chloride organic HAP concentrations for the one resin grade calculated as specified in paragraph (c)(2)(i) of this section for each stripper or calculate the 24-hour arithmetic average vinyl chloride and total non-vinyl chloride organic HAP concentrations for all strippers used to process the one grade of resin.

(d) Demonstration of continuous compliance. You must demonstrate continuous compliance for each resin stripper or for each group of resin strippers used to process the same resin type.

(1) On a daily basis, you must measure the concentration of vinyl chloride in stripped resin using the test method(s) and procedures specified in paragraph (e) of this section, and the procedures specified in paragraphs (c)(1)(iii) and (iv) of this section.

(2) On a monthly basis, you must measure the concentration of total non-vinyl chloride organic HAP in stripped resin using the test method(s) and procedures specified in paragraph (e) of this section, and the procedures specified in paragraphs (c)(1)(iii) and (iv) of this section.

(3) You must demonstrate continuous compliance with the vinyl chloride and total non-vinyl chloride organic HAP emission limit for stripped resin in Table 1 or 2 to this subpart as specified in paragraphs (c)(2)(i) and (ii) of this section.

(e) Test methods and procedures for determining concentration of vinyl chloride and total non-vinyl chloride organic HAP. You must determine the concentration of vinyl chloride and total non-vinyl chloride organic HAP using the test methods and procedures specified in paragraphs (e)(1) through (3) of this section. Upon request, the owner or operator shall make available to the Administrator such records as may be necessary to determine the conditions of performance tests.

(1) For measuring total non-vinyl chloride organic HAP, you must use the methods specified in paragraphs (e)(1)(i) through (iv) of this section.

(i) SW-846-8260B (incorporated by reference, see §63.14) for analysis of volatile organic compounds listed in Table 10 of this subpart.

(ii) SW-846-8270D (incorporated by reference, see §63.14) for analysis of semivolatile organic compounds listed in table 10 of this subpart.

(iii) SW-846-8315A (incorporated by reference, see §63.14) for analysis of aldehyde compounds listed in table 10 of this subpart.

(iv) SW-846-8015C (incorporated by reference, see §63.14) for analysis of alcohol compounds listed in table 10 of this subpart.

(2) For measuring vinyl chloride, you must use Method 107 at 40 CFR part 61, appendix B.

(3) When using the methods specified in paragraphs (e)(1) and (2) of this section, for sample collection, preservation, transport, and analysis, you must minimize loss of HAP and maintain sample integrity.

(f) Method for calculating total non-vinyl chloride organic HAP concentration. For each stripped resin sample analyzed using the methods specified in paragraph (e) of this section, calculate the sum of the measured concentrations of each HAP analyzed as required in paragraphs (b)(1)(i) and (b)(1)(ii) of this section by using Equation 2 to this section.

eCFR graphic er17ap12.018.gif

View or download PDF

Where:

CTNVCH = Concentration of total non-vinyl chloride organic HAP compounds in the stripped resin sample, in parts per million by weight (ppmw).

Ci = Concentration of individual HAP present in the stripped resin sample analyzed pursuant to paragraphs (b)(1)(i) and (b)(1)(ii) of this section excluding vinyl chloride, in ppmw, where a value of zero should be used for any HAP concentration that is below the detection limit.

§63.11965   What are my general compliance requirements for wastewater?

(a) The concentration of vinyl chloride and total non-vinyl chloride organic HAP in each process wastewater stream containing greater than the limits specified in Table 1 or 2 to this subpart, measured immediately as it leaves a piece of process equipment and before being mixed with any other process wastewater stream, must be reduced to the limits specified in Table 1 or 2 to this subpart. The applicable limits in Table 1 or 2 to this subpart must be met before the process wastewater stream is mixed with any other process wastewater stream containing vinyl chloride or total non-vinyl chloride organic HAP concentrations less than the applicable limits specified in Table 1 or 2 to this subpart, before being exposed to the atmosphere, and before being discharged from the affected source.

(b) Initial determination of process wastewater streams that need to be treated. You must determine which process wastewater streams require treatment as specified in paragraphs (b)(1) and (2) of this section and meet the requirements of paragraphs (c) and (d) of this section.

(1) You must collect process wastewater samples as specified in paragraphs (b)(1)(i) and (ii) of this section.

(i) For treated process wastewater streams, you must collect process wastewater samples at the outlet of the treatment process and before the process wastewater stream is mixed with any other process wastewater stream containing vinyl chloride or total non-vinyl chloride organic HAP concentrations less than the applicable limits specified in Table 1 or 2 to this subpart, before being exposed to the atmosphere, and before being discharged from the affected source.

(ii) For untreated process wastewater streams, you must collect process wastewater samples at the location immediately as the stream leaves a piece of process equipment, before being mixed with any other process stream or process wastewater stream, before being exposed to the atmosphere, and before being discharged from the affected source.

(2) You must measure the concentration of vinyl chloride and total non-vinyl chloride organic HAP using the test methods and procedures specified in §63.11980.

(c) Requirements for process wastewater streams that must be treated. Each process wastewater stream that has a vinyl chloride or total non-vinyl chloride organic HAP concentration equal to or greater than the limits specified in Table 1 or 2 to this subpart, determined pursuant to paragraph (a) of this section must be treated to reduce the concentration of vinyl chloride or total non-vinyl chloride organic HAP to below the applicable limits specified in Table 1 or 2 to this subpart. You must route wastewater streams through hard-piping to the treatment process and route the vent stream from the treatment process to a closed vent system and control device meeting the requirements of §§63.11925 through 63.11950. You must also meet the initial and continuous compliance requirements specified in §63.11970(a) and §63.11975.

(d) Requirements for process wastewater streams that do not need to be treated. For each process wastewater stream that has a vinyl chloride or total non-vinyl chloride organic HAP concentration less than the limits specified in Table 1 or 2 to this subpart, determined pursuant to paragraph (a) of this section, you must meet the initial and continuous compliance requirements specified in §§63.11970(b) and 63.11975(c).

(e) Maintenance wastewater. You must comply with the requirements specified in §63.105 of subpart F of this part.

(f) Determination of total non-vinyl chloride organic HAP. You must develop a facility-specific list of HAP that are expected to be present in each process wastewater stream at your PVCPU. This list must be continuously updated and must be available for inspection by the Administrator. This list must include the identification of each HAP expected to be present in each process wastewater stream, and the CAS number for each HAP.

(1) For the purposes of demonstrating initial and continuous compliance as required in §§63.11970 and 63.11975 of this subpart, you must meet the requirements specified in paragraphs (f)(1)(i) and (ii) of this section.

(i) You must analyze each process wastewater sample for all HAP listed in Table 10 to this subpart using the test methods specified in §63.11980(a)(2) and (3).

(ii) You must also analyze each process wastewater sample for any HAP that are not listed in Table 10 to this subpart but are expected to be present in that sample based on your facility-specific list of HAP using the appropriate test method specified in §63.11980(a)(2).

(2) [Reserved]

§63.11970   What are my initial compliance requirements for process wastewater?

(a) Demonstration of initial compliance for process wastewater streams that must be treated. For each process wastewater stream that must be treated as specified in §63.11965(b) and (c), you must conduct an initial performance test for the wastewater treatment process, measuring the concentration of vinyl chloride and total non-vinyl chloride organic HAP in the wastewater stream at the outlet of the wastewater treatment process before the wastewater is exposed to the atmosphere, mixed with any other process stream, and before being discharged from the affected facility, using the test method(s) and procedures specified in §63.11980(a).

(b) Demonstration of initial compliance for process wastewater streams that are not required to be treated. For each process wastewater stream that has a vinyl chloride or total non-vinyl chloride organic HAP concentration less than the limits specified in Tables 1 or 2 to this subpart, you must use the measurement specified in §63.11965(b)(1)(ii) to demonstrate initial compliance.

§63.11975   What are my continuous compliance requirements for process wastewater?

(a) For each process wastewater stream that must be treated to reduce the concentration of vinyl chloride or total non-vinyl chloride organic HAP as specified in §63.11965(b) and (c), you must demonstrate continuous compliance as specified in paragraph (b) of this section. For each process wastewater stream for which you initially determine in §63.11970(b) that treatment is not required to reduce either vinyl chloride or total non-vinyl chloride organic HAP concentration, you must demonstrate continuous compliance as specified in paragraph (c) of this section.

(b) For each process wastewater stream that must be treated according to §63.11965(b), you must demonstrate continuous compliance with the emission limits for vinyl chloride and total non-vinyl chloride organic HAP specified in Table 1 or 2 to this subpart by following the procedures specified in paragraphs (b)(1) and (2) of this section.

(1) Following your demonstration of initial compliance in §63.11970(a), make monthly measurements of the vinyl chloride and total non-vinyl chloride organic HAP concentrations using the procedures and methods specified in §63.11965(b)(1) and (2).

(2) You must demonstrate continuous compliance with the emission limits in Table 1 or 2 to this subpart on a monthly basis, using the monthly concentration measurement specified in paragraph (b)(1) of this section.

(c) For each wastewater stream for which you initially determine in §63.11970(b) that treatment is not required to reduce the vinyl chloride or total non-vinyl chloride organic HAP concentration, you must demonstrate continuous compliance as specified in paragraphs (c)(1) and (2) of this section.

(1) Conduct annual performance tests, measuring the vinyl chloride and total non-vinyl chloride organic HAP concentrations using the procedures and methods specified in §63.11965(b)(1) and (2).

(2) If any annual performance test conducted as specified in paragraph (c)(1) of this section results in a concentration of vinyl chloride or total non-vinyl chloride organic HAP in the process wastewater stream that is greater than or equal to the emission limits in Table 1 or 2 to this subpart, then you must meet the requirements of §63.11965(c) and you must demonstrate initial and continuous compliance as specified in §63.11970 and this section.

§63.11980   What are the test methods and calculation procedures for process wastewater?

(a) Performance test methods and procedures. You must determine the concentration of vinyl chloride and total non-vinyl chloride organic HAP using the test methods and procedures specified in paragraphs (a)(1) through (4) of this section. Upon request, the owner or operator shall make available to the Administrator such records as may be necessary to determine the conditions of performance tests.

(1) You must conduct performance tests during worst-case operating conditions for the PVCPU when the process wastewater treatment process is operating as close as possible to maximum operating conditions. If the wastewater treatment process will be operating at several different sets of operating conditions, you must supplement the testing with additional testing, modeling or engineering assessments to demonstrate compliance with the emission limits.

(2) For measuring total non-vinyl chloride organic HAP, you must conduct sampling and analysis using the methods specified in paragraphs (a)(2)(i) through (iv) of this section.

(i) SW-846-8260B (incorporated by reference, see §63.14) for analysis of volatile organic compounds listed in Table 10 of this subpart.

(ii) SW-846-8270D (incorporated by reference, see §63.14) for analysis of semivolatile organic compounds.

(iii) SW-846-8315A (incorporated by reference, see §63.14) for analysis of aldehyde compounds.

(iv) SW-846-8015C (incorporated by reference, see §63.14) for analysis of alcohol compounds.

(3) For measuring vinyl chloride, you must use Method 107 at 40 CFR part 61, appendix B.

(4) When using the methods in paragraphs (a)(2) and (3) of this section, you must meet the requirements in paragraphs (a)(4)(i) through (iii) of this section.

(i) Sample collection may consist of grab or composite samples.

(ii) Samples must be taken before the process wastewater stream is exposed to the atmosphere.

(iii) You must ensure that sample collection, preservation, transport, and analysis minimizes loss of HAP and maintains sample integrity.

(b) Method for calculating total non-vinyl chloride organic HAP concentration. For each process wastewater stream analyzed using the methods specified in paragraph (a) of this section, calculate the sum of the measured concentrations of each HAP analyzed as required in §63.11965(f)(1) by using Equation 1 to this section.

eCFR graphic er17ap12.019.gif

View or download PDF

Where:

CTNVCH = Concentration of total non-vinyl chloride organic HAP, in parts per million by weight (ppmw).

Ci = Concentration of individual HAP present in the sample analyzed pursuant to §63.11965(f)(1) excluding vinyl chloride, in ppmw, where a value of zero should be used for any HAP concentration that is below the detection limit.

Notifications, Reports and Records

§63.11985   What notifications and reports must I submit and when?

In addition to the notifications and reports required in subpart A of this part, as specified in Table 4 to this subpart, you must submit the additional information and reports specified in paragraphs (a) through (c) of this section, as applicable.

(a) Notification of compliance status. When submitting the notification of compliance status required in §63.9(h), you must also include the information specified in paragraphs (a)(1) through (9) of this section, as applicable.

(1) You must include an identification of the storage vessels subject to this subpart, including the capacity and liquid stored for each vessel. You must submit the information specified in paragraph (a)(2) of this section for each pressure vessel.

(2) You must include the information specified in §63.1039(a) for equipment leaks.

(3) You must include an identification of the heat exchange systems that are subject to the requirements of this subpart.

(4) You must include the operating limit for each monitoring parameter identified for each control device used to meet the emission limits in Table 1 or 2 to this subpart, as determined pursuant to §63.11935(d). This report must include the information in §63.11935(d)(2), as applicable.

(5) You must include the records specified in paragraphs (a)(5)(i) through (iii) of this section, as applicable, for process vents.

(i) You must include the performance test records specified in §63.11990(f)(1), as applicable. These reports must include one complete test report for each test method used for each process vent. A complete test report must include a brief process description, sampling site description, description of sampling and analysis procedures and any modifications to standard procedures, quality assurance procedures, record of operating conditions during the test, record of preparation of standards, record of calibrations, raw data sheets for field sampling, raw data sheets for field and laboratory analyses, documentation of calculations and any other information required by the test method. For additional tests performed for the same kind of emission point using the same method, the results and any other information required in applicable sections of this subpart must be submitted, but a complete test report is not required.

(ii) You must include the information specified in paragraphs (a)(5)(ii)(A) through (C) of this section for batch process vent operations.

(A) Descriptions of worst-case operating and/or testing conditions for control devices including results of emissions profiles.

(B) Calculations used to demonstrate initial compliance according to §§63.11945 and 63.11950, including documentation of the proper operation of a process condenser(s) as specified in §63.11950(c)(2)(ii).

(C) Data and rationale used to support an engineering assessment to calculate emissions in accordance with §63.11950(i).

(iii) If you use a control device other than those listed in §63.11940 for your process vent, then you must include a description of the parameters to be monitored to ensure the control device is operated in conformance with its design and achieves the specified emission limitation; an explanation of the criteria used to select the parameter; and a description of the methods and procedures that will be used to demonstrate that the parameter indicates proper operation of the control device, the schedule for this demonstration, and a statement that you will establish an operating limit for the monitored parameter as specified in paragraph (a)(4) of this section.

(6) [Reserved]

(7) You must include the records specified in paragraphs (a)(7)(i) and (ii) of this section, as applicable, for resin strippers.

(i) You must include an identification of each resin stripper and resin type subject to the requirements of this subpart.

(ii) You must include results of the initial testing used to determine initial compliance with the stripped resin limits in Table 1 or 2 to this subpart.

(8) You must include the records specified in paragraphs (a)(8)(i) and (ii) of this section, as applicable, for process wastewater.

(i) You must include an identification of each process wastewater stream subject to the requirements of this subpart, and the results of your determination for each stream as to whether it must be treated to meet the limits of Table 1 or 2 to this subpart. You must also include a description of the treatment process to be used for each process wastewater stream that requires treatment.

(ii) You must include results of the initial sampling used to determine initial compliance with the vinyl chloride and total non-vinyl chloride organic HAP limits in Table 1 or 2 to this subpart.

(9) You must include a certification of compliance, signed by a responsible official, as applicable that states the following:

(i) “This facility complies with the requirements in this subpart for storage vessels.”

(ii) “This facility complies with the requirements in this subpart for equipment leaks.”

(iii) “This facility complies with the requirements in this subpart for heat exchange systems.”

(iv) “This facility complies with the requirements in this subpart for HAP emissions from process vents.”

(v) “This facility complies with the requirements in this subpart for other emission sources.”

(vi) “This facility complies with the requirements in this subpart for the stripped resin.”

(vii) “This facility complies with the requirements in this subpart for wastewater.”

(b) Compliance reports. When submitting the excess emissions and continuous monitoring system performance report and summary report required in §63.10(e)(3), you must also include the information specified in paragraphs (b)(1) through (12) of this section, as applicable. This report is referred to in this subpart as your compliance report.

(1) You must include a copy of the inspection record specified in §63.11990(b)(2) for each storage vessel when a defect, failure, or leak is detected. You must also include a copy of the applicable information specified in §63.1039(b)(5) through (8) of subpart UU of this part for each pressure vessel.

(2) You must include the information specified in §63.1039(b) for equipment leaks, except for releases from pressure relief devices. For any releases from pressure relief devices, you must submit the report specified in paragraph (c)(7) of this section instead of the information specified in §63.1039(b)(4) of subpart UU of this part.

(3) You must include the information specified in paragraphs (b)(3)(i) through (vi) of this section for heat exchange systems.

(i) The number of heat exchange systems in HAP service.

(ii) The number of heat exchange systems in HAP service found to be leaking.

(iii) A summary of the monitoring data that indicate a leak, including the number of leaks determined to be equal to or greater than the leak definition.

(iv) If applicable, the date a leak was identified, the date the source of the leak was identified and the date of repair.

(v) If applicable, a summary of each delayed repair, including the original date and reason for the delay and the date of repair, if repaired during the reporting period.

(vi) If applicable, an estimate of total VOC or vinyl chloride emissions for each delayed repair over the reporting period.

(4) You must include the records specified in paragraphs (b)(4)(i) through (iii) of this section, as applicable, for process vents, resin strippers, and wastewater.

(i) Deviations using CEMS or CPMS. For each deviation from an emission limit or operating limit where a CEMS or CPMS is being used to comply with the process vent emission limits in Table 1 or 2 to this subpart, you must include the information in paragraphs (b)(4)(i)(A) through (E) of this section.

(A) For CEMS, the 3-hour block average value calculated for any period when the value is higher than an emission limit in Table 1 or 2 to this subpart or when the value does not meet the data availability requirements defined in §63.11890(c).

(B) For CPMS, the average value calculated for any day (based on the data averaging periods for compliance specified in Table 5 to this subpart) that does not meet your operating limit established according to §63.11935(d) or that does not meet the data availability requirements specified in §63.11890(c).

(C) The cause for the calculated emission level or operating parameter level to not meet the established emission limit or operating limit.

(D) For deviations caused by lack of monitoring data, the duration of periods when monitoring data were not collected.

(E) Operating logs of batch process operations for each day during which the deviation occurred, including a description of the operating scenario(s) during the deviation.

(ii) New operating scenario. Include each new operating scenario that has been operated since the time period covered by the last compliance report and has not been submitted in the notification of compliance status report or a previous compliance report. For each new operating scenario, you must provide verification that the operating conditions for any associated control or treatment device have not been exceeded and constitute proper operation for the new operating scenario. You must provide any required calculations and engineering analyses that have been performed for the new operating scenario. For the purposes of this paragraph (b)(4)(ii), a revised operating scenario for an existing process is considered to be a new operating scenario when one or more of the data elements listed in §63.11990(e)(4) have changed.

(iii) Process changes. You must document process changes, or changes made to any of the information submitted in the notification of compliance status report or a previous compliance report, that is not within the scope of an existing operating scenario, in the compliance report. The notification must include all of the information in paragraphs (b)(4)(iii)(A) through (C) of this section.

(A) A description of the process change.

(B) Revisions to any of the information reported in the original notification of compliance status report as provided in paragraph (a) of this section.

(C) Information required by the notification of compliance status report, as provided in paragraph (a) of this section, for changes involving the addition of processes, components, or equipment at the affected source.

(5) You must submit the applicable information specified in paragraphs (b)(5)(i) through (iii) of this section for process vents.

(i) For catalytic thermal oxidizers for which you have selected the alternative monitoring specified in §63.11940(b)(3), results of the annual catalyst sampling and inspections required by §63.11940(b)(3)(i) and (ii) including any subsequent corrective actions taken.

(ii) For regenerative adsorbers, results of the adsorber bed outlet volatile organic compounds concentration measurements specified in §63.11940(d)(7).

(iii) For non-regenerative adsorbers, results of the adsorber bed outlet volatile organic compounds concentration measurements specified in §63.11940(e)(2).

(6) You must include the records specified in §63.11990(j) for other emission sources.

(7) For resin stripper operations, you must include results of daily vinyl chloride and monthly total non-vinyl chloride organic HAP concentration results for each resin type produced within the PVCPU that did not meet the stripped resin emission limits in Table 1 or 2 to this subpart, as applicable.

(8) You must include the information specified in paragraphs (b)(8)(i) and (ii) of this section for your wastewater streams.

(i) Results of daily vinyl chloride and monthly total non-vinyl chloride organic HAP concentration results for each process wastewater stream discharged from the affected source that did not meet the process wastewater emission limits in Tables 1 or 2 to this subpart.

(ii) If you must comply with §63.11965, then you must include any other applicable information that is required by the reporting requirements specified in §63.146.

(9) For closed vent systems subject to the requirements of §63.11930, you must include the information specified in paragraphs (b)(9)(i) through (iv) of this section, as applicable.

(i) As applicable, records as specified in §63.11930(g)(1)(i) for all times when flow was detected in the bypass line, the vent stream was diverted from the control device, or the flow indicator was not operating.

(ii) As applicable, records as specified in §63.11930(g)(1)(ii) for all occurrences of all periods when a bypass of the system was indicated (the seal mechanism is broken, the bypass line valve position has changed, or the key for a lock-and-key type lock has been checked out, and records of any car-seal that has been broken).

(iii) Records of all times when monitoring of the system was not performed as specified in §63.11930(d) and (e), or repairs were not performed as specified in §63.11930(f), or records were not kept as specified in §63.11930(g)(2).

(iv) Records of each time an alarm on a closed vent system operating in vacuum service is triggered as specified in §63.11930(h) including the cause for the alarm and the corrective action taken.

(10) Closed vent system in vacuum service, bypass deviation, or pressure vessel closure device deviation report. If any pressure vessel closure device or closed vent system that contains a bypass has directly discharged to the atmosphere, or any closed vent system that is designed to be in vacuum service and is operating and but not in vacuum service, as specified in §63.11910(c)(4), §63.11930(c) or §63.11930(h), you must submit to the Administrator the following information:

(i) The source, nature and cause of the discharge.

(ii) The date, time and duration of the discharge.

(iii) An estimate of the quantity of vinyl chloride and total HAP emitted during the discharge and the method used for determining this quantity.

(iv) The actions taken to prevent this discharge.

(v) The measures adopted to prevent future such discharges

(11) Affirmative defense report. If you seek to assert an affirmative defense, as provided in §63.11895, then you must submit a written report as specified in §63.11895(b) to demonstrate, with all necessary supporting documentation, that you have met the requirements set forth in §63.11895(a).

(12) Overlap with Title V reports. Information required by this subpart, which is submitted with a Title V periodic report, does not need to be included in a subsequent compliance report required by this subpart or subpart referenced by this subpart. The Title V report must be referenced in the compliance report required by this subpart.

(c) Other notifications and reports. You must submit the other notification and reports, as specified in paragraphs (c)(1) through (9) of this section, as applicable.

(1) Notification of inspection. To provide the Administrator the opportunity to have an observer present, you must notify the Administrator at least 30 days before an inspection required by §63.11910(a)(3). If an inspection is unplanned and you could not have known about the inspection 30 days in advance, then you must notify the Administrator at least 7 days before the inspection. Notification must be made by telephone immediately followed by written documentation demonstrating why the inspection was unplanned. Alternatively, the notification including the written documentation may be made in writing and sent so that it is received by the Administrator at least 7 days before the inspection. If a delegated state or local agency is notified, you are not required to notify the Administrator. A delegated state or local agency may waive the requirement for notification of inspections.

(2) Batch precompliance report. You must submit a batch precompliance report at least 6 months prior to the compliance date of this subpart that includes a description of the test conditions, data, calculations and other information used to establish operating limits according to §63.11935(d) for all batch operations. If you use an engineering assessment as specified in §63.11950(i), then you must also include data or other information supporting a finding that the emissions estimation equations in §63.11950(a) through (h) are inappropriate. If the EPA disapproves the report, then you must still be in compliance with the emission limitations and work practice standards of this subpart by your compliance date. To change any of the information submitted in the report, you must notify the EPA 60 days before you implement the planned change.

(3) Other control device reporting provisions. If you are using a control device other than those listed in this subpart, then you must submit the information as specified in paragraphs (c)(3)(i) through (iii) of this section.

(i) A description of the proposed control device.

(ii) A description of the parameter(s) to be monitored to ensure the control device is operated in conformance with its design and achieves the performance level as specified in this subpart and an explanation of the criteria used to select the parameter(s).

(iii) The frequency and content of monitoring, recording, and reporting if monitoring and recording is not continuous, or if the compliance report information, as specified in paragraph (b)(4)(i)(A) of this section, will not contain 3-hour block average values when the monitored parameter value does not meet the established operating limit. The rationale for the proposed monitoring, recording and reporting system must be included.

(4) Request for approval to use alternative monitoring methods. Prior to your initial notification of compliance status, you may submit requests for approval to use alternatives to the continuous operating parameter monitoring specified in this rule, as provided for in §63.11940(h), following the same procedure as specified in §63.8. The information specified in paragraphs (c)(4)(i) and (ii) of this section must be included.

(i) A description of the proposed alternative system.

(ii) Information justifying your request for an alternative method, such as the technical or economic infeasibility, or the impracticality, of the affected source using the required method.

(5) Request for approval to monitor alternative parameters. Prior to your initial notification of compliance status, you may submit requests for approval to monitor a different parameter than those established in §63.11935(d), following the same procedure as specified for alternative monitoring methods in §63.8. The information specified in paragraphs (c)(5)(i) through (iii) of this section must be included in the request.

(i) A description of the parameter(s) to be monitored to ensure the control technology or pollution prevention measure is operated in conformance with its design and achieves the specified emission limit and an explanation of the criteria used to select the parameter(s).

(ii) A description of the methods and procedures that will be used to demonstrate that the parameter indicates proper operation of the control device, the schedule for this demonstration, and a statement that you will establish an operating limit for the monitored parameter(s) as part of the notification of compliance status if required under this subpart, unless this information has already been submitted.

(iii) The frequency and content of monitoring, recording, and reporting, if monitoring and recording is not continuous. The rationale for the proposed monitoring, recording, and reporting system must be included.

(6) [Reserved]

(7) Pressure relief device deviation report. If any pressure relief device in HAP service has discharged to the atmosphere as specified in §63.11915(c), then you must submit to the Administrator within 10 days of the discharge the following information:

(i) The source, nature, and cause of the discharge.

(ii) The date, time, and duration of the discharge.

(iii) An estimate of the quantity of vinyl chloride and total HAP emitted during the discharge and the method used for determining this quantity.

(iv) The actions taken to prevent this discharge.

(v) The measures adopted to prevent future such discharges.

(8) Commencing and ceasing operation of continuous emissions monitoring systems. Before starting or stopping the use of CEMS you must notify the Administrator as specified in §63.11935(b)(7).

(9) Data submittal. (i) Within 60 days after the date of completing each performance test (see §63.2) required by this subpart, you must submit the results of performance tests electronically to the EPA's WebFIRE database by using the Compliance and Emissions Data Reporting Interface (CEDRI) that is accessed through the EPA's Central Data Exchange (CDX) (http://www.epa.gov/cdx). Performance test data must be submitted in the file format generated through use of the EPA's Electronic Reporting Tool (ERT) (see http://www.epa.gov/ttn/chief/ert/ert_tool.html). Only data collected using test methods compatible with ERT are subject to this requirement to be submitted electronically to WebFIRE. Owners or operators who claim that some of the information being submitted for performance tests is confidential business information (CBI) must submit a complete ERT file including information claimed to be CBI on a compact disk or other commonly used electronic storage media (including, but not limited to, flash drives) to the EPA. The electronic media must be clearly marked as CBI and mailed to U.S. EPA/OAPQS/CORE CBI Office, Attention: WebFIRE Administrator, MD C404-02, 4930 Old Page Rd., Durham, NC 27703. The same ERT file with the CBI omitted must be submitted to the EPA via CDX as described earlier in this paragraph. At the discretion of the delegated authority, you must also submit these reports, including the confidential business information, to the delegated authority in the format specified by the delegated authority.

(ii) Within 60 days after the date of completing each CEMS performance evaluation test (see §63.2), you must submit the relative accuracy test audit data electronically into the EPA's CDX by using the ERT, as mentioned in paragraph (c)(9)(i) of this section. Only data collected using test methods compatible with ERT are subject to this requirement to be submitted electronically to the EPA's CDX.

(iii) All reports required by this subpart not subject to the requirements in paragraphs (c)(9)(i) and (ii) of this section must be sent to the Administrator at the appropriate address listed in §63.13. The Administrator or the delegated authority may request a report in any form suitable for the specific case (e.g., by electronic media such as Excel spreadsheet, on CD or hard copy). The Administrator retains the right to require submittal of reports subject to paragraphs (c)(9)(i) and (ii) of this section in paper format.

§63.11990   What records must I keep?

You must keep records as specified in paragraphs (a) through (j) of this section, as applicable.

(a) Copies of reports. You must keep a copy of each notification and report that you submit to comply with this subpart, including all documentation supporting any notification or report. You must also keep copies of the current versions of the site-specific performance evaluation test plan, site-specific monitoring plan, and the equipment leak detection and repair plan.

(b) Storage vessels. For storage vessels, you must maintain the records specified in paragraphs (b)(1) through (6) of this section.

(1) You must keep a record of the dimensions of the storage vessel, an analysis of the capacity of the storage vessel and an identification of the liquid stored.

(2) Inspection records for fixed roofs complying with §63.11910 including the information specified in paragraphs (b)(2)(i) and (ii) of this section.

(i) Record the date of each inspection required by §63.11910(a)(3).

(ii) For each defect detected during an inspection required by §63.11910(a)(3), record the location of the defect, a description of the defect, the date of detection and corrective action taken to repair the defect. In the event that repair of the defect is delayed in accordance with §63.11910(a)(4)(ii), also record the reason for the delay and the date that completion of repair of the defect is expected.

(3) [Reserved]

(4) For pressure vessels, you must keep the records specified in paragraph (c) of this section for each pressure vessel.

(5) For internal and external floating roof storage vessels, you must maintain the records required in §63.1065 of subpart WW of this part.

(6) For fixed roof storage vessels that route emissions through a closed vent system to a control device, during periods of planned routine maintenance of a control device, record the day and time at which planned routine maintenance periods begin and end, and the type of maintenance performed on the control device. If you need more than 240 hr/yr, keep a record that explains why additional time up to 360 hr/yr was needed and describes how you minimized the amount of additional time needed.

(c) Equipment leaks. For equipment leaks, you must maintain the records specified in §63.1038 of subpart UU of this part for equipment leaks and a record of the information specified in §63.11930(g)(4) for monitoring instrument calibrations conducted according to §63.11930(e)(2).

(d) Heat exchange systems. For a heat exchange system subject to this subpart, you must keep the records specified in paragraphs (d)(1) through (6) of this section.

(1) Identification of all heat exchangers at the facility and the measured or estimated average annual HAP concentration of process fluid or intervening cooling fluid processed in each heat exchanger.

(2) Identification of all heat exchange systems that are in HAP service. For each heat exchange system that is subject to this subpart, you must include identification of all heat exchangers within each heat exchange system, identification of the individual heat exchangers in HAP service within each heat exchange system, and for closed-loop recirculation systems, the cooling tower included in each heat exchange system.

(3) Identification of all heat exchange systems that are exempt from the monitoring requirements according to the provisions in §63.11920(b) and the provision under which the heat exchange system is exempt.

(4) Results of the following monitoring data for each monitoring event:

(i) Date/time of event.

(ii) Heat exchange exit line flow or cooling tower return line flow at the sampling location, gallons/minute.

(iii) Monitoring method employed.

(iv) The measured cooling water concentration for each of target analyte (parts per billion by weight).

(v) Calibration and recovery information identified in the test method used.

(5) The date when a leak was identified and the date when the heat exchanger was repaired or taken out of service.

(6) If a repair is delayed, the reason for the delay, the schedule for completing the repair, and the estimate of potential emissions for the delay of repair.

(e) Process vent monitoring. You must include the records specified in paragraphs (e)(1) through (4) of this section, as applicable, for process vent monitoring.

(1) Continuous records. Where this subpart requires a continuous record using CEMS or CPMS, you must maintain, at a minimum, the records specified in §63.10(b)(2)(vii)(A).

(2) Excluded data. In any average computed to determine compliance, you must exclude monitoring data recorded during periods specified in paragraphs (e)(2)(i) through (iii) of this section.

(i) Periods of non-operation of the process unit (or portion thereof), resulting in cessation of the emissions to which the monitoring applies.

(ii) Periods of no flow to a control device.

(iii) Monitoring system malfunctions, repairs associated with monitoring system malfunctions or required monitoring system quality assurance or control activities, as specified in §63.11890(c)(2).

(3) Records of calculated emission and operating parameter values. You must retain for 5 years, a record of CEMS and CPMS data as specified in paragraphs (e)(3)(i) and (ii) of this section, unless an alternative recordkeeping system has been requested and approved.

(i) Except as specified in paragraph (e)(3)(ii) of this section, retain for 5 years, the records of the average values for each continuously monitored operating parameter and pollutant specified in §§63.11925(e)(3)(ii) and 63.11925(e)(4)(ii)(B) for CEMS and CPMS.

(ii) In lieu of calculating and recording the average value specified in paragraphs (e)(3)(i) of this section, if all 1-hour averages specified in §63.11935(e) demonstrate compliance with your parameter operating limit or the applicable pollutant emission limit in Table 1 or 2 to this subpart for the block average period, you may record a statement that all recorded 1-hour averages met the operating limit or emission limit, as applicable, and retain for 5 years this statement and all recorded CPMS or CEMS data for the block average period.

(4) Information to be included in records. You must keep records of each operating scenario as specified in paragraphs (e)(4)(i) through (viii) of this section, as applicable.

(i) You must keep a schedule or log of operating scenarios, updated each time a different operating scenario is put into effect.

(ii) A description of the process and the type of process components used.

(iii) An identification of related process vents including their associated emissions episodes.

(iv) The applicable control requirements of this subpart for process vents.

(v) The control device, including a description of operating and testing conditions.

(vi) Combined emissions that are routed to the same control device.

(vii) The applicable monitoring requirements of this subpart and any operating limit that assures compliance for all emissions routed to the control device.

(viii) Calculations and engineering analyses required to demonstrate compliance.

(f) Process vents. You must include the records specified in paragraphs (f)(1) and (2) of this section, as applicable, for process vents.

(1) Records of performance tests as required in §63.10(b)(2)(viii). You must also collect the applicable control device operating parameters required in §63.11940 over the full period of the performance test.

(2) If you use a control device to comply with this subpart and you are required to use CPMS, then you must keep up-to-date and readily accessible records for your process vents as specified in paragraphs (f)(2)(i) through (iv) of this section, as applicable.

(i) If you use a flow indicator, then you must keep records of periods of no flow to the control device, including the start and stop time and dates of periods of flow and no flow.

(ii) If you use a catalytic oxidizer for which you have selected the alternative monitoring specified in §63.11940(b)(3), then you must also maintain records of the results of the annual catalyst sampling and inspections required by §63.11940(b)(3)(i) and (ii) including any subsequent corrective actions taken.

(iii) If you use a regenerative adsorber as specified in §63.11940(d), then the records specified in paragraphs (f)(2)(iii)(A) through (H) of this section, as applicable, must be kept.

(A) Records of total regeneration stream mass flow for each adsorber-bed regeneration cycle.

(B) Records of the temperature of the adsorber bed after each regeneration and within 15 minutes of completing any cooling cycle.

(C) For non-vacuum and non-steam regeneration systems, records of the temperature of the adsorber bed during each regeneration except during any temperature regulating (cooling or warming to bring bed temperature closer to vent gas temperature) portion of the regeneration cycle.

(D) If adsorber regeneration vacuum is monitored pursuant to §63.11940(d)(4), then you must keep records of the vacuum profile over time and the amount of time the vacuum level is below the minimum vacuum target for each adsorber-bed regeneration cycle.

(E) Records of the regeneration frequency and duration.

(F) Daily records of the verification inspections, including the visual observations and/or any activation of an automated alarm or shutdown system with a written entry into a log book or other permanent form of record.

(G) Records of the maximum volatile organic compound or HAP outlet concentration observed over the last 5 minutes of the adsorption cycle for each adsorber bed. Records must be weekly or for every regeneration cycle if the regeneration cycle is greater than 1 week.

(H) Records of the date and time the adsorbent had last been replaced.

(iv) If you use a non-regenerative adsorber as specified in §63.11940(e), then the records specified in paragraphs (f)(2)(iv)(A) through (C) of this section, as applicable, must be kept.

(A) A record of the average life of the bed, as determined by §63.11940(e)(1), including the date the average life was determined.

(B) Daily, weekly, or monthly records of the maximum volatile organic compound or HAP outlet concentration, as specified by §63.11940(e)(2).

(C) Records of bed replacement including the date and time the adsorbent had last been replaced, and the date and time in which breakthrough is detected.

(g) Closed vent systems. You must keep the records specified in paragraphs (g)(1) through (6) of this section, and you must record any additional information as specified in §63.11930, as applicable.

(1) Each alarm triggered because flow was detected in a bypass as specified in §63.11930(g)(1)(i).

(2) Inspections of seals or closure mechanisms as specified in §63.11930(g)(1)(ii).

(3) Copies of compliance reports for closed vent system leak inspections as specified in §63.11985(b)(9) and §63.11930(g)(2) and (3).

(4) Instrument calibration records as specified in §63.11930(g)(4).

(5) Unsafe-to-inspect equipment as specified in §63.11930(g)(5).

(6) Pressure alarms as specified by §63.11930(h)(2) and (3).

(h) Resin strippers. For resin strippers, you must maintain the records specified in paragraphs (h)(1) and (2) of this section.

(1) All resin sampling data, including daily measurements of the concentration of vinyl chloride and monthly measurements of the total non-vinyl chloride organic HAP compounds in the stripped resin for each type and grade of resin produced. Each sample must be identified by the resin type and resin grade, the date and time the sample was taken, identification of the resin stripper from which the sample was taken, and the corresponding quantity (pounds) of resin processed by the stripper for the batch or over the time period represented by the sample.

(2) The total quantity (pounds) of each resin grade produced per day and the total quantity of resin processed by each resin stripper, identified by resin type and resin grade, per day.

(i) Process wastewater. For treatment processes, you must maintain the records specified in paragraphs (i)(1) through (5) of this section.

(1) A description of the process wastewater generation activities and treatment process.

(2) Records of the treatment determinations specified in §63.11965(b) for each wastewater stream and the type of treatment applied if required in §63.11965(c).

(3) Records of the initial performance test specified in §63.11970(a) and (b).

(4) All testing data, including monthly measurements of the concentrations of vinyl chloride and the concentration of total non-vinyl chloride organic HAP in each process wastewater stream required to be measured, as specified in §63.11975.

(5) You must keep any other applicable records that are required by the recordkeeping requirements specified in §63.147 of subpart G of this part.

(j) Other emission sources. You must keep the records specified in paragraphs (j)(1) and (2) of this section.

(1) All engineering calculations, testing, sampling, and monitoring results and data specified in §63.11955.

(2) Each occurrence that you do not comply with the requirements in §63.11955.

§63.11995   In what form and how long must I keep my records?

(a) You must keep records for 5 years in a form suitable and readily available for expeditious review, as specified in §63.10(b)(1).

(b) You must keep each record on site for at least 2 years, as specified in §63.10(b)(1). You can keep the records off site for the remaining 3 years. Records may be maintained in hard copy or computer-readable format including, but not limited to, on paper, microfilm, hard disk drive, floppy disk, compact disk, magnetic tape or microfiche.

§63.12000   Who implements and enforces this subpart?

(a) This subpart can be implemented and enforced by the Administrator, as defined in §63.2, or a delegated authority such as your state, local or tribal agency. If the Administrator has delegated authority to your state, local or tribal agency, then that agency (as well as the Administrator) has the authority to implement and enforce this subpart. You should contact your EPA Regional Office to find out if this subpart is delegated to your state, local or tribal agency.

(b) In delegating implementation and enforcement authority of this subpart to a state, local or tribal agency, the authorities listed in paragraphs (b)(1) through (4) of this section are retained by the Administrator and are not transferred to the state, local or tribal agency, however, the EPA retains oversight of this subpart and can take enforcement actions, as appropriate.

(1) Approval of alternatives to the emission limits, operating limits, and work practice standards specified in this subpart.

(2) Approval of a major change to test methods, as defined in §63.90, approval of any proposed analysis methods, and approval of any proposed test methods.

(3) Approval of a major change to monitoring, as defined in §63.90.

(4) Approval of a major change to recordkeeping and reporting, as defined in §63.90.

Definitions

§63.12005   What definitions apply to this subpart?

Terms used in this subpart are defined in the Clean Air Act, in §63.2, and in this section, as follows:

Affirmative defense means, in the context of an enforcement proceeding, a response or defense put forward by a defendant, regarding which the defendant has the burden of proof, and the merits of which are independently and objectively evaluated in a judicial or administrative proceeding.

Batch emission episode means a discrete venting episode that is associated with a single unit operation. A unit operation may have more than one batch emission episode. For example, a displacement of vapor resulting from the charging of a vessel with HAP will result in a discrete emission episode that will last through the duration of the charge and will have an average flowrate equal to the rate of the charge. If the vessel is then heated, there will also be another discrete emission episode resulting from the expulsion of expanded vapor. Both emission episodes may occur in the same vessel or unit operation. There are possibly other emission episodes that may occur from the vessel or other process components, depending on process operations.

Batch operation means a noncontinuous operation involving intermittent or discontinuous feed into process components, and, in general, involves the emptying of the process components after the operation ceases and prior to beginning a new operation. Addition of raw material and withdrawal of product do not occur simultaneously in a batch operation.

Batch process vent means a vent from a batch operation from a PVCPU through which a HAP-containing gas stream has the potential to be released to the atmosphere except that it is required by this subpart to routed to a closed vent system and control device. Emissions for all emission episodes associated with the unit operation(s) are part of the batch process vent. Batch process vents also include vents with intermittent flow from continuous operations. Examples of batch process vents include, but are not limited to, vents on condensers used for product recovery, polymerization reactors, and process tanks.

Bottoms receiver means a tank that collects bottoms from continuous distillation before the stream is sent for storage or for further downstream processing. A rundown tank is an example of a bottoms receiver.

Bulk process means a process for producing polyvinyl chloride resin that is characterized by a two-step anhydrous polymerization process: the formation of small resin particles in a pre-polymerization reactor using small amounts of vinyl chloride monomer, an initiator, and agitation; and the growth of the resin particles in a post-polymerization reactor using additional vinyl chloride monomer. Resins produced using the bulk process are referred to as bulk resins.

Bypass means diverting a process vent or closed vent system stream to the atmosphere such that it does not first pass through an emission control device.

Calendar year means the period between January 1 and December 31, inclusive for a given year.

Capacity means the nominal figure or rating given by the manufacturer of the storage vessel, condenser, or other process component.

Car-seal means a seal that is placed on a device that is used to change the position of a valve (e.g., from opened to closed) in such a way that the position of the valve cannot be changed without breaking the seal.

Closed vent system means a system that is not open to the atmosphere and is composed of piping, ductwork, connections, and, if necessary, flow inducing devices that collect or transport gas or vapor from an emission point to a control device.

Combustion device means an individual unit used for the combustion of organic emissions, such as a flare, incinerator, process heater, or boiler.

Conservation vent means an automatically operated (e.g., weight-loaded or spring-loaded) safety device used to prevent the operating pressure of a storage vessel from exceeding the maximum allowable working pressure of the process component. Conservation vents must be designed to open only when the operating pressure of the storage vessel exceeds the maximum allowable working pressure of the process component. Conservation vents open and close to permit only the intake or outlet relief necessary to keep the storage vessel within permissible working pressures, and reseal automatically.

Container means a portable unit in which a material can be stored, transported, treated, disposed of or otherwise handled. Examples of containers include, but are not limited to, drums, pails, and portable cargo containers known as “portable tanks” or “totes.” Container does not include transport vehicles or barges.

Continuous emission monitoring system (CEMS) means the total equipment that may be required to meet the data acquisition and availability requirements of this subpart, used to sample, condition (if applicable), analyze, and provide a record of emissions.

Continuous operation means any operation that is not a batch operation.

Continuous parameter monitoring system (CPMS) means the total equipment that may be required to meet the data acquisition and availability requirements of this part, used to sample, condition (if applicable), analyze, and provide a record of process or control system parameters.

Continuous process vent means a vent from a continuous PVCPU operation through which a HAP-containing gas stream has the potential to be released to the atmosphere except that it is required by this subpart to routed to a closed vent system and control device and has the following characteristics:

(1) The gas stream originates as a continuous flow from any continuous PVCPU operation during operation of the PVCPU.

(2) The discharge into the closed vent system and control device meets at least one of the following conditions:

(i) Is directly from any continuous operation.

(ii) Is from any continuous operation after passing solely (i.e., without passing through any other unit operation for a process purpose) through one or more recovery devices within the PVCPU.

(iii) Is from a device recovering only mechanical energy from a gas stream that comes either directly from any continuous operation, or from any continuous operation after passing solely (i.e., without passing through any other unit operation for a process purpose) through one or more recovery devices within the PVCPU.

Continuous PVCPU operation means any operation that is not a batch operation or an operation that generates a miscellaneous process vent.

Continuous record means documentation, either in hard copy or computer readable form, of data values measured at least once every 15 minutes and recorded at the frequency specified in §63.11990(e)(1).

Control device means, with the exceptions noted in this definition, a combustion device, recovery device, recapture device or any combination of these devices used to comply with this subpart. Process condensers are not control devices.

Control system means the combination of the closed vent system and the control devices used to collect and control vapors or gases from a regulated emission source.

Cooling tower means a heat removal device used to remove the heat absorbed in circulating cooling water systems by transferring the heat to the atmosphere using natural or mechanical draft.

Cooling tower return line means the main water trunk lines at the inlet to the cooling tower before exposure to the atmosphere.

Corrective action plan means a description of all reasonable interim and long-term measures, if any, that are available, and an explanation of why the selected corrective action is the best alternative, including, but not limited to, any consideration of cost-effectiveness.

Day means a calendar day, unless otherwise specified in this subpart.

Dioxin/furans means total tetra- through octachlorinated dibenzo-p-dioxins and dibenzofurans.

Dispersion process means a process for producing polyvinyl chloride resin that is characterized by the formation of the polymers in soap micelles that contain small amounts of vinyl chloride monomer. Emulsifiers are used to disperse vinyl chloride monomer in the water phase. Initiators used in the dispersion process are soluble in water. Resins produced using the dispersion process are referred to as latex or dispersion resins.

Empty or emptying means the partial or complete removal of stored liquid from a storage vessel. Storage vessels that contain liquid only as a result of the liquid clinging to the walls or bottoms, or resting in pools due to bottom irregularities, are considered completely empty.

Equipment means each pump, compressor, agitator, pressure relief device, sampling connection system, open-ended valve or line, valve, connector and instrumentation system in HAP service; and any control devices or systems used to comply with this subpart.

Fill or filling means the introduction of liquid into a storage vessel, but not necessarily to capacity.

First attempt at repair, for the purposes of this subpart, means to take action for the purpose of stopping or reducing leakage of organic material to the atmosphere, followed by monitoring as specified in §63.11930(f) to verify whether the leak is repaired, unless the owner or operator determines by other means that the leak is not repaired.

Fixed roof storage vessel means a vessel with roof that is mounted (i.e., permanently affixed) on a storage vessel and that does not move with fluctuations in stored liquid level.

Flow indicator means a device that indicates whether gas flow is, or whether the valve position would allow gas flow to be, present in a line.

Gasholder means a surge control vessel with a bell that is floating in a vessel filled with water that is used to store gases from the PVC production process prior to being recovered or sent to a process vent control device. The bell rises and falls as low-pressure gases enter and leave the space beneath the bell and the water provides a seal between the enclosed gas within the floating bell and the ambient air.

Grade means the subdivision of PVC resin that describes it as a unique resin, i.e., the most exact description of a type of resin with no further subdivision. Examples include low molecular weight suspension resins and general purpose suspension resins.

Hard-piping means pipes or tubing that are manufactured and properly installed using good engineering judgment and an appropriate standard method published by a consensus-based standards organization if such a method exists or you may use an industry standard practice. Consensus-based standards organizations include, but are not limited to, American National Standards Institute (ANSI, 1819 L Street NW., 6th floor, Washington, DC 20036, (202) 293-8020, http://www.ansi.org).

Heat exchange system means a device or collection of devices used to transfer heat from process fluids to water without intentional direct contact of the process fluid with the water (i.e., non-contact heat exchanger) and to transport and/or cool the water in a closed-loop recirculation system (cooling tower system) or a once-through system (e.g., river or pond water). For closed-loop recirculation systems, the heat exchange system consists of a cooling tower, all heat exchangers that are serviced by that cooling tower and all water lines to and from the heat exchanger(s). For once-through systems, the heat exchange system consists of one or more heat exchangers servicing an individual process unit and all water lines to and from the heat exchanger(s). Intentional direct contact with process fluids results in the formation of a wastewater.

Heat exchanger exit line means the cooling water line from the exit of one or more heat exchangers (where cooling water leaves the heat exchangers) to either the entrance of the cooling tower return line or prior to exposure to the atmosphere or mixing with non-cooling water streams, in, as an example, a once-through cooling system, whichever occurs first.

In HAP service means that a process component either contains or contacts a liquid that is at least 5-percent HAP by weight or a gas that is at least 5 percent by volume HAP as determined according to the provisions of §63.180(d). For the purposes of this definition, the term “organic HAP” as used in §63.180(d) means HAP. The provisions of §63.180(d) also specify how to determine that a process component is not in HAP service.

In vacuum service means that the process component is operating at an internal pressure that is at least 5 kilopascals (kPa) (0.7 pounds per square inch absolute) below ambient pressure.

Incinerator means an enclosed combustion device with an enclosed fire box that is used for destroying organic compounds. Auxiliary fuel may be used to heat waste gas to combustion temperatures. Any energy recovery section present is not physically formed into one manufactured or assembled unit with the combustion section; rather, the energy recovery section is a separate section following the combustion section and the two are joined by ducts or connections carrying flue gas. This energy recovery section limitation does not apply to an energy recovery section used solely to preheat the incoming vent stream or combustion air.

Maintenance wastewater means wastewater generated by the draining of process fluid from components in the PVCPU into an individual drain system prior to or during maintenance activities. Maintenance wastewater can be generated during planned and unplanned shutdowns and during periods not associated with a shutdown. Examples of activities that can generate maintenance wastewaters include descaling of heat exchanger tubing bundles, hydroblasting PVCPU process components such as polymerization reactors, vessels and heat exchangers, draining of low legs and high point bleeds, draining of pumps into an individual drain system, draining of portions of the PVCPU for repair and water used to wash out process components or equipment after the process components or equipment has already been opened to the atmosphere and has met the requirements of §63.11955.

Maximum representative operating conditions means process operating conditions that result in the most challenging condition for the control device. The most challenging condition for the control device may include, but is not limited to, the highest or lowest HAP mass loading rate to the control device, the highest or lowest HAP mass loading rate of constituents that approach the limits of solubility for scrubbing media, the highest or lowest HAP mass loading rate of constituents that approach limits of solubility for scrubbing media.

Maximum true vapor pressure means the equilibrium partial pressure exerted by the total HAP in the stored or transferred liquid at the temperature equal to the highest calendar-month average of the liquid storage or transfer temperature for liquids stored or transferred above or below the ambient temperature or at the local maximum monthly average temperature as reported by the National Weather Service for liquids stored or transferred at the ambient temperature, as determined by any one of the following methods or references:

(1) In accordance with methods described in API MPMS 19.2 (incorporated by reference, see §63.14).

(2) As obtained from standard reference texts.

(3) As determined by ASTM D2879-83 or ASTM D2879-96 (incorporated by reference, see §63.14).

(4) Any other method approved by the Administrator.

Miscellaneous vent means gaseous emissions from samples, loading and unloading lines, slip gauges, process wastewater treatment systems and pressure relief devices that are routed through a closed vent system to a control device and that are not equipment leaks.

Nonstandard batch means a batch process that is operated outside of the range of operating conditions that are documented in an existing operating scenario, but is still a reasonably anticipated event. For example, a nonstandard batch occurs when additional processing or processing at different operating conditions must be conducted to produce a product that is normally produced under the conditions described by the standard batch. A nonstandard batch may be necessary as a result of a malfunction, but it is not itself a malfunction.

Operating block means a period of time that is equal to the time from the beginning to end of batch process operations within a process.

Operating day means a 24-hour period between 12 midnight and the following midnight during which PVC is produced at any time in the PVCPU. It is not necessary for PVC to be produced for the entire 24-hour period.

Operating scenario means, for the purposes of reporting and recordkeeping, any specific operation of a regulated process as described by reports specified in §63.11985(b)(4)(ii) and records specified in §63.11990(e)(4).

Plant site means all contiguous or adjoining property that is under common control, including properties that are separated only by a road or other public right-of-way. Common control includes properties that are owned, leased or operated by the same entity, parent entity, subsidiary or any combination thereof.

Polymerization reactor means any vessel in which vinyl chloride is partially or totally polymerized into polyvinyl chloride. For bulk processes, the polymerization reactor includes pre-polymerization reactors and post-polymerization reactors.

Polyvinyl chloride means either polyvinyl chloride homopolymer or polyvinyl chloride copolymer.

Polyvinyl chloride and copolymers production process unit or PVCPU means a collection of process components assembled and connected by hard-piping or duct work, used to process raw materials and to manufacture polyvinyl chloride and/or polyvinyl chloride copolymers. A PVCPU includes, but is not limited to, polymerization reactors; resin stripping operations; resin blend tanks; resin centrifuges; resin dryers; resin product separators; recovery devices; reactant and raw material charge vessels and tanks, holding tanks, mixing and weighing tanks; finished resin product storage tanks or storage silos; finished resin product loading operations; connected ducts and piping; equipment including pumps, compressors, agitators, pressure relief devices, sampling connection systems, open-ended valves or lines, valves and connectors and instrumentation systems. A PVCPU does not include chemical manufacturing process units, as defined in §63.101, that produce vinyl chloride monomer or other raw materials used in the PVC polymerization process.

Polyvinyl chloride copolymer means a synthetic thermoplastic polymer that is derived from the simultaneous polymerization of vinyl chloride and another monomer such as vinyl acetate. Polyvinyl chloride copolymer is produced by different processes, including, but not limited to, suspension, dispersion/emulsion, suspension blending, and solution processes.

Polyvinyl chloride homopolymer means a synthetic thermoplastic polymer that is derived from the polymerization of vinyl chloride and has the general chemical structure (-H2CCHCl-)n. Polyvinyl chloride homopolymer is typically a white powder or colorless granule. Polyvinyl chloride homopolymer is produced by different processes, including (but not limited to), suspension, dispersion/emulsion, blending, and bulk processes.

Pressure relief device means a safety device used to prevent operating pressures from exceeding the maximum allowable working pressure of the process component. A common pressure relief device is a spring-loaded pressure relief valve.

Pressure vessel means a vessel that is used to store liquids or gases and is designed not to vent to the atmosphere as a result of compression of the vapor headspace in the pressure vessel during filling of the pressure vessel to its design capacity.

Process change means an addition to or change in a PVCPU and/or its associated process components that creates one or more emission points or changes the characteristics of an emission point such that a new or different emission limit, operating parameter limit, or work practice requirement applies to the added or changed emission points. Examples of process changes include, but are not limited to, changes in production capacity, production rate, or catalyst type, or whenever there is replacement, removal, or addition of recovery device components. For purposes of this definition, process changes do not include process upsets, changes that do not alter the process component configuration and operating conditions, and unintentional, temporary process changes. A process change does not include moving within a range of conditions identified in the standard batch, and a nonstandard batch does not constitute a process change.

Process component means any unit operation or group of units operations or any part of a process or group of parts of a process that are assembled to perform a specific function (e.g., polymerization reactor, dryers, etc.). Process components include equipment, as defined in this section.

Process condenser means a condenser whose primary purpose is to recover material as an integral part of a batch process. All condensers recovering condensate from a batch process at or above the boiling point or all condensers in line prior to a vacuum source are considered process condensers. Typically, a primary condenser or condensers in series are considered to be integral to the batch regulated process if they are capable of and normally used for the purpose of recovering chemicals for fuel value (i.e., net positive heating value), use, reuse or for sale for fuel value, use or reuse. This definition does not apply to a condenser that is used to remove materials that would hinder performance of a downstream recovery device as follows:

(1) To remove water vapor that would cause icing in a downstream condenser.

(2) To remove water vapor that would negatively affect the adsorption capacity of carbon in a downstream carbon adsorber.

(3) To remove high molecular weight organic compounds or other organic compounds that would be difficult to remove during regeneration of a downstream adsorber.

Process tank means a tank or other vessel (e.g., pressure vessel) that is used within an affected source to both: (1) Collect material discharged from a feedstock storage vessel, process tank, or other PVCPU process component, and (2) discharge the material to another process tank, process component, byproduct storage vessel, or product storage vessel.

Process unit means the process components assembled and connected by pipes or ducts to process raw and/or intermediate materials and to manufacture an intended product. For the purpose of this subpart, process unit includes, but is not limited to, polyvinyl chloride production process.

Process vent means a vent stream that is the result of the manifolding of each and all batch process vent, continuous process vent, or miscellaneous vent resulting from the affected facility into a closed vent system and into a common header that is routed to a control device. The process vent standards apply at the outlet of the control device. A process vent is either a PVC-only process vent or a PVC-combined process vent.

Process wastewater means wastewater that comes into direct contact with HAP or results from the production or use of any raw material, intermediate product, finished product, by-product, or waste product containing HAP, but that has not been discharged untreated as wastewater. Examples are product tank drawdown or feed tank drawdown; water formed during a chemical reaction or used as a reactant; water used to wash impurities from organic products or reactants; water used to cool or quench organic vapor streams through direct contact; water discarded from a control device; and condensed steam from jet ejector systems pulling vacuum on vessels containing organics. Gasholder seal water is not process wastewater until it is removed from the gasholder.

Process wastewater treatment system means a specific technique or collection of techniques that remove or destroy the organics in a process wastewater stream to comply with §§63.11965, 63.11970, and 63.11975.

Product means a polymer produced using the same monomers and varying in additives (e.g., initiators, terminators, etc.); catalysts; or in the relative proportions of monomers, that is manufactured by a process unit. With respect to polymers, more than one recipe may be used to produce the same product, and there can be more than one grade of a product. Product also means a chemical that is not a polymer, which is manufactured by a process unit. By-products, isolated intermediates, impurities, wastes, and trace contaminants are not considered products.

PVC-combined process vent means a process vent that originates from a PVCPU and is combined with one or more process vents originating from another source category prior to being controlled or emitted to the atmosphere.

PVC-only process vent means a process vent that originates from a PVCPU and is not combined with a process vent originating from another source category prior to being controlled or emitted to the atmosphere.

Recipe means a specific composition from among the range of possible compositions that may occur within a product, as defined in this section. A recipe is determined by the proportions of monomers and, if present, other reactants and additives that are used to make the recipe.

Recovery device means an individual process component capable of and normally used for the purpose of recovering chemicals for fuel value (i.e., net positive heating value), use, reuse, or for sale for fuel value, use, or reuse. Examples of process components that may be recovery devices include absorbers, adsorbers, condensers, oil-water separators or organic-water separators, or organic removal devices such as decanters, strippers (e.g., wastewater steam and vacuum strippers), or thin-film evaporation units. For purposes of this subpart, recovery devices are control devices.

Repaired, for the purposes of this subpart, means equipment that is adjusted or otherwise altered to eliminate a leak as defined in the applicable sections of this subpart; and unless otherwise specified in applicable provisions of this subpart, is inspected as specified in §63.11930(f) to verify that emissions from the equipment are below the applicable leak definition.

Resin stripper means a unit that removes organic compounds from a raw polyvinyl chloride and copolymer product. In the production of a polymer, stripping is a discrete step that occurs after the polymerization reaction and before drying or other finishing operations. Examples of types of stripping include steam stripping, vacuum stripping, or other methods of devolatilization. For the purposes of this subpart, devolatilization that occurs in dryers or other finishing operations is not resin stripping. Resin stripping may occur in a polymerization reactor or in a batch or continuous stripper separate from the polymerization reactor where resin stripping occurs.

Root cause analysis means an assessment conducted through a process of investigation to determine the primary cause, and any other significant contributing cause(s), of a discharge of gases in excess of specified thresholds.

Sensor means a device that measures a physical quantity or the change in a physical quantity, such as temperature, pressure, flow rate, pH, or liquid level.

Slip gauge means a gauge that has a probe that moves through the gas/liquid interface in a storage vessel and indicates the level of product in the vessel by the physical state of the material the gauge discharges.

Solution process means a process for producing polyvinyl chloride copolymer resin that is characterized by the anhydrous formation of the polymer through precipitation. Polymerization occurs in an organic solvent in the presence of an initiator where vinyl chloride monomer and co-monomers are soluble in the solvent, but the polymer is not. The PVC copolymer is a granule suspended in the solvent, which then precipitates out of solution. Emulsifiers and suspending agents are not used in the solution process. PVC copolymer resins produced using the solution process are referred to as solution resins.

Specific gravity monitoring device means a unit of equipment used to monitor specific gravity and having a minimum accuracy of ±0.02 specific gravity units.

Standard procedure means a formal written procedure officially adopted by the plant owner or operator and available on a routine basis to those persons responsible for carrying out the procedure.

Storage vessel means a tank or other vessel (e.g., pressure vessel) that is part of an affected source and is used to store a gaseous, liquid, or solid feedstock, byproduct, or product that contains organic HAP. Storage vessel does not include:

(1) Vessels permanently attached to motor vehicles such as trucks, railcars, barges, or ships;

(2) Process tanks;

(3) Vessels with capacities smaller than 10,040 gallons;

(4) Vessels storing organic liquids that contain organic HAP only as impurities;

(5) Bottoms receiver tanks;

(6) Surge control vessels; and

(7) Wastewater storage tanks. Wastewater storage tanks are covered under the wastewater provisions.

Stripped resin means the material exiting the resin stripper that contains polymerized vinyl chloride.

Supplemental combustion air means the air that is added to a vent stream after the vent stream leaves the unit operation. Air that is part of the vent stream as a result of the nature of the unit operation is not considered supplemental combustion air. Air required to operate combustion device burner(s) is not considered supplemental combustion air. Air required to ensure the proper operation of catalytic oxidizers, to include the intermittent addition of air upstream of the catalyst bed to maintain a minimum threshold flow rate through the catalyst bed or to avoid excessive temperatures in the catalyst bed, is not considered to be supplemental combustion air.

Surge control vessel means feed drums, recycle drums, and intermediate vessels used as a part of any continuous operation. Surge control vessels are used within an affected source when in-process storage, mixing, or management of flow rates or volumes is needed to introduce material into continuous operations. Surge control vessels also include gasholders.

Suspension blending process means a process for producing polyvinyl chloride resin that is similar to the suspension polymerization process, but employs a rate of agitation that is significantly higher than the highest range for non-blending suspension resins. The suspension blending process uses a recipe that creates extremely small resin particles, generally equal to or less than 100 microns in size, with a glassy surface and very little porosity. The suspension blending process concentrates the resins using a centrifuge that is specifically designed to handle these small particles. Polyvinyl chloride resins produced using the suspension blending process are referred to as suspension blending resins and are typically blended with dispersion resins.

Suspension process means a process for producing polyvinyl chloride resin that is characterized by the formation of the polymers in droplets of liquid vinyl chloride monomer or other co-monomers suspended in water. The droplets are formed by agitation and the use of protective colloids or suspending agents. Initiators used in the suspension process are soluble in vinyl chloride monomer. Polyvinyl chloride resins produced using the suspension process are referred to as suspension resins.

Table 10 HAP means a HAP compound listed in table 10 of this subpart.

Total non-vinyl chloride organic HAP means, for the purposes of this subpart, the sum of the measured concentrations of each HAP, as calculated according to the procedures specified in §§63.11960(f) and 63.11980(b).

Type of resin means the broad classification of PVC homopolymer and copolymer resin referring to the basic manufacturing process for producing that resin, including, but not limited to, suspension, dispersion/emulsion, suspension blending, bulk, and solution processes.

Unloading operations means the transfer of organic liquids from a transport vehicle, container, or storage vessel to process components within the affected source.

Wastewater means process wastewater and maintenance wastewater. The following are not considered wastewater for the purposes of this subpart:

(1) Stormwater from segregated sewers;

(2) Water from fire-fighting and deluge systems, including testing of such systems;

(3) Spills;

(4) Water from safety showers;

(5) Samples of a size not greater than reasonably necessary for the method of analysis that is used;

(6) Equipment leaks;

(7) Wastewater drips from procedures such as disconnecting hoses after cleaning lines; and

(8) Noncontact cooling water.

Wastewater stream means a stream that contains only wastewater as defined in this section.

Work practice standard means any design, equipment, work practice or operational standard, or combination thereof, that is promulgated pursuant to section 112(h) of the Clean Air Act.

§§63.12006-63.12099   [Reserved]

Table 1 to Subpart HHHHHHH of Part 63—Emission Limits and Standards for Existing Affected Sources

For this type of emission
point .  .  .
And for this air pollutant .  .  .And for an affected source producing this type of PVC
resin .  .  .
You must meet this emission
limit .  .  .
1. PVC-only process ventsaa. Vinyl chlorideAll resin types6.0 parts per million by volume (ppmv).
   b. Total hydrocarbonsAll resin types9.7 ppmv measured as propane.
   c. Total organic HAPbAll resin types56 ppmv.
   d. Hydrogen chlorideAll resin types78 ppmv.
   e. Dioxins/furans (toxic equivalency basis)All resin types0.038 nanograms per dry standard cubic meter (ng/dscm).
2. PVC-combined process ventsaa. Vinyl chlorideAll resin types1.1 ppmv.
   b. Total hydrocarbonsAll resin types4.2 ppmv measured as propane.
   c. Total organic HAPbAll resin types9.8 ppmv.
   d. Hydrogen chlorideAll resin types380 ppmv.
   e. Dioxins/furans (toxic equivalency basis)All resin types0.051 ng/dscm.
3. Stripped resina. Vinyl chloridei. Bulk resin7.1 parts per million by weight (ppmw).
   ii. Dispersion resin1300 ppmw.
   iii. Suspension resin37 ppmw.
   iv. Suspension blending resin140 ppmw.
   v. Copolymer resin790 ppmw.
   b. Total non-vinyl chloride organic HAPi. Bulk resin170 ppmw.
   ii. Dispersion resin240 ppmw.
   iii. Suspension resin670 ppmw.
   iv. Suspension blending resin500 ppmw.
   v. Copolymer resin1900 ppmw.
4. Process Wastewatera. Vinyl chlorideAll resin types6.8 ppmw.
   b. Total non-vinyl chloride organic HAPAll resin types110 ppmw.

aEmission limits at 3 percent oxygen, dry basis.

bTotal organic HAP is alternative compliance limit for THC.

Table 2 to Subpart HHHHHHH of Part 63—Emission Limits and Standards for New Affected Sources

For this type of emission
point .  .  .
And for this air pollutant .  .  .And for an affected source producing this type of PVC
resin .  .  .
You must meet this emission
limit .  .  .
1. PVC-only process ventsaa. Vinyl chlorideAll resin types0.56 ppmv.
   b. Total hydrocarbonsAll resin types7.0 ppmv measured as propane.
   c. Total organic HAPbAll resin types5.5 ppmv.
   d. Hydrogen chlorideAll resin types0.17 ppmv.
   e. Dioxins/furans (toxic equivalency basis)All resin types0.038 ng/dscm.
2. PVC-combined process ventsaa. Vinyl chlorideAll resin types0.56 ppmv.
   b. Total hydrocarbonsAll resin types2.3 ppmv measured as propane.
   c. Total organic HAPbAll resin types5.5 ppmv.
   d. Hydrogen chlorideAll resin types1.4 ppmv.
   e. Dioxins/furans (toxic equivalency basis)All resin types0.034 nanograms per dry standard cubic meter (ng/dscm).
3. Stripped resina. Vinyl chloridei. Bulk resin7.1 parts per million by weight (ppmw).
   ii. Dispersion resin480 ppmw.
   iii. Suspension resin7.3 ppmw.
   iv. Suspension blending resin140 ppmw.
   v. Copolymer—all resin types790 ppmw.
   b. Total non-vinyl chloride organic HAPi. Bulk resin170 ppmw.
   ii. Dispersion resin66 ppmw.
   iii. Suspension resin15 ppmw.
   iv. Suspension blending resin500 ppmw.
   v. Copolymer resin1900 ppmw.
4. Process Wastewatera. Vinyl chlorideAll resin types0.28 ppmw.
   b. Total non-vinyl chloride organic HAPAll resin types0.018 ppmw.

aEmission limits at 3 percent oxygen, dry basis.

bTotal organic HAP is alternative compliance limit for THC.

Table 3 to Subpart HHHHHHH of Part 63—Summary of Control Requirements for Storage Vessels at New and Existing Sources

If the storage vessel capacity (gallons) is .  .  .And the vapor pressurea (psia)
is .  .  .
Then, you must use the following type of storage vessel .  .  .
≥20,000 but <40,000≥4Internal floating roof, external floating roof, or fixed roof vented to a closed vent system and control device achieving 95 percent reduction.b
≥40,000≥0.75Internal floating roof, external floating roof, or fixed roof vented to a closed vent system and control device achieving 95 percent reduction.b
Any capacity.>11.1Pressure vessel.c
All other capacity and vapor pressure combinationsFixed roof.d

aMaximum true vapor pressure of total HAP at storage temperature.

bIf using a fixed roof storage vessel vented to a closed vent system and control device, you must meet the requirements in §63.11910(a) for fixed roof storage vessels. If using an internal floating roof storage vessel or external floating roof storage vessels, you must meet the requirements in §63.11910(b) for internal floating roof storage vessels or external floating roof storage vessels, as applicable.

cMeeting the requirements of §63.11910(c) for pressure vessels.

dMeeting the requirements in §63.11910(a) for fixed roof storage vessels.

Table 4 to Subpart HHHHHHH of Part 63—Applicability of the General Provisions to Part 63

Citation Subject Applies to subpart HHHHHHH Comment
§63.1(a)(1)-(a)(4), (a)(6), (a)(10)-(a)(12), (b)(1), (b)(3), (c)(1), (c)(2), (c)(5), (e)ApplicabilityYes.
§63.1(a)(5), (a)(7)-(a)(9), (b)(2), (c)(3), (c)(4), (d)[Reserved]No.
§63.2DefinitionsYesAdditional definitions are found in §63.12005.
§63.3Units and abbreviationsYes.
§63.4(a)(1), (a)(2), (b), (c)Prohibited activities and circumventionYes.
§63.4(a)(3)-(a)(5)[Reserved]No.
§63.5(a), (b)(1), (b)(3), (b)(4), (b)(6), (d)-(f)Preconstruction review and notification requirementsYes.
§63.5(b)(2), (b)(5), (c)[Reserved]No.
§63.6(a), (b)(1)-(b)(5), (b)(7), (c)(1), (c)(2), (c)(5), (e)(1)(iii), (f)(2), (f)(3), (g), (i), (j)Compliance with standards and maintenance requirementsYes§63.11875 specifies compliance dates.
§63.6(b)(6), (c)(3), (c)(4), (d), (e)(2), (e)(3)(ii), (h)(2)(ii), (h)(3), (h)(5)(iv)[Reserved]No
§63.6(e)(1)(i), (e)(1)(ii), (e)(3), (f)(1)Startup, shutdown, and malfunction provisionsNo. See §63.11890(b) for general duty requirement
§63.6(h)(1), (h)(2)(i), (h)(2)(iii), (h)(4), (h)(5)(i)-(h)(5)(iii), (h)(5)(v), (h)(6)-(h)(9)Compliance with opacity and visible emission standardsNoSubpart HHHHHHH does not specify opacity or visible emission standards.
§63.7(a)(1), (a)(2), (a)(3), (a)(4), (b)-(d), (e)(2)-(e)(4), (f), (g)(1), (g)(3), (h)Performance testing requirementsYes.
§63.7(a)(2)(i)-(viii)[Reserved]No.
§63.7(a)(2)(ix)Performance testing requirementsYes.
§63.7(e)(1)Performance testingNo. See especially §63.11945, 63.11960(d), 63.11980(a)
§63.7(g)(2)[Reserved]No.
§63.8(a)(1), (a)(2), (a)(4), (b), (c)(1)(i), (c)(1)(ii), (c)(2)-(c)(4), (c)(6)-(c)(8)Monitoring requirementsYesExcept cross reference in §63.8(c)(1)(i) to §63.6(e)(1) is replaced with a cross-reference to §63.11890(b).
§63.8(a)(3)[Reserved]No.
§63.8(c)(1)(iii)Requirement to develop SSM plan for continuous monitoring systemsNo.
§63.8(c)(5)Continuous opacity monitoring system minimum proceduresNoSubpart HHHHHHH does not have opacity or visible emission standards.
§63.8(d)Written procedures for continuous monitoring systemsYes, except for last sentence, which refers to an SSM plan. SSM plans are not required
§63.8(e)Continuous monitoring systems performance evaluationYes.
§63.8(f)Use of an alternative monitoring methodYes.
§63.8(g)Reduction of monitoring dataYesExcept that the minimum data collection requirements are specified in §63.11935(e).
§63.9(a), (b)(1), (b)(2), (b)(4)(i), (b)(4)(v), (b)(5), (c)-(e), (g)(1), (g)(3), (h)(1)-(h)(3), (h)(5), (h)(6), (i), (j)Notification requirementsYes.
§63.9(f)Notification of opacity and visible emission observationsNoSubpart HHHHHHH does not have opacity or visible emission standards.
§63.9(g)(2)Use of continuous opacity monitoring system dataNoSubpart HHHHHHH does not require the use of continuous opacity monitoring system.
§63.9(b)(3), (b)(4)(ii)-(iv), (h)(4)[Reserved]No.
§63.10(a), (b)(1)Recordkeeping and reporting requirementsYes.
§63.10(b)(2)(i)Recordkeeping of occurrence and duration of startups and shutdownsNo.
§63.10(b)(2)(ii)Recordkeeping of malfunctionsNo. See §§63.11895(b), 63.11985(b)(4)(i), 63.11985(b)(9) through (11), and 63.11985(c)(7)
§63.10(b)(2)(iii)Maintenance recordsYes.
§63.10(b)(2)(iv), (b)(2)(v)Actions taken to minimize emissions during SSMNo.
§63.10(b)(2)(vi)Recordkeeping for CMS malfunctionsYes.
§63.10(b)(2)(vii)-(x)Other CMS requirementsYes.
§63.10(b)(2)(xi)-(xiv)Other recordkeeping requirementsYes.
§63.10(b)(3)Recordkeeping requirement for applicability determinationsYes.
§63.10(c)(1), (c)(5), (c)(6)Additional recordkeeping requirements for sources with continuous monitoring systemsYes.
§63.10(c)(2)-(4), (c)(9)[Reserved]No.
§63.10(c)(7)Additional recordkeeping requirements for CMS—identifying exceedances and excess emissions during SSMYes.
§63.10(c)(8)Additional recordkeeping requirements for CMS—identifying exceedances and excess emissionsYes.
§63.10(c)(10)Recording nature and cause of malfunctionsNo. See §§63.11895(b), 63.11985(b)(4)(i), 63.11985(b)(9) through (11), and 63.11985(c)(7)
63.10(c)(11), (c)(12)Recording corrective actionsNo. See §§63.11895(b), 63.11985(b)(4)(i), 63.11985(b)(9) through (11), and 63.11985(c)(7)
§63.10(c)(13)-(14)Records of the total process operating time during the reporting period and procedures that are part of the continuous monitoring system quality control programYes.
§63.10(c)(15)Use SSM planNo.
§63.10(d)(1)General reporting requirementsYes.
§63.10(d)(2)Performance test resultsYes.
§63.10(d)(3)Opacity or visible emissions observationsNoSubpart HHHHHHH does not specify opacity or visible emission standards.
§63.10(d)(4)Progress reportsYes.
§63.10(d)(5)SSM reportsNo. See §§63.11895(b), 63.11985(b)(4)(i), 63.11985(b)(9) through (11), and 63.11985(c)(7)
§63.10(e)(1)Additional continuous monitoring system reports—generalYes.
§63.10(e)(2)(i)Results of continuous monitoring system performance evaluationsYes.
§63.10(e)(2)(ii)Results of continuous opacity monitoring system performance evaluationsNoSubpart HHHHHHH does not require the use of continuous opacity monitoring system.
§63.10(e)(3)Excess emissions/continuous monitoring system performance reportsYes.
§63.10(e)(4)Continuous opacity monitoring system data reportsNoSubpart HHHHHHH does not require the use of continuous opacity monitoring system.
§63.10(f)Recordkeeping/reporting waiverYes.
63.11(a)Control device and work practice requirements—applicabilityYes.
§63.11(b)FlaresNoFacilities subject to subpart HHHHHHH do not use flares as control devices, as specified in §63.11925(b).
§63.11(c)-(e)Alternative work practice for monitoring equipment for leaksYes.
§63.12State authority and delegationsYes§63.12000 identifies types of approval authority that are not delegated.
§63.13AddressesYes.
§63.14Incorporations by referenceYesSubpart HHHHHHH incorporates material by reference.
§63.15Availability of information and confidentialityYes.
§63.16Performance track provisionsYes.

Table 5 to Subpart HHHHHHH of Part 63—Operating Parameters, Operating Limits and Data Monitoring, Recording and Compliance Frequencies for Process Vents

For these control devices, you must monitor these operating parameters .  .  .Establish the following operating limit during your initial performance
test .  .  .
Monitor, record, and demonstrate continuous compliance using these minimum
frequencies
Data measurementData recordingData averaging period for compliance
Process Vents
Any Control device
Flow to/from the control deviceN/AContinuousN/ADate and time of flow start and stop.
Thermal Oxidizers
Temperature (in fire box or downstream ductwork prior to heat exchange)Minimum temperatureContinuousEvery 15 minutes3-hour block average.
Temperature differential across catalyst bedMinimum temperature differentialContinuousEvery 15 minutes3-hour block average.
Inlet temperature to catalyst bed and catalyst conditionMinimum inlet temperature and catalyst condition as specified in 63.11940 (b)(3)Continuous for temperature, annual for catalyst conditionEvery 15 minutes for temperature, annual for catalyst condition3-hour block average for temperature, annual for catalyst condition.
Absorbers and Acid Gas Scrubbers
Influent liquid flowMinimum inlet liquid flowContinuousEvery 15 minutes3-hour block average.
Influent liquid flow and gas stream flowMinimum influent liquid flow to gas stream flow ratioContinuousEvery 15 minutes3-hour block average.
Pressure dropMinimum pressure dropContinuousEvery 15 minutes3-hour block average.
Exhaust gas temperatureMaximum exhaust gas temperatureContinuousEvery 15 minutes3-hour block average.
Change in specific gravity of scrubber liquidMinimum change in specific gravityContinuousEvery 15 minutes3-hour block average.
pH of effluent liquidMinimum pHContinuousEvery 15 minutes3-hour block average.
Causticity of effluent liquidMinimum causticityContinuousEvery 15 minutes3-hour block average.
Conductivity of effluent liquidMinimum conductivityContinuousEvery 15 minutes3-hour block average.
Regenerative Adsorber
Regeneration stream flow.Minimum total flow per regeneration cycleContinuousN/ATotal flow for each regeneration cycle.
Adsorber bed temperature.Maximum temperatureContinuously after regeneration and within 15 minutes of completing any temperature regulationEvery 15 minutes after regeneration and within 15 minutes of completing any temperature regulation3-hour block average.
Adsorber bed temperature.Minimum temperatureContinuously during regeneration except during any temperature regulating portion of the regeneration cycleN/AAverage of regeneration cycle.
Vacuum and duratio of regenerationMinimum vacuum and period of time for regenerationContinuousN/AAverage vacuum and duration of regeneration.
Regeneration frequencyMinimum regeneration frequency and durationContinuousN/ADate and time of regeneration start and stop.
Adsorber operation valve sequencing and cycle timeCorrect valve sequencing and minimum cycle timeDailyDailyN/A.
Non-Regenerative Adsorber
Average adsorber bed life.N/ADaily until breakthrough for 3 adsorber bed change-outsN/AN/A.
Outlet VOC concentration of the first adsorber bed in seriesLimits in Table 1 or 2 of this subpartDaily, except monthly (if more than 2 months bed life remaining) or weekly (if more than 2 weeks bed life remaining)N/ADaily, weekly, or monthly.
Condenser
TemperatureMaximum outlet temperatureContinuousEvery 15 minutes3-hour block average.

Table 6 to Subpart HHHHHHH of Part 63—Toxic Equivalency Factors

Dioxin/furan congenerToxic
equivalency
factor
2,3,7,8-tetrachlorodibenzo-p-dioxin1
1,2,3,7,8-pentachlorodibenzo-p-dioxin1
1,2,3,4,7,8-hexachlorodibenzo-p-dioxin0.1
1,2,3,7,8,9-hexachlorodibenzo-p-dioxin0.1
1,2,3,6,7,8-hexachlorodibenzo-p-dioxin0.1
1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin0.01
octachlorodibenzo-p-dioxin0.0003
2,3,7,8-tetrachlorodibenzofuran0.1
2,3,4,7,8-pentachlorodibenzofuran0.3
1,2,3,7,8-pentachlorodibenzofuran0.03
1,2,3,4,7,8-hexachlorodibenzofuran0.1
1,2,3,6,7,8-hexachlorodibenzofuran0.1
1,2,3,7,8,9-hexachlorodibenzofuran0.1
2,3,4,6,7,8-hexachlorodibenzofuran0.1
1,2,3,4,6,7,8-heptachlorodibenzofuran0.01
1,2,3,4,7,8,9-heptachlorodibenzofuran0.01
Octachlorodibenzofuran0.0003

Table 7 to Subpart HHHHHHH of Part 63—Calibration and Accuracy Requirements for Continuous Parameter Monitoring Systems

If you monitor this parameter .  .  .Then your accuracy requirements are .  .  .And your inspection/calibration frequency
requirements are .  .  .
1. Temperature (non-cryogenic temperature ranges).±1 percent of temperature measured or 2.8 degrees Celsius (5 degrees Fahrenheit) whichever is greaterEvery 12 months.
2. Temperature (cryogenic temperature ranges).±2.5 percent of temperature measured or 2.8 degrees Celsius (5 degrees Fahrenheit) whichever is greaterEvery 12 months.
3. Liquid flow rate±2 percent of the normal range of flowa. Every 12 months.
b. You must select a measurement location where swirling flow or abnormal velocity distributions due to upstream and downstream disturbances at the point of measurement do not exist.
4. Gas flow rate±5 percent of the flow rate or 10 cubic feet per minute, whichever is greatera. Every 12 months.
b. Check all mechanical connections for leakage at least annually.
c. At least annually, conduct a visual inspection of all components of the flow CPMS for physical and operational integrity and all electrical connections for oxidation and galvanic corrosion if your flow CPMS is not equipped with a redundant flow sensor.
5. pH or caustic strength±0.2 pH unitsEvery 8 hours of process operation check the pH or caustic strength meter's calibration on at least two points.
6. Conductivity±5 percent of normal rangeEvery 12 months.
7. Mass flow rate±5 percent of normal rangeEvery 12 months.
8. Pressure±5 percent or 0.12 kilopascals (0.5 inches of water column) whichever is greatera. Calibration is required every 12 months.
b. Check all mechanical connections for leakage at least annually.
c. At least annually perform a visual inspection of all components for integrity, oxidation and galvanic corrosion if CPMS is not equipped with a redundant pressure sensor.

Table 8 to Subpart HHHHHHH of Part 63—Methods and Procedures for Conducting Performance Tests for Process Vents

For each control device used to meet the emission limit in Table 1 or 2 to this subpart for the following pollutant .  .  .You must .  .  .Using .  .  .
1. Total hydrocarbonsa. Measure the total hydrocarbon concentration at the outlet of the final control device or in the stackMethod 25A at 40 CFR part 60, appendix A-7. Conduct each test run for a minimum of 1 hour.
2. Total organic HAPa. Measure the total organic HAP concentration at the outlet of the final control device or in the stacki. Method 18 at 40 CFR part 60, appendix A-6 and ASTM D6420-99.a Conduct each test run for a minimum of 1 hour.
ii. Method 320 at 40 CFR part 63, appendix A and ASTM D6348-03.a Conduct each test run for a minimum of 1 hour.
3. Vinyl chloridea. Measure the vinyl chloride concentration at the outlet of the final control device or in the stackMethod 18 at 40 CFR part 60, appendix A-6. Conduct each test run for a minimum of 1 hour.
4. Hydrogen chloridea. Measure hydrogen chloride concentrations at the outlet of the final control device or in the stacki. Method 26 at 40 CFR part 60, appendix A-8, collect 60 dry standard liters of gas per test run; or
ii. Method 26A at 40 CFR part 60, appendix A-8, collect 1 dry standard cubic meter of gas per test run.
5. Dioxin/furana. Measure dioxin/furan concentrations on a toxic equivalency basis (and report total mass per isomer) at the outlet of the final control device or in the stackMethod 23 at 40 CFR part 60, appendix A-7 and collect 5 dry standard cubic meters of gas per test run.
6. Any pollutant from a continuous, batch, or combination of continuous and batch process vent(s)a. Select sampling port locations and the number of traverse pointsMethod 1 or 1A at 40 CFR part 60, appendix A-1.
   b. Determine gas velocity and volumetric flow rateMethod 2, 2A, 2C, 2D, 2F, or 2G at 40 CFR part 60, appendix A-1 and A-2.
   c. Conduct gas molecular weight analysis and correct concentrations the specified percent oxygen in Table 1 or 2 to this subpartMethod 3, 3A, or 3B at 40 CFR part 60, appendix A-2 using the same sampling site and time as HAP samples.
   d. Measure gas moisture contentMethod 4 at 40 CFR part 60, appendix A-3.

aIncorporated by reference, see §63.14.

Table 9 to Subpart HHHHHHH of Part 63—Procedures for Conducting Sampling of Stripped Resin and Process Wastewater

For demonstrating .  .  .For the following emission points and types of processes .  .  .Collect samples according to the following schedule .  .  .
Vinyl chloride .  .  .Total non-vinyl chloride organic HAP .  .  .
Each stripped resin stream
1. Initial compliancea. ContinuousEvery 8 hours or for each grade, whichever is more frequent during a 24 hour periodEvery 8 hours or for each grade, whichever is more frequent during a 24 hour period.
   b. Batch1 grab sample for each batch produced during a 24 hour period1 grab sample for each batch produced during a 24 hour period.
2. Continuous compliancea. ContinuousOn a daily basis, 1 grab sample every 8 hours or for each grade, whichever is more frequent during a 24 hour periodOn a monthly basis, 1 grab sample every 8 hours or for each grade, whichever is more frequent during a 24 hour period.
   b. BatchOn a daily basis, 1 grab sample for each batch produced during a 24 hour periodOn a monthly basis, 1 grab sample for each batch produced during a 24 hour period.
Each process wastewater stream
3. Initial complianceN/A1 grab sample1 grab sample.
4. Continuous complianceN/A1 grab sample per month1 grab sample per month.

Table 10 to Subpart HHHHHHH of Part 63—HAP Subject to the Resin and Process Wastewater Provisions at New and Existing Sources

CAS No.HAPAnalyte categoryTest method
107211Ethylene glycolAlcoholSW-846-8015C.a
67561MethanolAlcoholSW-846-8015C.a
75070AcetaldehydeAldehydeSW-846-8315A.a
50000FormaldehydeAldehydeSW-846-8315A.a
512852,4-dinitrophenolSVOCSW-846-8270D.a
98862AcetophenoneSVOCSW-846-8270D.a
117817Bis(2-ethylhexyl) phthalate (DEHP)SVOCSW-846-8270D.a
123319HydroquinoneSVOCSW-846-8270D.a
108952PhenolSVOCSW-846-8270D.a
793451,1,2,2-tetrachloroethaneVOCSW-846-8260B.a
1069901,3-butadieneVOCSW-846-8260B.a
5408412,2,4-trimethylpentaneVOCSW-846-8260B.a
71432BenzeneVOCSW-846-8260B.a
108907ChlorobenzeneVOCSW-846-8260B.a
67663ChloroformVOCSW-846-8260B.a
126998ChloropreneVOCSW-846-8260B.a
98828CumeneVOCSW-846-8260B.a
75003Ethyl chloride (Chloroethane)VOCSW-846-8260B.a
100414EthylbenzeneVOCSW-846-8260B.a
107062Ethylene dichloride (1,2-Dichloroethane)VOCSW-846-8260B.a
75343Ethylidene dichloride (1,1-Dichloroethane)VOCSW-846-8260B.a
74873Methyl chloride (Chloromethane)VOCSW-846-8260B.a
75092Methylene chlorideVOCSW-846-8260B.a
110543n-HexaneVOCSW-846-8260B.a
108883TolueneVOCSW-846-8260B.a
71556/79005TrichloroethaneVOCSW-846-8260B.a
108054Vinyl acetateVOCSW-846-8260B.a
593602Vinyl bromideVOCSW-846-8260B.a
75014Vinyl chlorideVOCMethod 107 at 40 CFR part 61, appendix B.
75354Vinylidene chloride (1,1-Dichloroethylene)VOCSW-846-8260B.a
1330207Xylenes (isomers and mixtures)VOCSW-846-8260B.a

aIncorporated by reference, see §63.14.

Appendix A to Part 63—Test Methods Pollutant Measurement Methods From Various Waste Media

Method 301—Field Validation of

Sec.

Using Method 301

1.0   What is the purpose of Method 301?

2.0   When must I use Method 301?

3.0   What does Method 301 include?

4.0   How do I perform Method 301?

Reference Materials

5.0   What reference materials must I use?

Sampling Procedures

6.0   What sampling procedures must I use?

7.0   How do I ensure sample stability?

Bias and Precision

8.0   What are the requirements for bias?

9.0   What are the requirements for precision?

10.0   What calculations must I perform for isotopic spiking?

11.0   What calculations must I perform for comparison with a validated method if I am using quadruplet replicate sampling systems?

12.0   What calculations must I perform for analyte spiking?

13.0   How do I conduct tests at similar sources?

Optional Requirements

14.0   How do I use and conduct ruggedness testing?

15.0   How do I determine the Limit of Detection (LOD) for the alternative method?

Other Requirements and Information

16.0   How do I apply for approval to use an alternative test method?

17.0   How do I request a waiver?

18.0   Where can I find additional information

Using Method 301

1.0   What is the purpose of Method 301?

The purpose of Method 301 is to provide a set of procedures that you, the owner or operator of an affected source subject to requirements under 40 CFR part 63 can use to validate an alternative test method to a test method required in 40 CFR part 63 or to validate a stand-alone alternative test method based on established precision and bias criteria. If you use Method 301 to validate your proposed alternative method, you must use the procedures described in this method. This method describes the minimum procedures that you must use to validate an alternative test method to meet 40 CFR part 63 compliance requirements. If you choose to propose a validation method other than Method 301, you must submit and obtain the Administrator's approval for the alternative validation method.

2.0   When must I use Method 301?

If you want to use an alternative test method to meet requirements in a subpart of 40 CFR part 63, you can use Method 301 to validate the alternative test method. You must request approval to use this alternative test method according to the procedures in Sections 16 and 63.7(f). You must receive the Administrator's written approval to use the alternative test method before you use the alternative test method to meet requirements under 40 CFR part 63. In some cases, the Administrator may decide to waive the requirement to use Method 301 for alternative test methods. Section 17 describes the requirements for obtaining a waiver.

3.0   What does Method 301 include?

3.1   Procedures. This method includes minimum procedures to determine and document systematic error (bias) and random error (precision) of measured concentrations from exhaust gases, wastewater, sludge, and other media. It contains procedures for ensuring sample stability if such procedures are not included in the test method. This method also includes optional procedures for ruggedness and detection limits.

3.2   Definitions.

Affected source means affected source as defined in 40 CFR 63.2 and in the relevant subpart under 40 CFR part 63.

Alternative test method means the sampling and analytical methodology selected for field validation using the method described in this appendix.

Paired sampling system means a sampling system capable of obtaining two replicate samples that were collected as closely as possible in sampling time and sampling location.

Quadruplet sampling system means a sampling system capable of obtaining four replicate samples that were collected as closely as possible in sampling time and sampling location.

Surrogate compound means a compound that serves as a model for the types of compounds being analyzed (i.e., similar chemical structure, properties, behavior). The model can be distinguished by the method from the compounds being analyzed.

4.0   How do I perform Method 301?

First, you introduce a known concentration of an analyte or compare the alternative test method against a validated test method to determine the alternative test method's bias. Then, you collect multiple, collocated simultaneous samples to determine the alternative test method's precision. Alternatively, though it is not required, we allow validation testing over a broad range of concentrations over an extended time period to determine precision of a proposed alternative method. Sections 5.0 through 17.0 describe the procedures in detail.

Reference Materials

5.0   What reference materials must I use?

You must use reference materials (a material or substance whose one or more properties are sufficiently homogenous to the analyte) that are traceable to a national standards body (e.g., National Institute of Standards and Technology (NIST)) at the level of the applicable emission limitation or standard that the subpart in 40 CFR part 63 requires. If you want to expand the applicable range of the method, you must conduct additional runs with higher and lower analyte concentrations. You must obtain information about your analyte according to the procedures in Sections 5.1 through 5.4.

5.1   Exhaust Gas Tests Concentration. You must get a known concentration of each analyte from an independent source such as a speciality gas manufacturer, specialty chemical company, or chemical laboratory. You must also get the manufacturer's certification for the analyte concentration and stability.

5.2   Tests for Other Waste Media. You must get the pure liquid components of each analyte from an independent manufacturer. The manufacturer must certify the purity and shelf life of the pure liquid components. You must dilute the pure liquid components in the same type medium as the waste from the affected source.

5.3   Surrogate Analytes. If you demonstrate to the Administrator's satisfaction that a surrogate compound behaves as the analyte does, then you may use surrogate compounds for highly toxic or reactive compounds. A surrogate may be an isotope or one that contains a unique element (for example, chlorine) that is not present in the source or a derivation of the toxic or reactive compound if the derivative formation is part of the method's procedure. You may use laboratory experiments or literature data to show behavioral acceptability.

5.4   Isotopically Labeled Materials. Isotope mixtures may contain the isotope and the natural analyte. The isotope labeled analyte concentration must be more than five times the natural concentration of the analyte.

Sampling Procedures

6.0   What sampling procedures must I use?

You may determine bias and precision by comparing against a validated test method, using isotopic sampling, or using analyte spiking (or the equivalent). Isotopic sampling can only be used for procedures requiring mass spectrometry or radiological procedures. You must collect samples according to the requirements in Table 1. You must perform the sampling according to the procedures in Sections 6.1 through 6.4.

6.1   Isotopic Spiking. Spike all 12 samples with the analyte at the concentration in the applicable emission limitation or standard in the subpart of 40 CFR part 63. If there is no applicable emission limitation or standard, spike at the expected level of the samples. Follow the appropriate spiking procedures in Sections 6.3.1 through 6.3.2 for the applicable waste medium.

6.2   Analyte Spiking. In each quadruplet set, spike half of the samples (two out of the four) with the analyte according to the applicable procedure in Section 6.3.

6.3   Spiking Procedure.

6.3.1   Gaseous Analyte with Sorbent or Impinger Sampling Trains. Sample the analyte (in the laboratory or in the field) at a concentration that is close to the concentration in the applicable emission limitation or standard in the subpart of 40 CFR Part 63 (or the expected sample concentration where there is no standard) for the time required by the method, and then sample the gas stream for an equal amount of time. The time for sampling both the analyte and gas stream should be equal; however, the time should be adjusted to avoid sorbent breakthrough. The stack gas and the gaseous analyte may be sampled at the same time. The analyte must be introduced as close to the tip of the sampling train as possible.

6.3.2   Gaseous Analyte with Sample Container (Bag or Canister). Spike the sample containers after completion of each test run with an amount equal to the concentration in the applicable emission limitation or standard in the subpart of 40 CFR part 63 (or the expected sample concentration where there is no standard). The final concentration of the analyte would be approximately equal to the analyte concentration in the stack plus the applicable emission standard (corrected for spike volume). The volume amount of analyte must be less than 10 percent of the sample volume.

6.3.3   Liquid and Solid Analyte with Sorbent or Impinger Trains. Spike the trains with an amount equal to the concentration in the applicable emission limitation or standard in the subpart of 40 CFR part 63 (or the expected sample concentration where there is no standard) before sampling the stack gas. If possible, do the spiking in the field. If it is not possible to do the spiking in the field, you can do it in the laboratory.

6.3.4   Liquid and Solid Analyte with Sample Container (Bag or Canister). Spike the containers at the completion of each test run with an amount equal to the concentration in the applicable emission limitation or standard in the subpart of 40 CFR part 63 (or the expected sample concentration where there is no standard).

6.4   Probe Placement and Arrangement for Stationary Source Stack or Duct Sampling. To sample a stationary source as defined in 40 CFR 63.2, you must place the probe according to the procedures in this subsection. You must place the probes in the same horizontal plane.

6.4.1   Paired Sampling Probes. For paired sampling probes, the probe tip should be 2.5 cm from the outside edge of the other sample probe, with a pitot tube on the outside of each probe. The Administrator may approve a validation request where other paired arrangements for the pitot tube (where required) are used.

6.4.2   Quadruplet Sampling Probes. For quadruplet sampling probes, the tips should be in a 6.0 cm × 6.0 cm square area measured from the center line of the opening of the probe tip with a single pitot tube (where required) in the center or two pitot tubes (where required) with their location on either side of the probe tip configuration. You must propose an alternative arrangement whenever the cross-sectional area of the probe tip configuration is approximately five percent or more of the stack or duct cross-sectional area.

7.0   How do I ensure sample stability?

7.1   Developing Storage and Analysis Procedures. If the alternative test method includes well-established procedures supported by experimental data for sample storage and the time within which the collected samples must be analyzed, you must store the samples according to the procedures in the alternative test method. You are not required to conduct the procedures in Section 7.2 or 7.3. If the alternative test method does not include such procedures, you must propose procedures for storing and analyzing samples to ensure sample stability. At a minimum, your proposed procedures must meet the requirements in Section 7.2 or 7.3. The minimum storage time should be as soon as possible, but no longer than 72 hours after collection of the sample. The maximum storage time should be no longer than two weeks.

7.2   Storage and Sampling Procedures for Stack Test Emissions. You must store and analyze samples of stack test emissions according to Table 3. If you are using analyte spiking procedures, you must include equal numbers of spiked and unspiked samples.

7.3   Storage and Sampling Procedures for Testing Other Waste Media (e.g., Soil/Sediment, Solid Waste, Water/Liquid). You must analyze half of the replicate samples at the proposed minimum storage time and the other half at the proposed maximum storage time or within two weeks of the initial analysis to identify the effect of storage times on analyte samples. The minimum storage time should be as soon as possible, but no longer than seven days after collection of the sample.

7.4   Sample Stability. After you have conducted sampling and analysis according to Section 7.2 or 7.3, compare the results at the minimum and maximum storage times. Calculate the difference in the results using Equation 301-1.

eCFR graphic er18my11.002.gif

View or download PDF

Where:

di = difference between the results of the ith sample.

Rmini = results from the ith sample at the minimum storage time.

Rmaxi = results from the ith sample at the maximum storage time.

7.4.1   Standard Deviation. Determine the standard deviation (SDd) of the differences (di's) of the paired samples using Equation 301-2.

eCFR graphic er18my11.003.gif

View or download PDF

Where:

di = The difference between the results of the ith sample, Rmini − Rmaxi.

dm = The mean of the paired sample differences.

n = Total number of paired samples.

7.4.2   t Test. Test the difference in the results for statistical significance by calculating the t-statistic and determining if the mean of the differences between the initial results and the results after storage is significant at the 95 percent confidence level and n − 1 degrees of freedom. Calculate the value of the t-statistic using Equation 301-3.

eCFR graphic er18my11.004.gif

View or download PDF

Where:

n = The total number of paired samples.

Compare the calculated t-statistic with the critical value of the t-statistic from Table 2. If the calculated t-value is less than the critical value, the difference is not statistically significant; thus, the sampling and analysis procedure ensures stability, and you may submit a request for validation of the proposed alternative test method. If the calculated t-value is greater than the critical value, the difference is statistically significant, and you must repeat the procedures in Section 7.2 or 7.3 with new samples using shorter proposed maximum storage times.

Bias and Precision

8.0   What are the requirements for bias?

You must establish bias by comparing the results of the sampling using the alternative test method against a reference value. The bias must be no more than ±10 percent without the use of correction factors, and no more than ±30 percent with the use of correction factors for bias values between 10 and 30 percent for the alternative test method to be acceptable.

9.0   What are the requirements for precision?

At a minimum, you must use paired sampling systems to establish precision. If you are using analyte spiking, including isotopic samples, the precision expressed as the relative standard deviation (RSD) of the alternative test method at the level of the applicable emission limitation or standard in the subpart of 40 CFR part 63 must be less than or equal to 20 percent. For samples with a precision greater than 20 percent but less than 50 percent, a minimum of nine sample runs will be required. If you are comparing to a validated test method, the alternative test method must be at least as precise as the validated method at the level of the applicable emission limitation or standard in the subpart of 40 CFR part 63 as determined by an F test (Section 11.2.2).

10.0   What calculations must I perform for isotopic spiking?

You must analyze the bias, precision, relative standard deviation, and data acceptance for isotopic spiking tests according to the provisions in Sections 10.1 through 10.3.

10.1   Numerical Bias. Calculate the numerical value of the bias using the results from the analysis of the isotopically spiked field samples and the calculated value of the isotopically labeled spike according to Equation 301-4.

eCFR graphic er18my11.005.gif

View or download PDF

Where:

B = Bias at the spike level.

Sm = Mean of the measured values of the isotopically spiked samples.

CS = Calculated value of the isotopically labeled spike.

10.2   Standard Deviation. Calculate the standard deviation of the Si values according to Equation 301-5.

eCFR graphic er18my11.006.gif

View or download PDF

Where:

Si = Measured value of the isotopically labeled analyte in the i-th field sample,

n = Number of isotopically spiked samples, 12.

10.3   t Test. Test the bias for statistical significance by calculating the t-statistic using Equation 301-6. Use the standard deviation determined in Section 10.2 and the numerical bias determined in Section 10.1.

eCFR graphic er18my11.007.gif

View or download PDF

Compare the calculated t-value with the critical value of the two-sided t-distribution at the 95 percent confidence level and n-1 degrees of freedom. When spiking is conducted according to the procedures specified in Sections 6.2 and 6.4 as required, this critical value is 2.201 for the 11 degrees of freedom. If the calculated t-value is less than the critical value, the bias is not statistically significant, and the bias of the candidate test method is acceptable. If the calculated t-value is greater than the critical value, the bias is statistically significant, and you must evaluate the relative magnitude of the bias using Equation 301-7.

eCFR graphic er18my11.008.gif

View or download PDF

Where:

BR = Relative bias.

If the relative bias is less than or equal to ten percent, the bias of the candidate test method is acceptable and no correction factors are required. If the relative bias is greater than 10 percent but less than 30 percent, and if you correct all future data collected with the method for the magnitude of the bias, the bias of the candidate test method is acceptable. If either of the preceding two cases applies, you may continue to evaluate the method by calculating its precision. If not, the candidate method will not meet the requirements of Method 301.

10.4   Relative Standard Deviation. Calculate the RSD according to Equation 301-8.

eCFR graphic er18my11.009.gif

View or download PDF

Where:

Sm = The measured mean of the isotopically labeled spiked samples.

The data and alternative test method are unacceptable if the RSD is greater than 20 percent.

11.0   What calculations must I perform for comparison with a validated method if I am using quadruplet replicate sampling systems?

If you are using quadruplet replicate sampling systems to compare an alternative test method to a validated method, then you must analyze the data according to the provisions in this section. If the data from the alternative test method fail either the bias or precision test, the data and the alternative test method are unacceptable. If the Administrator determines that the affected source has highly variable emission rates, the Administrator may require additional precision checks.

11.1   Bias Analysis. Test the bias for statistical significance at the 95 percent confidence level by calculating the t-statistic.

11.1.1   Bias. Determine the bias, which is defined as the mean of the differences between the alternative test method and the validated method (dm). Calculate di according to Equation 301-9.

eCFR graphic er18my11.010.gif

View or download PDF

Where:

V1i = First measured value with the validated method in the i-th sample.

V2i = Second measured value with the validated method in the i-th sample.

P1i = First measured value with the alternative test method in the i-th sample.

2i = Second measured value with the alternative test method in the i-th sample.

11.1.2   Standard Deviation of the Differences. Calculate the standard deviation of the differences, SDd, using Equation 301-2.

11.1.3   t Test. Calculate the t-statistic using Equation 301-3, where n is the total number of test sample differences (di). For the quadruplet sampling system procedure in Section 6.1 and Table 1, n equals four. Compare the calculated t-statistic with the critical value of the t-statistic, and determine if the bias is significant at the 95 percent confidence level. When four runs are conducted, as specified in Section 6.2 and Table 1, the critical value of the t-statistic is 3.182 for three degrees of freedom. If the calculated t-value is less than the critical value, the bias is not statistically significant and the data are acceptable. If the calculated t-value is greater than the critical value, the bias is statistically significant, and you must evaluate the relative magnitude of the bias using Equation 301-10.

eCFR graphic er18my11.011.gif

View or download PDF

Where:

B = Bias − mean of the di's.

VS = Mean measured by the validated method.

If the relative bias is less than or equal to 10 percent, the bias of the candidate test method is acceptable and no correction factors are required. If the relative bias is greater than 10 percent but less than 30 percent, and if you correct all future data collected with the method for the magnitude of the bias, the bias of the candidate test method is acceptable. If either of the preceding two cases applies, you may continue to evaluate the method by calculating its precision. If not, the candidate method will not meet the requirements of Method 301.

11.2   Precision. Compare the estimated variance (or standard deviation) of the alternative test method to that of the validated method. If a significant difference is determined using the F test, the alternative test method and the results are rejected. If the F test does not show a significant difference, then the alternative test method has acceptable precision. Use the value furnished with the method. Calculate the estimated variance of the validated method using Equation 301-11.

11.2.1   Alternative Test Method Variance. Calculate the estimated variance of the alternative test method, Sp2, according to Equation 301-11.

eCFR graphic er18my11.012.gif

View or download PDF

Where:

di = The difference between the i-th pair of samples collected with the alternative test method.

n = Number of samples and the degrees of freedom.

11.2.2   F Test. Determine if the estimated variance of the alternative test method is greater than that of the validated method by calculating the F-value using Equation 301-12.

eCFR graphic er18my11.013.gif

View or download PDF

Where:

Sp2 = The estimated variance of the alternative method.

Sv2 = The estimated variance of the validated method.

Compare the experimental F value with the one-sided confidence level for F. The one-sided confidence level of 95 percent for F is 6.388 when the procedure specified in Section 6.1 and Table 1 for quadruplet trains is followed. If the calculated F is outside the critical range, the difference in precision is significant, and the data and the candidate test method are unacceptable.

12.0   What calculations must I perform for analyte spiking?

You must analyze the data for analyte spike testing according to this section.

12.1   Bias Analysis. Test the bias for statistical significance at the 95 percent confidence level by calculating the t-statistic.

12.1.1   Bias. Determine the bias using the results from the analysis of the spiked field samples, the unspiked field samples, and the calculated value of the spike using Equation 301-13.

eCFR graphic er18my11.014.gif

View or download PDF

Where:

S1i = First measured value of the ith spiked sample.

S2i = Second measured value of the ith spiked sample.

M1i = First measured value of the ith unspiked sample.

M2i = Second measured value of the ith unspiked sample.

CS = Calculted value of the spiked level.

12.1.2   Standard Deviation of the Differences. Calculate the standard deviation of the differences, SDd, using Equation 301-2.

12.1.3   t Test. Calculate the t-statistic using Equation 301-3, where n is the total number of test sample differences (di). For the quadruplet sampling system procedure in Table 1, n equals six. Compare the calculated t-statistic with the critical value of the t-statistic, and determine if the bias is significant at the 95 percent confidence level. When six runs are conducted, as specified in Table 1, the two-sided confidence level critical value is 2.571 for the five degrees of freedom. If the relative bias is less than or equal to 10 percent with no correction factors, or the bias is greater than 10 percent but less than 30 percent with the use of correction factors, then the data are acceptable. Proceed to evaluate precision of the candidate test method.

eCFR graphic er18my11.015.gif

View or download PDF

Where:

B = Bias − mean of the di's.

VS = Mean measured by the validated method.

12.2   Precision. Calculate the standard deviation and the relative standard deviation of the candidate test method. The relative standard deviation of the candidate test method can be calculated using Equation 301-8.

13.0   How do I conduct tests at similar sources?

If the Administrator has approved the use of an alternative test method to a test method required in 40 CFR part 63 for an affected source, and the Administrator has approved the use of the alternative test method at your similar source according to the procedures in Section 17.1.1, you must meet the requirements in this section. You must have at least three replicate samples for each test that you conduct at the similar source. You must average the results of the samples to determine the pollutant concentration.

Optional Requirements

14.0   How do I use and conduct ruggedness testing?

If you want to use a validated test method at a concentration that is different from the concentration in the applicable emission limitation in the subpart of 40 CFR part 63 or for a source category that is different from the source category that the test method specifies, then you must conduct ruggedness testing according to the procedures in Citation 18.16 of Section 18.0 and submit a request for a waiver according to Section 17.1.1.

Ruggedness testing is a laboratory study to determine the sensitivity of a method to parameters such as sample collection rate, interferant concentration, collecting medium temperature, and sample recovery temperature. You conduct ruggedness testing by changing several variables simultaneously instead of changing one variable at a time. For example, you can determine the effect of seven variables in eight experiments instead of one. (W.J. Youden, Statistical Manual of the Association of Official Analytical Chemists, Association of Official Analytical Chemists, Washington, DC, 1975, pp. 33-36).

15.0   How do I determine the Limit of Detection for the alternative method?

15.1   Limit of Detection. The Limit of Detection (LOD) is the lowest level above which you may obtain quantitative results with an acceptable degree of confidence. For this protocol, the LOD is defined as three times the standard deviation, So, at the blank level.

15.2   Purpose. The LOD will be used to establish the lower limit of the test method. If the estimated LOD is no more than twice the calculated LOD, use Procedure I in Table 4 to determine So. If the LOD is greater than twice the calculated LOD, use Procedure II in Table 4 to determine So. For radiochemical methods, use the Multi-Agency Radiological Laboratory Analytical Protocols (MARLAP) Manual (i.e., use the minimum detectable concentration (MDC) and not the LOD) available at http://www.epa.gov/radiation/docs/marlap/402-b-04-001c-20_final.pdf.

Other Requirements and Information

16.0   How do I apply for approval to use an alternative test method?

16.1 Submitting Requests. You must request to use an alternative test method according to the procedures in Section 63.7(f). You may not use an alternative test method to meet any requirement under 40 CFR part 63 until the Administrator has approved your request. The request must include a field validation report containing the information in Section 16.2. The request must be submitted to the Director, Air Quality Assessment Division, U.S. Environmental Protection Agency, C304-02, Research Triangle Park, NC 27711.

16.2   Field Validation Report. The field validation report must contain the information in Sections 16.2.1 through 16.2.8.

16.2.1   Regulatory objectives for the testing, including a description of the reasons for the test, applicable emission limits, and a description of the source.

16.2.2   Summary of the results and calculations shown in Sections 6.0 through 16, as applicable.

16.2.3   Analyte certification and value(s).

16.2.4   Discussion of laboratory evaluations.

16.2.5   Discussion of field sampling.

16.2.6   Discussion of sample preparations and analysis.

16.2.7   Storage times of samples (and extracts, if applicable).

16.2.8   Reasons for eliminating any results.

17.0   How do I request a waiver?

17.1   Conditions for Waivers. If you meet one of the criteria in Sections 17.1.1 through 17.1.2, the Administrator may waive the requirement to use the procedures in this method to validate an alternative test method. In addition, if EPA currently recognizes an appropriate test method or considers the analyst's test method to be satisfactory for a particular source, the Administrator may waive the use of this protocol or may specify a less rigorous validation procedure.

17.1.1   Similar Sources. If the alternative test method that you want to use has been validated at another source and you can demonstrate to the Administrator's satisfaction that your affected source is similar to that source, then the Administrator may waive the requirement for you to validate the alternative test method. One procedure you may use to demonstrate the applicability of the method to your affected source is by conducting a ruggedness test as described in Section 14.0.

17.1.2   Documented Methods. If the bias and precision of the alternative test method that you are proposing have been demonstrated through laboratory tests or protocols different from this method, and you can demonstrate to the Administrator's satisfaction that the bias and precision apply to your application, then the Administrator may waive the requirement to use this method or to use part of this method.

17.2   Submitting Applications for Waivers. You must sign and submit each request for a waiver from the requirements in this method in writing. The request must be submitted to the Director, Air Quality Assessment Division, U.S. Environmental Protection Agency, C304-02, Research Triangle Park, NC 27711.

17.3   Information Application for Waiver. The request for a waiver must contain a thorough description of the test method, the intended application, and results of any validation or other supporting documents. The request for a waiver must contain, at a minimum, the information in Sections 17.3.1 through 17.3.4. The Administrator may request additional information if necessary to determine whether this method can be waived for a particular application.

17.3.1   A Clearly Written Test Method. The method should be written preferably in the format of 40 CFR part 60, Appendix A Test Methods. It must include an applicability statement, concentration range, precision, bias (accuracy), and minimum and maximum storage time in which samples must be analyzed.

17.3.2   Summaries of previous validation tests or other supporting documents. If a different procedure from that described in this method was used, you must submit documents substantiating the bias and precision values to the Administrator's satisfaction.

17.3.3   Ruggedness Testing Results. You must submit results of ruggedness testing conducted according to Section 14.0, sample stability conducted according to Section 7.0, and detection limits conducted according to Section 15.0, as applicable. For example, you would not need to submit ruggedness testing results if you will be using the method at the same concentration level as the concentration level at which it was validated.

17.3.4   Applicability Statement and Basis for Waiver Approval. Your discussion of the applicability statement and basis for approval of the waiver should address the following as applicable: Applicable regulation, emission standards, effluent characteristics, and process operations.

18.0   Where can I find additional information?

You can find additional information in the references in Sections 18.1 through 18.16.

18.1   Albritton, J.R., G.B. Howe, S.B. Tompkins, R.K.M. Jayanty, and C.E. Decker. 1989. Stability of Parts-Per-Million Organic Cylinder Gases and Results of Source Test Analysis Audits, Status Report No. 11. Environmental Protection Agency Contract 68-02-4125. Research Triangle Institute, Research Triangle Park, NC. September.

18.2   ASTM Standard E 1169-89 (current version), “Standard Guide for Conducting Ruggedness Tests,” available from ASTM, 100 Barr Harbor Drive, West Conshohoken, PA 19428.

18.3   DeWees, W.G., P.M. Grohse, K.K. Luk, and F.E. Butler. 1989. Laboratory and Field Evaluation of a Methodology for Speciating Nickel Emissions from Stationary Sources. EPA Contract 68-02-4442. Prepared for Atmospheric Research and Environmental Assessment Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711. January.

18.4   International Conference on Harmonization of Technical Requirements for the Registration of Pharmaceuticals for Human Use, ICH-Q2A, “Text on Validation of Analytical Procedures,” 60 FR 11260 (March 1995).

18.5   International Conference on Harmonization of Technical Requirements for the Registration of Pharmaceuticals for Human Use, ICH-Q2b, “Validation of Analytical Procedures: Methodology,” 62 FR 27464 (May 1997).

18.6   Keith, L.H., W. Crummer, J. Deegan Jr., R.A. Libby, J.K. Taylor, and G. Wentler. 1983. Principles of Environmental Analysis. American Chemical Society, Washington, DC.

18.7   Maxwell, E.A. 1974. Estimating variances from one or two measurements on each sample. Amer. Statistician 28:96-97.

18.8   Midgett, M.R. 1977. How EPA Validates NSPS Methodology. Environ. Sci. & Technol. 11(7):655-659.

18.9   Mitchell, W.J., and M.R. Midgett. 1976. Means to evaluate performance of stationary source test methods. Environ. Sci. & Technol. 10:85-88.

18.10   Plackett, R.L., and J.P. Burman. 1946. The design of optimum multifactorial experiments. Biometrika, 33:305.

18.11   Taylor, J.K. 1987. Quality Assurance of Chemical Measurements. Lewis Publishers, Inc., pp. 79-81.

18.12   U.S. Environmental Protection Agency. 1978. Quality Assurance Handbook for Air Pollution Measurement Systems: Volume III. Stationary Source Specific Methods. Publication No. EPA-600/4-77-027b. Office of Research and Development Publications, 26 West St. Clair St., Cincinnati, OH 45268.

18.13   U.S. Environmental Protection Agency. 1981. A Procedure for Establishing Traceability of Gas Mixtures to Certain National Bureau of Standards Standard Reference Materials. Publication No. EPA-600/7-81-010. Available from the U.S. EPA, Quality Assurance Division (MD-77), Research Triangle Park, NC 27711.

18.14   U.S. Environmental Protection Agency. 1991. Protocol for The Field Validation of Emission Concentrations From Stationary Sources. Publication No. 450/4-90-015. Available from the U.S. EPA, Emission Measurement Technical Information Center, Technical Support Division (MD-14), Research Triangle Park, NC 27711.

18.15   Wernimont, G.T., “Use of Statistics to Develop and Evaluate Analytical Methods,” AOAC, 1111 North 19th Street, Suite 210, Arlington, VA 22209. USA, 78-82 (1987).

18.16   Youden, W.J. Statistical techniques for collaborative tests. Statistical Manual of the Association of Official Analytical Chemists, Association of Official Analytical Chemists, Washington, DC, 1975, pp. 33-36.

Table 1 to Appendix A—Sampling Procedures

If you are . . .You must collect . . .
comparing against a validated method9 sets of replicate samples using a paired sampling system (a total of 18 samples) or 4 sets of replicate samples using a quadruplet sampling system (a total of 16 samples). In each sample set, you must use the validated test method to collect and analyze half of the samples.
using isotopic spiking (can only be used for procedures requiring mass spectrometry)a total of 12 replicate samples. You may collect the samples either by obtaining 6 sets of paired samples or 3 sets of quadruplet samples.
using analyte spikinga total of 24 samples using the quadruplet sampling system (a total of 6 sets of replicate samples).

Table 2 to Appendix A—Critical Values of t for the Two Tailed 95 Percent Confidence Limit

Degrees of freedomt95
112.706
24.303
33.182
42.776
52.571
62.447
72.365
82.306
92.262
102.228

Table 3 to Appendix A—Storage and Sampling Procedures for Stack Test Emissions

If you are . . .With . . .Then you must . . .
using isotopic or analyte spiking proceduressample container (bag or canister) and impinger sampling systemsanalyze 6 of the samples within 7 days and then analyze the same 6 samples at the proposed maximum storage time or 2 weeks after the initial analysis.
   sorbent and impinger sampling systems that require extraction or digestionextract or digest 6 of the samples within 7 days and extract or digest 6 other samples at the proposed maximum storage time or 2 weeks after the first extraction or digestion. Analyze an aliquot of the first 6 extracts (digestates) within 7 days and proposed maximum storage times or 2 weeks after the initial analysis. This will allow analysis of extract storage impacts.
   sorbent sampling systems that require thermal desorptionanalyze 6 samples within 7 days. Analyze another set of 6 samples at the proposed maximum storage time or within 2 weeks of the initial analysis.
comparing an alternative test method against a validated test methodsampling method that does not include sorbent and impinger sampling systems that require extraction or digestionanalyze half of the samples (8 or 9) within 7 days and half of the samples (8 or 9) at the proposed maximum storage time or within 2 weeks of the initial analysis.
   sorbent and impinger sampling systems that require extraction or digestionextract or digest 6 of the samples within 7 days and extract or digest 6 other samples at the proposed maximum storage time or within 2 weeks of the first extraction or digestion. Analyze an aliquot of the first 6 extracts (digestates) within 7 days and at the proposed maximum storage times or within 2 weeks of the initial analysis. This will allow analysis of extract storage impacts.

Table 4 to Appendix A—Procedures for Estimating So

If the estimated LOD (LOD1, expected approximate LOD concentration level) is no more than twice the calculated LOD, use Procedure I as follows. Estimate the LOD (LOD1) and prepare a test standard at this level. The test standard could consist of a dilution of the analyte described in Section 5.0If the estimated LOD (LOD1, expected approximate LOD concentration level) is greater than twice the calculated LOD, use Procedure II as follows. Prepare two additional standards (LOD2 and LOD3) at concentration levels lower than the standard used in Procedure I (LOD1).
Using the normal sampling and analytical procedures for the method, sample and analyze this standard at least 7 times in the laboratorySample and analyze each of these standards (LOD2 and LOD3) at least 7 times.
Calculate the standard deviation, S1, of the measured valuesCalculate the standard deviation (S2 and S3) for each concentration level.
Calculate the LOD0 (referred to as the calculated LOD) as 3 times S1, where S0 = S1Plot the standard deviations of the three test standards (S1, S2 and S3) as a function of concentration.
   Draw a best-fit straight line through the data points and extrapolate to zero concentration. The standard deviation at zero concentration is So.
   Calculate the LOD0 (referred to as the calculated LOD) as 3 times So.

Method 303—Determination of Visible Emissions From By-Product Coke Oven Batteries

Note: This method is not inclusive with respect to observer certification. Some material is incorporated by reference from other methods in appendix A to 40 CFR part 60. Therefore, to obtain reliable results, persons using this method should have a thorough knowledge of Method 9.

1.0   Scope and Application

1.1   Applicability. This method is applicable for the determination of visible emissions (VE) from the following by-product coke oven battery sources: charging systems during charging; doors, topside port lids, and offtake systems on operating coke ovens; and collecting mains. This method is also applicable for qualifying observers for visually determining the presence of VE. In order for the test method results to be indicative of plant performance, the time of day of the run should vary.

2.0   Summary of Method

2.1   A certified observer visually determines the VE from coke oven battery sources. Certification procedures are presented. This method does not require that opacity of emissions be determined or that magnitude be differentiated.

3.0   Definitions

3.1   Bench means the platform structure in front of the oven doors.

3.2   By-product Coke Oven Battery means a source consisting of a group of ovens connected by common walls, where coal undergoes destructive distillation under positive pressure to produce coke and coke oven gas, from which by-products are recovered.

3.3   Charge or charging period means the period of time that commences when coal begins to flow into an oven through a topside port and ends when the last charging port is recapped.

3.4   Charging system means an apparatus used to charge coal to a coke oven (e.g., a larry car for wet coal charging systems).

3.5   Coke oven door means each end enclosure on the push side and the coking side of an oven. The chuck, or leveler-bar, door is considered part of the push side door. The coke oven door area includes the entire area on the vertical face of a coke oven between the bench and the top of the battery between two adjacent buck stays.

3.6   Coke side means the side of a battery from which the coke is discharged from ovens at the end of the coking cycle.

3.7   Collecting main means any apparatus that is connected to one or more offtake systems and that provides a passage for conveying gases under positive pressure from the by-product coke oven battery to the by-product recovery system.

3.8   Consecutive charges means charges observed successively, excluding any charge during which the observer's view of the charging system or topside ports is obscured.

3.9   Damper-off means to close off the gas passage between the coke oven and the collecting main, with no flow of raw coke oven gas from the collecting main into the oven or into the oven's offtake system(s).

3.10   Decarbonization period means the period of time for combusting oven carbon that commences when the oven lids are removed from an empty oven or when standpipe caps of an oven are opened. The period ends with the initiation of the next charging period for that oven.

3.11   Larry car means an apparatus used to charge coal to a coke oven with a wet coal charging system.

3.12   Log average means logarithmic average as calculated in Section 12.4.

3.13   Offtake system means any individual oven apparatus that is stationary and provides a passage for gases from an oven to a coke oven battery collecting main or to another oven. Offtake system components include the standpipe and standpipe caps, goosenecks, stationary jumper pipes, mini-standpipes, and standpipe and gooseneck connections.

3.14   Operating oven means any oven not out of operation for rebuild or maintenance work extensive enough to require the oven to be skipped in the charging sequence.

3.15   Oven means a chamber in the coke oven battery in which coal undergoes destructive distillation to produce coke.

3.16   Push side means the side of the battery from which the coke is pushed from ovens at the end of the coking cycle.

3.17   Run means the observation of visible emissions from topside port lids, offtake systems, coke oven doors, or the charging of a single oven in accordance with this method.

3.18   Shed means an enclosure that covers the side of the coke oven battery, captures emissions from pushing operations and from leaking coke oven doors on the coke side or push side of the coke oven battery, and routes the emissions to a control device or system.

3.19   Standpipe cap means An apparatus used to cover the opening in the gooseneck of an offtake system.

3.20   Topside port lid means a cover, removed during charging or decarbonizing, that is placed over the opening through which coal can be charged into the oven of a by-product coke oven battery.

3.21   Traverse time means accumulated time for a traverse as measured by a stopwatch. Traverse time includes time to stop and write down oven numbers but excludes time waiting for obstructions of view to clear or for time to walk around obstacles.

3.22   Visible Emissions or VE means any emission seen by the unaided (except for corrective lenses) eye, excluding steam or condensing water.

4.0   Interferences [Reserved]

5.0   Safety

5.1   Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method may not address all of the safety problems associated with its use. It is the responsibility of the user of this test method to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to performing this test method.

5.2   Safety Training. Because coke oven batteries have hazardous environments, the training materials and the field training (Section 10.0) shall cover the precautions required by the company to address health and safety hazards. Special emphasis shall be given to the Occupational Safety and Health Administration (OSHA) regulations pertaining to exposure of coke oven workers (see Reference 3 in Section 16.0). In general, the regulation requires that special fire-retardant clothing and respirators be worn in certain restricted areas of the coke oven battery. The OSHA regulation also prohibits certain activities, such as chewing gum, smoking, and eating in these areas.

6.0   Equipment and Supplies [Reserved]

7.0   Reagents and Standards [Reserved]

8.0   Sample Collection, Preservation, Transport, and Storage [Reserved]

9.0   Quality Control [Reserved]

10.0   Calibration and Standardization

Observer certification and training requirements are as follows:

10.1   Certification Procedures. This method requires only the determination of whether VE occur and does not require the determination of opacity levels; therefore, observer certification according to Method 9 in appendix A to part 60 of this chapter is not required to obtain certification under this method. However, in order to receive Method 303 observer certification, the first-time observer (trainee) shall have attended the lecture portion of the Method 9 certification course. In addition, the trainee shall successfully complete the Method 303 training course, satisfy the field observation requirement, and demonstrate adequate performance and sufficient knowledge of Method 303. The Method 303 training course shall be conducted by or under the sanction of the EPA and shall consist of classroom instruction and field observations, and a proficiency test.

10.1.1   The classroom instruction shall familiarize the trainees with Method 303 through lecture, written training materials, and a Method 303 demonstration video. A successful completion of the classroom portion of the Method 303 training course shall be demonstrated by a perfect score on a written test. If the trainee fails to answer all of the questions correctly, the trainee may review the appropriate portion of the training materials and retake the test.

10.1.2   The field observations shall be a minimum of 12 hours and shall be completed before attending the Method 303 certification course. Trainees shall observe the operation of a coke oven battery as it pertains to Method 303, including topside operations, and shall also practice conducting Method 303 or similar methods. During the field observations, trainees unfamiliar with coke battery operations shall receive instruction from an experienced coke oven observer familiar with Method 303 or similar methods and with the operation of coke batteries. The trainee must verify completion of at least 12 hours of field observation prior to attending the Method 303 certification course.

10.1.3   All trainees must demonstrate proficiency in the application of Method 303 to a panel of three certified Method 303 observers, including an ability to differentiate coke oven emissions from condensing water vapor and smoldering coal. Each panel member shall have at least 120 days experience in reading visible emissions from coke ovens. The visible emissions inspections that will satisfy the experience requirement must be inspections of coke oven battery fugitive emissions from the emission points subject to emission standards under subpart L of this part (i.e., coke oven doors, topside port lids, offtake system(s), and charging operations), using either Method 303 or predecessor State or local test methods. A “day's experience” for a particular inspection is a day on which one complete inspection was performed for that emission point under Method 303 or a predecessor State or local method. A “day's experience” does not mean 8 or 10 hours performing inspections, or any particular time expressed in minutes or hours that may have been spent performing them. Thus, it would be possible for an individual to qualify as a Method 303 panel member for some emission points, but not others (e.g., an individual might satisfy the experience requirement for coke oven doors, but not topside port lids). Until November 15, 1994, the EPA may waive the certification requirement (but not the experience requirement) for panel members. The composition of the panel shall be approved by the EPA. The panel shall observe the trainee in a series of training runs and a series of certification runs. There shall be a minimum of 1 training run for doors, topside port lids, and offtake systems, and a minimum of 5 training runs (i.e., 5 charges) for charging. During training runs, the panel can advise the trainee on proper procedures. There shall be a minimum of 3 certification runs for doors, topside port lids, and offtake systems, and a minimum of 15 certification runs for charging (i.e., 15 charges). The certifications runs shall be unassisted. Following the certification test runs, the panel shall approve or disapprove certification based on the trainee's performance during the certification runs. To obtain certification, the trainee shall demonstrate to the satisfaction of the panel a high degree of proficiency in performing Method 303. To aid in evaluating the trainee's performance, a checklist, provided by the EPA, will be used by the panel members.

10.2   Observer Certification/Recertification. The coke oven observer certification is valid for 1 year from date of issue. The observer shall recertify annually by viewing the training video and answering all of the questions on the certification test correctly. Every 3 years, an observer shall be required to pass the proficiency test in Section 10.1.3 in order to be certified.

10.3   The EPA (or applicable enforcement agency) shall maintain records reflecting a certified observer's successful completion of the proficiency test, which shall include the completed proficiency test checklists for the certification runs.

10.4   An owner or operator of a coke oven battery subject to subpart L of this part may observe a training and certification program under this section.

11.0   Procedure

11.1   Procedure for Determining VE from Charging Systems During Charging.

11.1.1   Number of Oven Charges. Refer to §63.309(c)(1) of this part for the number of oven charges to observe. The observer shall observe consecutive charges. Charges that are nonconsecutive can only be observed when necessary to replace observations terminated prior to the completion of a charge because of visual interferences. (See Section 11.1.5).

11.1.2   Data Records. Record all the information requested at the top of the charging system inspection sheet (Figure 303-1). For each charge, record the identification number of the oven being charged, the approximate beginning time of the charge, and the identification of the larry car used for the charge.

11.1.3   Observer Position. Stand in an area or move to positions on the topside of the coke oven battery with an unobstructed view of the entire charging system. For wet coal charging systems or non-pipeline coal charging systems, the observer should have an unobstructed view of the emission points of the charging system, including larry car hoppers, drop sleeves, and the topside ports of the oven being charged. Some charging systems are configured so that all emission points can only be seen from a distance of five ovens. For other batteries, distances of 8 to 12 ovens are adequate.

11.1.4   Observation. The charging period begins when coal begins to flow into the oven and ends when the last charging port is recapped. During the charging period, observe all of the potential sources of VE from the entire charging system. For wet coal charging systems or non-pipeline coal charging systems, sources of VE typically include the larry car hoppers, drop sleeves, slide gates, and topside ports on the oven being charged. Any VE from an open standpipe cap on the oven being charged is included as charging VE.

11.1.4.1   Using an accumulative-type stopwatch with unit divisions of at least 0.5 seconds, determine the total time VE are observed as follows. Upon observing any VE emerging from any part of the charging system, start the stopwatch. Stop the watch when VE are no longer observed emerging, and restart the watch when VE reemerges.

11.1.4.2   When VE occur simultaneously from several points during a charge, consider the sources as one. Time overlapping VE as continuous VE. Time single puffs of VE only for the time it takes for the puff to emerge from the charging system. Continue to time VE in this manner for the entire charging period. Record the accumulated time to the nearest 0.5 second under “Visible emissions, seconds” on Figure 303-1.

11.1.5   Visual Interference. If fugitive VE from other sources at the coke oven battery site (e.g., door leaks or condensing water vapor from the coke oven wharf) prevent a clear view of the charging system during a charge, stop the stopwatch and make an appropriate notation under “Comments” on Figure 303-1. Label the observation an observation of an incomplete charge, and observe another charge to fulfill the requirements of Section 11.1.1.

11.1.6   VE Exemptions. Do not time the following VE:

11.1.6.1   The VE from burning or smoldering coal spilled on top of the oven, topside port lid, or larry car surfaces;

Note: The VE from smoldering coal are generally white or gray. These VE generally have a plume of less than 1 meter long. If the observer cannot safely and with reasonable confidence determine that VE are from charging, do not count them as charging emissions.

11.1.6.2   The VE from the coke oven doors or from the leveler bar; or

11.1.6.3   The VE that drift from the top of a larry car hopper if the emissions had already been timed as VE from the drop sleeve.

Note: When the slide gate on a larry car hopper closes after the coal has been added to the oven, the seal may not be airtight. On occasions, a puff of smoke observed at the drop sleeves is forced past the slide gate up into the larry car hopper and may drift from the top; time these VE either at the drop sleeves or the hopper. If the larry car hopper does not have a slide gate or the slide gate is left open or partially closed, VE may quickly pass through the larry car hopper without being observed at the drop sleeves and will appear as a strong surge of smoke; time these as charging VE.

11.1.7   Total Time Record. Record the total time that VE were observed for each charging operation in the appropriate column on the charging system inspection sheet.

11.1.8   Determination of Validity of a Set of Observations. Five charging observations (runs) obtained in accordance with this method shall be considered a valid set of observations for that day. No observation of an incomplete charge shall be included in a daily set of observations that is lower than the lowest reading for a complete charge. If both complete and incomplete charges have been observed, the daily set of observations shall include the five highest values observed. Four or three charging observations (runs) obtained in accordance with this method shall be considered a valid set of charging observations only where it is not possible to obtain five charging observations, because visual interferences (see Section 11.1.5) or inclement weather prevent a clear view of the charging system during charging. However, observations from three or four charges that satisfy these requirements shall not be considered a valid set of charging observations if use of such set of observations in a calculation under Section 12.4 would cause the value of A to be less than 145.

11.1.9   Log Average. For each day on which a valid daily set of observations is obtained, calculate the daily 30-day rolling log average of seconds of visible emissions from the charging operation for each battery using these data and the 29 previous valid daily sets of observations, in accordance with Section 12.4.

11.2.   Procedure for Determining VE from Coke Oven Door Areas. The intent of this procedure is to determine VE from coke oven door areas by carefully observing the door area from a standard distance while walking at a normal pace.

11.2.1   Number of Runs. Refer to §63.309(c)(1) of this part for the appropriate number of runs.

11.2.2   Battery Traverse. To conduct a battery traverse, walk the length of the battery on the outside of the pusher machine and quench car tracks at a steady, normal walking pace, pausing to make appropriate entries on the door area inspection sheet (Figure 303-2). A single test run consists of two timed traverses, one for the coke side and one for the push side. The walking pace shall be such that the duration of the traverse does not exceed an average of 4 seconds per oven door, excluding time spent moving around stationary obstructions or waiting for other obstructions to move from positions blocking the view of a series of doors. Extra time is allowed for each leak (a maximum of 10 additional seconds for each leaking door) for the observer to make the proper notation. A walking pace of 3 seconds per oven door has been found to be typical. Record the actual traverse time with a stopwatch.

11.2.2.1   Include in the traverse time only the time spent observing the doors and recording door leaks. To measure actual traverse time, use an accumulative-type stopwatch with unit divisions of 0.5 seconds or less. Exclude interruptions to the traverse and time required for the observer to move to positions where the view of the battery is unobstructed, or for obstructions, such as the door machine, to move from positions blocking the view of a series of doors.

11.2.2.2   Various situations may arise that will prevent the observer from viewing a door or a series of doors. Prior to the door inspection, the owner or operator may elect to temporarily suspend charging operations for the duration of the inspection, so that all of the doors can be viewed by the observer. The observer has two options for dealing with obstructions to view: (a) Stop the stopwatch and wait for the equipment to move or the fugitive emissions to dissipate before completing the traverse; or (b) stop the stopwatch, skip the affected ovens, and move to an unobstructed position to continue the traverse. Restart the stopwatch and continue the traverse. After the completion of the traverse, if the equipment has moved or the fugitive emissions have dissipated, inspect the affected doors. If the equipment is still preventing the observer from viewing the doors, then the affected doors may be counted as not observed. If option (b) is used because of doors blocked by machines during charging operations, then, of the affected doors, exclude the door from the most recently charged oven from the inspection. Record the oven numbers and make an appropriate notation under “Comments” on the door area inspection sheet (Figure 303-2).

11.2.2.3   When batteries have sheds to control emissions, conduct the inspection from outside the shed unless the doors cannot be adequately viewed. In this case, conduct the inspection from the bench. Be aware of special safety considerations pertinent to walking on the bench and follow the instructions of company personnel on the required equipment and procedures. If possible, conduct the bench traverse whenever the bench is clear of the door machine and hot coke guide.

11.2.3   Observations. Record all the information requested at the top of the door area inspection sheet (Figure 303-2), including the number of non-operating ovens. Record the clock time at the start of the traverse on each side of the battery. Record which side is being inspected (i.e., coke side or push side). Other information may be recorded at the discretion of the observer, such as the location of the leak (e.g., top of the door, chuck door, etc.), the reason for any interruption of the traverse, or the position of the sun relative to the battery and sky conditions (e.g., overcast, partly sunny, etc.).

11.2.3.1   Begin the test run by starting the stopwatch and traversing either the coke side or the push side of the battery. After completing one side, stop the watch. Complete this procedure on the other side. If inspecting more than one battery, the observer may view the push sides and the coke sides sequentially.

11.2.3.2   During the traverse, look around the entire perimeter of each oven door. The door is considered leaking if VE are detected in the coke oven door area. The coke oven door area includes the entire area on the vertical face of a coke oven between the bench and the top of the battery between two adjacent buck stays (e.g., the oven door, chuck door, between the masonry brick, buck stay or jamb, or other sources). Record the oven number and make the appropriate notation on the door area inspection sheet (Figure 303-2).

Note: Multiple VE from the same door area (e.g., VE from both the chuck door and the push side door) are counted as only one emitting door, not as multiple emitting doors.

11.2.3.3   Do not record the following sources as door area VE:

11.2.3.3.1   VE from ovens with doors removed. Record the oven number and make an appropriate notation under “Comments;”

11.2.3.3.2   VE from ovens taken out of service. The owner or operator shall notify the observer as to which ovens are out of service. Record the oven number and make an appropriate notation under “Comments;” or

11.2.3.3.3   VE from hot coke that has been spilled on the bench as a result of pushing.

11.2.4   Criteria for Acceptance. After completing the run, calculate the maximum time allowed to observe the ovens using the equation in Section 12.2. If the total traverse time exceeds T, void the run, and conduct another run to satisfy the requirements of §63.309(c)(1) of this part.

11.2.5   Percent Leaking Doors. For each day on which a valid observation is obtained, calculate the daily 30-day rolling average for each battery using these data and the 29 previous valid daily observations, in accordance with Section 12.5.

11.3   Procedure for Determining VE from Topside Port Lids and Offtake Systems.

11.3.1   Number of Runs. Refer to §63.309(c)(1) of this part for the number of runs to be conducted. Simultaneous runs or separate runs for the topside port lids and offtake systems may be conducted.

11.3.2   Battery Traverse. To conduct a topside traverse of the battery, walk the length of the battery at a steady, normal walking pace, pausing only to make appropriate entries on the topside inspection sheet (Figure 303-3). The walking pace shall not exceed an average rate of 4 seconds per oven, excluding time spent moving around stationary obstructions or waiting for other obstructions to move from positions blocking the view. Extra time is allowed for each leak for the observer to make the proper notation. A walking pace of 3 seconds per oven is typical. Record the actual traverse time with a stopwatch.

11.3.3   Topside Port Lid Observations. To observe lids of the ovens involved in the charging operation, the observer shall wait to view the lids until approximately 5 minutes after the completion of the charge. Record all the information requested on the topside inspection sheet (Figure 303-3). Record the clock time when traverses begin and end. If the observer's view is obstructed during the traverse (e.g., steam from the coke wharf, larry car, etc.), follow the guidelines given in Section 11.2.2.2.

11.3.3.1   To perform a test run, conduct a single traverse on the topside of the battery. The observer shall walk near the center of the battery but may deviate from this path to avoid safety hazards (such as open or closed charging ports, luting buckets, lid removal bars, and topside port lids that have been removed) and any other obstacles. Upon noting VE from the topside port lid(s) of an oven, record the oven number and port number, then resume the traverse. If any oven is dampered-off from the collecting main for decarbonization, note this under “Comments” for that particular oven.

Note: Count the number of topside ports, not the number of points, exhibiting VE, i.e., if a topside port has several points of VE, count this as one port exhibiting VE.

11.3.3.2   Do not count the following as topside port lid VE:

11.3.3.2.1   VE from between the brickwork and oven lid casing or VE from cracks in the oven brickwork. Note these VE under “Comments;”

11.3.3.2.2   VE from topside ports involved in a charging operation. Record the oven number, and make an appropriate notation (e.g., not observed because ports open for charging) under “Comments;”

11.3.3.2.3   Topside ports having maintenance work done. Record the oven number and make an appropriate notation under “Comments;” or

11.3.3.2.4   Condensing water from wet-sealing material. Ports with only visible condensing water from wet-sealing material are counted as observed but not as having VE.

11.3.3.2.5   Visible emissions from the flue inspection ports and caps.

11.3.4   Offtake Systems Observations. To perform a test run, traverse the battery as in Section 11.3.3.1. Look ahead and back two to four ovens to get a clear view of the entire offtake system for each oven. Consider visible emissions from the following points as offtake system VE: (a) the flange between the gooseneck and collecting main (“saddle”), (b) the junction point of the standpipe and oven (“standpipe base”), (c) the other parts of the offtake system (e.g., the standpipe cap), and (d) the junction points with ovens and flanges of jumper pipes.

11.3.4.1   Do not stray from the traverse line in order to get a “closer look” at any part of the offtake system unless it is to distinguish leaks from interferences from other sources or to avoid obstacles.

11.3.4.2   If the centerline does not provide a clear view of the entire offtake system for each oven (e.g., when standpipes are longer than 15 feet), the observer may conduct the traverse farther from (rather than closer to) the offtake systems.

11.3.4.3   Upon noting a leak from an offtake system during a traverse, record the oven number. Resume the traverse. If the oven is dampered-off from the collecting main for decarbonization and VE are observed, note this under “Comments” for that particular oven.

11.3.4.4   If any part or parts of an offtake system have VE, count it as one emitting offtake system. Each stationary jumper pipe is considered a single offtake system.

11.3.4.5   Do not count standpipe caps open for a decarbonization period or standpipes of an oven being charged as source of offtake system VE. Record the oven number and write “Not observed” and the reason (i.e., decarb or charging) under “Comments.”

Note: VE from open standpipes of an oven being charged count as charging emissions. All VE from closed standpipe caps count as offtake leaks.

11.3.5   Criteria for Acceptance. After completing the run (allow 2 traverses for batteries with double mains), calculate the maximum time allowed to observe the topside port lids and/or offtake systems using the equation in Section 12.3. If the total traverse time exceeds T, void the run and conduct another run to satisfy the requirements of §63.309(c)(1) of this part.

11.3.6   In determining the percent leaking topside port lids and percent leaking offtake systems, do not include topside port lids or offtake systems with VE from the following ovens:

11.3.6.1   Empty ovens, including ovens undergoing maintenance, which are properly dampered off from the main.

11.3.6.2   Ovens being charged or being pushed.

11.3.6.3   Up to 3 full ovens that have been dampered off from the main prior to pushing.

11.3.6.4   Up to 3 additional full ovens in the pushing sequence that have been dampered off from the main for offtake system cleaning, for decarbonization, for safety reasons, or when a charging/pushing schedule involves widely separated ovens (e.g., a Marquard system); or that have been dampered off from the main for maintenance near the end of the coking cycle. Examples of reasons that ovens are dampered off for safety reasons are to avoid exposing workers in areas with insufficient clearance between standpipes and the larry car, or in areas where workers could be exposed to flames or hot gases from open standpipes, and to avoid the potential for removing a door on an oven that is not dampered off from the main.

11.3.7   Percent Leaking Topside Port Lids and Offtake Systems. For each day on which a valid observation is obtained, calculate the daily 30-day rolling average for each battery using these data and the 29 previous valid daily observations, in accordance with Sections 12.6 and 12.7.

11.4   Procedure for Determining VE from Collecting Mains.

11.4.1   Traverse. To perform a test run, traverse both the collecting main catwalk and the battery topside along the side closest to the collecting main. If the battery has a double main, conduct two sets of traverses for each run, i.e., one set for each main.

11.4.2   Data Recording. Upon noting VE from any portion of a collection main, identify the source and approximate location of the source of VE and record the time under “Collecting main” on Figure 303-3; then resume the traverse.

11.4.3   Collecting Main Pressure Check. After the completion of the door traverse, the topside port lids, and offtake systems, compare the collecting main pressure during the inspection to the collecting main pressure during the previous 8 to 24 hours. Record the following: (a) the pressure during inspection, (b) presence of pressure deviation from normal operations, and (c) the explanation for any pressure deviation from normal operations, if any, offered by the operators. The owner or operator of the coke battery shall maintain the pressure recording equipment and conduct the quality assurance/quality control (QA/QC) necessary to ensure reliable pressure readings and shall keep the QA/QC records for at least 6 months. The observer may periodically check the QA/QC records to determine their completeness. The owner or operator shall provide access to the records within 1 hour of an observer's request.

12.0   Data Analysis and Calculations

12.1   Nomenclature.

A = 150 or the number of valid observations (runs). The value of A shall not be less than 145, except for purposes of determinations under §63.306(c) (work practice plan implementation) or §63.306(d) (work practice plan revisions) of this part. No set of observations shall be considered valid for such a recalculation that otherwise would not be considered a valid set of observations for a calculation under this paragraph.

Di = Number of doors on non-operating ovens.

Dno = Number of doors not observed.

Dob = Total number of doors observed on operating ovens.

Dt = Total number of oven doors on the battery.

e = 2.72

J = Number of stationary jumper pipes.

L = Number of doors with VE.

Lb = Yard-equivalent reading.

Ls = Number of doors with VE observed from the bench under sheds.

Ly = Number of doors with VE observed from the yard.

Ly = Number of doors with VE observed from the yard on the push side.

ln = Natural logarithm.

N = Total number of ovens in the battery.

Ni = Total number of inoperable ovens.

PNO = Number of ports not observed.

Povn = Number of ports per oven.

PVE = Number of topside port lids with VE.

PLD = Percent leaking coke oven doors for the test run.

PLL = Percent leaking topside port lids for the run.

PLO = Percent leaking offtake systems.

T = Total time allowed for traverse, seconds.

Tovn = Number of offtake systems (excluding jumper pipes) per oven.

TNO = Number of offtake systems not observed.

TVE = Number of offtake systems with VE.

Xi = Seconds of VE during the ith charge.

Z = Number of topside port lids or offtake systems with VE.

12.2   Criteria for Acceptance for VE Determinations from Coke Oven Door Areas. After completing the run, calculate the maximum time allowed to observe the ovens using the following equation:

eCFR graphic er17oc00.535.gif

View or download PDF

12.3   Criteria for Acceptance for VE Determinations from Topside Port Lids and Offtake Systems. After completing the run (allow 2 traverses for batteries with double mains), calculate the maximum time allowed to observe the topside port lids and/or offtake systems by the following equation:

eCFR graphic er17oc00.536.gif

View or download PDF

12.4   Average Duration of VE from Charging Operations. Use Equation 303-3 to calculate the daily 30-day rolling log average of seconds of visible emissions from the charging operation for each battery using these current day's observations and the 29 previous valid daily sets of observations.

eCFR graphic er17oc00.537.gif

View or download PDF

12.5   Percent Leaking Doors (PLD). Determine the total number of doors for which observations were made on the coke oven battery as follows:

eCFR graphic er17oc00.538.gif

View or download PDF

12.5.1   For each test run (one run includes both the coke side and the push side traverses), sum the number of doors with door area VE. For batteries subject to an approved alternative standard under §63.305 of this part, calculate the push side and the coke side PLD separately.

12.5.2   Calculate percent leaking doors by using Equation 303-5:

eCFR graphic er17oc00.539.gif

View or download PDF

12.5.3   When traverses are conducted from the bench under sheds, calculate the coke side and the push side separately. Use Equation 303-6 to calculate a yard-equivalent reading:

eCFR graphic er17oc00.540.gif

View or download PDF

If Lb is less than zero, use zero for Lb in Equation 303-7 in the calculation of PLD.

12.5.3.1   Use Equation 303-7 to calculate PLD:

eCFR graphic er17oc00.541.gif

View or download PDF

Round off PLD to the nearest hundredth of 1 percent and record as the percent leaking coke oven doors for the run.

12.5.3.2   Average Percent Leaking Doors. Use Equation 303-8 to calculate the daily 30-day rolling average percent leaking doors for each battery using these current day's observations and the 29 previous valid daily sets of observations.

eCFR graphic er17oc00.542.gif

View or download PDF

12.6   Topside Port Lids. Determine the percent leaking topside port lids for each run as follows:

eCFR graphic er17oc00.543.gif

View or download PDF

12.6.1   Round off this percentage to the nearest hundredth of 1 percent and record this percentage as the percent leaking topside port lids for the run.

12.6.2   Average Percent Leaking Topside Port Lids. Use Equation 303-10 to calculate the daily 30-day rolling average percent leaking topside port lids for each battery using these current day's observations and the 29 previous valid daily sets of observations.

eCFR graphic er17oc00.544.gif

View or download PDF

12.7   Offtake Systems. Determine the percent leaking offtake systems for the run as follows:

eCFR graphic er17oc00.545.gif

View or download PDF

12.7.1   Round off this percentage to the nearest hundredth of 1 percent and record this percentage as the percent leaking offtake systems for the run.

12.7.2   Average Percent Leaking Offtake Systems. Use Equation 303-12 to calculate the daily 30-day rolling average percent leaking offtake systems for each battery using these current day's observations and the 29 previous valid daily sets of observations.

eCFR graphic er17oc00.546.gif

View or download PDF

13.0   Method Performance [Reserved]

14.0   Pollution Prevention [Reserved]

15.0   Waste Management [Reserved]

16.0   References.

1. Missan, R., and A. Stein. Guidelines for Evaluation of Visible Emissions Certification, Field Procedures, Legal Aspects, and Background Material. U.S. Environmental Protection Agency. EPA Publication No. EPA-340/1-75-007. April 1975.

2. Wohlschlegel, P., and D. E. Wagoner. Guideline for Development of a Quality Assurance Program: Volume IX—Visual Determination of Opacity Emission from Stationary Sources. U.S. Environmental Protection Agency. EPA Publication No. EPA-650/4-74-005i. November 1975.

3. U.S. Occupational Safety and Health Administration. Code of Federal Regulations. Title 29, Chapter XVII, Section 1910.1029(g). Washington, D.C. Government Printing Office. July 1, 1990.

4. U.S. Environmental Protection Agency. National Emission Standards for Hazardous Air Pollutants; Coke Oven Emissions from Wet-Coal Charged By-Product Coke Oven Batteries; Proposed Rule and Notice of Public Hearing. Washington, D.C. Federal Register. Vol. 52, No. 78 (13586). April 23, 1987.

17.0   Tables, Diagrams, Flowcharts, and Validation Data

Company name:

Battery no.: ___ Date: ___ Run no.: ___

City, State:
Observer name:
Company representative(s):
Charge No. Oven
No.
Clock time Visible
emissions,
seconds
Comments
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   

Figure 303-1. Charging System Inspection

Company name:
Battery no.:
Date:
City, State:
Total no. of ovens in battery:
Observer name:
Certification expiration date:
Inoperable ovens:
Company representative(s):
Traverse time CS:
Traverse time PS:
Valid run (Y or N):
Time traverse started/completed PS/CS Door No. Comments
(No. of blocked doors, interruptions to traverse, etc.)
   
   
   
   
   
   
   
   
   
   
   
   

Figure 303-2. Door Area Inspection.

Company name:
Battery no.:
Date:
City, State:
Total no. of ovens in battery:
Observer name:
Certification expiration date:
Inoperable ovens:
Company representative(s):
Total no. of lids:
Total no. of offtakes:
Total no. of jumper pipes:
Ovens not observed:
Total traverse time:
Valid run (Y or N):
Time traverse started/completed Type of Inspection
(lids, offtakes, collecting main)
Location of VE
(Oven #/Port #)
Comments
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   

Figure 303-3. Topside Inspection

Method 303A—Determination of Visible Emissions From Nonrecovery Coke Oven Batteries

Note: This method does not include all of the specifications pertaining to observer certification. Some material is incorporated by reference from other methods in this part and in appendix A to 40 CFR Part 60. Therefore, to obtain reliable results, persons using this method should have a thorough knowledge of Method 9 and Method 303.

1.0   Scope and Application

1.1   Applicability. This method is applicable for the determination of visible emissions (VE) from leaking doors at nonrecovery coke oven batteries.

2.0   Summary of Method

2.1   A certified observer visually determines the VE from coke oven battery sources while walking at a normal pace. This method does not require that opacity of emissions be determined or that magnitude be differentiated.

3.0   Definitions

3.1   Bench means the platform structure in front of the oven doors.

3.2   Coke oven door means each end enclosure on the push side and the coking side of an oven.

3.3   Coke side means the side of a battery from which the coke is discharged from ovens at the end of the coking cycle.

3.4   Nonrecovery coke oven battery means a source consisting of a group of ovens connected by common walls and operated as a unit, where coal undergoes destructive distillation under negative pressure to produce coke, and which is designed for the combustion of coke oven gas from which by-products are not recovered.

3.5   Operating oven means any oven not out of operation for rebuild or maintenance work extensive enough to require the oven to be skipped in the charging sequence.

3.6   Oven means a chamber in the coke oven battery in which coal undergoes destructive distillation to produce coke.

3.7   Push side means the side of the battery from which the coke is pushed from ovens at the end of the coking cycle.

3.8   Run means the observation of visible emissions from coke oven doors in accordance with this method.

3.9   Shed means an enclosure that covers the side of the coke oven battery, captures emissions from pushing operations and from leaking coke oven doors on the coke side or push side of the coke oven battery, and routes the emissions to a control device or system.

3.10   Traverse time means accumulated time for a traverse as measured by a stopwatch. Traverse time includes time to stop and write down oven numbers but excludes time waiting for obstructions of view to clear or for time to walk around obstacles.

3.11   Visible Emissions or VE means any emission seen by the unaided (except for corrective lenses) eye, excluding steam or condensing water.

4.0   Interferences [Reserved]

5.0   Safety

5.1   Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method may not address all of the safety problems associated with its use. It is the responsibility of the user of this test method to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to performing this test method.

5.2   Safety Training. Because coke oven batteries have hazardous environments, the training materials and the field training (Section 10.0) shall cover the precautions required by the company to address health and safety hazards. Special emphasis shall be given to the Occupational Safety and Health Administration (OSHA) regulations pertaining to exposure of coke oven workers (see Reference 3 in Section 16.0). In general, the regulation requires that special fire-retardant clothing and respirators be worn in certain restricted areas of the coke oven battery. The OSHA regulation also prohibits certain activities, such as chewing gum, smoking, and eating in these areas.

6.0   Equipment and Supplies [Reserved]

7.0   Reagents and Standards [Reserved]

8.0   Sample Collection, Preservation, Transport, and Storage [Reserved]

9.0   Quality Control [Reserved]

10.0   Calibration and Standardization.

10.1   Training. This method requires only the determination of whether VE occur and does not require the determination of opacity levels; therefore, observer certification according to Method 9 in Appendix A to Part 60 is not required. However, the first-time observer (trainee) shall have attended the lecture portion of the Method 9 certification course. Furthermore, before conducting any VE observations, an observer shall become familiar with nonrecovery coke oven battery operations and with this test method by observing for a minimum of 4 hours the operation of a nonrecovery coke oven battery in the presence of personnel experienced in performing Method 303 assessments.

11.0   Procedure

The intent of this procedure is to determine VE from coke oven door areas by carefully observing the door area while walking at a normal pace.

11.1   Number of Runs. Refer to §63.309(c)(1) of this part for the appropriate number of runs.

11.2   Battery Traverse. To conduct a battery traverse, walk the length of the battery on the outside of the pusher machine and quench car tracks at a steady, normal walking pace, pausing to make appropriate entries on the door area inspection sheet (Figure 303A-1). The walking pace shall be such that the duration of the traverse does not exceed an average of 4 seconds per oven door, excluding time spent moving around stationary obstructions or waiting for other obstructions to move from positions blocking the view of a series of doors. Extra time is allowed for each leak (a maximum of 10 additional seconds for each leaking door) for the observer to make the proper notation. A walking pace of 3 seconds per oven door has been found to be typical. Record the actual traverse time with a stopwatch. A single test run consists of two timed traverses, one for the coke side and one for the push side.

11.2.1   Various situations may arise that will prevent the observer from viewing a door or a series of doors. The observer has two options for dealing with obstructions to view: (a) Wait for the equipment to move or the fugitive emissions to dissipate before completing the traverse; or (b) skip the affected ovens and move to an unobstructed position to continue the traverse. Continue the traverse. After the completion of the traverse, if the equipment has moved or the fugitive emissions have dissipated, complete the traverse by inspecting the affected doors. Record the oven numbers and make an appropriate notation under “Comments” on the door area inspection sheet (Figure 303A-1).

Note: Extra time incurred for handling obstructions is not counted in the traverse time.

11.2.2   When batteries have sheds to control pushing emissions, conduct the inspection from outside the shed, if the shed allows such observations, or from the bench. Be aware of special safety considerations pertinent to walking on the bench and follow the instructions of company personnel on the required equipment and operations procedures. If possible, conduct the bench traverse whenever the bench is clear of the door machine and hot coke guide.

11.3   Observations. Record all the information requested at the top of the door area inspection sheet (Figure 303A-1), including the number of non-operating ovens. Record which side is being inspected, i.e., coke side or push side. Other information may be recorded at the discretion of the observer, such as the location of the leak (e.g., top of the door), the reason for any interruption of the traverse, or the position of the sun relative to the battery and sky conditions (e.g., overcast, partly sunny, etc.).

11.3.1   Begin the test run by traversing either the coke side or the push side of the battery. After completing one side, traverse the other side.

11.3.2   During the traverse, look around the entire perimeter of each oven door. The door is considered leaking if VE are detected in the coke oven door area. The coke oven door area includes the entire area on the vertical face of a coke oven between the bench and the top of the battery and the adjacent doors on both sides. Record the oven number and make the appropriate notation on the door area inspection sheet (Figure 303A-1).

11.3.3   Do not record the following sources as door area VE:

11.3.3.1   VE from ovens with doors removed. Record the oven number and make an appropriate notation under “Comments”;

11.3.3.2   VE from ovens where maintenance work is being conducted. Record the oven number and make an appropriate notation under “Comments”; or

11.3.3.3   VE from hot coke that has been spilled on the bench as a result of pushing.

12.0   Data Analysis and Calculations

Same as Method 303, Section 12.1, 12.2, 12.3, 12.4, and 12.5.

13.0   Method Performance [Reserved]

14.0   Pollution Prevention [Reserved]

15.0   Waste Management [Reserved]

16.0   References

Same as Method 303, Section 16.0.

17.0   Tables, Diagrams, Flowcharts, and Validation Data

Company name:
Battery no.:
Date:
City, State:
Total no. of ovens in battery:
Observer name:
Certification expiration date:
Inoperable ovens:
Company representative(s):
Traverse time CS:
Traverse time PS:
Valid run (Y or N):
Time traverse started/completed PS/CS Door No. Comments
(No. of blocked doors, interruptions to traverse, etc.)
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   
   

Figure 303A-1. Door Area Inspection

Method 304A: Determination of Biodegradation Rates of Organic Compounds (Vent Option)

1.0   Scope and Application

1.1   Applicability. This method is applicable for the determination of biodegradation rates of organic compounds in an activated sludge process. The test method is designed to evaluate the ability of an aerobic biological reaction system to degrade or destroy specific components in waste streams. The method may also be used to determine the effects of changes in wastewater composition on operation. The biodegradation rates determined by utilizing this method are not representative of a full-scale system. The rates measured by this method shall be used in conjunction with the procedures listed in appendix C of this part to calculate the fraction emitted to the air versus the fraction biodegraded.

2.0   Summary of Method

2.1   A self-contained benchtop bioreactor system is assembled in the laboratory. A sample of mixed liquor is added and the waste stream is then fed continuously. The benchtop bioreactor is operated under conditions nearly identical to the target full-scale activated sludge process. Bioreactor temperature, dissolved oxygen concentration, average residence time in the reactor, waste composition, biomass concentration, and biomass composition of the full-scale process are the parameters which are duplicated in the benchtop bioreactor. Biomass shall be removed from the target full-scale activated sludge unit and held for no more than 4 hours prior to use in the benchtop bioreactor. If antifoaming agents are used in the full-scale system, they shall also be used in the benchtop bioreactor. The feed flowing into and the effluent exiting the benchtop bioreactor are analyzed to determine the biodegradation rates of the target compounds. The flow rate of the exit vent is used to calculate the concentration of target compounds (utilizing Henry's law) in the exit gas stream. If Henry's law constants for the compounds of interest are not known, this method cannot be used in the determination of the biodegradation rate and Method 304B is the suggested method. The choice of analytical methodology for measuring the compounds of interest at the inlet and outlet to the benchtop bioreactor are left to the discretion of the source, except where validated methods are available.

3.0   Definitions [Reserved]

4.0   Interferences [Reserved]

5.0   Safety

5.1   If explosive gases are produced as a byproduct of biodegradation and could realistically pose a hazard, closely monitor headspace concentration of these gases to ensure laboratory safety. Placement of the benchtop bioreactor system inside a laboratory hood is recommended regardless of byproducts produced.

6.0.   Equipment and Supplies

Note: Figure 304A-1 illustrates a typical laboratory apparatus used to measure biodegradation rates. While the following description refers to Figure 304A-1, the EPA recognizes that alternative reactor configurations, such as alternative reactor shapes and locations of probes and the feed inlet, will also meet the intent of this method. Ensure that the benchtop bioreactor system is self-contained and isolated from the atmosphere (except for the exit vent stream) by leak-checking fittings, tubing, etc.

6.1   Benchtop Bioreactor. The biological reaction is conducted in a biological oxidation reactor of at least 6 liters capacity. The benchtop bioreactor is sealed and equipped with internal probes for controlling and monitoring dissolved oxygen and internal temperature. The top of the reactor is equipped for aerators, gas flow ports, and instrumentation (while ensuring that no leaks to the atmosphere exist around the fittings).

6.2   Aeration gas. Aeration gas is added to the benchtop bioreactor through three diffusers, which are glass tubes that extend to the bottom fifth of the reactor depth. A pure oxygen pressurized cylinder is recommended in order to maintain the specified oxygen concentration. Install a blower (e.g., Diaphragm Type, 15 SCFH capacity) to blow the aeration gas into the reactor diffusers. Measure the aeration gas flow rate with a rotameter (e.g., 0-15 SCFH recommended). The aeration gas will rise through the benchtop bioreactor, dissolving oxygen into the mixture in the process. The aeration gas must provide sufficient agitation to keep the solids in suspension. Provide an exit for the aeration gas from the top flange of the benchtop bioreactor through a water-cooled (e.g., Allihn-type) vertical condenser. Install the condenser through a gas-tight fitting in the benchtop bioreactor closure. Install a splitter which directs a portion of the gas to an exit vent and the rest of the gas through an air recycle pump back to the benchtop bioreactor. Monitor and record the flow rate through the exit vent at least 3 times per day throughout the day.

6.3   Wastewater Feed. Supply the wastewater feed to the benchtop bioreactor in a collapsible low-density polyethylene container or collapsible liner in a container (e.g., 20 L) equipped with a spigot cap (collapsible containers or liners of other material may be required due to the permeability of some volatile compounds through polyethylene). Obtain the wastewater feed by sampling the wastewater feed in the target process. A representative sample of wastewater shall be obtained from the piping leading to the aeration tank. This sample may be obtained from existing sampling valves at the discharge of the wastewater feed pump, or collected from a pipe discharging to the aeration tank, or by pumping from a well-mixed equalization tank upstream from the aeration tank. Alternatively, wastewater can be pumped continuously to the laboratory apparatus from a bleed stream taken from the equalization tank of the full-scale treatment system.

6.3.1   Refrigeration System. Keep the wastewater feed cool by ice or by refrigeration to 4 °C. If using a bleed stream from the equalization tank, refrigeration is not required if the residence time in the bleed stream is less than five minutes.

6.3.2   Wastewater Feed Pump. The wastewater is pumped from the refrigerated container using a variable-speed peristaltic pump drive equipped with a peristaltic pump head. Add the feed solution to the benchtop bioreactor through a fitting on the top flange. Determine the rate of feed addition to provide a retention time in the benchtop bioreactor that is numerically equivalent to the retention time in the full-scale system. The wastewater shall be fed at a rate sufficient to achieve 90 to 100 percent of the full-scale system residence time.

6.3.3   Treated wastewater feed. The benchtop bioreactor effluent exits at the bottom of the reactor through a tube and proceeds to the clarifier.

6.4   Clarifier. The effluent flows to a separate closed clarifier that allows separation of biomass and effluent (e.g., 2-liter pear-shaped glass separatory funnel, modified by removing the stopcock and adding a 25-mm OD glass tube at the bottom). Benchtop bioreactor effluent enters the clarifier through a tube inserted to a depth of 0.08 m (3 in.) through a stopper at the top of the clarifier. System effluent flows from a tube inserted through the stopper at the top of the clarifier to a drain (or sample bottle when sampling). The underflow from the clarifier leaves from the glass tube at the bottom of the clarifier. Flexible tubing connects this fitting to the sludge recycle pump. This pump is coupled to a variable speed pump drive. The discharge from this pump is returned through a tube inserted in a port on the side of the benchtop bioreactor. An additional port is provided near the bottom of the benchtop bioreactor for sampling the reactor contents. The mixed liquor from the benchtop bioreactor flows into the center of the clarifier. The clarified system effluent separates from the biomass and flows through an exit near the top of the clarifier. There shall be no headspace in the clarifier.

6.5   Temperature Control Apparatus. Capable of maintaining the system at a temperature equal to the temperature of the full-scale system. The average temperature should be maintained within ±2 °C of the set point.

6.5.1   Temperature Monitoring Device. A resistance type temperature probe or a thermocouple connected to a temperature readout with a resolution of 0.1 °C or better.

6.5.2   Benchtop Bioreactor Heater. The heater is connected to the temperature control device.

6.6   Oxygen Control System. Maintain the dissolved oxygen concentration at the levels present in the full-scale system. Target full-scale activated sludge systems with dissolved oxygen concentration below 2 mg/L are required to maintain the dissolved oxygen concentration in the benchtop ioreactor within 0.5 mg/L of the target dissolved oxygen level. Target full-scale activated sludge systems with dissolved oxygen concentration above 2 mg/L are required to maintain the dissolved oxygen concentration in the benchtop bioreactor within 1.5 mg/L of the target dissolved oxygen concentration; however, for target full-scale activated sludge systems with dissolved oxygen concentrations above 2 mg/L, the dissolved oxygen concentration in the benchtop bioreactor may not drop below 1.5 mg/L. If the benchtop bioreactor is outside the control range, the dissolved oxygen is noted and the reactor operation is adjusted.

6.6.1   Dissolved Oxygen Monitor. Dissolved oxygen is monitored with a polarographic probe (gas permeable membrane) connected to a dissolved oxygen meter (e.g., 0 to 15 mg/L, 0 to 50 °C).

6.6.2   Benchtop Bioreactor Pressure Monitor. The benchtop bioreactor pressure is monitored through a port in the top flange of the reactor. This is connected to a gauge control with a span of 13-cm water vacuum to 13-cm water pressure or better. A relay is activated when the vacuum exceeds an adjustable setpoint which opens a solenoid valve (normally closed), admitting oxygen to the system. The vacuum setpoint controlling oxygen addition to the system shall be set at approximately 2.5 ±0.5 cm water and maintained at this setting except during brief periods when the dissolved oxygen concentration is adjusted.

6.7   Connecting Tubing. All connecting tubing shall be Teflon or equivalent in impermeability. The only exception to this specification is the tubing directly inside the pump head of the wastewater feed pump, which may be Viton, Silicone or another type of flexible tubing.

Note: Mention of trade names or products does not constitute endorsement by the U.S. Environmental Protection Agency.

7.0   Reagents and Standards

7.1   Wastewater. Obtain a representative sample of wastewater at the inlet to the full-scale treatment plant if there is an existing full-scale treatment plant (see section 6.3). If there is no existing full-scale treatment plant, obtain the wastewater sample as close to the point of determination as possible. Collect the sample by pumping the wastewater into the 20-L collapsible container. The loss of volatiles shall be minimized from the wastewater by collapsing the container before filling, by minimizing the time of filling, and by avoiding a headspace in the container after filling. If the wastewater requires the addition of nutrients to support the biomass growth and maintain biomass characteristics, those nutrients are added and mixed with the container contents after the container is filled.

7.2   Biomass. Obtain the biomass or activated sludge used for rate constant determination in the bench-scale process from the existing full-scale process or from a representative biomass culture (e.g., biomass that has been developed for a future full-scale process). This biomass is preferentially obtained from a thickened acclimated mixed liquor sample. Collect the sample either by bailing from the mixed liquor in the aeration tank with a weighted container, or by collecting aeration tank effluent at the effluent overflow weir. Transport the sample to the laboratory within no more than 4 hours of collection. Maintain the biomass concentration in the benchtop bioreactor at the level of the full-scale system +10 percent throughout the sampling period of the test method.

8.0   Sample Collection, Preservation, Storage, and Transport

8.1   Benchtop Bioreactor Operation. Charge the mixed liquor to the benchtop bioreactor, minimizing headspace over the liquid surface to minimize entrainment of mixed liquor in the circulating gas. Fasten the benchtop bioreactor headplate to the reactor over the liquid surface. Maintain the temperature of the contents of the benchtop bioreactor system at the temperature of the target full-scale system, ±2 °C, throughout the testing period. Monitor and record the temperature of the benchtop bioreactor contents at least to the nearest 0.1 °C.

8.1.1   Wastewater Storage. Collect the wastewater sample in the 20-L collapsible container. Store the container at 4 °C throughout the testing period. Connect the container to the benchtop bioreactor feed pump.

8.1.2   Wastewater Flow Rate.

8.1.2.1   The hydraulic residence time of the aeration tank is calculated as the ratio of the volume of the tank (L) to the flow rate (L/min). At the beginning of a test, the container shall be connected to the feed pump and solution shall be pumped to the benchtop bioreactor at the required flow rate to achieve the calculated hydraulic residence time of wastewater in the aeration tank.

eCFR graphic er17oc00.547.gif

View or download PDF

Where:

Qtest = wastewater flow rate (L/min)

Qfs = average flow rate of full-scale process (L/min)

Vfs = volume of full-scale aeration tank (L)

8.1.2.2   The target flow rate in the test apparatus is the same as the flow rate in the target full-scale process multiplied by the ratio of benchtop bioreactor volume (e.g., 6 L) to the volume of the full-scale aeration tank. The hydraulic residence time shall be maintained at 90 to 100 percent of the residence time maintained in the full-scale unit. A nominal flow rate is set on the pump based on a pump calibration. Changes in the elasticity of the tubing in the pump head and the accumulation of material in the tubing affect this calibration. The nominal pumping rate shall be changed as necessary based on volumetric flow measurements. Discharge the benchtop bioreactor effluent to a wastewater storage, treatment, or disposal facility, except during sampling or flow measurement periods.

8.1.3   Sludge Recycle Rate. Set the sludge recycle rate at a rate sufficient to prevent accumulation in the bottom of the clarifier. Set the air circulation rate sufficient to maintain the biomass in suspension.

8.1.4   Benchtop Bioreactor Operation and Maintenance. Temperature, dissolved oxygen concentration, exit vent flow rate, benchtop bioreactor effluent flow rate, and air circulation rate shall be measured and recorded three times throughout each day of benchtop bioreactor operation. If other parameters (such as pH) are measured and maintained in the target full-scale unit, these parameters, where appropriate, shall be monitored and maintained to target full-scale specifications in the benchtop bioreactor. At the beginning of each sampling period (Section 8.2), sample the benchtop bioreactor contents for suspended solids analysis. Take this sample by loosening a clamp on a length of tubing attached to the lower side port. Determine the suspended solids gravimetrically by the Gooch crucible/glass fiber filter method for total suspended solids, in accordance with Standard Methods3 or equivalent. When necessary, sludge shall be wasted from the lower side port of the benchtop bioreactor, and the volume that is wasted shall be replaced with an equal volume of the reactor effluent. Add thickened activated sludge mixed liquor as necessary to the benchtop bioreactor to increase the suspended solids concentration to the desired level. Pump this mixed liquor to the benchtop bioreactor through the upper side port (Item 24 in Figure 304A-1). Change the membrane on the dissolved oxygen probe before starting the test. Calibrate the oxygen probe immediately before the start of the test and each time the membrane is changed.

8.1.5   Inspection and Correction Procedures. If the feed line tubing becomes clogged, replace with new tubing. If the feed flow rate is not within 5 percent of target flow any time the flow rate is measured, reset pump or check the flow measuring device and measure flow rate again until target flow rate is achieved.

8.2   Test Sampling. At least two and one half hydraulic residence times after the system has reached the targeted specifications shall be permitted to elapse before the first sample is taken. Effluent samples of the clarifier discharge (Item 20 in Figure 304A-1) and the influent wastewater feed are collected in 40-mL septum vials to which two drops of 1:10 hydrochloric acid (HCl) in water have been added. Sample the clarifier discharge directly from the drain line. These samples will be composed of the entire flow from the system for a period of several minutes. Feed samples shall be taken from the feed pump suction line after temporarily stopping the benchtop bioreactor feed, removing a connector, and squeezing the collapsible feed container. Store both influent and effluent samples at 4 °C immediately after collection and analyze within 8 hours of collection.

8.2.1   Frequency of Sampling. During the test, sample and analyze the wastewater feed and the clarifier effluent at least six times. The sampling intervals shall be separated by at least 8 hours. During any individual sampling interval, sample the wastewater feed simultaneously with or immediately after the effluent sample. Calculate the relative standard deviation (RSD) of the amount removed (i.e., effluent concentration—wastewater feed concentration). The RSD values shall be <15 percent. If an RSD value is >15 percent, continue sampling and analyzing influent and effluent sets of samples until the RSD values are within specifications.

8.2.2   Sampling After Exposure of System to Atmosphere. If, after starting sampling procedures, the benchtop bioreactor system is exposed to the atmosphere (due to leaks, maintenance, etc.), allow at least one hydraulic residence time to elapse before resuming sampling.

9.0   Quality Control

9.1   Dissolved Oxygen. Fluctuation in dissolved oxygen concentration may occur for numerous reasons, including undetected gas leaks, increases and decreases in mixed liquor suspended solids resulting from cell growth and solids loss in the effluent stream, changes in diffuser performance, cycling of effluent flow rate, and overcorrection due to faulty or sluggish dissolved oxygen probe response. Control the dissolved oxygen concentration in the benchtop bioreactor by changing the proportion of oxygen in the circulating aeration gas. Should the dissolved oxygen concentration drift below the designated experimental condition, bleed a small amount of aeration gas from the system on the pressure side (i.e., immediately upstream of one of the diffusers). This will create a vacuum in the system, triggering the pressure sensitive relay to open the solenoid valve and admit oxygen to the system. Should the dissolved oxygen concentration drift above the designated experimental condition, slow or stop the oxygen input to the system until the dissolved oxygen concentration approaches the correct level.

9.2   Sludge Wasting.

9.2.1   Determine the suspended solids concentration (section 8.1.4) at the beginning of a test, and once per day thereafter during the test. If the test is completed within a two day period, determine the suspended solids concentration after the final sample set is taken. If the suspended solids concentration exceeds the specified concentration, remove a fraction of the sludge from the benchtop bioreactor. The required volume of mixed liquor to remove is determined as follows:

eCFR graphic er17oc00.548.gif

View or download PDF

Where:

Vw is the wasted volume (Liters),

Vr is the volume of the benchtop bioreactor (Liters),

Sm is the measured solids (g/L), and

Ss is the specified solids (g/L).

9.2.2   Remove the mixed liquor from the benchtop bioreactor by loosening a clamp on the mixed liquor sampling tube and allowing the required volume to drain to a graduated flask. Clamp the tube when the correct volume has been wasted. Replace the volume of the liquid wasted by pouring the same volume of effluent back into the benchtop bioreactor. Dispose of the waste sludge properly.

9.3   Sludge Makeup. In the event that the suspended solids concentration is lower than the specifications, add makeup sludge back into the benchtop bioreactor. Determine the amount of sludge added by the following equation:

eCFR graphic er17oc00.549.gif

View or download PDF

Where:

Vw is the volume of sludge to add (Liters),

Vr is the volume of the benchtop bioreactor (Liters),

Sw is the solids in the makeup sludge (g/L),

Sm is the measured solids (g/L), and Ss is the specified solids (g/L).

10.0   Calibration and Standardization

10.1   Wastewater Pump Calibration. Determine the wastewater flow rate by collecting the system effluent for a time period of at least one hour, and measuring the volume with a graduated cylinder. Record the collection time period and volume collected. Determine flow rate. Adjust the pump speed to deliver the specified flow rate.

10.2   Calibration Standards. Prepare calibration standards from pure certified standards in an aqueous medium. Prepare and analyze three concentrations of calibration standards for each target component (or for a mixture of components) in triplicate daily throughout the analyses of the test samples. At each concentration level, a single calibration shall be within 5 percent of the average of the three calibration results. The low and medium calibration standards shall bracket the expected concentration of the effluent (treated) wastewater. The medium and high standards shall bracket the expected influent concentration.

11.0   Analytical Procedures

11.1   Analysis. If the identity of the compounds of interest in the wastewater is not known, a representative sample of the wastewater shall be analyzed in order to identify all of the compounds of interest present. A gas chromatography/mass spectrometry screening method is recommended.

11.1.1   After identifying the compounds of interest in the wastewater, develop and/or use one or more analytical techniques capable of measuring each of those compounds (more than one analytical technique may be required, depending on the characteristics of the wastewater). Test Method 18, found in appendix A of 40 CFR 60, may be used as a guideline in developing the analytical technique. Purge and trap techniques may be used for analysis providing the target components are sufficiently volatile to make this technique appropriate. The limit of quantitation for each compound shall be determined (see reference 1). If the effluent concentration of any target compound is below the limit of quantitation determined for that compound, the operation of the Method 304 unit may be altered to attempt to increase the effluent concentration above the limit of quantitation. Modifications to the method shall be approved prior to the test. The request should be addressed to Method 304 contact, Emissions Measurement Center, Mail Drop 19, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711.

12.0   Data Analysis and Calculations

12.1   Nomenclature. The following symbols are used in the calculations.

Ci = Average inlet feed concentration for a compound of interest, as analyzed (mg/L)

Co = Average outlet (effluent) concentration for a compound of interest, as analyzed (mg/L)

X = Biomass concentration, mixed liquor suspended solids (g/L)

t = Hydraulic residence time in the benchtop bioreactor (hours)

V = Volume of the benchtop bioreactor (L)

Q = Flow rate of wastewater into the benchtop bioreactor, average (L/hour)

12.2   Residence Time. The hydraulic residence time of the benchtop bioreactor is equal to the ratio of the volume of the benchtop bioreactor (L) to the flow rate (L/h):

eCFR graphic er17oc00.550.gif

View or download PDF

12.3   Rate of Biodegradation. Calculate the rate of biodegradation for each component with the following equation:

eCFR graphic er17oc00.551.gif

View or download PDF

12.4   First-Order Biorate Constant. Calculate the first-order biorate constant (K1) for each component with the following equation:

eCFR graphic er17oc00.552.gif

View or download PDF

12.5   Relative Standard Deviation (RSD). Determine the standard deviation of both the influent and effluent sample concentrations (S) using the following equation:

eCFR graphic er17oc00.553.gif

View or download PDF

12.6   Determination of Percent Air Emissions and Percent Biodegraded. Use the results from this test method and follow the applicable procedures in appendix C of 40 CFR part 63, entitled, “Determination of the Fraction Biodegraded (Fbio) in a Biological Treatment Unit” to determine Fbio.

13.0   Method Performance [Reserved]

14.0   Pollution Prevention [Reserved]

15.0   Waste Management [Reserved]

16.0   References

1. “Guidelines for data acquisition and data quality evaluation in Environmental Chemistry,” Daniel MacDoughal, Analytical Chemistry, Volume 52, p. 2242, 1980.

2. Test Method 18, 40 CFR 60, appendix A.

3. Standard Methods for the Examination of Water and Wastewater, 16th Edition, Method 209C, Total Suspended Solids Dried at 103-105 °C, APHA, 1985.

4. Water7, Hazardous Waste Treatment, Storage, and Disposal Facilities (TSDF)—Air Emission Models, U.S. Environmental Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.

5. Chemdat7, Hazardous Waste Treatment, Storage, and Disposal Facilities (TSDF)—Air Emission Models, U.S. Environmental Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.

17.0   Tables, Diagrams, Flowcharts, and Validation Data

eCFR graphic er17oc00.554.gif

View or download PDF

Method 304B: Determination of Biodegradation Rates of Organic Compounds (Scrubber Option)

1.0   Scope and Application

1.1   Applicability. This method is applicable for the determination of biodegradation rates of organic compounds in an activated sludge process. The test method is designed to evaluate the ability of an aerobic biological reaction system to degrade or destroy specific components in waste streams. The method may also be used to determine the effects of changes in wastewater composition on operation. The biodegradation rates determined by utilizing this method are not representative of a full-scale system. Full-scale systems embody biodegradation and air emissions in competing reactions. This method measures biodegradation in absence of air emissions. The rates measured by this method shall be used in conjunction with the procedures listed in appendix C of this part to calculate the fraction emitted to the air versus the fraction biodegraded.

2.0   Summary of Method

2.1   A self-contained benchtop bioreactor system is assembled in the laboratory. A sample of mixed liquor is added and the waste stream is then fed continuously. The benchtop bioreactor is operated under conditions nearly identical to the target full-scale activated sludge process, except that air emissions are not a factor. The benchtop bioreactor temperature, dissolved oxygen concentration, average residence time in the reactor, waste composition, biomass concentration, and biomass composition of the target full-scale process are the parameters which are duplicated in the laboratory system. Biomass shall be removed from the target full-scale activated sludge unit and held for no more than 4 hours prior to use in the benchtop bioreactor. If antifoaming agents are used in the full-scale system, they shall also be used in the benchtop bioreactor. The feed flowing into and the effluent exiting the benchtop bioreactor are analyzed to determine the biodegradation rates of the target compounds. The choice of analytical methodology for measuring the compounds of interest at the inlet and outlet to the benchtop bioreactor are left to the discretion of the source, except where validated methods are available.

3.0   Definitions [Reserved]

4.0   Interferences [Reserved]

5.0   Safety

5.1   If explosive gases are produced as a byproduct of biodegradation and could realistically pose a hazard, closely monitor headspace concentration of these gases to ensure laboratory safety. Placement of the benchtop bioreactor system inside a laboratory hood is recommended regardless of byproducts produced.

6.0   Equipment and Supplies

Note: Figure 304B-1 illustrates a typical laboratory apparatus used to measure biodegradation rates. While the following description refers to Figure 304B-1, the EPA recognizes that alternative reactor configurations, such as alternative reactor shapes and locations of probes and the feed inlet, will also meet the intent of this method. Ensure that the benchtop bioreactor system is self-contained and isolated from the atmosphere by leak-checking fittings, tubing, etc.

6.1   Benchtop Bioreactor. The biological reaction is conducted in a biological oxidation reactor of at least 6-liters capacity. The benchtop bioreactor is sealed and equipped with internal probes for controlling and monitoring dissolved oxygen and internal temperature. The top of the benchtop bioreactor is equipped for aerators, gas flow ports, and instrumentation (while ensuring that no leaks to the atmosphere exist around the fittings).

6.2   Aeration gas. Aeration gas is added to the benchtop bioreactor through three diffusers, which are glass tubes that extend to the bottom fifth of the reactor depth. A pure oxygen pressurized cylinder is recommended in order to maintain the specified oxygen concentration. Install a blower (e.g., Diaphragm Type, 15 SCFH capacity) to blow the aeration gas into the benchtop bioreactor diffusers. Measure the aeration gas flow rate with a rotameter (e.g., 0-15 SCFH recommended). The aeration gas will rise through the benchtop bioreactor, dissolving oxygen into the mixture in the process. The aeration gas must provide sufficient agitation to keep the solids in suspension. Provide an exit for the aeration gas from the top flange of the benchtop bioreactor through a water-cooled (e.g., Allihn-type) vertical condenser. Install the condenser through a gas-tight fitting in the benchtop bioreactor closure. Design the system so that at least 10 percent of the gas flows through an alkaline scrubber containing 175 mL of 45 percent by weight solution of potassium hydroxide (KOH) and 5 drops of 0.2 percent alizarin yellow dye. Route the balance of the gas through an adjustable scrubber bypass. Route all of the gas through a 1-L knock-out flask to remove entrained moisture and then to the intake of the blower. The blower recirculates the gas to the benchtop bioreactor.

6.3   Wastewater Feed. Supply the wastewater feed to the benchtop bioreactor in a collapsible low-density polyethylene container or collapsible liner in a container (e.g., 20 L) equipped with a spigot cap (collapsible containers or liners of other material may be required due to the permeability of some volatile compounds through polyethylene). Obtain the wastewater feed by sampling the wastewater feed in the target process. A representative sample of wastewater shall be obtained from the piping leading to the aeration tank. This sample may be obtained from existing sampling valves at the discharge of the wastewater feed pump, or collected from a pipe discharging to the aeration tank, or by pumping from a well-mixed equalization tank upstream from the aeration tank. Alternatively, wastewater can be pumped continuously to the laboratory apparatus from a bleed stream taken from the equalization tank of the full-scale treatment system.

6.3.1   Refrigeration System. Keep the wastewater feed cool by ice or by refrigeration to 4 °C. If using a bleed stream from the equalization tank, refrigeration is not required if the residence time in the bleed stream is less than five minutes.

6.3.2   Wastewater Feed Pump. The wastewater is pumped from the refrigerated container using a variable-speed peristaltic pump drive equipped with a peristaltic pump head. Add the feed solution to the benchtop bioreactor through a fitting on the top flange. Determine the rate of feed addition to provide a retention time in the benchtop bioreactor that is numerically equivalent to the retention time in the target full-scale system. The wastewater shall be fed at a rate sufficient to achieve 90 to 100 percent of the target full-scale system residence time.

6.3.3   Treated wastewater feed. The benchtop bioreactor effluent exits at the bottom of the reactor through a tube and proceeds to the clarifier.

6.4   Clarifier. The effluent flows to a separate closed clarifier that allows separation of biomass and effluent (e.g., 2-liter pear-shaped glass separatory funnel, modified by removing the stopcock and adding a 25-mm OD glass tube at the bottom). Benchtop bioreactor effluent enters the clarifier through a tube inserted to a depth of 0.08 m (3 in.) through a stopper at the top of the clarifier. System effluent flows from a tube inserted through the stopper at the top of the clarifier to a drain (or sample bottle when sampling). The underflow from the clarifier leaves from the glass tube at the bottom of the clarifier. Flexible tubing connects this fitting to the sludge recycle pump. This pump is coupled to a variable speed pump drive. The discharge from this pump is returned through a tube inserted in a port on the side of the benchtop bioreactor. An additional port is provided near the bottom of the benchtop bioreactor for sampling the reactor contents. The mixed liquor from the benchtop bioreactor flows into the center of the clarifier. The clarified system effluent separates from the biomass and flows through an exit near the top of the clarifier. There shall be no headspace in the clarifier.

6.5   Temperature Control Apparatus. Capable of maintaining the system at a temperature equal to the temperature of the full-scale system. The average temperature should be maintained within ±2 °C of the set point.

6.5.1   Temperature Monitoring Device. A resistance type temperature probe or a thermocouple connected to a temperature readout with a resolution of 0.1 °C or better.

6.5.2   Benchtop Bioreactor Heater. The heater is connected to the temperature control device.

6.6   Oxygen Control System. Maintain the dissolved oxygen concentration at the levels present in the full-scale system. Target full-scale activated sludge systems with dissolved oxygen concentration below 2 mg/L are required to maintain the dissolved oxygen concentration in the benchtop bioreactor within 0.5 mg/L of the target dissolved oxygen level. Target full-scale activated sludge systems with dissolved oxygen concentration above 2 mg/L are required to maintain the dissolved oxygen concentration in the benchtop bioreactor within 1.5 mg/L of the target dissolved oxygen concentration; however, for target full-scale activated sludge systems with dissolved oxygen concentrations above 2 mg/L, the dissolved oxygen concentration in the benchtop bioreactor may not drop below 1.5 mg/L. If the benchtop bioreactor is outside the control range, the dissolved oxygen is noted and the reactor operation is adjusted.

6.6.1   Dissolved Oxygen Monitor. Dissolved oxygen is monitored with a polarographic probe (gas permeable membrane) connected to a dissolved oxygen meter (e.g., 0 to 15 mg/L, 0 to 50 °C).

6.6.2   Benchtop Bioreactor Pressure Monitor. The benchtop bioreactor pressure is monitored through a port in the top flange of the reactor. This is connected to a gauge control with a span of 13-cm water vacuum to 13-cm water pressure or better. A relay is activated when the vacuum exceeds an adjustable setpoint which opens a solenoid valve (normally closed), admitting oxygen to the system. The vacuum setpoint controlling oxygen addition to the system shall be set at approximately 2.5 ±0.5 cm water and maintained at this setting except during brief periods when the dissolved oxygen concentration is adjusted.

6.7   Connecting Tubing. All connecting tubing shall be Teflon or equivalent in impermeability. The only exception to this specification is the tubing directly inside the pump head of the wastewater feed pump, which may be Viton, Silicone or another type of flexible tubing.

Note: Mention of trade names or products does not constitute endorsement by the U.S. Environmental Protection Agency.

7.0.   Reagents and Standards

7.1   Wastewater. Obtain a representative sample of wastewater at the inlet to the full-scale treatment plant if there is an existing full-scale treatment plant (See Section 6.3). If there is no existing full-scale treatment plant, obtain the wastewater sample as close to the point of determination as possible. Collect the sample by pumping the wastewater into the 20-L collapsible container. The loss of volatiles shall be minimized from the wastewater by collapsing the container before filling, by minimizing the time of filling, and by avoiding a headspace in the container after filling. If the wastewater requires the addition of nutrients to support the biomass growth and maintain biomass characteristics, those nutrients are added and mixed with the container contents after the container is filled.

7.2   Biomass. Obtain the biomass or activated sludge used for rate constant determination in the bench-scale process from the existing full-scale process or from a representative biomass culture (e.g., biomass that has been developed for a future full-scale process). This biomass is preferentially obtained from a thickened acclimated mixed liquor sample. Collect the sample either by bailing from the mixed liquor in the aeration tank with a weighted container, or by collecting aeration tank effluent at the effluent overflow weir. Transport the sample to the laboratory within no more than 4 hours of collection. Maintain the biomass concentration in the benchtop bioreactor at the level of the target full-scale system +10 percent throughout the sampling period of the test method.

8.0   Sample Collection, Preservation, Storage, and Transport

8.1   Benchtop Bioreactor Operation. Charge the mixed liquor to the benchtop bioreactor, minimizing headspace over the liquid surface to minimize entrainment of mixed liquor in the circulating gas. Fasten the benchtop bioreactor headplate to the reactor over the liquid surface. Maintain the temperature of the contents of the benchtop bioreactor system at the temperature of the target full-scale system, ±2 °C, throughout the testing period. Monitor and record the temperature of the reactor contents at least to the nearest 0.1 °C.

8.1.1   Wastewater Storage. Collect the wastewater sample in the 20-L collapsible container. Store the container at 4 °C throughout the testing period. Connect the container to the benchtop bioreactor feed pump.

8.1.2   Wastewater Flow Rate.

8.1.2.1   The hydraulic residence time of the aeration tank is calculated as the ratio of the volume of the tank (L) to the flow rate (L/min). At the beginning of a test, the container shall be connected to the feed pump and solution shall be pumped to the benchtop bioreactor at the required flow rate to achieve the calculated hydraulic residence time of wastewater in the aeration tank.

eCFR graphic er17oc00.555.gif

View or download PDF

Where:

Qtest = wastewater flow rate (L/min)

Qfs = average flow rate of full-scale process (L/min)

Vfs = volume of full-scale aeration tank (L)

8.1.2.2   The target flow rate in the test apparatus is the same as the flow rate in the target full-scale process multiplied by the ratio of benchtop bioreactor volume (e.g., 6 L) to the volume of the full-scale aeration tank. The hydraulic residence time shall be maintained at 90 to 100 percent of the residence time maintained in the target full-scale unit. A nominal flow rate is set on the pump based on a pump calibration. Changes in the elasticity of the tubing in the pump head and the accumulation of material in the tubing affect this calibration. The nominal pumping rate shall be changed as necessary based on volumetric flow measurements. Discharge the benchtop bioreactor effluent to a wastewater storage, treatment, or disposal facility, except during sampling or flow measurement periods.

8.1.3   Sludge Recycle Rate. Set the sludge recycle rate at a rate sufficient to prevent accumulation in the bottom of the clarifier. Set the air circulation rate sufficient to maintain the biomass in suspension.

8.1.4   Benchtop Bioreactor Operation and Maintenance. Temperature, dissolved oxygen concentration, flow rate, and air circulation rate shall be measured and recorded three times throughout each day of testing. If other parameters (such as pH) are measured and maintained in the target full-scale unit, these parameters shall, where appropriate, be monitored and maintained to full-scale specifications in the benchtop bioreactor. At the beginning of each sampling period (section 8.2), sample the benchtop bioreactor contents for suspended solids analysis. Take this sample by loosening a clamp on a length of tubing attached to the lower side port. Determine the suspended solids gravimetrically by the Gooch crucible/glass fiber filter method for total suspended solids, in accordance with Standard Methods3 or equivalent. When necessary, sludge shall be wasted from the lower side port of the benchtop bioreactor, and the volume that is wasted shall be replaced with an equal volume of the benchtop bioreactor effluent. Add thickened activated sludge mixed liquor as necessary to the benchtop bioreactor to increase the suspended solids concentration to the desired level. Pump this mixed liquor to the benchtop bioreactor through the upper side port (Item 24 in Figure 304B-1). Change the membrane on the dissolved oxygen probe before starting the test. Calibrate the oxygen probe immediately before the start of the test and each time the membrane is changed. The scrubber solution shall be replaced each weekday with 175 mL 45 percent W/W KOH solution to which five drops of 0.2 percent alizarin yellow indicator in water have been added. The potassium hydroxide solution in the alkaline scrubber shall be changed if the alizarin yellow dye color changes.

8.1.5   Inspection and Correction Procedures. If the feed line tubing becomes clogged, replace with new tubing. If the feed flow rate is not within 5 percent of target flow any time the flow rate is measured, reset pump or check the flow measuring device and measure flow rate again until target flow rate is achieved.

8.2   Test Sampling. At least two and one half hydraulic residence times after the system has reached the targeted specifications shall be permitted to elapse before the first sample is taken. Effluent samples of the clarifier discharge (Item 20 in Figure 304B-1) and the influent wastewater feed are collected in 40-mL septum vials to which two drops of 1:10 hydrochloric acid (HCl) in water have been added. Sample the clarifier discharge directly from the drain line. These samples will be composed of the entire flow from the system for a period of several minutes. Feed samples shall be taken from the feed pump suction line after temporarily stopping the benchtop bioreactor feed, removing a connector, and squeezing the collapsible feed container. Store both influent and effluent samples at 4 °C immediately after collection and analyze within 8 hours of collection.

8.2.1   Frequency of Sampling. During the test, sample and analyze the wastewater feed and the clarifier effluent at least six times. The sampling intervals shall be separated by at least 8 hours. During any individual sampling interval, sample the wastewater feed simultaneously with or immediately after the effluent sample. Calculate the RSD of the amount removed (i.e., effluent concentration—wastewater feed concentration). The RSD values shall be <15 percent. If an RSD value is >15 percent, continue sampling and analyzing influent and effluent sets of samples until the RSD values are within specifications.

8.2.2   Sampling After Exposure of System to Atmosphere. If, after starting sampling procedures, the benchtop bioreactor system is exposed to the atmosphere (due to leaks, maintenance, etc.), allow at least one hydraulic residence time to elapse before resuming sampling.

9.0   Quality Control

9.1   Dissolved Oxygen. Fluctuation in dissolved oxygen concentration may occur for numerous reasons, including undetected gas leaks, increases and decreases in mixed liquor suspended solids resulting from cell growth and solids loss in the effluent stream, changes in diffuser performance, cycling of effluent flow rate, and overcorrection due to faulty or sluggish dissolved oxygen probe response. Control the dissolved oxygen concentration in the benchtop bioreactor by changing the proportion of oxygen in the circulating aeration gas. Should the dissolved oxygen concentration drift below the designated experimental condition, bleed a small amount of aeration gas from the system on the pressure side (i.e., immediately upstream of one of the diffusers). This will create a vacuum in the system, triggering the pressure sensitive relay to open the solenoid valve and admit oxygen to the system. Should the dissolved oxygen concentration drift above the designated experimental condition, slow or stop the oxygen input to the system until the dissolved oxygen concentration approaches the correct level.

9.2   Sludge Wasting.

9.2.1   Determine the suspended solids concentration (section 8.1.4) at the beginning of a test, and once per day thereafter during the test. If the test is completed within a two day period, determine the suspended solids concentration after the final sample set is taken. If the suspended solids concentration exceeds the specified concentration, remove a fraction of the sludge from the benchtop bioreactor. The required volume of mixed liquor to remove is determined as follows:

eCFR graphic er17oc00.556.gif

View or download PDF

Where:

Vw is the wasted volume (Liters),

Vr is the volume of the benchtop bioreactor (Liters),

Sm is the measured solids (g/L), and

Ss is the specified solids (g/L).

9.2.2   Remove the mixed liquor from the benchtop bioreactor by loosening a clamp on the mixed liquor sampling tube and allowing the required volume to drain to a graduated flask. Clamp the tube when the correct volume has been wasted. Replace the volume of the liquid wasted by pouring the same volume of effluent back into the benchtop bioreactor. Dispose of the waste sludge properly.

9.3   Sludge Makeup. In the event that the suspended solids concentration is lower than the specifications, add makeup sludge back into the benchtop bioreactor. Determine the amount of sludge added by the following equation:

eCFR graphic er17oc00.557.gif

View or download PDF

Where:

Vw is the volume of sludge to add (Liters),

Vr is the volume of the benchtop bioreactor (Liters),

Sw is the solids in the makeup sludge (g/L),

Sm is the measured solids (g/L), and

Ss is the specified solids (g/L).

10.0   Calibration and Standardizations

10.1   Wastewater Pump Calibration. Determine the wastewater flow rate by collecting the system effluent for a time period of at least one hour, and measuring the volume with a graduated cylinder. Record the collection time period and volume collected. Determine flow rate. Adjust the pump speed to deliver the specified flow rate.

10.2   Calibration Standards. Prepare calibration standards from pure certified standards in an aqueous medium. Prepare and analyze three concentrations of calibration standards for each target component (or for a mixture of components) in triplicate daily throughout the analyses of the test samples. At each concentration level, a single calibration shall be within 5 percent of the average of the three calibration results. The low and medium calibration standards shall bracket the expected concentration of the effluent (treated) wastewater. The medium and high standards shall bracket the expected influent concentration.

11.0   Analytical Test Procedures

11.1   Analysis. If the identity of the compounds of interest in the wastewater is not known, a representative sample of the wastewater shall be analyzed in order to identify all of the compounds of interest present. A gas chromatography/mass spectrometry screening method is recommended.

11.1.1   After identifying the compounds of interest in the wastewater, develop and/or use one or more analytical technique capable of measuring each of those compounds (more than one analytical technique may be required, depending on the characteristics of the wastewater). Method 18, found in appendix A of 40 CFR 60, may be used as a guideline in developing the analytical technique. Purge and trap techniques may be used for analysis providing the target components are sufficiently volatile to make this technique appropriate. The limit of quantitation for each compound shall be determined.1 If the effluent concentration of any target compound is below the limit of quantitation determined for that compound, the operation of the Method 304 unit may be altered to attempt to increase the effluent concentration above the limit of quantitation. Modifications to the method shall be approved prior to the test. The request should be addressed to Method 304 contact, Emissions Measurement Center, Mail Drop 19, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711.

12.0   Data Analysis and Calculations

12.1   Nomenclature. The following symbols are used in the calculations.

Ci = Average inlet feed concentration for a compound of interest, as analyzed (mg/L)

Co = Average outlet (effluent) concentration for a compound of interest, as analyzed (mg/L)

X = Biomass concentration, mixed liquor suspended solids (g/L)

t = Hydraulic residence time in the benchtop bioreactor (hours)

V = Volume of the benchtop bioreactor (L)

Q = Flow rate of wastewater into the benchtop bioreactor, average (L/hour)

12.2   Residence Time. The hydraulic residence time of the benchtop bioreactor is equal to the ratio of the volume of the benchtop bioreactor (L) to the flow rate (L/h)

eCFR graphic er17oc00.558.gif

View or download PDF

12.3   Rate of Biodegradation. Calculate the rate of biodegradation for each component with the following equation:

eCFR graphic er17oc00.559.gif

View or download PDF

12.4   First-Order Biorate Constant. Calculate the first-order biorate constant (K1) for each component with the following equation:

eCFR graphic er17oc00.560.gif

View or download PDF

12.5   Relative Standard Deviation (RSD). Determine the standard deviation of both the influent and effluent sample concentrations (S) using the following equation:

eCFR graphic er17oc00.561.gif

View or download PDF

12.6   Determination of Percent Air Emissions and Percent Biodegraded. Use the results from this test method and follow the applicable procedures in appendix C of 40 CFR Part 63, entitled, “Determination of the Fraction Biodegraded (Fbio) in a Biological Treatment Unit” to determine Fbio.

13.0   Method Performance [Reserved]

14.0   Pollution Prevention [Reserved]

15.0   Waste Management [Reserved]

16.0   References

1. “Guidelines for data acquisition and data quality evaluation in Environmental Chemistry”, Daniel MacDoughal, Analytical Chemistry, Volume 52, p. 2242, 1980.

2. Test Method 18, 40 CFR 60, Appendix A.

3. Standard Methods for the Examination of Water and Wastewater, 16th Edition, Method 209C, Total Suspended Solids Dried at 103-105 °C, APHA, 1985.

4. Water—7, Hazardous Waste Treatment, Storage, and Disposal Facilities (TSDF)—Air Emission Models, U.S. Environmental Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.

5. Chemdat7, Hazardous Waste Treatment, Storage, and Disposal Facilities (TSDF)—Air Emission Models, U.S. Environmental Protection Agency, EPA-450/3-87-026, Review Draft, November 1989.

17.0   Tables, Diagrams, Flowcharts, and Validation Data

eCFR graphic er17oc00.562.gif

View or download PDF

Method 305: Measurement of Emission Potential of Individual Volatile Organic Compounds in Waste

Note: This method does not include all of the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and analytical) essential to its performance. Some material is incorporated by reference from other methods in 40 CFR Part 60, Appendix A. Therefore, to obtain reliable results, persons using this method should have a thorough knowledge of at least Method 25D.

1.0   Scope and Application

1.1   Analyte. Volatile Organics. No CAS No. assigned.

1.2   Applicability. This procedure is used to determine the emission potential of individual volatile organics (VOs) in waste.

1.3   Data Quality Objectives. Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.

2.0   Summary of Method

2.1   The heated purge conditions established by Method 25D (40 CFR Part 60, Appendix A) are used to remove VOs from a 10 gram sample of waste suspended in a 50/50 solution of polyethylene glycol (PEG) and water. The purged VOs are quantified by using the sample collection and analytical techniques (e.g. gas chromatography) appropriate for the VOs present in the waste. The recovery efficiency of the sample collection and analytical technique is determined for each waste matrix. A correction factor is determined for each compound (if acceptable recovery criteria requirements are met of 70 to 130 percent recovery for every target compound), and the measured waste concentration is corrected with the correction factor for each compound. A minimum of three replicate waste samples shall be analyzed.

3.0   Definitions [Reserved]

4.0   Interferences [Reserved]

5.0   Safety

5.1   Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method may not address all of the safety problems associated with its use. It is the responsibility of the user of this test method to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to performing this test method.

6.0   Equipment and Supplies

6.1   Method 25D Purge Apparatus.

6.1.1   Purge Chamber. The purge chamber shall accommodate the 10 gram sample of waste suspended in a matrix of 50 mL of PEG and 50 mL of deionized, hydrocarbon-free water. Three fittings are used on the glass chamber top. Two #7 Ace-threads are used for the purge gas inlet and outlet connections. A #50 Ace-thread is used to connect the top of the chamber to the base (see Figure 305-1). The base of the chamber has a side-arm equipped with a #22 Sovirel fitting to allow for easy sample introductions into the chamber. The dimensions of the chamber are shown in Figure 305-1.

6.1.2   Flow Distribution Device (FDD). The FDD enhances the gas-to-liquid contact for improved purging efficiency. The FDD is a 6 mm OD (0.2 in) by 30 cm (12 in) long glass tube equipped with four arm bubblers as shown in Figure 305-1. Each arm shall have an opening of 1 mm (0.04 in) in diameter.

6.1.3   Coalescing Filter. The coalescing filter serves to discourage aerosol formation of sample gas once it leaves the purge chamber. The glass filter has a fritted disc mounted 10 cm (3.9 in) from the bottom. Two #7 Ace-threads are used for the inlet and outlet connections. The dimensions of the chamber are shown in Figure 305-2.

6.1.4   Oven. A forced convection airflow oven capable of maintaining the purge chamber and coalescing filter at 75 ±2 °C (167 ±3.6 °F).

6.1.5   Toggle Valve. An on/off valve constructed from brass or stainless steel rated to 100 psig. This valve is placed in line between the purge nitrogen source and the flow controller.

6.1.6   Flow Controller. High-quality stainless steel flow controller capable of restricting a flow of nitrogen to 6 ±0.06 L/min (0.2 ±0.002 ft3/min) at 40 psig.

6.1.7   Polyethylene Glycol Cleaning System.

6.1.7.1   Round-Bottom Flask. One liter, three-neck glass round-bottom flask for cleaning PEG. Standard taper 24/40 joints are mounted on each neck.

6.1.7.2   Heating Mantle. Capable of heating contents of the 1-L flask to 120 °C (248 °F).

6.1.7.3   Nitrogen Bubbler. Teflon® or glass tube, 0.25 in OD (6.35 mm).

6.1.7.4   Temperature Sensor. Partial immersion glass thermometer.

6.1.7.5   Hose Adapter. Glass with 24/40 standard tapered joint.

6.2   Volatile Organic Recovery System.

6.2.1   Splitter Valve (Optional). Stainless steel cross-pattern valve capable of splitting nominal flow rates from the purge flow of 6 L/min (0.2 ft3/min). The valve shall be maintained at 75 + 2 °C (167 ±3.6 °F) in the heated zone and shall be placed downstream of the coalescing filter. It is recommended that 0.125 in OD (3.175 mm) tubing be used to direct the split vent flow from the heated zone. The back pressure caused by the 0.125 in OD (3.175 mm) tubing is critical for maintaining proper split valve operation.

Note: The splitter valve design is optional; it may be used in cases where the concentration of a pollutant would saturate the adsorbents.

6.2.2   Injection Port. Stainless steel 14 in OD (6.35 mm) compression fitting tee with a 6 mm (0.2 in) septum fixed on the top port. The injection port is the point of entry for the recovery study solution. If using a gaseous standard to determine recovery efficiency, connect the gaseous standard to the injection port of the tee.

6.2.3   Knockout Trap (Optional but Recommended). A 25 mL capacity glass reservoir body with a full-stem impinger (to avoid leaks, a modified midget glass impinger with a screw cap and ball/socket clamps on the inlet and outlet is recommended). The empty impinger is placed in an ice water bath between the injection port and the sorbent cartridge. Its purpose is to reduce the water content of the purge gas (saturated at 75 °C (167 °F)) before the sorbent cartridge.

6.2.4   Insulated Ice Bath. A 350 mL dewar or other type of insulated bath is used to maintain ice water around the knockout trap.

6.2.5   Sorbent Cartridges. Commercially available glass or stainless steel cartridge packed with one or more appropriate sorbents. The amount of adsorbent packed in the cartridge depends on the breakthrough volume of the test compounds but is limited by back pressure caused by the packing (not to exceed 7 psig). More than one sorbent cartridge placed in series may be necessary depending upon the mixture of the measured components.

6.2.6   Volumetric Glassware. Type A glass 10 mL volumetric flasks for measuring a final volume from the water catch in the knockout trap.

6.2.7   Thermal Desorption Unit. A clam-shell type oven, used for the desorption of direct thermal desorption sorbent tubes. The oven shall be capable of increasing the temperature of the desorption tubes rapidly to recommended desorption temperature.

6.2.8   Ultrasonic Bath. Small bath used to agitate sorbent material and desorption solvent. Ice water shall be used in the bath because of heat transfer caused by operation of the bath.

6.2.9   Desorption Vials. Four-dram (15 mL) capacity borosilicate glass vials with Teflon-lined caps.

6.3   Analytical System. A gas chromatograph (GC) is commonly used to separate and quantify compounds from the sample collection and recovery procedure. Method 18 (40 CFR Part 60, Appendix A) may be used as a guideline for determining the appropriate GC column and GC detector based on the test compounds to be determined. Other types of analytical instrumentation may be used (HPLC) in lieu of GC systems as long as the recovery efficiency criteria of this method are met.

6.3.1   Gas Chromatograph (GC). The GC shall be equipped with a constant-temperature liquid injection port or a heated sampling loop/valve system, as appropriate. The GC oven shall be temperature-programmable over the useful range of the GC column. The choice of detectors is based on the test compounds to be determined.

6.3.2   GC Column. Select the appropriate GC column based on (1) literature review or previous experience, (2) polarity of the analytes, (3) capacity of the column, or (4) resolving power (e.g., length, diameter, film thickness) required.

6.3.3   Data System. A programmable electronic integrator for recording, analyzing, and storing the signal generated by the detector.

7.0   Reagents and Standards

7.1   Method 25D Purge Apparatus.

7.1.1   Polyethylene Glycol (PEG). Ninety-eight percent pure organic polymer with an average molecular weight of 400 g/mol. Volatile organics are removed from the PEG prior to use by heating to 120 ±5 °C (248 ±9 °F) and purging with pure nitrogen at 1 L/min (0.04 ft3/min) for 2 hours. After purging and heating, the PEG is maintained at room temperature under a nitrogen purge maintained at 1 L/min (0.04 ft3/min) until used. A typical apparatus used to clean the PEG is shown in Figure 305-3.

7.1.2   Water. Organic-free deionized water is required.

7.1.3   Nitrogen. High-purity nitrogen (less than 0.5 ppm total hydrocarbons) is used to remove test compounds from the purge matrix. The source of nitrogen shall be regulated continuously to 40 psig before the on/off toggle valve.

7.2   Volatile Organic Recovery System.

7.2.1   Water. Organic-free deionized water is required.

7.2.2   Desorption Solvent (when used). Appropriate high-purity (99.99 percent) solvent for desorption shall be used. Analysis shall be performed (utilizing the same analytical technique as that used in the analysis of the waste samples) on each lot to determine purity.

7.3   Analytical System. The gases required for GC operation shall be of the highest obtainable purity (hydrocarbon free). Consult the operating manual for recommended settings.

8.0   Sample Collection, Preservation, Storage, and Transport

8.1   Assemble the glassware and associated fittings (see Figures 305-3 and 305-4, as appropriate) and leak-check the system (approximately 7 psig is the target pressure). After an initial leak check, mark the pressure gauge and use the initial checkpoint to monitor for leaks throughout subsequent analyses. If the pressure in the system drops below the target pressure at any time during analysis, that analysis shall be considered invalid.

8.2   Recovery Efficiency Determination. Determine the individual recovery efficiency (RE) for each of the target compounds in duplicate before the waste samples are analyzed. To determine the RE, generate a water blank (Section 11.1) and use the injection port to introduce a known volume of spike solution (or certified gaseous standard) containing all of the target compounds at the levels expected in the waste sample. Introduce the spike solution immediately after the nitrogen purge has been started (Section 8.3.2). Follow the procedures outlined in Section 8.3.3. Analyze the recovery efficiency samples using the techniques described in Section 11.2. Determine the recovery efficiency (Equation 305-1, Section 12.2) by comparing the amount of compound recovered to the theoretical amount spiked. Determine the RE twice for each compound; the relative standard deviation, (RSD) shall be ≤10 percent for each compound. If the RSD for any compound is not ≤10 percent, modify the sampling/analytical procedure and complete an RE study in duplicate, or continue determining RE until the RSD meets the acceptable criteria. The average RE shall be 0.70 ≤RE ≤1.30 for each compound. If the average RE does not meet these criteria, an alternative sample collection and/or analysis technique shall be developed and the recovery efficiency determination shall be repeated for that compound until the criteria are met for every target compound. Example modifications of the sampling/analytical system include changing the adsorbent material, changing the desorption solvent, utilizing direct thermal desorption of test compounds from the sorbent tubes, utilizing another analytical technique.

8.3   Sample Collection and Recovery.

8.3.1   The sample collection procedure in Method 25D shall be used to collect (into a preweighed vial) 10 g of waste into PEG, cool, and ship to the laboratory. Remove the sample container from the cooler and wipe the exterior to remove any ice or water. Weigh the container and sample to the nearest 0.01 g and record the weight. Pour the sample from the container into the purge flask. Rinse the sample container three times with approximately 6 mL of PEG (or the volume needed to total 50 mL of PEG in the purge flask), transferring the rinses to the purge flask. Add 50 mL of organic-free deionized water to the purge flask. Cap the purge flask tightly in between each rinse and after adding all the components into the flask.

8.3.2   Allow the oven to equilibrate to 75 ±2 °C (167 ±3.6 °F). Begin the sample recovery process by turning the toggle valve on, thus allowing a 6 L/min flow of pure nitrogen through the purge chamber.

8.3.3   Stop the purge after 30 min. Immediately remove the sorbent tube(s) from the apparatus and cap both ends. Remove the knockout trap and transfer the water catch to a 10 mL volumetric flask. Rinse the trap with organic-free deionized water and transfer the rinse to the volumetric flask. Dilute to the 10 mL mark with water. Transfer the water sample to a sample vial and store at 4 °C (39.2 °F) with zero headspace. The analysis of the contents of the water knockout trap is optional for this method. If the target compounds are water soluble, analysis of the water is recommended; meeting the recovery efficiency criteria in these cases would be difficult without adding the amount captured in the knockout trap.

9.0   Quality Control

9.1   Miscellaneous Quality Control Measures.

Section Quality control measure Effect
8.1Sampling equipment leak-checkEnsures accurate measurement of sample volume.
8.2Recovery efficiency (RE) determination for each measured compound.Ensures accurate sample collection and analysis.
8.3Calibration of analytical instrument with at least 3 calibration standards.Ensures linear measurement of compounds over the instrument span.

10.0   Calibration and Standardization

10.1   The analytical instrument shall be calibrated with a minimum of three levels of standards for each compound whose concentrations bracket the concentration of test compounds from the sorbent tubes. Liquid calibration standards shall be used for calibration in the analysis of the solvent extracts. The liquid calibration standards shall be prepared in the desorption solvent matrix. The calibration standards may be prepared and injected individually or as a mixture. If thermal desorption and focusing (onto another sorbent or cryogen focusing) are used, a certified gaseous mixture or a series of gaseous standards shall be used for calibration of the instrument. The gaseous standards shall be focused and analyzed in the same manner as the samples.

10.2   The analytical system shall be certified free from contaminants before a calibration is performed (see Section 11.1). The calibration standards are used to determine the linearity of the analytical system. Perform an initial calibration and linearity check by analyzing the three calibration standards for each target compound in triplicate starting with the lowest level and continuing to the highest level. If the triplicate analyses do not agree within 5 percent of their average, additional analyses will be needed until the 5 percent criteria is met. Calculate the response factor (Equation 305-3, Section 12.4) from the average area counts of the injections for each concentration level. Average the response factors of the standards for each compound. The linearity of the detector is acceptable if the response factor of each compound at a particular concentration is within 10 percent of the overall mean response factor for that compound. Analyze daily a mid-level calibration standard in duplicate and calculate a new response factor. Compare the daily response factor average to the average response factor calculated for the mid-level calibration during the initial linearity check; repeat the three-level calibration procedure if the daily average response factor differs from the initial linearity check mid-level response factor by more than 10 percent. Otherwise, proceed with the sample analysis.

11.0   Analytical Procedure

11.1   Water Blank Analysis. A water blank shall be analyzed daily to determine the cleanliness of the purge and recovery system. A water blank is generated by adding 60 mL of organic-free deionized water to 50 mL of PEG in the purge chamber. Treat the blank as described in Sections 8.3.2 and 8.3.3. The purpose of the water blank is to insure that no contaminants exist in the sampling and analytical apparatus which would interfere with the quantitation of the target compounds. If contaminants are present, locate the source of contamination, remove it, and repeat the water blank analysis.

11.2   Sample Analysis. Sample analysis in the context of this method refers to techniques to remove the target compounds from the sorbent tubes, separate them using a chromatography technique, and quantify them with an appropriate detector. Two types of sample extraction techniques typically used for sorbents include solvent desorption or direct thermal desorption of test compounds to a secondary focusing unit (either sorbent or cryogen based). The test compounds are then typically transferred to a GC system for analysis. Other analytical systems may be used (e.g., HPLC) in lieu of GC systems as long as the recovery efficiency criteria of this method are met.

11.2.1   Recover the test compounds from the sorbent tubes that require solvent desorption by transferring the adsorbent material to a sample vial containing the desorption solvent. The desorption solvent shall be the same as the solvent used to prepare calibration standards. The volume of solvent depends on the amount of adsorbed material to be desorbed (1.0 mL per 100 mg of adsorbent material) and also on the amount of test compounds present. Final volume adjustment and or dilution can be made so that the concentration of test compounds in the desorption solvent is bracketed by the concentration of the calibration solutions. Ultrasonicate the desorption solvent for 15 min in an ice bath. Allow the sample to sit for a period of time so that the adsorbent material can settle to the bottom of the vial. Transfer the solvent with a pasteur pipet (minimizing the amount of adsorbent material taken) to another vial and store at 4 °C (39.2 °F).

11.2.2   Analyze the desorption solvent or direct thermal desorption tubes from each sample using the same analytical parameters used for the calibration standard. Calculate the total weight detected for each compound (Equation 305-4, Section 12.5). The slope (area/amount) and y-intercept are calculated from the line bracketed between the two closest calibration points. Correct the concentration of each waste sample with the appropriate recovery efficiency factor and the split flow ratio (if used). The final concentration of each individual test compound is calculated by dividing the corrected measured weight for that compound by the weight of the original sample determined in Section 8.3.1 (Equation 305-5, Section 12.6).

11.2.3   Repeat the analysis for the three samples collected in Section 8.3. Report the corrected concentration of each of the waste samples, average waste concentration, and relative standard deviation (Equation 305-6, Section 12.7).

12.0   Data Analysis and Calculations.

12.1   Nomenclature.

AS = Mean area counts of test compound in standard.

AU = Mean area counts of test compound in sample desorption solvent.

b = Y-intercept of the line formed between the two closest calibration standards that bracket the concentration of the sample.

CT = Amount of test compound (µg) in calibration standard.

CF = Correction for adjusting final amount of sample detected for losses during individual sample runs.

FP = Nitrogen flow through the purge chamber (6 L/min).

FS = Nitrogen split flow directed to the sample recovery system (use 6 L/min if split flow design was not used).

PPM = Final concentration of test compound in waste sample [µg/g (which is equivalent to parts per million by weight (ppmw))].

RE = Recovery efficiency for adjusting final amount of sample detected for losses due to inefficient trapping and desorption techniques.

R.F. = Response factor for test compound, calculated from a calibration standard.

S = Slope of the line (area counts/CT) formed between two closest calibration points that bracket the concentration of the sample.

WC = Weight of test compound expected to be recovered in spike solution based on theoretical amount (µg).

WE = Weight of vial and PEG (g).

WF = Weight of vial, PEG and waste sample (g).

WS = Weight of original waste sample (g).

WT = Corrected weight of test compound measured (µg) in sample.

WX = Weight of test compound measured during analysis of recovery efficiency spike samples (µg).

12.2   Recovery efficiency for determining trapping/desorption efficiency of individual test compounds in the spike solution, decimal value.

eCFR graphic er17oc00.563.gif

View or download PDF

12.3   Weight of waste sample (g).

eCFR graphic er17oc00.564.gif

View or download PDF

12.4   Response factor for individual test compounds.

eCFR graphic er17oc00.565.gif

View or download PDF

12.5   Corrected weight of a test compound in the sample, in µg.

eCFR graphic er17oc00.566.gif

View or download PDF

12.6   Final concentration of a test compound in the sample in ppmw.

eCFR graphic er17oc00.567.gif

View or download PDF

12.7   Relative standard deviation (RSD) calculation.

eCFR graphic er17oc00.568.gif

View or download PDF

13.0   Method Performance [Reserved]

14.0   Pollution Prevention [Reserved]

15.0   Waste Management [Reserved]

16.0   References [Reserved]

17.0   Tables, Diagrams, Flowcharts, and Validation Data

eCFR graphic er17oc00.569.gif

View or download PDF

eCFR graphic er17oc00.570.gif

View or download PDF

eCFR graphic er17oc00.571.gif

View or download PDF

eCFR graphic er17oc00.572.gif

View or download PDF

Method 306—Determination of Chromium Emissions From Decorative and Hard Chromium Electroplating and Chromium Anodizing Operations—Isokinetic Method

Note: This method does not include all of the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and analytical) essential to its performance. Some material is incorporated by reference from other methods in 40 CFR Part 60, Appendix A. Therefore, to obtain reliable results, persons using this method should have a thorough knowledge of at least Method 5.

1.0   Scope and Application

1.1   Analytes.

Analyte CAS No. Sensitivity
Chromium7440-47-3See Sec. 13.2.

1.2   Applicability. This method applies to the determination of chromium (Cr) in emissions from decorative and hard chrome electroplating facilities, chromium anodizing operations, and continuous chromium plating operations at iron and steel facilities.

1.3   Data Quality Objectives. [Reserved]

2.0   Summary of Method

2.1   Sampling. An emission sample is extracted isokinetically from the source using an unheated Method 5 sampling train (40 CFR Part 60, Appendix A), with a glass nozzle and probe liner, but with the filter omitted. The sample time shall be at least two hours. The Cr emissions are collected in an alkaline solution containing 0.1 N sodium hydroxide (NaOH) or 0.1 N sodium bicarbonate (NaHCO3). The collected samples are recovered using an alkaline solution and are then transported to the laboratory for analysis.

2.2   Analysis.

2.2.1   Total chromium samples with high chromium concentrations (≥35 µg/L) may be analyzed using inductively coupled plasma emission spectrometry (ICP) at 267.72 nm.

Note: The ICP analysis is applicable for this method only when the solution analyzed has a Cr concentration greater than or equal to 35 µg/L or five times the method detection limit as determined according to appendix B in 40 CFR part 136. Similarly, inductively coupled plasma-mass spectroscopy (ICP-MS) may be used for total chromium analysis provided the procedures for ICP-MS analysis described in Method 6020 or 6020A (EPA Office of Solid Waste, publication SW-846) are followed.

2.2.2   Alternatively, when lower total chromium concentrations (<35 µg/L) are encountered, a portion of the alkaline sample solution may be digested with nitric acid and analyzed by graphite furnace atomic absorption spectroscopy (GFAAS) at 357.9 nm.

2.2.3   If it is desirable to determine hexavalent chromium (Cr+6) emissions, the samples may be analyzed using an ion chromatograph equipped with a post-column reactor (IC/PCR) and a visible wavelength detector. To increase sensitivity for trace levels of Cr+6, a preconcentration system may be used in conjunction with the IC/PCR.

3.0   Definitions

3.1   Total Chromium—measured chromium content that includes both major chromium oxidation states (Cr+3, Cr+3).

3.2   May—Implies an optional operation.

3.3   Digestion—The analytical operation involving the complete (or nearly complete) dissolution of the sample in order to ensure the complete solubilization of the element (analyte) to be measured.

3.4   Interferences—Physical, chemical, or spectral phenomena that may produce a high or low bias in the analytical result.

3.5   Analytical System—All components of the analytical process including the sample digestion and measurement apparatus.

3.6   Sample Recovery—The quantitative transfer of sample from the collection apparatus to the sample preparation (digestion, etc.) apparatus. This term should not be confused with analytical recovery.

3.7   Matrix Modifier—A chemical modification to the sample during GFAAS determinations to ensure that the analyte is not lost during the measurement process (prior to the atomization stage)

3.8   Calibration Reference Standards—Quality control standards used to check the accuracy of the instrument calibration curve prior to sample analysis.

3.9   Continuing Check Standard—Quality control standards used to verify that unacceptable drift in the measurement system has not occurred.

3.10   Calibration Blank—A blank used to verify that there has been no unacceptable shift in the baseline either immediately following calibration or during the course of the analytical measurement.

3.11   Interference Check—An analytical/measurement operation that ascertains whether a measurable interference in the sample exists.

3.12   Interelement Correction Factors—Factors used to correct for interfering elements that produce a false signal (high bias).

3.13   Duplicate Sample Analysis—Either the repeat measurement of a single solution or the measurement of duplicate preparations of the same sample. It is important to be aware of which approach is required for a particular type of measurement. For example, no digestion is required for the ICP determination and the duplicate instrument measurement is therefore adequate whereas duplicate digestion/instrument measurements are required for GFAAS.

3.14   Matrix Spiking—Analytical spikes that have been added to the actual sample matrix either before (Section 9.2.5.2) or after (Section 9.1.6). Spikes added to the sample prior to a preparation technique (e.g., digestion) allow for the assessment of an overall method accuracy while those added after only provide for the measurement accuracy determination.

4.0   Interferences

4.1   ICP Interferences.

4.1.1   ICP Spectral Interferences. Spectral interferences are caused by: overlap of a spectral line from another element; unresolved overlap of molecular band spectra; background contribution from continuous or recombination phenomena; and, stray light from the line emission of high-concentrated elements. Spectral overlap may be compensated for by correcting the raw data with a computer and measuring the interfering element. At the 267.72 nm Cr analytical wavelength, iron, manganese, and uranium are potential interfering elements. Background and stray light interferences can usually be compensated for by a background correction adjacent to the analytical line. Unresolved overlap requires the selection of an alternative chromium wavelength. Consult the instrument manufacturer's operation manual for interference correction procedures.

4.1.2   ICP Physical Interferences. High levels of dissolved solids in the samples may cause significant inaccuracies due to salt buildup at the nebulizer and torch tips. This problem can be controlled by diluting the sample or by extending the rinse times between sample analyses. Standards shall be prepared in the same solution matrix as the samples (i.e., 0.1 N NaOH or 0.1 N NaHCO3).

4.1.3   ICP Chemical Interferences. These include molecular compound formation, ionization effects and solute vaporization effects, and are usually not significant in the ICP procedure, especially if the standards and samples are matrix matched.

4.2   GFAAS Interferences.

4.2.1   GFAAS Chemical Interferences. Low concentrations of calcium and/or phosphate may cause interferences; at concentrations above 200 µg/L, calcium's effect is constant and eliminates the effect of phosphate. Calcium nitrate is therefore added to the concentrated analyte to ensure a known constant effect. Other matrix modifiers recommended by the instrument manufacturer may also be considered.

4.2.2   GFAAS Cyanide Band Interferences. Nitrogen should not be used as the purge gas due to cyanide band interference.

4.2.3   GFAAS Spectral Interferences. Background correction may be required because of possible significant levels of nonspecific absorption and scattering at the 357.9 nm analytical wavelength.

4.2.4   GFAAS Background Interferences. Zeeman or Smith-Hieftje background correction is recommended for interferences resulting from high levels of dissolved solids in the alkaline impinger solutions.

4.3   IC/PCR Interferences.

4.3.1   IC/PCR Chemical Interferences. Components in the sample matrix may cause Cr+6 to convert to trivalent chromium (Cr+3) or cause Cr+3 to convert to Cr+6. The chromatographic separation of Cr+6 using ion chromatography reduces the potential for other metals to interfere with the post column reaction. For the IC/PCR analysis, only compounds that coelute with Cr+6 and affect the diphenylcarbazide reaction will cause interference.

4.3.2   IC/PCR Background Interferences. Periodic analyses of reagent water blanks are used to demonstrate that the analytical system is essentially free of contamination. Sample cross-contamination can occur when high-level and low-level samples or standards are analyzed alternately and can be eliminated by thorough purging of the sample loop. Purging of the sample can easily be achieved by increasing the injection volume to ten times the size of the sample loop.

5.0   Safety

5.1   Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method may not address all of the safety problems associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to performing this test method.

5.2   Hexavalent chromium compounds have been listed as carcinogens although chromium (III) compounds show little or no toxicity. Chromium can be a skin and respiratory irritant.

6.0   Equipment and Supplies

6.1   Sampling Train.

6.1.1   A schematic of the sampling train used in this method is shown in Figure 306-1. The train is the same as shown in Method 5, Section 6.0 (40 CFR Part 60, Appendix A) except that the probe liner is unheated, the particulate filter is omitted, and quartz or borosilicate glass must be used for the probe nozzle and liner in place of stainless steel.

6.1.2   Probe fittings of plastic such as Teflon, polypropylene, etc. are recommended over metal fittings to prevent contamination. If desired, a single combined probe nozzle and liner may be used, but such a single glass assembly is not a requirement of this methodology.

6.1.3   Use 0.1 N NaOH or 0.1 N NaHCO3 in the impingers in place of water.

6.1.4   Operating and maintenance procedures for the sampling train are described in APTD-0576 of Method 5. Users should read the APTD-0576 document and adopt the outlined procedures. Alternative mercury-free thermometers may be used if the thermometers are, at a minimum, equivalent in terms of performance or suitably effective for the specific temperature measurement application.

6.1.5   Similar collection systems which have been approved by the Administrator may be used.

6.2   Sample Recovery. Same as Method 5, [40 CFR Part 60, Appendix A], with the following exceptions:

6.2.1   Probe-Liner and Probe-Nozzle Brushes. Brushes are not necessary for sample recovery. If a probe brush is used, it must be non-metallic.

6.2.2   Sample Recovery Solution. Use 0.1 N NaOH or 0.1 N NaHCO3, whichever is used as the impinger absorbing solution, in place of acetone to recover the sample.

6.2.3   Sample Storage Containers. Polyethylene, with leak-free screw cap, 250 mL, 500 mL or 1,000 mL.

6.3   Analysis.

6.3.1   General. For analysis, the following equipment is needed.

6.3.1.1   Phillips Beakers. (Phillips beakers are preferred, but regular beakers may also be used.)

6.3.1.2   Hot Plate.

6.3.1.3   Volumetric Flasks. Class A, various sizes as appropriate.

6.3.1.4   Assorted Pipettes.

6.3.2   Analysis by ICP.

6.3.2.1   ICP Spectrometer. Computer-controlled emission spectrometer with background correction and radio frequency generator.

6.3.2.2   Argon Gas Supply. Welding grade or better.

6.3.3   Analysis by GFAAS.

6.3.3.1   Chromium Hollow Cathode Lamp or Electrodeless Discharge Lamp.

6.3.3.2   Graphite Furnace Atomic Absorption Spectrophotometer.

6.3.3.3   Furnace Autosampler.

6.3.4   Analysis by IC/PCR.

6.3.4.1   IC/PCR System. High performance liquid chromatograph pump, sample injection valve, post-column reagent delivery and mixing system, and a visible detector, capable of operating at 520 nm-540 nm, all with a non-metallic (or inert) flow path. An electronic peak area mode is recommended, but other recording devices and integration techniques are acceptable provided the repeatability criteria and the linearity criteria for the calibration curve described in Section 10.4 can be satisfied. A sample loading system is required if preconcentration is employed.

6.3.4.2   Analytical Column. A high performance ion chromatograph (HPIC) non-metallic column with anion separation characteristics and a high loading capacity designed for separation of metal chelating compounds to prevent metal interference. Resolution described in Section 11.6 must be obtained. A non-metallic guard column with the same ion-exchange material is recommended.

6.3.4.3   Preconcentration Column (for older instruments). An HPIC non-metallic column with acceptable anion retention characteristics and sample loading rates must be used as described in Section 11.6.

6.3.4.4   Filtration Apparatus for IC/PCR.

6.3.4.4.1   Teflon, or equivalent, filter holder to accommodate 0.45-µm acetate, or equivalent, filter, if needed to remove insoluble particulate matter.

6.3.4.4.2   0.45-µm Filter Cartridge. For the removal of insoluble material. To be used just prior to sample injection/analysis.

7.0   Reagents and Standards

Note: Unless otherwise indicated, all reagents should conform to the specifications established by the Committee on Analytical Reagents of the American Chemical Society (ACS reagent grade). Where such specifications are not available, use the best available grade. Reagents should be checked by the appropriate analysis prior to field use to assure that contamination is below the analytical detection limit for the ICP or GFAAS total chromium analysis; and that contamination is below the analytical detection limit for Cr+6 using IC/PCR for direct injection or, if selected, preconcentration.

7.1   Sampling.

7.1.1   Water. Reagent water that conforms to ASTM Specification D1193-77 or 91 Type II (incorporated by reference see §63.14). All references to water in the method refer to reagent water unless otherwise specified. It is recommended that water blanks be checked prior to preparing the sampling reagents to ensure that the Cr content is less than three (3) times the anticipated detection limit of the analytical method.

7.1.2   Sodium Hydroxide (NaOH) Absorbing Solution, 0.1 N. Dissolve 4.0 g of sodium hydroxide in 1 liter of water to obtain a pH of approximately 8.5.

7.1.3   Sodium Bicarbonate (NaHCO3) Absorbing Solution, 0.1 N. Dissolve approximately 8.5 g of sodium bicarbonate in 1 liter of water to obtain a pH of approximately 8.3.

7.1.4   Chromium Contamination.

7.1.4.1   The absorbing solution shall not exceed the QC criteria noted in Section 7.1.1 (≤3 times the instrument detection limit).

7.1.4.2   When the Cr+6 content in the field samples exceeds the blank concentration by at least a factor of ten (10), Cr+6 blank concentrations ≥10 times the detection limit will be allowed.

Note: At sources with high concentrations of acids and/or SO2, the concentration of NaOH or NaHCO3 should be ≥0.5 N to insure that the pH of the solution remains at or above 8.5 for NaOH and 8.0 for NaHCO3 during and after sampling.

7.1.5   Silica Gel. Same as in Method 5.

7.2   Sample Recovery.

7.2.1   0.1 N NaOH or 0.1 N NaHCO3. Use the same solution for the sample recovery that is used for the impinger absorbing solution.

7.2.2   pH Indicator Strip, for IC/PCR. pH indicator capable of determining the pH of solutions between the pH range of 7 and 12, at 0.5 pH increments.

7.3   Sample Preparation and Analysis.

7.3.1   Nitric Acid (HNO3), Concentrated, for GFAAS. Trace metals grade or better HNO3 must be used for reagent preparation. The ACS reagent grade HNO3 is acceptable for cleaning glassware.

7.3.2   HNO3, 1.0% (v/v), for GFAAS. Prepare, by slowly stirring, 10 mL of concentrated HNO3) into 800 mL of reagent water. Dilute to 1,000 mL with reagent water. The solution shall contain less than 0.001 mg Cr/L.

7.3.3   Calcium Nitrate Ca(NO3)2 Solution (10 µg Ca/mL) for GFAAS analysis. Prepare the solution by weighing 40.9 mg of Ca(NO3)2 into a 1 liter volumetric flask. Dilute with reagent water to 1 liter.

7.3.4   Matrix Modifier, for GFAAS. See instrument manufacturer's manual for suggested matrix modifier.

7.3.5   Chromatographic Eluent, for IC/PCR. The eluent used in the analytical system is ammonium sulfate based.

7.3.5.1   Prepare by adding 6.5 mL of 29 percent ammonium hydroxide (NH4OH) and 33 g of ammonium sulfate ((NH4)2SO4) to 500 mL of reagent water. Dilute to 1 liter with reagent water and mix well.

7.3.5.2   Other combinations of eluents and/or columns may be employed provided peak resolution, repeatability, linearity, and analytical sensitivity as described in Sections 9.3 and 11.6 are acceptable.

7.3.6   Post-Column Reagent, for IC/PCR. An effective post-column reagent for use with the chromatographic eluent described in Section 7.3.5 is a diphenylcarbazide (DPC)-based system. Dissolve 0.5 g of 1,5-diphenylcarbazide in 100 mL of ACS grade methanol. Add 500 mL of reagent water containing 50 mL of 96 percent spectrophotometric grade sulfuric acid. Dilute to 1 liter with reagent water.

7.3.7   Chromium Standard Stock Solution (1000 mg/L). Procure a certified aqueous standard or dissolve 2.829 g of potassium dichromate (K2Cr2O7), in reagent water and dilute to 1 liter.

7.3.8   Calibration Standards for ICP or IC/PCR. Prepare calibration standards for ICP or IC/PCR by diluting the Cr standard stock solution (Section 7.3.7) with 0.1 N NaOH or 0.1 N NaHCO3, whichever is used as the impinger absorbing solution, to achieve a matrix similar to the actual field samples. Suggested levels are 0, 50, 100, and 200 µg Cr/L for ICP, and 0, 1, 5, and 10 µg Cr+6/L for IC/PCR.

7.3.9   Calibration Standards for GFAAS. Chromium solutions for GFAAS calibration shall contain 1.0 percent (v/v) HNO3. The zero standard shall be 1.0 percent (v/v) HNO3. Calibration standards should be prepared daily by diluting the Cr standard stock solution (Section 7.3.7) with 1.0 percent HNO3. Use at least four standards to make the calibration curve. Suggested levels are 0, 10, 50, and 100 µg Cr/L.

7.4   Glassware Cleaning Reagents.

7.4.1   HNO3, Concentrated. ACS reagent grade or equivalent.

7.4.2   Water. Reagent water that conforms to ASTM Specification D1193-77 or 91 Type II.

7.4.3   HNO3, 10 percent (v/v). Add by stirring 500 mL of concentrated HNO3 into a flask containing approximately 4,000 mL of reagent water. Dilute to 5,000 mL with reagent water. Mix well. The reagent shall contain less than 2 µg Cr/L.

8.0   Sample Collection, Preservation, Holding Times, Storage, and Transport

Note: Prior to sample collection, consideration should be given to the type of analysis (Cr+6 or total Cr) that will be performed. Which analysis option(s) will be performed will determine which sample recovery and storage procedures will be required to process the sample.

8.1   Sample Collection. Same as Method 5 (40 CFR part 60, appendix A), with the following exceptions.

8.1.1   Omit the particulate filter and filter holder from the sampling train. Use a glass nozzle and probe liner instead of stainless steel. Do not heat the probe. Place 100 mL of 0.1 N NaOH or 0.1 N NaHCO3 in each of the first two impingers, and record the data for each run on a data sheet such as shown in Figure 306-2.

8.1.2   Clean all glassware prior to sampling in hot soapy water designed for laboratory cleaning of glassware. Next, rinse the glassware three times with tap water, followed by three additional rinses with reagent water. Then soak the glassware in 10% (v/v) HNO3 solution for a minimum of 4 hours, rinse three times with reagent water, and allow to air dry. Cover all glassware openings where contamination can occur with Parafilm, or equivalent, until the sampling train is assembled for sampling.

8.1.3   Train Operation. Follow the basic procedures outlined in Method 5 in conjunction with the following instructions. Train sampling rate shall not exceed 0.030 m3/min (1.0 cfm) during a run.

8.2   Sample Recovery. Follow the basic procedures of Method 5, with the exceptions noted.

8.2.1   A particulate filter is not recovered from this train.

8.2.2   Tester shall select either the total Cr or Cr+6 sample recovery option.

8.2.3   Samples to be analyzed for both total Cr and Cr+6, shall be recovered using the Cr+6 sample option (Section 8.2.6).

8.2.4   A field reagent blank shall be collected for either of the Cr or the Cr+6 analysis. If both analyses (Cr and Cr+6) are to be conducted on the samples, collect separate reagent blanks for each analysis.

Note: Since particulate matter is not usually present at chromium electroplating and/or chromium anodizing operations, it is not necessary to filter the Cr+6 samples unless there is observed sediment in the collected solutions. If it is necessary to filter the Cr+6 solutions, please refer to Method 0061, Determination of Hexavalent Chromium Emissions From Stationary Sources, Section 7.4, Sample Preparation in SW-846 (see Reference 1).

8.2.5   Total Cr Sample Option.

8.2.5.1   Container No. 1. Measure the volume of the liquid in the first, second, and third impingers and quantitatively transfer into a labeled sample container.

8.2.5.2   Use approximately 200 to 300 mL of the 0.1 N NaOH or 0.1 N NaHCO3 absorbing solution to rinse the probe nozzle, probe liner, three impingers, and connecting glassware; add this rinse to Container No. 1.

8.2.6   Cr+6 Sample Option.

8.2.6.1   Container No. 1. Measure and record the pH of the absorbing solution contained in the first impinger at the end of the sampling run using a pH indicator strip. The pH of the solution must be ≥8.5 for NaOH and ≥8.0 for NaHCO3. If it is not, discard the collected sample, increase the normality of the NaOH or NaHCO3 impinger absorbing solution to 0.5 N or to a solution normality approved by the Administrator and collect another air emission sample.

8.2.6.2   After determining the pH of the first impinger solution, combine and measure the volume of the liquid in the first, second, and third impingers and quantitatively transfer into the labeled sample container. Use approximately 200 to 300 mL of the 0.1 N NaOH or 0.1 N NaHCO3 absorbing solution to rinse the probe nozzle, probe liner, three impingers, and connecting glassware; add this rinse to Container No. 1.

8.2.7   Field Reagent Blank.

8.2.7.1   Container No. 2.

8.2.7.2   Place approximately 500 mL of the 0.1 N NaOH or 0.1 N NaHCO3 absorbing solution into a labeled sample container.

8.3   Sample Preservation, Storage, and Transport.

8.3.1   Total Cr Sample Option. Samples to be analyzed for total Cr need not be refrigerated.

8.3.2   Cr+6 Sample Option. Samples to be analyzed for Cr+6 must be shipped and stored at 4 °C. Allow Cr+6 samples to return to ambient temperature prior to analysis.

8.4   Sample Holding Times.

8.4.1   Total Cr Sample Option. Samples to be analyzed for total Cr shall be analyzed within 60 days of collection.

8.4.2   Cr+6 Sample Option. Samples to be analyzed for Cr+6 shall be analyzed within 14 days of collection.

9.0   Quality Control

9.1   ICP Quality Control.

9.1.1   ICP Calibration Reference Standards. Prepare a calibration reference standard using the same alkaline matrix as the calibration standards; it should be at least 10 times the instrumental detection limit.

9.1.1.1   This reference standard must be prepared from a different Cr stock solution source than that used for preparation of the calibration curve standards.

9.1.1.2   Prior to sample analysis, analyze at least one reference standard.

9.1.1.3   The calibration reference standard must be measured within 10 percent of it's true value for the curve to be considered valid.

9.1.1.4   The curve must be validated before sample analyses are performed.

9.1.2   ICP Continuing Check Standard.

9.1.2.1   Perform analysis of the check standard with the field samples as described in Section 11.2 (at least after every 10 samples, and at the end of the analytical run).

9.1.2.2   The check standard can either be the mid-range calibration standard or the reference standard. The results of the check standard shall agree within 10 percent of the expected value; if not, terminate the analyses, correct the problem, recalibrate the instrument, and rerun all samples analyzed subsequent to the last acceptable check standard analysis.

9.1.3   ICP Calibration Blank.

9.1.3.1   Perform analysis of the calibration blank with the field samples as described in Section 11.2 (at least after every 10 samples, and at the end of the analytical run).

9.1.3.2   The results of the calibration blank shall agree within three standard deviations of the mean blank value. If not, analyze the calibration blank two more times and average the results. If the average is not within three standard deviations of the background mean, terminate the analyses, correct the problem, recalibrate, and reanalyze all samples analyzed subsequent to the last acceptable calibration blank analysis.

9.1.4   ICP Interference Check. Prepare an interference check solution that contains known concentrations of interfering elements that will provide an adequate test of the correction factors in the event of potential spectral interferences.

9.1.4.1   Two potential interferences, iron and manganese, may be prepared as 1000 µg/mL and 200 µg/mL solutions, respectively. The solutions should be prepared in dilute HNO3 (1-5 percent). Particular care must be used to ensure that the solutions and/or salts used to prepare the solutions are of ICP grade purity (i.e., that no measurable Cr contamination exists in the salts/solutions). Commercially prepared interfering element check standards are available.

9.1.4.2   Verify the interelement correction factors every three months by analyzing the interference check solution. The correction factors are calculated according to the instrument manufacturer's directions. If the interelement correction factors are used properly, no false Cr should be detected.

9.1.4.3   Negative results with an absolute value greater than three (3) times the detection limit are usually the results of the background correction position being set incorrectly. Scan the spectral region to ensure that the correction position has not been placed on an interfering peak.

9.1.5   ICP Duplicate Sample Analysis. Perform one duplicate sample analysis for each compliance sample batch (3 runs).

9.1.5.1   As there is no sample preparation required for the ICP analysis, a duplicate analysis is defined as a repeat analysis of one of the field samples. The selected sample shall be analyzed using the same procedures that were used to analyze the original sample.

9.1.5.2   Duplicate sample analyses shall agree within 10 percent of the original measurement value.

9.1.5.3   Report the original analysis value for the sample and report the duplicate analysis value as the QC check value. If agreement is not achieved, perform the duplicate analysis again. If agreement is not achieved the second time, perform corrective action to identify and correct the problem before analyzing the sample for a third time.

9.1.6   ICP Matrix Spiking. Spiked samples shall be prepared and analyzed daily to ensure that there are no matrix effects, that samples and standards have been matrix-matched, and that the laboratory equipment is operating properly.

9.1.6.1   Spiked sample recovery analyses should indicate a recovery for the Cr spike of between 75 and 125 percent.

9.1.6.2   Cr levels in the spiked sample should provide final solution concentrations that are within the linear portion of the calibration curve, as well as, at a concentration level at least: equal to that of the original sample; and, ten (10) times the detection limit.

9.1.6.3   If the spiked sample concentration meets the stated criteria but exceeds the linear calibration range, the spiked sample must be diluted with the field absorbing solution.

9.1.6.4   If the recoveries for the Cr spiked samples do not meet the specified criteria, perform corrective action to identify and correct the problem prior to reanalyzing the samples.

9.1.7   ICP Field Reagent Blank.

9.1.7.1   Analyze a minimum of one matrix-matched field reagent blank (Section 8.2.4) per sample batch to determine if contamination or memory effects are occurring.

9.1.7.2   If contamination or memory effects are observed, perform corrective action to identify and correct the problem before reanalyzing the samples.

9.2   GFAAS Quality Control.

9.2.1   GFAAS Calibration Reference Standards. The calibration curve must be verified by using at least one calibration reference standard (made from a reference material or other independent standard material) at or near the mid-range of the calibration curve.

9.2.1.1   The calibration curve must be validated before sample analyses are performed.

9.2.1.2   The calibration reference standard must be measured within 10 percent of its true value for the curve to be considered valid.

9.2.2   GFAAS Continuing Check Standard.

9.2.2.1   Perform analysis of the check standard with the field samples as described in Section 11.4 (at least after every 10 samples, and at the end of the analytical run).

9.2.2.2   These standards are analyzed, in part, to monitor the life and performance of the graphite tube. Lack of reproducibility or a significant change in the signal for the check standard may indicate that the graphite tube should be replaced.

9.2.2.3   The check standard may be either the mid-range calibration standard or the reference standard.

9.2.2.4   The results of the check standard shall agree within 10 percent of the expected value.

9.2.2.5   If not, terminate the analyses, correct the problem, recalibrate the instrument, and reanalyze all samples analyzed subsequent to the last acceptable check standard analysis.

9.2.3   GFAAS Calibration Blank.

9.2.3.1   Perform analysis of the calibration blank with the field samples as described in Section 11.4 (at least after every 10 samples, and at the end of the analytical run).

9.2.3.2   The calibration blank is analyzed to monitor the life and performance of the graphite tube as well as the existence of any memory effects. Lack of reproducibility or a significant change in the signal, may indicate that the graphite tube should be replaced.

9.2.3.3   The results of the calibration blank shall agree within three standard deviations of the mean blank value.

9.2.3.4   If not, analyze the calibration blank two more times and average the results. If the average is not within three standard deviations of the background mean, terminate the analyses, correct the problem, recalibrate, and reanalyze all samples analyzed subsequent to the last acceptable calibration blank analysis.

9.2.4   GFAAS Duplicate Sample Analysis. Perform one duplicate sample analysis for each compliance sample batch (3 runs).

9.2.4.1   A digested aliquot of the selected sample is processed and analyzed using the identical procedures that were used for the whole sample preparation and analytical efforts.

9.2.4.2   Duplicate sample analyses results incorporating duplicate digestions shall agree within 20 percent for sample results exceeding ten (10) times the detection limit.

9.2.4.3   Report the original analysis value for the sample and report the duplicate analysis value as the QC check value.

9.2.4.4   If agreement is not achieved, perform the duplicate analysis again. If agreement is not achieved the second time, perform corrective action to identify and correct the problem before analyzing the sample for a third time.

9.2.5   GFAAS Matrix Spiking.

9.2.5.1   Spiked samples shall be prepared and analyzed daily to ensure that (1) correct procedures are being followed, (2) there are no matrix effects and (3) all equipment is operating properly.

9.2.5.2   Cr spikes are added prior to any sample preparation.

9.2.5.3   Cr levels in the spiked sample should provide final solution concentrations that are within the linear portion of the calibration curve, as well as, at a concentration level at least: equal to that of the original sample; and, ten (10) times the detection limit.

9.2.5.4   Spiked sample recovery analyses should indicate a recovery for the Cr spike of between 75 and 125 percent.

9.2.5.5   If the recoveries for the Cr spiked samples do not meet the specified criteria, perform corrective action to identify and correct the problem prior to reanalyzing the samples.

9.2.6   GFAAS Method of Standard Additions.

9.2.6.1   Method of Standard Additions. Perform procedures in Section 5.4 of Method 12 (40 CFR Part 60, Appendix A)

9.2.6.2   Whenever sample matrix problems are suspected and standard/sample matrix matching is not possible or whenever a new sample matrix is being analyzed, perform referenced procedures to determine if the method of standard additions is necessary.

9.2.7   GFAAS Field Reagent Blank.

9.2.7.1   Analyze a minimum of one matrix-matched field reagent blank (Section 8.2.4) per sample batch to determine if contamination or memory effects are occurring.

9.2.7.2 If contamination or memory effects are observed, perform corrective action to identify and correct the problem before reanalyzing the samples.

9.3   IC/PCR Quality Control.

9.3.1   IC/PCR Calibration Reference Standards.

9.3.1.1   Prepare a calibration reference standard at a concentration that is at or near the mid-point of the calibration curve using the same alkaline matrix as the calibration standards. This reference standard should be prepared from a different Cr stock solution than that used to prepare the calibration curve standards. The reference standard is used to verify the accuracy of the calibration curve.

9.3.1.2   The curve must be validated before sample analyses are performed. Prior to sample analysis, analyze at least one reference standard with an expected value within the calibration range.

9.3.1.3   The results of this reference standard analysis must be within 10 percent of the true value of the reference standard for the calibration curve to be considered valid.

9.3.2   IC/PCR Continuing Check Standard and Calibration Blank.

9.3.2.1   Perform analysis of the check standard and the calibration blank with the field samples as described in Section 11.6 (at least after every 10 samples, and at the end of the analytical run).

9.3.2.2   The result from the check standard must be within 10 percent of the expected value.

9.3.2.3   If the 10 percent criteria is exceeded, excessive drift and/or instrument degradation may have occurred, and must be corrected before further analyses can be performed.

9.3.2.4   The results of the calibration blank analyses must agree within three standard deviations of the mean blank value.

9.3.2.5   If not, analyze the calibration blank two more times and average the results.

9.3.2.6   If the average is not within three standard deviations of the background mean, terminate the analyses, correct the problem, recalibrate, and reanalyze all samples analyzed subsequent to the last acceptable calibration blank analysis.

9.3.3   IC/PCR Duplicate Sample Analysis.

9.3.3.1   Perform one duplicate sample analysis for each compliance sample batch (3 runs).

9.3.3.2   An aliquot of the selected sample is prepared and analyzed using procedures identical to those used for the emission samples (for example, filtration and/or, if necessary, preconcentration).

9.3.3.3   Duplicate sample injection results shall agree within 10 percent for sample results exceeding ten (10) times the detection limit.

9.3.3.4   Report the original analysis value for the sample and report the duplicate analysis value as the QC check value.

9.3.3.5   If agreement is not achieved, perform the duplicate analysis again.

9.3.3.6   If agreement is not achieved the second time, perform corrective action to identify and correct the problem prior to analyzing the sample for a third time.

9.3.4   ICP/PCR Matrix Spiking. Spiked samples shall be prepared and analyzed with each sample set to ensure that there are no matrix effects, that samples and standards have been matrix-matched, and that the equipment is operating properly.

9.3.4.1   Spiked sample recovery analysis should indicate a recovery of the Cr+6 spike between 75 and 125 percent.

9.3.4.2   The spiked sample concentration should be within the linear portion of the calibration curve and should be equal to or greater than the concentration of the original sample. In addition, the spiked sample concentration should be at least ten (10) times the detection limit.

9.3.4.3   If the recoveries for the Cr+6 spiked samples do not meet the specified criteria, perform corrective action to identify and correct the problem prior to reanalyzing the samples.

9.3.5   IC/PCR Field Reagent Blank.

9.3.5.1   Analyze a minimum of one matrix-matched field reagent blank (Section 8.2.4) per sample batch to determine if contamination or memory effects are occurring.

9.3.5.2   If contamination or memory effects are observed, perform corrective action to identify and correct the problem before reanalyzing the samples.

10.0   Calibration and Standardization

10.1   Sampling Train Calibration. Perform calibrations described in Method 5, (40 CFR part 60, appendix A). The alternate calibration procedures described in Method 5, may also be used.

10.2   ICP Calibration.

10.2.1   Calibrate the instrument according to the instrument manufacturer's recommended procedures, using a calibration blank and three standards for the initial calibration.

10.2.2   Calibration standards should be prepared fresh daily, as described in Section 7.3.8. Be sure that samples and calibration standards are matrix matched. Flush the system with the calibration blank between each standard.

10.2.3   Use the average intensity of multiple exposures (3 or more) for both standardization and sample analysis to reduce random error.

10.2.4   Employing linear regression, calculate the correlation coefficient .

10.2.5   The correlation coefficient must equal or exceed 0.995.

10.2.6   If linearity is not acceptable, prepare and rerun another set of calibration standards or reduce the range of the calibration standards, as necessary.

10.3   GFAAS Calibration.

10.3.1   For instruments that measure directly in concentration, set the instrument software to display the correct concentration, if applicable.

10.3.2   Curve must be linear in order to correctly perform the method of standard additions which is customarily performed automatically with most instrument computer-based data systems.

10.3.3   The calibration curve (direct calibration or standard additions) must be prepared daily with a minimum of a calibration blank and three standards that are prepared fresh daily.

10.3.4   The calibration curve acceptance criteria must equal or exceed 0.995.

10.3.5   If linearity is not acceptable, prepare and rerun another set of calibration standards or reduce the range of calibration standards, as necessary.

10.4   IC/PCR Calibration.

10.4.1   Prepare a calibration curve using the calibration blank and three calibration standards prepared fresh daily as described in Section 7.3.8.

10.4.2   The calibration curve acceptance criteria must equal or exceed 0.995.

10.4.3   If linearity is not acceptable, remake and/or rerun the calibration standards. If the calibration curve is still unacceptable, reduce the range of the curve.

10.4.4   Analyze the standards with the field samples as described in Section 11.6.

11.0   Analytical Procedures

Note: The method determines the chromium concentration in µg Cr/mL. It is important that the analyst measure the field sample volume prior to analyzing the sample. This will allow for conversion of µg Cr/mL to µg Cr/sample.

11.1   ICP Sample Preparation.

11.1.1   The ICP analysis is performed directly on the alkaline impinger solution; acid digestion is not necessary, provided the samples and standards are matrix matched.

11.1.2   The ICP analysis should only be employed when the solution analyzed has a Cr concentration greater than 35 µg/L or five times the method detection limit as determined according to Appendix B in 40 CFR Part 136 or by other commonly accepted analytical procedures.

11.2   ICP Sample Analysis.

11.2.1   The ICP analysis is applicable for the determination of total chromium only.

11.2.2   ICP Blanks. Two types of blanks are required for the ICP analysis.

11.2.2.1   Calibration Blank. The calibration blank is used in establishing the calibration curve. For the calibration blank, use either 0.1 N NaOH or 0.1 N NaHCO3, whichever is used for the impinger absorbing solution. The calibration blank can be prepared fresh in the laboratory; it does not have to be prepared from the same batch of solution that was used in the field. A sufficient quantity should be prepared to flush the system between standards and samples.

11.2.2.2   Field Reagent Blank. The field reagent blank is collected in the field during the testing program. The field reagent blank (Section 8.2.4) is an aliquot of the absorbing solution prepared in Section 7.1.2. The reagent blank is used to assess possible contamination resulting from sample processing.

11.2.3   ICP Instrument Adjustment.

11.2.3.1   Adjust the ICP instrument for proper operating parameters including wavelength, background correction settings (if necessary), and interfering element correction settings (if necessary).

11.2.3.2   The instrument must be allowed to become thermally stable before beginning measurements (usually requiring at least 30 min of operation prior to calibration). During this warmup period, the optical calibration and torch position optimization may be performed (consult the operator's manual).

11.2.4   ICP Instrument Calibration.

11.2.4.1   Calibrate the instrument according to the instrument manufacturer's recommended procedures, and the procedures specified in Section 10.2.

11.2.4.2   Prior to analyzing the field samples, reanalyze the highest calibration standard as if it were a sample.

11.2.4.3   Concentration values obtained should not deviate from the actual values or from the established control limits by more than 5 percent, whichever is lower (see Sections 9.1 and 10.2).

11.2.4.4   If they do, follow the recommendations of the instrument manufacturer to correct the problem.

11.2.5   ICP Operational Quality Control Procedures.

11.2.5.1   Flush the system with the calibration blank solution for at least 1 min before the analysis of each sample or standard.

11.2.5.2   Analyze the continuing check standard and the calibration blank after each batch of 10 samples.

11.2.5.3   Use the average intensity of multiple exposures for both standardization and sample analysis to reduce random error.

11.2.6   ICP Sample Dilution.

11.2.6.1   Dilute and reanalyze samples that are more concentrated than the linear calibration limit or use an alternate, less sensitive Cr wavelength for which quality control data have already been established.

11.2.6.2   When dilutions are performed, the appropriate factors must be applied to sample measurement results.

11.2.7   Reporting Analytical Results. All analytical results should be reported in µg Cr/mL using three significant figures. Field sample volumes (mL) must be reported also.

11.3   GFAAS Sample Preparation.

11.3.1   GFAAS Acid Digestion. An acid digestion of the alkaline impinger solution is required for the GFAAS analysis.

11.3.1.1   In a beaker, add 10 mL of concentrated HNO3 to a 100 mL sample aliquot that has been well mixed. Cover the beaker with a watch glass. Place the beaker on a hot plate and reflux the sample to near dryness. Add another 5 mL of concentrated HNO3 to complete the digestion. Again, carefully reflux the sample volume to near dryness. Rinse the beaker walls and watch glass with reagent water.

11.3.1.2   The final concentration of HNO3 in the solution should be 1 percent (v/v).

11.3.1.3   Transfer the digested sample to a 50-mL volumetric flask. Add 0.5 mL of concentrated HNO3 and 1 mL of the 10 µg/mL of Ca(NO3)2. Dilute to 50 mL with reagent water.

11.3.2   HNO3 Concentration. A different final volume may be used based on the expected Cr concentration, but the HNO3 concentration must be maintained at 1 percent (v/v).

11.4   GFAAS Sample Analysis.

11.4.1   The GFAAS analysis is applicable for the determination of total chromium only.

11.4.2   GFAAS Blanks. Two types of blanks are required for the GFAAS analysis.

11.4.2.1   Calibration Blank. The 1.0 percent HNO3 is the calibration blank which is used in establishing the calibration curve.

11.4.2.2   Field Reagent Blank. An aliquot of the 0.1 N NaOH solution or the 0.1 N NaHCO3 prepared in Section 7.1.2 is collected for the field reagent blank. The field reagent blank is used to assess possible contamination resulting from processing the sample.

11.4.2.2.1   The reagent blank must be subjected to the entire series of sample preparation and analytical procedures, including the acid digestion.

11.4.2.2.2   The reagent blank's final solution must contain the same acid concentration as the sample solutions.

11.4.3   GFAAS Instrument Adjustment.

11.4.3.1   The 357.9 nm wavelength line shall be used.

11.4.3.2   Follow the manufacturer's instructions for all other spectrophotometer operating parameters.

11.4.4   Furnace Operational Parameters. Parameters suggested by the manufacturer should be employed as guidelines.

11.4.4.1   Temperature-sensing mechanisms and temperature controllers can vary between instruments and/or with time; the validity of the furnace operating parameters must be periodically confirmed by systematically altering the furnace parameters while analyzing a standard. In this manner, losses of analyte due to higher-than-necessary temperature settings or losses in sensitivity due to less than optimum settings can be minimized.

11.4.4.2   Similar verification of furnace operating parameters may be required for complex sample matrices (consult instrument manual for additional information). Calibrate the GFAAS system following the procedures specified in Section 10.3.

11.4.5   GFAAS Operational Quality Control Procedures.

11.4.5.1   Introduce a measured aliquot of digested sample into the furnace and atomize.

11.4.5.2   If the measured concentration exceeds the calibration range, the sample should be diluted with the calibration blank solution (1.0 percent HNO3) and reanalyzed.

11.4.5.3   Consult the operator's manual for suggested injection volumes. The use of multiple injections can improve accuracy and assist in detecting furnace pipetting errors.

11.4.5.4   Analyze a minimum of one matrix-matched reagent blank per sample batch to determine if contamination or any memory effects are occurring.

11.4.5.5   Analyze a calibration blank and a continuing check standard after approximately every batch of 10 sample injections.

11.4.6   GFAAS Sample Dilution.

11.4.6.1   Dilute and reanalyze samples that are more concentrated than the instrument calibration range.

11.4.6.2   If dilutions are performed, the appropriate factors must be applied to sample measurement results.

11.4.7   Reporting Analytical Results.

11.4.7.1   Calculate the Cr concentrations by the method of standard additions (see operator's manual) or, from direct calibration. All dilution and/or concentration factors must be used when calculating the results.

11.4.7.2   Analytical results should be reported in µg Cr/mL using three significant figures. Field sample volumes (mL) must be reported also.

11.5   IC/PCR Sample Preparation.

11.5.1   Sample pH. Measure and record the sample pH prior to analysis.

11.5.2   Sample Filtration. Prior to preconcentration and/or analysis, filter all field samples through a 0.45-µm filter. The filtration step should be conducted just prior to sample injection/analysis.

11.5.2.1   Use a portion of the sample to rinse the syringe filtration unit and acetate filter and then collect the required volume of filtrate.

11.5.2.2   Retain the filter if total Cr is to be determined also.

11.5.3   Sample Preconcentration (older instruments).

11.5.3.1   For older instruments, a preconcentration system may be used in conjunction with the IC/PCR to increase sensitivity for trace levels of Cr+6.

11.5.3.2   The preconcentration is accomplished by selectively retaining the analyte on a solid absorbent, followed by removal of the analyte from the absorbent (consult instrument manual).

11.5.3.3   For a manual system, position the injection valve so that the eluent displaces the concentrated Cr+6 sample, transferring it from the preconcentration column and onto the IC anion separation column.

11.6   IC/PCR Sample Analyses.

11.6.1   The IC/PCR analysis is applicable for hexavalent chromium measurements only.

11.6.2   IC/PCR Blanks. Two types of blanks are required for the IC/PCR analysis.

11.6.2.1   Calibration Blank. The calibration blank is used in establishing the analytical curve. For the calibration blank, use either 0.1 N NaOH or 0.1 N NaHCO3, whichever is used for the impinger solution. The calibration blank can be prepared fresh in the laboratory; it does not have to be prepared from the same batch of absorbing solution that is used in the field.

11.6.2.2   Field Reagent Blank. An aliquot of the 0.1 N NaOH solution or the 0.1 N NaHCO3 solution prepared in Section 7.1.2 is collected for the field reagent blank. The field reagent blank is used to assess possible contamination resulting from processing the sample.

11.6.3   Stabilized Baseline. Prior to sample analysis, establish a stable baseline with the detector set at the required attenuation by setting the eluent and post-column reagent flow rates according to the manufacturers recommendations.

Note: As long as the ratio of eluent flow rate to PCR flow rate remains constant, the standard curve should remain linear. Inject a sample of reagent water to ensure that no Cr+6 appears in the water blank.

11.6.4   Sample Injection Loop. Size of injection loop is based on standard/sample concentrations and the selected attenuator setting.

11.6.4.1   A 50-µL loop is normally sufficient for most higher concentrations.

11.6.4.2   The sample volume used to load the injection loop should be at least 10 times the loop size so that all tubing in contact with the sample is thoroughly flushed with the new sample to prevent cross contamination.

11.6.5   IC/PCR Instrument Calibration.

11.6.5.1   First, inject the calibration standards prepared, as described in Section 7.3.8 to correspond to the appropriate concentration range, starting with the lowest standard first.

11.6.5.2   Check the performance of the instrument and verify the calibration using data gathered from analyses of laboratory blanks, calibration standards, and a quality control sample.

11.6.5.3   Verify the calibration by analyzing a calibration reference standard. If the measured concentration exceeds the established value by more than 10 percent, perform a second analysis. If the measured concentration still exceeds the established value by more than 10 percent, terminate the analysis until the problem can be identified and corrected.

11.6.6   IC/PCR Instrument Operation.

11.6.6.1   Inject the calibration reference standard (as described in Section 9.3.1), followed by the field reagent blank (Section 8.2.4), and the field samples.

11.6.6.1.1   Standards (and QC standards) and samples are injected into the sample loop of the desired size (use a larger size loop for greater sensitivity). The Cr+6 is collected on the resin bed of the column.

11.6.6.1.2   After separation from other sample components, the Cr+6 forms a specific complex in the post-column reactor with the DPC reaction solution, and the complex is detected by visible absorbance at a maximum wavelength of 540 nm.

11.6.6.1.3   The amount of absorbance measured is proportional to the concentration of the Cr+6 complex formed.

11.6.6.1.4   The IC retention time and the absorbance of the Cr+6 complex with known Cr+6 standards analyzed under identical conditions must be compared to provide both qualitative and quantitative analyses.

11.6.6.1.5   If a sample peak appears near the expected retention time of the Cr+6 ion, spike the sample according to Section 9.3.4 to verify peak identity.

11.6.7   IC/PCR Operational Quality Control Procedures.

11.6.7.1   Samples should be at a pH ≥8.5 for NaOH and ≥8.0 if using NaHCO3; document any discrepancies.

11.6.7.2   Refrigerated samples should be allowed to equilibrate to ambient temperature prior to preparation and analysis.

11.6.7.3   Repeat the injection of the calibration standards at the end of the analytical run to assess instrument drift. Measure areas or heights of the Cr+6/DPC complex chromatogram peaks.

11.6.7.4   To ensure the precision of the sample injection (manual or autosampler), the response for the second set of injected standards must be within 10 percent of the average response.

11.6.7.5   If the 10 percent criteria duplicate injection cannot be achieved, identify the source of the problem and rerun the calibration standards.

11.6.7.6   Use peak areas or peak heights from the injections of calibration standards to generate a linear calibration curve. From the calibration curve, determine the concentrations of the field samples.

11.6.8   IC/PCR Sample Dilution.

11.6.8.1   Samples having concentrations higher than the established calibration range must be diluted into the calibration range and re-analyzed.

11.6.8.2   If dilutions are performed, the appropriate factors must be applied to sample measurement results.

11.6.9   Reporting Analytical Results. Results should be reported in µg Cr+6/mL using three significant figures. Field sample volumes (mL) must be reported also.

12.0   Data Analysis and Calculations

12.1   Pretest Calculations.

12.1.1   Pretest Protocol (Site Test Plan).

12.1.1.1   The pretest protocol should define and address the test data quality objectives (DQOs), with all assumptions, that will be required by the end user (enforcement authority); what data are needed? why are the data needed? how will the data be used? what are method detection limits? and what are estimated target analyte levels for the following test parameters.

12.1.1.1.1   Estimated source concentration for total chromium and/or Cr+6.

12.1.1.1.2   Estimated minimum sampling time and/or volume required to meet method detection limit requirements (Appendix B 40 CFR Part 136) for measurement of total chromium and/or Cr+6.

12.1.1.1.3   Demonstrate that planned sampling parameters will meet DQOs. The protocol must demonstrate that the planned sampling parameters calculated by the tester will meet the needs of the source and the enforcement authority.

12.1.1.2   The pre-test protocol should include information on equipment, logistics, personnel, process operation, and other resources necessary for an efficient and coordinated test.

12.1.1.3   At a minimum, the pre-test protocol should identify and be approved by the source, the tester, the analytical laboratory, and the regulatory enforcement authority. The tester should not proceed with the compliance testing before obtaining approval from the enforcement authority.

12.1.2   Post Test Calculations.

12.1.2.1   Perform the calculations, retaining one extra decimal figure beyond that of the acquired data. Round off figures after final calculations.

12.1.2.2   Nomenclature.

CS = Concentration of Cr in sample solution, µg Cr/mL.

Ccr = Concentration of Cr in stack gas, dry basis, corrected to standard conditions, mg/dscm.

D = Digestion factor, dimension less.

F = Dilution factor, dimension less.

MCr = Total Cr in each sample, µg.

Vad = Volume of sample aliquot after digestion, mL.

Vaf = Volume of sample aliquot after dilution, mL.

Vbd = Volume of sample aliquot submitted to digestion, mL.

Vbf = Volume of sample aliquot before dilution, mL.

VmL = Volume of impinger contents plus rinses, mL.

Vm(std) = Volume of gas sample measured by the dry gas meter, corrected to standard conditions, dscm.

12.1.2.3   Dilution Factor. The dilution factor is the ratio of the volume of sample aliquot after dilution to the volume before dilution. This ratio is given by the following equation:

eCFR graphic er17oc00.573.gif

View or download PDF

12.1.2.4   Digestion Factor. The digestion factor is the ratio of the volume of sample aliquot after digestion to the volume before digestion. This ratio is given by Equation 306-2.

eCFR graphic er17oc00.574.gif

View or download PDF

12.1.2.5   Total Cr in Sample. Calculate MCr, the total µg Cr in each sample, using the following equation:

eCFR graphic er17oc00.575.gif

View or download PDF

12.1.2.6   Average Dry Gas Meter Temperature and Average Orifice Pressure Drop. Same as Method 5.

12.1.2.7   Dry Gas Volume, Volume of Water Vapor, Moisture Content. Same as Method 5.

12.1.2.8   Cr Emission Concentration (CCr). Calculate CCr, the Cr concentration in the stack gas, in mg/dscm on a dry basis, corrected to standard conditions using the following equation:

eCFR graphic er17oc00.576.gif

View or download PDF

12.1.2.9   Isokinetic Variation, Acceptable Results. Same as Method 5.

13.0   Method Performance

13.1   Range. The recommended working range for all of the three analytical techniques starts at five times the analytical detection limit (see also Section 13.2.2). The upper limit of all three techniques can be extended indefinitely by appropriate dilution.

13.2   Sensitivity.

13.2.1   Analytical Sensitivity. The estimated instrumental detection limits listed are provided as a guide for an instrumental limit. The actual method detection limits are sample and instrument dependent and may vary as the sample matrix varies.

13.2.1.2   ICP Analytical Sensitivity. The minimum estimated detection limits for ICP, as reported in Method 6010A and the recently revised Method 6010B of SW-846 (Reference 1), are 7.0 µg Cr/L and 4.7 µg Cr/L, respectively.

13.2.1.3   GFAAS Analytical Sensitivity. The minimum estimated detection limit for GFAAS, as reported in Methods 7000A and 7191 of SW-846 (Reference 1), is 1 µg Cr/L.

13.2.1.4   IC/PCR Analytical Sensitivity. The minimum detection limit for IC/PCR with a preconcentrator, as reported in Methods 0061 and 7199 of SW-846 (Reference 1), is 0.05 µg Cr+6/L.

1.3.2.1.5   Determination of Detection Limits. The laboratory performing the Cr+6 measurements must determine the method detection limit on a quarterly basis using a suitable procedure such as that found in 40 CFR, Part 136, Appendix B. The determination should be made on samples in the appropriate alkaline matrix. Normally this involves the preparation (if applicable) and consecutive measurement of seven (7) separate aliquots of a sample with a concentration <5 times the expected detection limit. The detection limit is 3.14 times the standard deviation of these results.

13.2.2   In-stack Sensitivity. The in-stack sensitivity depends upon the analytical detection limit, the volume of stack gas sampled, the total volume of the impinger absorbing solution plus the rinses, and, in some cases, dilution or concentration factors from sample preparation. Using the analytical detection limits given in Sections 13.2.1.1, 13.2.1.2, and 13.2.1.3; a stack gas sample volume of 1.7 dscm; a total liquid sample volume of 500 mL; and the digestion concentration factor of 12 for the GFAAS analysis; the corresponding in-stack detection limits are 0.0014 mg Cr/dscm to 0.0021 mg Cr/dscm for ICP, 0.00015 mg Cr/dscm for GFAAS, and 0.000015 mg Cr+6/dscm for IC/PCR with preconcentration.

Note: It is recommended that the concentration of Cr in the analytical solutions be at least five times the analytical detection limit to optimize sensitivity in the analyses. Using this guideline and the same assumptions for impinger sample volume, stack gas sample volume, and the digestion concentration factor for the GFAAS analysis (500 mL,1.7 dscm, and 1/2, respectively), the recommended minimum stack concentrations for optimum sensitivity are 0.0068 mg Cr/dscm to 0.0103 mg Cr/dscm for ICP, 0.00074 mg Cr/dscm for GFAAS, and 0.000074 mg Cr+6/dscm for IC/PCR with preconcentration. If required, the in-stack detection limits can be improved by either increasing the stack gas sample volume, further reducing the volume of the digested sample for GFAAS, improving the analytical detection limits, or any combination of the three.

13.3   Precision.

13.3.1   The following precision data have been reported for the three analytical methods. In each case, when the sampling precision is combined with the reported analytical precision, the resulting overall precision may decrease.

13.3.2   Bias data is also reported for GFAAS.

13.4   ICP Precision.

13.4.1   As reported in Method 6010B of SW-846 (Reference 1), in an EPA round-robin Phase 1 study, seven laboratories applied the ICP technique to acid/distilled water matrices that had been spiked with various metal concentrates. For true values of 10, 50, and 150 µg Cr/L; the mean reported values were 10, 50, and 149 µg Cr/L; and the mean percent relative standard deviations were 18, 3.3, and 3.8 percent, respectively.

13.4.2   In another multi laboratory study cited in Method 6010B, a mean relative standard of 8.2 percent was reported for an aqueous sample concentration of approximately 3750 µg Cr/L.

13.5   GFAAS Precision. As reported in Method 7191 of SW-846 (Reference 1), in a single laboratory (EMSL), using Cincinnati, Ohio tap water spiked at concentrations of 19, 48, and 77 µg Cr/L, the standard deviations were ±0.1, ±0.2, and ±0.8, respectively. Recoveries at these levels were 97 percent, 101 percent, and 102 percent, respectively.

13.6   IC/PCR Precision. As reported in Methods 0061 and 7199 of SW-846 (Reference 1), the precision of IC/PCR with sample preconcentration is 5 to 10 percent. The overall precision for sewage sludge incinerators emitting 120 ng/dscm of Cr+6 and 3.5 µg/dscm of total Cr was 25 percent and 9 percent, respectively; and for hazardous waste incinerators emitting 300 ng/dscm of C+6 the precision was 20 percent.

14.0   Pollution Prevention

14.1   The only materials used in this method that could be considered pollutants are the chromium standards used for instrument calibration and acids used in the cleaning of the collection and measurement containers/labware, in the preparation of standards, and in the acid digestion of samples. Both reagents can be stored in the same waste container.

14.2   Cleaning solutions containing acids should be prepared in volumes consistent with use to minimize the disposal of excessive volumes of acid.

14.3   To the extent possible, the containers/vessels used to collect and prepare samples should be cleaned and reused to minimize the generation of solid waste.

15.0   Waste Management

15.1   It is the responsibility of the laboratory and the sampling team to comply with all federal, state, and local regulations governing waste management, particularly the discharge regulations, hazardous waste identification rules, and land disposal restrictions; and to protect the air, water, and land by minimizing and controlling all releases from field operations.

15.2   For further information on waste management, consult The Waste Management Manual for Laboratory Personnel and Less is Better—Laboratory Chemical Management for Waste Reduction, available from the American Chemical Society's Department of Government Relations and Science Policy, 1155 16th Street NW, Washington, DC 20036.

16.0   References

1. “Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, SW-846, Third Edition,” as amended by Updates I, II, IIA, IIB, and III. Document No. 955-001-000001. Available from Superintendent of Documents, U.S. Government Printing Office, Washington, DC, November 1986.

2. Cox, X.B., R.W. Linton, and F.E. Butler. Determination of Chromium Speciation in Environmental Particles—A Multi-technique Study of Ferrochrome Smelter Dust. Accepted for publication in Environmental Science and Technology.

3. Same as Section 17.0 of Method 5, References 2, 3, 4, 5, and 7.

4. California Air Resources Board, “Determination of Total Chromium and Hexavalent Chromium Emissions from Stationary Sources.” Method 425, September 12, 1990.

5. The Merck Index. Eleventh Edition. Merck & Co., Inc., 1989.

6. Walpole, R.E., and R.H. Myers. “Probability and Statistics for Scientists and Engineering.” 3rd Edition. MacMillan Publishing Co., NewYork, N.Y., 1985.

17.0   Tables, Diagrams, Flowcharts, and Validation Data

eCFR graphic er17oc00.577.gif

View or download PDF

eCFR graphic er17oc00.578.gif

View or download PDF

Method 306A—Determination of Chromium Emissions From Decorative and Hard Chromium Electroplating and Chromium Anodizing Operations

Note: This method does not include all of the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and analytical) essential to its performance. Some material is incorporated by reference from other methods in 40 CFR Part 60, Appendix A and in this part. Therefore, to obtain reliable results, persons using this method should have a thorough knowledge of at least Methods 5 and 306.

1.0   Scope and Application

1.1   Analyte. Chromium. CAS Number (7440-47-3).

1.2   Applicability.

1.2.1   This method applies to the determination of chromium (Cr) in emissions from decorative and hard chromium electroplating facilities, chromium anodizing operations, and continuous chromium plating at iron and steel facilities. The method is less expensive and less complex to conduct than Method 306. Correctly applied, the precision and bias of the sample results should be comparable to those obtained with the isokinetic Method 306. This method is applicable for the determination of air emissions under nominal ambient moisture, temperature, and pressure conditions.

1.2.2   The method is also applicable to electroplating and anodizing sources controlled by wet scrubbers.

1.3   Data Quality Objectives.

1.3.1   Pretest Protocol.

1.3.1.1   The pretest protocol should define and address the test data quality objectives (DQOs), with all assumptions, that will be required by the end user (enforcement authority); what data are needed? why are the data needed? how will data be used? what are method detection limits? and what are estimated target analyte levels for the following test parameters.

1.3.1.1.1   Estimated source concentration for total chromium and/or Cr+6.

1.3.1.1.2   Estimated minimum sampling time and/or volume required to meet method detection limit requirements (Appendix B 40 CFR Part 136) for measurement of total chromium and/or Cr+6.

1.3.1.1.3   Demonstrate that planned sampling parameters will meet DQOs. The protocol must demonstrate that the planned sampling parameters calculated by the tester will meet the needs of the source and the enforcement authority.

1.3.1.2   The pre-test protocol should include information on equipment, logistics, personnel, process operation, and other resources necessary for an efficient and coordinated performance test.

1.3.1.3   At a minimum, the pre-test protocol should identify and be approved by the source, the tester, the analytical laboratory, and the regulatory enforcement authority. The tester should not proceed with the compliance testing before obtaining approval from the enforcement authority.

2.0   Summary of Method

2.1   Sampling.

2.1.1   An emission sample is extracted from the source at a constant sampling rate determined by a critical orifice and collected in a sampling train composed of a probe and impingers. The proportional sampling time at the cross sectional traverse points is varied according to the stack gas velocity at each point. The total sample time must be at least two hours.

2.1.2   The chromium emission concentration is determined by the same analytical procedures described in Method 306: inductively-coupled plasma emission spectrometry (ICP), graphite furnace atomic absorption spectrometry (GFAAS), or ion chromatography with a post-column reactor (IC/PCR).

2.1.2.1   Total chromium samples with high chromium concentrations (≥35 µg/L) may be analyzed using inductively coupled plasma emission spectrometry (ICP) at 267.72 nm.

Note: The ICP analysis is applicable for this method only when the solution analyzed has a Cr concentration greater than or equal to 35 µg/L or five times the method detection limit as determined according to Appendix B in 40 CFR Part 136.

2.1.2.2   Alternatively, when lower total chromium concentrations (<35 µg/L) are encountered, a portion of the alkaline sample solution may be digested with nitric acid and analyzed by graphite furnace atomic absorption spectroscopy (GFAAS) at 357.9 nm.

2.1.2.3   If it is desirable to determine hexavalent chromium (Cr+6) emissions, the samples may be analyzed using an ion chromatograph equipped with a post-column reactor (IC/PCR) and a visible wavelength detector. To increase sensitivity for trace levels of Cr+6, a preconcentration system may be used in conjunction with the IC/PCR.

3.0   Definitions

3.1   Total Chromium—measured chromium content that includes both major chromium oxidation states (Cr+3, Cr+6).

3.2   May—Implies an optional operation.

3.3   Digestion—The analytical operation involving the complete (or nearly complete) dissolution of the sample in order to ensure the complete solubilization of the element (analyte) to be measured.

3.4   Interferences—Physical, chemical, or spectral phenomena that may produce a high or low bias in the analytical result.

3.5   Analytical System—All components of the analytical process including the sample digestion and measurement apparatus.

3.6   Sample Recovery—The quantitative transfer of sample from the collection apparatus to the sample preparation (digestion, etc.) apparatus. This term should not be confused with analytical recovery.

4.0   Interferences

4.1   Same as in Method 306, Section 4.0.

5.0   Safety

5.1   Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method does not purport to address all of the safety issues associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to performing this test method.

5.2   Chromium and some chromium compounds have been listed as carcinogens although Chromium (III) compounds show little or no toxicity. Chromium is a skin and respiratory irritant.

6.0   Equipment and Supplies

Note: Mention of trade names or specific products does not constitute endorsement by the Environmental Protection Agency.

6.1   Sampling Train. A schematic of the sampling train is shown in Figure 306A-1. The individual components of the train are available commercially, however, some fabrication and assembly are required.

6.1.1   Probe Nozzle/Tubing and Sheath.

6.1.1.1   Use approximately 6.4-mm ( 14 -in.) inside diameter (ID) glass or rigid plastic tubing approximately 20 cm (8 in.) in length with a short 90 degree bend at one end to form the sampling nozzle. Grind a slight taper on the nozzle end before making the bend. Attach the nozzle to flexible tubing of sufficient length to enable collection of a sample from the stack.

6.1.1.2   Use a straight piece of larger diameter rigid tubing (such as metal conduit or plastic water pipe) to form a sheath that begins about 2.5 cm (1 in.) from the 90 ° bend on the nozzle and encases and supports the flexible tubing.

6.1.2 Type S Pitot Tube. Same as Method 2, Section 6.1 (40 CFR Part 60, Appendix A).

6.1.3   Temperature Sensor.

6.1.3.1   A thermocouple, liquid-filled bulb thermometer, bimetallic thermometer, mercury-in-glass thermometer, or other sensor capable of measuring temperature to within 1.5 percent of the minimum absolute stack temperature.

6.1.3.2   The temperature sensor shall either be positioned near the center of the stack, or be attached to the pitot tube as directed in Section 6.3 of Method 2.

6.1.4   Sample Train Connectors.

6.1.4.1   Use thick wall flexible plastic tubing (polyethylene, polypropylene, or polyvinyl chloride) 6.4-mm ( 14 -in.) to 9.5-mm ( 38 -in.) ID to connect the train components.

6.1.4.2   A combination of rigid plastic tubing and thin wall flexible tubing may be used as long as tubing walls do not collapse when leak-checking the train. Metal tubing cannot be used.

6.1.5   Impingers. Three, one-quart capacity, glass canning jars with vacuum seal lids, or three Greenburg-Smith (GS) design impingers connected in series, or equivalent, may be used.

6.1.5.1   One-quart glass canning jar. Three separate jar containers are required: (1) the first jar contains the absorbing solution; (2) the second is empty and is used to collect any reagent carried over from the first container; and (3) the third contains the desiccant drying agent.

6.1.5.2   Canning Jar Connectors. The jar containers are connected by leak-tight inlet and outlet tubes installed in the lids of each container for assembly with the train. The tubes may be made of 6.4 mm ( 14 -in.) ID glass or rigid plastic tubing. For the inlet tube of the first impinger, heat the glass or plastic tubing and draw until the tubing separates. Fabricate the necked tip to form an orifice tip that is approximately 2.4 mm ( 332 -in.) ID.

6.1.5.2.1   When assembling the first container, place the orifice tip end of the tube approximately 4.8 mm ( 316 -in.) above the inside bottom of the jar.

6.1.5.2.2   For the second container, the inlet tube need not be drawn and sized, but the tip should be approximately 25 mm (1 in.) above the bottom of the jar.

6.1.5.2.3   The inlet tube of the third container should extend to approximately 12.7 mm ( 12 -in.) above the bottom of the jar.

6.1.5.2.4   Extend the outlet tube for each container approximately 50 mm (2 in.) above the jar lid and downward through the lid, approximately 12.7 mm ( 12 -in.) beneath the bottom of the lid.

6.1.5.3   Greenburg-Smith Impingers. Three separate impingers of the Greenburg-Smith (GS) design as described in Section 6.0 of Method 5 are required. The first GS impinger shall have a standard tip (orifice/plate), and the second and third GS impingers shall be modified by replacing the orifice/plate tube with a 13 mm ( 12 -in.) ID glass tube, having an unrestricted opening located 13 mm ( 12 -in.) from the bottom of the outer flask.

6.1.5.4   Greenburg-Smith Connectors. The GS impingers shall be connected by leak-free ground glass “U” tube connectors or by leak-free non-contaminating flexible tubing. The first impinger shall contain the absorbing solution, the second is empty and the third contains the desiccant drying agent.

6.1.6   Manometer. Inclined/vertical type, or equivalent device, as described in Section 6.2 of Method 2 (40 CFR Part 60, Appendix A).

6.1.7   Critical Orifice. The critical orifice is a small restriction in the sample line that is located upstream of the vacuum pump. The orifice produces a constant sampling flow rate that is approximately 0.021 cubic meters per minute (m3/min) or 0.75 cubic feet per minute (cfm).

6.1.7.1   The critical orifice can be constructed by sealing a 2.4-mm ( 332 -in.) ID brass tube approximately 14.3 mm ( 916 -in.) in length inside a second brass tube that is approximately 8 mm ( 516 -in.) ID and 14.3-mm ( 916 -in.) in length .

6.1.7.2   Materials other than brass can be used to construct the critical orifice as long as the flow through the sampling train can be maintained at approximately 0.021 cubic meter per minute (0.75) cfm.

6.1.8   Connecting Hardware. Standard pipe and fittings, 9.5-mm ( 38 -in.), 6.4-mm ( 14 -in.) or 3.2-mm ( 18 -in.) ID, may be used to assemble the vacuum pump, dry gas meter and other sampling train components.

6.1.9   Vacuum Gauge. Capable of measuring approximately 760 mm Hg (30 in. Hg) vacuum in 25.4 mm HG (1 in. Hg) increments. Locate vacuum gauge between the critical orifice and the vacuum pump.

6.1.10   Pump Oiler. A glass oil reservoir with a wick mounted at the vacuum pump inlet that lubricates the pump vanes. The oiler should be an in-line type and not vented to the atmosphere. See EMTIC Guideline Document No. GD-041.WPD for additional information.

6.1.11   Vacuum Pump. Gast Model 0522-V103-G18DX, or equivalent, capable of delivering at least 1.5 cfm at 15 in. Hg vacuum.

6.1.12   Oil Trap/Muffler. An empty glass oil reservoir without wick mounted at the pump outlet to control the pump noise and prevent oil from reaching the dry gas meter.

6.1.13   By-pass Fine Adjust Valve (Optional). Needle valve assembly 6.4-mm ( 14 -in.), Whitey 1 RF 4-A, or equivalent, that allows for adjustment of the train vacuum.

6.1.13.1   A fine-adjustment valve is positioned in the optional pump by-pass system that allows the gas flow to recirculate through the pump. This by-pass system allows the tester to control/reduce the maximum leak-check vacuum pressure produced by the pump.

6.1.13.1.1   The tester must conduct the post test leak check at a vacuum equal to or greater than the maximum vacuum encountered during the sampling run.

6.1.13.1.2   The pump by-pass assembly is not required, but is recommended if the tester intends to leak-check the 306A train at the vacuum experienced during a run.

6.1.14   Dry Gas Meter. An Equimeter Model 110 test meter or, equivalent with temperature sensor(s) installed (inlet/outlet) to monitor the meter temperature. If only one temperature sensor is installed, locate the sensor at the outlet side of the meter. The dry gas meter must be capable of measuring the gaseous volume to within ±2% of the true volume.

Note: The Method 306 sampling train is also commercially available and may be used to perform the Method 306A tests. The sampling train may be assembled as specified in Method 306A with the sampling rate being operated at the delta H@ specified for the calibrated orifice located in the meter box. The Method 306 train is then operated as described in Method 306A.

6.2   Barometer. Mercury aneroid barometer, or other barometer equivalent, capable of measuring atmospheric pressure to within ±2.5 mm Hg (0.1 in. Hg).

6.2.1   A preliminary check of the barometer shall be made against a mercury-in-glass reference barometer or its equivalent.

6.2.2   Tester may elect to obtain the absolute barometric pressure from a nearby National Weather Service station.

6.2.2.1   The station value (which is the absolute barometric pressure) must be adjusted for elevation differences between the weather station and the sampling location. Either subtract 2.5 mm Hg (0.1 in. Hg) from the station value per 30 m (100 ft) of elevation increase or add the same for an elevation decrease.

6.2.2.2   If the field barometer cannot be adjusted to agree within 0.1 in. Hg of the reference barometric, repair or discard the unit. The barometer pressure measurement shall be recorded on the sampling data sheet.

6.3   Sample Recovery. Same as Method 5, Section 6.2 (40 CFR Part 60, Appendix A), with the following exceptions:

6.3.1   Probe-Liner and Probe-Nozzle Brushes. Brushes are not necessary for sample recovery. If a probe brush is used, it must be non-metallic.

6.3.2   Wash Bottles. Polyethylene wash bottle, for sample recovery absorbing solution.

6.3.3   Sample Recovery Solution. Use 0.1 N NaOH or 0.1 N NaHCO3, whichever is used as the impinger absorbing solution, to replace the acetone.

6.3.4   Sample Storage Containers.

6.3.4.1   Glass Canning Jar. The first canning jar container of the sampling train may serve as the sample shipping container. A new lid and sealing plastic wrap shall be substituted for the container lid assembly.

6.3.4.2   Polyethylene or Glass Containers. Transfer the Greenburg-Smith impinger contents to precleaned polyethylene or glass containers. The samples shall be stored and shipped in 250-mL, 500-mL or 1000-mL polyethylene or glass containers with leak-free, non metal screw caps.

6.3.5   pH Indicator Strip, for Cr+6 Samples. pH indicator strips, or equivalent, capable of determining the pH of solutions between the range of 7 and 12, at 0.5 pH increments.

6.3.6   Plastic Storage Containers. Air tight containers to store silica gel.

6.4   Analysis. Same as Method 306, Section 6.3.

7.0   Reagents and Standards.

Note: Unless otherwise indicated, all reagents shall conform to the specifications established by the Committee on Analytical Reagents of the American Chemical Society (ACS reagent grade). Where such specifications are not available, use the best available grade. It is recommended, but not required, that reagents be checked by the appropriate analysis prior to field use to assure that contamination is below the analytical detection limit for the ICP or GFAAS total chromium analysis; and that contamination is below the analytical detection limit for Cr+6 using IC/PCR for direct injection or, if selected, preconcentration.

7.1   Sampling.

7.1.1   Water. Reagent water that conforms to ASTM Specification D1193 Type II (incorporated by reference see §63.14). All references to water in the method refer to reagent water unless otherwise specified. It is recommended that water blanks be checked prior to preparing the sampling reagents to ensure that the Cr content is less than three (3) times the anticipated detection limit of the analytical method.

7.1.2   Sodium Hydroxide (NaOH) Absorbing Solution, 0.1 N. Dissolve 4.0 g of sodium hydroxide in 1 liter of water to obtain a pH of approximately 8.5.

7.1.3   Sodium Bicarbonate (NaHCO3) Absorbing Solution, 0.1 N. Dissolve approximately 8.5 g of sodium bicarbonate in 1 liter of water to obtain a pH of approximately 8.3.

7.1.4   Chromium Contamination.

7.1.4.1   The absorbing solution shall not exceed the QC criteria noted in Method 306, Section 7.1.1 (≤3 times the instrument detection limit).

7.1.4.2   When the Cr+6 content in the field samples exceeds the blank concentration by at least a factor of ten (10), Cr+6 blank levels ≤10 times the detection limit will be allowed.

Note: At sources with high concentrations of acids and/or SO2, the concentration of NaOH or NaHCO3 should be ≥0.5 N to insure that the pH of the solution remains at or above 8.5 for NaOH and 8.0 for NaHCO3 during and after sampling.

7.1.3   Desiccant. Silica Gel, 6-16 mesh, indicating type. Alternatively, other types of desiccants may be used, subject to the approval of the Administrator.

7.2   Sample Recovery. Same as Method 306, Section 7.2.

7.3   Sample Preparation and Analysis. Same as Method 306, Section 7.3.

7.4   Glassware Cleaning Reagents. Same as Method 306, Section 7.4.

8.0   Sample Collection, Recovery, Preservation, Holding Times, Storage, and Transport

Note: Prior to sample collection, consideration should be given as to the type of analysis (Cr+6 or total Cr) that will be performed. Deciding which analysis will be performed will enable the tester to determine which appropriate sample recovery and storage procedures will be required to process the sample.

8.1   Sample Collection.

8.1.1   Pretest Preparation.

8.1.1.1   Selection of Measurement Site. Locate the sampling ports as specified in Section 11.0 of Method 1 (40 CFR Part 60, Appendix A).

8.1.1.2   Location of Traverse Points.

8.1.1.2.1   Locate the traverse points as specified in Section 11.0 of Method 1 (40 CFR Part 60, Appendix A). Use a total of 24 sampling points for round ducts and 24 or 25 points for rectangular ducts. Mark the pitot and sampling probe to identify the sample traversing points.

8.1.1.2.2   For round ducts less than 12 inches in diameter, use a total of 16 points.

8.1.1.3   Velocity Pressure Traverse. Perform an initial velocity traverse before obtaining samples. The Figure 306A-2 data sheet may be used to record velocity traverse data.

8.1.1.3.1   To demonstrate that the flow rate is constant over several days of testing, perform complete traverses at the beginning and end of each day's test effort, and calculate the deviation of the flow rate for each daily period. The beginning and end flow rates are considered constant if the deviation does not exceed 10 percent. If the flow rate exceeds the 10 percent criteria, either correct the inconsistent flow rate problem, or obtain the Administrator's approval for the test results.

8.1.1.3.2   Perform traverses as specified in Section 8.0 of Method 2, but record only the Δp (velocity pressure) values for each sampling point. If a mass emission rate is desired, stack velocity pressures shall be recorded before and after each test, and an average stack velocity pressure determined for the testing period.

8.1.1.4   Verification of Absence of Cyclonic Flow. Check for cyclonic flow during the initial traverse to verify that it does not exist. Perform the cyclonic flow check as specified in Section 11.4 of Method 1 (40 CFR Part 60, Appendix A).

8.1.1.4.1   If cyclonic flow is present, verify that the absolute average angle of the tangential flow does not exceed 20 degrees. If the average value exceeds 20 degrees at the sampling location, the flow condition in the stack is unacceptable for testing.

8.1.1.4.2   Alternative procedures, subject to approval of the Administrator, e.g., installing straightening vanes to eliminate the cyclonic flow, must be implemented prior to conducting the testing.

8.1.1.5   Stack Gas Moisture Measurements. Not required. Measuring the moisture content is optional when a mass emission rate is to be calculated.

8.1.1.5.1   The tester may elect to either measure the actual stack gas moisture during the sampling run or utilize a nominal moisture value of 2 percent.

8.1.1.5.2   For additional information on determining sampling train moisture, please refer to Method 4 (40 CFR Part 60, Appendix A).

8.1.1.6   Stack Temperature Measurements. If a mass emission rate is to be calculated, a temperature sensor must be placed either near the center of the stack, or attached to the pitot tube as described in Section 8.3 of Method 2. Stack temperature measurements, shall be recorded before and after each test, and an average stack temperature determined for the testing period.

8.1.1.7   Point Sampling Times. Since the sampling rate of the train (0.75 cfm) is maintained constant by the critical orifice, it is necessary to calculate specific sampling times for each traverse point in order to obtain a proportional sample.

8.1.1.7.1   If the sampling period (3 runs) is to be completed in a single day, the point sampling times shall be calculated only once.

8.1.1.7.2   If the sampling period is to occur over several days, the sampling times must be calculated daily using the initial velocity pressure data recorded for that day. Determine the average of the Δp values obtained during the velocity traverse (Figure 306A-2).

8.1.1.7.3   If the stack diameter is less than 12 inches, use 7.5 minutes in place of 5 minutes in the equation and 16 sampling points instead of 24 or 25 points. Calculate the sampling times for each traverse point using the following equation:

eCFR graphic er17oc00.579.gif

View or download PDF

Where:

n = Sampling point number.

Δp = Average pressure differential across pitot tube, mm H2O (in. H2O).

ΔPavg = Average of Δp values, mm H2O (in. H2O).

Note: Convert the decimal fractions for minutes to seconds.

8.1.1.8   Pretest Preparation. It is recommended, but not required, that all items which will be in contact with the sample be cleaned prior to performing the testing to avoid possible sample contamination (positive chromium bias). These items include, but are not limited to: Sampling probe, connecting tubing, impingers, and jar containers.

8.1.1.8.1   Sample train components should be: (1) Rinsed with hot tap water; (2) washed with hot soapy water; (3) rinsed with tap water; (4) rinsed with reagent water; (5) soaked in a 10 percent (v/v) nitric acid solution for at least four hours; and (6) rinsed throughly with reagent water before use.

8.1.1.8.2   At a minimum, the tester should, rinse the probe, connecting tubing, and first and second impingers twice with either 0.1 N sodium hydroxide (NaOH) or 0.1 N sodium bicarbonate (NaHCO3) and discard the rinse solution.

8.1.1.8.3   If separate sample shipping containers are to be used, these also should be precleaned using the specified cleaning procedures.

8.1.1.9   Preparation of Sampling Train. Assemble the sampling train as shown in Figure 306A-1. Secure the nozzle-liner assembly to the outer sheath to prevent movement when sampling.

8.1.1.9.1   Place 250 mL of 0.1 N NaOH or 0.1 N NaHCO3 absorbing solution into the first jar container or impinger. The second jar/impinger is to remain empty. Place 6 to 16 mesh indicating silica gel, or equivalent desiccant into the third jar/impinger until the container is half full ( 300 to 400 g).

8.1.1.9.2   Place a small cotton ball in the outlet exit tube of the third jar to collect small silica gel particles that may dislodge and impair the pump and/or gas meter.

8.1.1.10   Pretest Leak-Check. A pretest leak-check is recommended, but not required. If the tester opts to conduct the pretest leak-check, the following procedures shall be performed: (1) Place the jar/impinger containers into an ice bath and wait 10 minutes for the ice to cool the containers before performing the leak check and/or start sampling; (2) to perform the leak check, seal the nozzle using a piece of clear plastic wrap placed over the end of a finger and switch on the pump; and (3) the train system leak rate should not exceed 0.02 cfm at a vacuum of 380 mm Hg (15 in. Hg) or greater. If the leak rate does exceed the 0.02 cfm requirement, identify and repair the leak area and perform the leak check again.

Note: Use caution when releasing the vacuum following the leak check. Always allow air to slowly flow through the nozzle end of the train system while the pump is still operating. Switching off the pump with vacuum on the system may result in the silica gel being pulled into the second jar container.

8.1.1.11   Leak-Checks During Sample Run. If, during the sampling run, a component (e.g., jar container) exchange becomes necessary, a leak-check shall be conducted immediately before the component exchange is made. The leak-check shall be performed according to the procedure outlined in Section 8.1.1.10 of this method. If the leakage rate is found to be ≤0.02 cfm at the maximum operating vacuum, the results are acceptable. If, however, a higher leak rate is obtained, either record the leakage rate and correct the sample volume as shown in Section 12.3 of Method 5 or void the sample and initiate a replacement run. Following the component change, leak-checks are optional, but are recommended as are the pretest leak-checks.

8.1.1.12   Post Test Leak Check. Remove the probe assembly and flexible tubing from the first jar/impinger container. Seal the inlet tube of the first container using clear plastic wrap and switch on the pump. The vacuum in the line between the pump and the critical orifice must be ≥15 in. Hg. Record the vacuum gauge measurement along with the leak rate observed on the train system.

8.1.1.12.1   If the leak rate does not exceed 0.02 cfm, the results are acceptable and no sample volume correction is necessary.

8.1.1.12.2   If, however, a higher leak rate is obtained (>0.02 cfm), the tester shall either record the leakage rate and correct the sample volume as shown in Section 12.3 of Method 5, or void the sampling run and initiate a replacement run.   After completing the leak-check, slowly release the vacuum at the first container while the pump is still operating. Afterwards, switch-off the pump.

8.1.2   Sample Train Operation.

8.1.2.1   Data Recording. Record all pertinent process and sampling data on the data sheet (see Figure 306A-3). Ensure that the process operation is suitable for sample collection.

8.1.2.2   Starting the Test. Place the probe/nozzle into the duct at the first sampling point and switch on the pump. Start the sampling using the time interval calculated for the first point. When the first point sampling time has been completed, move to the second point and continue to sample for the time interval calculated for that point; sample each point on the traverse in this manner. Maintain ice around the sample containers during the run.

8.1.2.3   Critical Flow. The sample line between the critical orifice and the pump must operate at a vacuum of ≥380 mm Hg (≥15 in. Hg) in order for critical flow to be maintained. This vacuum must be monitored and documented using the vacuum gauge located between the critical orifice and the pump.

Note: Theoretically, critical flow for air occurs when the ratio of the orifice outlet absolute pressure to the orifice inlet absolute pressure is less than a factor of 0.53. This means that the system vacuum should be at least ≥356 mm Hg (≥14 in. Hg) at sea level and 305 mm Hg ( 12 in. Hg) at higher elevations.

8.1.2.4   Completion of Test.

8.1.2.4.1   Circular Stacks. Complete the first port traverse and switch off the pump. Testers may opt to perform a leak-check between the port changes to verify the leak rate however, this is not mandatory. Move the sampling train to the next sampling port and repeat the sequence. Be sure to record the final dry gas meter reading after completing the test run. After performing the post test leak check, disconnect the jar/impinger containers from the pump and meter assembly and transport the probe, connecting tubing, and containers to the sample recovery area.

8.1.2.4.2   Rectangle Stacks. Complete each port traverse as per the instructions provided in 8.1.2.4.1.

Note: If an approximate mass emission rate is to be calculated, measure and record the stack velocity pressure and temperature before and after the test run.

8.2   Sample Recovery. After the train has been transferred to the sample recovery area, disconnect the tubing that connects the jar/impingers. The tester shall select either the total Cr or Cr+6 sample recovery option. Samples to be analyzed for both total Cr and Cr+6 shall be recovered using the Cr+6 sample option (Section 8.2.2).

Note: Collect a reagent blank sample for each of the total Cr or the Cr+6 analytical options. If both analyses (Cr and Cr+6) are to be conducted on the samples, collect separate reagent blanks for each analysis. Also, since particulate matter is not usually present at chromium electroplating and/or chromium anodizing operations, it is not necessary to filter the Cr+6 samples unless there is observed sediment in the collected solutions. If it is necessary to filter the Cr+6 solutions, please refer to Method 0061, Determination of Hexavalent Chromium Emissions from Stationary Sources, Section 7.4, Sample Preparation in SW-846 (see Reference 1).

8.2.1   Total Cr Sample Option.

8.2.1.1   Shipping Container No. 1. The first jar container may either be used to store and transport the sample, or if GS impingers are used, samples may be stored and shipped in precleaned 250-mL, 500-mL or 1000-mL polyethylene or glass bottles with leak-free, non-metal screw caps.

8.2.1.1.1   Unscrew the lid from the first jar/impinger container.

8.2.1.1.2   Lift the inner tube assembly almost out of the container, and using the wash bottle containing fresh absorbing solution, rinse the outside of the tube that was immersed in the container solution; rinse the inside of the tube as well, by rinsing twice from the top of the tube down through the inner tube into the container.

8.2.1.2   Recover the contents of the second jar/impinger container by removing the lid and pouring any contents into the first shipping container.

8.2.1.2.1   Rinse twice, using fresh absorbing solution, the inner walls of the second container including the inside and outside of the inner tube.

8.2.1.2.2   Rinse the connecting tubing between the first and second sample containers with absorbing solution and place the rinses into the first container.

8.2.1.3   Position the nozzle, probe and connecting plastic tubing in a vertical position so that the tubing forms a “U”.

8.2.1.3.1   Using the wash bottle, partially fill the tubing with fresh absorbing solution. Raise and lower the end of the plastic tubing several times to allow the solution to contact the internal surfaces. Do not allow the solution to overflow or part of the sample will be lost. Place the nozzle end of the probe over the mouth of the first container and elevate the plastic tubing so that the solution flows into the sample container.

8.2.1.3.2   Repeat the probe/tubing sample recovery procedure but allow the solution to flow out the opposite end of the plastic tubing into the sample container. Repeat the entire sample recovery procedure once again.

8.2.1.4   Use approximately 200 to 300 mL of the 0.1 N NaOH or 0.1 N NaHCO3 absorbing solution during the rinsing of the probe nozzle, probe liner, sample containers, and connecting tubing.

8.2.1.5   Place a piece of clear plastic wrap over the mouth of the sample jar to seal the shipping container. Use a standard lid and band assembly to seal and secure the sample in the jar.

8.2.1.5.1   Label the jar clearly to identify its contents, sample number and date.

8.2.1.5.2   Mark the height of the liquid level on the container to identify any losses during shipping and handling.

8.2.1.5.3   Prepare a chain-of-custody sheet to accompany the sample to the laboratory.

8.2.2   Cr+6 Sample Option.

8.2.2.1   Shipping Container No. 1. The first jar container may either be used to store and transport the sample, or if GS impingers are used, samples may be stored and shipped in precleaned 250-mL, 500-mL or 1000-mL polyethylene or glass bottles with leak-free non-metal screw caps.

8.2.2.1.1   Unscrew and remove the lid from the first jar container.

8.2.2.1.2   Measure and record the pH of the solution in the first container by using a pH indicator strip. The pH of the solution must be ≥8.5 for NaOH and ≥8.0 for NaHCO3. If not, discard the collected sample, increase the concentration of the NaOH or NaHCO3 absorbing solution to 0.5 M and collect another air emission sample.

8.2.2.2 After measuring the pH of the first container, follow sample recovery procedures described in Sections 8.2.1.1 through 8.2.1.5.

Note: Since particulate matter is not usually present at chromium electroplating and/or chromium anodizing facilities, it is not necessary to filter the Cr+6 samples unless there is observed sediment in the collected solutions. If it is necessary to filter the Cr+6 solutions, please refer to the EPA Method 0061, Determination of Hexavalent Chromium Emissions from Stationary Sources, Section 7.4, Sample Preparation in SW-846 (see Reference 5) for procedure.

8.2.3   Silica Gel Container. Observe the color of the indicating silica gel to determine if it has been completely spent and make a notation of its condition/color on the field data sheet. Do not use water or other liquids to remove and transfer the silica gel.

8.2.4   Total Cr and/or Cr+6 Reagent Blank.

8.2.4.1   Shipping Container No. 2. Place approximately 500 mL of the 0.1 N NaOH or 0.1 N NaHCO3 absorbing solution in a precleaned, labeled sample container and include with the field samples for analysis.

8.3   Sample Preservation, Storage, and Transport.

8.3.1   Total Cr Option. Samples that are to be analyzed for total Cr need not be refrigerated.

8.3.2   Cr+6 Option. Samples that are to be analyzed for Cr+6 must be shipped and stored at 4 °C (40 °F).

Note: Allow Cr+6 samples to return to ambient temperature prior to analysis.

8.4   Sample Holding Times.

8.4.1   Total Cr Option. Samples that are to be analyzed for total chromium must be analyzed within 60 days of collection.

8.4.2   Cr+6 Option. Samples that are to be analyzed for Cr+6 must be analyzed within 14 days of collection.

9.0   Quality Control

9.1   Same as Method 306, Section 9.0.

10.0   Calibration and Standardization

Note: Tester shall maintain a performance log of all calibration results.

10.1   Pitot Tube. The Type S pitot tube assembly shall be calibrated according to the procedures outlined in Section 10.1 of Method 2.

10.2   Temperature Sensor. Use the procedure in Section 10.3 of Method 2 to calibrate the in-stack temperature sensor.

10.3   Metering System.

10.3.1   Sample Train Dry Gas Meter Calibration. Calibrations may be performed as described in Section 16.2 of Method 5 by either the manufacturer, a firm who provides calibration services, or the tester.

10.3.2   Dry Gas Meter Calibration Coefficient (Ym). The meter calibration coefficient (Ym) must be determined prior to the initial use of the meter, and following each field test program. If the dry gas meter is new, the manufacturer will have specified the Ym value for the meter. This Ym value can be used as the pretest value for the first test. For subsequent tests, the tester must use the Ym value established during the pretest calibration.

10.3.3   Calibration Orifice. The manufacturer may have included a calibration orifice and a summary spreadsheet with the meter that may be used for calibration purposes. The spreadsheet will provide data necessary to determine the calibration for the orifice and meter (standard cubic feet volume, sample time, etc.). These data were produced when the initial Ym value was determined for the meter.

10.3.4   Ym Meter Value Verification or Meter Calibration.

10.3.4.1   The Ym meter value may be determined by replacing the sampling train critical orifice with the calibration orifice. Replace the critical orifice assembly by installing the calibration orifice in the same location. The inlet side of the calibration orifice is to be left open to the atmosphere and is not to be reconnected to the sample train during the calibration procedure.

10.3.4.2   If the vacuum pump is cold, switch on the pump and allow it to operate (become warm) for several minutes prior to starting the calibration. After stopping the pump, record the initial dry gas meter volume and meter temperature.

10.3.4.3   Perform the calibration for the number of minutes specified by the manufacturer's data sheet (usually 5 minutes). Stop the pump and record the final dry gas meter volume and temperature. Subtract the start volume from the stop volume to obtain the Vm and average the meter temperatures (tm).

10.3.5   Ym Value Calculation. Ym is the calculated value for the dry gas meter. Calculate Ym using the following equation:

eCFR graphic er17oc00.580.gif

View or download PDF

Where:

Pbar = Barometric pressure at meter, mm Hg, (in. Hg).

Pstd = Standard absolute pressure,

Metric = 760 mm Hg.

English = 29.92 in. Hg.

tm = Average dry gas meter temperature, °C, (°F).

Tm = Absolute average dry gas meter temperature,

Metric °K = 273 + tm (°C).

English °R = 460 + tm(°F).

Tstd = Standard absolute temperature,

Metric = 293 °K.

English = 528 °R.

Vm = Volume of gas sample as measured (actual) by dry gas meter, dcm,(dcf).

Vm(std),mfg = Volume of gas sample measured by manufacture's calibrated orifice and dry gas meter, corrected to standard conditions (pressure/temperature) dscm (dscf).

Ym = Dry gas meter calibration factor, (dimensionless).

10.3.6   Ym Comparison. Compare the Ym value provided by the manufacturer (Section 10.3.3) or the pretest Ym value to the post test Ym value using the following equation:

eCFR graphic er17oc00.581.gif

View or download PDF

10.3.6.1   If this ratio is between 0.95 and 1.05, the designated Ym value for the meter is acceptable for use in later calculations.

10.3.6.1.1   If the value is outside the specified range, the test series shall either be: 1) voided and the samples discarded; or 2) calculations for the test series shall be conducted using whichever meter coefficient value (i.e., manufacturers's/pretest Ym value or post test Ym value) produces the lowest sample volume.

10.3.6.1.2   If the post test dry gas meter Ym value differs by more than 5% as compared to the pretest value, either perform the calibration again to determine acceptability or return the meter to the manufacturer for recalibration.

10.3.6.1.3   The calibration may also be conducted as specified in Section 10.3 or Section 16.0 of Method 5 (40 CFR Part 60, Appendix A), except that it is only necessary to check the calibration at one flow rate of 0.75 cfm.

10.3.6.1.4   The calibration of the dry gas meter must be verified after each field test program using the same procedures.

Note: The tester may elect to use the Ym post test value for the next pretest Ym value; e.g., Test 1 post test Ym value and Test 2 pretest Ym value would be the same.

10.4   Barometer. Calibrate against a mercury barometer that has been corrected for temperature and elevation.

10.5   ICP Spectrometer Calibration. Same as Method 306, Section 10.2.

10.6   GFAA Spectrometer Calibration. Same as Method 306, Section 10.3.

10.7   IC/PCR Calibration. Same as Method 306, Section 10.4.

11.0   Analytical Procedures

Note: The method determines the chromium concentration in µg Cr/mL. It is important that the analyst measure the volume of the field sample prior to analyzing the sample. This will allow for conversion of µg Cr/mL to µg Cr/sample.

11.1   Analysis. Refer to Method 306 for sample preparation and analysis procedures.

12.0   Data Analysis and Calculations

12.1   Calculations. Perform the calculations, retaining one extra decimal point beyond that of the acquired data. When reporting final results, round number of figures consistent with the original data.

12.2   Nomenclature.

A = Cross-sectional area of stack, m2 (ft2).

Bws = Water vapor in gas stream, proportion by volume, dimensionless (assume 2 percent moisture = 0.02).

Cp = Pitot tube coefficient; “S” type pitot coefficient usually 0.840, dimensionless.

CS = Concentration of Cr in sample solution, µg Cr/mL.

CCr = Concentration of Cr in stack gas, dry basis, corrected to standard conditions µg/dscm (gr/dscf).

d = Diameter of stack, m (ft).

D = Digestion factor, dimensionless.

ER = Approximate mass emission rate, mg/hr (lb/hr).

F = Dilution factor, dimensionless.

L = Length of a square or rectangular duct, m (ft).

MCr = Total Cr in each sample, µg (gr).

Ms = Molecular weight of wet stack gas, wet basis, g/g-mole, (lb/lb-mole); in a nominal gas stream at 2% moisture the value is 28.62.

Pbar = Barometric pressure at sampling site, mm Hg (in. Hg).

Ps = Absolute stack gas pressure; in this case, usually the same value as the barometric pressure, mm Hg (in. Hg).

Pstd = Standard absolute pressure:

Metric = 760 mm Hg.

English = 29.92 in. Hg.

Qstd = Average stack gas volumetric flow, dry, corrected to standard conditions, dscm/hr (dscf/hr).

tm = Average dry gas meter temperature, °C (°F).

Tm = Absolute average dry gas meter temperature:

Metric °K = 273 + tm (°C).

English °R = 460 + tm(°F).

ts = Average stack temperature, °C (°F).

Ts = Absolute average stack gas temperature: Metric °K = 273 + ts (°C). English °R = 460 + ts(°F).

Tstd = Standard absolute temperature: Metric = 293 °K. English = 528 °R.

Vad = Volume of sample aliquot after digestion (mL).

Vaf = Volume of sample aliquot after dilution (mL).

Vbd = Volume of sample aliquot submitted to digestion (mL).

Vbf = Volume of sample aliquot before dilution (mL).

Vm = Volume of gas sample as measured (actual, dry) by dry gas meter, dcm (dcf).

VmL = Volume of impinger contents plus rinses (mL).

Vm(std) = Volume of gas sample measured by the dry gas meter, corrected to standard conditions (temperature/pressure), dscm (dscf).

vs = Stack gas average velocity, calculated by Method 2, Equation 2-9, m/sec (ft/sec).

W = Width of a square or rectangular duct, m (ft).

Ym = Dry gas meter calibration factor, (dimensionless).

Δp = Velocity head measured by the Type S pitot tube, cm H2O (in. H2O).

Δpavg = Average of Δp values, mm H2O (in. H2O).

12.3   Dilution Factor. The dilution factor is the ratio of the volume of sample aliquot after dilution to the volume before dilution. The dilution factor is usually calculated by the laboratory. This ratio is derived by the following equation:

eCFR graphic er17oc00.582.gif

View or download PDF

12.4   Digestion Factor. The digestion factor is the ratio of the volume of sample aliquot after digestion to the volume before digestion. The digestion factor is usually calculated by the laboratory. This ratio is derived by the following equation.

eCFR graphic er17oc00.583.gif

View or download PDF

12.5   Total Cr in Sample. Calculate MCr, the total µg Cr in each sample, using the following equation:

eCFR graphic er17oc00.584.gif

View or download PDF

12.6   Dry Gas Volume. Correct the sample volume measured by the dry gas meter to standard conditions (20 °C, 760 mm Hg or 68 °F, 29.92 in. Hg) using the following equation:

eCFR graphic er17oc00.585.gif

View or download PDF

Where:

K1 = Metric units—0.3855 °K/mm Hg.

English units—17.64 °R/in. Hg.

12.7   Cr Emission Concentration (CCr). Calculate CCr, the Cr concentration in the stack gas, in µg/dscm (µg/dscf) on a dry basis, corrected to standard conditions, using the following equation:

eCFR graphic er17oc00.586.gif

View or download PDF

Note: To convert µg/dscm (µg/dscf) to mg/dscm (mg/dscf), divide by 1000.

12.8   Stack Gas Velocity.

12.8.1   Kp = Velocity equation constant:

eCFR graphic er17oc00.587.gif

View or download PDF

eCFR graphic er17oc00.588.gif

View or download PDF

12.8.2   Average Stack Gas Velocity.

eCFR graphic er17oc00.589.gif

View or download PDF

12.9   Cross sectional area of stack.

eCFR graphic er17oc00.591.gif

View or download PDF

12.10   Average Stack Gas Dry Volumetric Flow Rate.

Note: The emission rate may be based on a nominal stack moisture content of 2 percent (0.02). To calculate an emission rate, the tester may elect to use either the nominal stack gas moisture value or the actual stack gas moisture collected during the sampling run.

Volumetric Flow Rate Equation:

eCFR graphic er17oc00.592.gif

View or download PDF

Where:

3600 = Conversion factor, sec/hr.

eCFR graphic er17oc00.593.gif

View or download PDF

Note: To convert Qstd from dscm/hr (dscf/hr) to dscm/min (dscf/min), divide Qstd by 60.

12.11   Mass emission rate, mg/hr (lb/hr):

eCFR graphic er17oc00.594.gif

View or download PDF

eCFR graphic er17oc00.595.gif

View or download PDF

13.0   Method Performance

13.1   Range. The recommended working range for all of the three analytical techniques starts at five times the analytical detection limit (see also Method 306, Section 13.2.2). The upper limit of all three techniques can be extended indefinitely by appropriate dilution.

13.2   Sensitivity.

13.2.1   Analytical Sensitivity. The estimated instrumental detection limits listed are provided as a guide for an instrumental limit. The actual method detection limits are sample and instrument dependent and may vary as the sample matrix varies.

13.2.1.1   ICP Analytical Sensitivity. The minimum estimated detection limits for ICP, as reported in Method 6010A and the recently revised Method 6010B of SW-846 (Reference 1), are 7.0 µg Cr/L and 4.7 µg Cr/L, respectively.

13.2.1.2   GFAAS Analytical Sensitivity. The minimum estimated detection limit for GFAAS, as reported in Methods 7000A and 7191 of SW-846 (Reference 1), is 1.0 µg Cr/L.

13.2.1.3   IC/PCR Analytical Sensitivity. The minimum detection limit for IC/PCR with a preconcentrator, as reported in Methods 0061 and 7199 of SW-846 (Reference 1), is 0.05 µg Cr+6/L.

13.2.2   In-stack Sensitivity. The in-stack sensitivity depends upon the analytical detection limit, the volume of stack gas sampled, and the total volume of the impinger absorbing solution plus the rinses. Using the analytical detection limits given in Sections 13.2.1.1, 13.2.1.2, and 13.2.1.3; a stack gas sample volume of 1.7 dscm; and a total liquid sample volume of 500 mL; the corresponding in-stack detection limits are 0.0014 mg Cr/dscm to 0.0021 mg Cr/dscm for ICP, 0.00029 mg Cr/dscm for GFAAS, and 0.000015 mg Cr+36/dscm for IC/PCR with preconcentration.

Note: It is recommended that the concentration of Cr in the analytical solutions be at least five times the analytical detection limit to optimize sensitivity in the analyses. Using this guideline and the same assumptions for impinger sample volume and stack gas sample volume (500 mL and 1.7 dscm, respectively), the recommended minimum stack concentrations for optimum sensitivity are 0.0068 mg Cr/dscm to 0.0103 mg Cr/dscm for ICP, 0.0015 mg Cr/dscm for GFAAS, and 0.000074 mg Cr+6 dscm for IC/PCR with preconcentration. If required, the in-stack detection limits can be improved by either increasing the sampling time, the stack gas sample volume, reducing the volume of the digested sample for GFAAS, improving the analytical detection limits, or any combination of the three.

13.3   Precision.

13.3.1   The following precision data have been reported for the three analytical methods. In each case, when the sampling precision is combined with the reported analytical precision, the resulting overall precision may decrease.

13.3.2   Bias data is also reported for GFAAS.

13.4   ICP Precision.

13.4.1   As reported in Method 6010B of SW-846 (Reference 1), in an EPA round-robin Phase 1 study, seven laboratories applied the ICP technique to acid/distilled water matrices that had been spiked with various metal concentrates. For true values of 10, 50, and 150 µg Cr/L; the mean reported values were 10, 50, and 149 µg Cr/L; and the mean percent relative standard deviations were 18, 3.3, and 3.8 percent, respectively.

13.4.2   In another multilaboratory study cited in Method 6010B, a mean relative standard of 8.2 percent was reported for an aqueous sample concentration of approximately 3750 µg Cr/L.

13.5   GFAAS Precision. As reported in Method 7191 of SW-846 (Reference 1), in a single laboratory (EMSL), using Cincinnati, Ohio tap water spiked at concentrations of 19, 48, and 77 µg Cr/L, the standard deviations were ±0.1, ±0.2, and ±0.8, respectively. Recoveries at these levels were 97 percent, 101 percent, and 102 percent, respectively.

13.6   IC/PCR Precision. As reported in Methods 0061 and 7199 of SW-846 (Reference 1), the precision of IC/PCR with sample preconcentration is 5 to 10 percent; the overall precision for sewage sludge incinerators emitting 120 ng/dscm of Cr+6 and 3.5 µg/dscm of total Cr is 25 percent and 9 percent, respectively; and for hazardous waste incinerators emitting 300 ng/dscm of Cr+6 the precision is 20 percent.

14.0   Pollution Prevention

14.1   The only materials used in this method that could be considered pollutants are the chromium standards used for instrument calibration and acids used in the cleaning of the collection and measurement containers/labware, in the preparation of standards, and in the acid digestion of samples. Both reagents can be stored in the same waste container.

14.2   Cleaning solutions containing acids should be prepared in volumes consistent with use to minimize the disposal of excessive volumes of acid.

14.3   To the extent possible, the containers/vessels used to collect and prepare samples should be cleaned and reused to minimize the generation of solid waste.

15.0   Waste Management

15.1   It is the responsibility of the laboratory and the sampling team to comply with all federal, state, and local regulations governing waste management, particularly the discharge regulations, hazardous waste identification rules, and land disposal restrictions; and to protect the air, water, and land by minimizing and controlling all releases from field operations.

15.2   For further information on waste management, consult The Waste Management Manual for Laboratory Personnel and Less is Better-Laboratory Chemical Management for Waste Reduction, available from the American Chemical Society's Department of Government Relations and Science Policy, 1155 16th Street NW, Washington, DC 20036.

16.0   References

1. F.R. Clay, Memo, Impinger Collection Efficiency—Mason Jars vs. Greenburg-Smith Impingers, Dec. 1989.

2. Segall, R.R., W.G. DeWees, F.R. Clay, and J.W. Brown. Development of Screening Methods for Use in Chromium Emissions Measurement and Regulations Enforcement. In: Proceedings of the 1989 EPA/A&WMA International Symposium-Measurement of Toxic and Related Air Pollutants, A&WMA Publication VIP-13, EPA Report No. 600/9-89-060, p. 785.

3. Clay, F.R., Chromium Sampling Method. In: Proceedings of the 1990 EPA/A&WMA International Symposium-Measurement of Toxic and Related Air Pollutants, A&WMA Publication VIP-17, EPA Report No. 600/9-90-026, p. 576.

4. Clay, F.R., Proposed Sampling Method 306A for the Determination of Hexavalent Chromium Emissions from Electroplating and Anodizing Facilities. In: Proceedings of the 1992 EPA/A&WMA International Symposium-Measurement of Toxic and Related Air Pollutants, A&WMA Publication VIP-25, EPA Report No. 600/R-92/131, p. 209.

5. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, SW-846, Third Edition as amended by Updates I, II, IIA, IIB, and III. Document No. 955-001-000001. Available from Superintendent of Documents, U.S. Government Printing Office, Washington, DC, November 1986.

17.0   Tables, Diagrams, Flowcharts, and Validation Data

eCFR graphic er17oc00.596.gif

View or download PDF

eCFR graphic er17oc00.597.gif

View or download PDF

eCFR graphic er17oc00.598.gif

View or download PDF

Method 306B—Surface Tension Measurement for Tanks Used at Decorative Chromium Electroplating and Chromium Anodizing Facilities

Note: This method does not include all of the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and analytical) essential to its performance. Some material is incorporated by reference from other methods in 40 CFR Part 60, Appendix A and in this part. Therefore, to obtain reliable results, persons using this method should have a thorough knowledge of at least Methods 5 and 306.

1.0   Scope and Application

1.1   Analyte. Not applicable.

1.2   Applicability. This method is applicable to all chromium electroplating and chromium anodizing operations, and continuous chromium plating at iron and steel facilities where a wetting agent is used in the tank as the primary mechanism for reducing emissions from the surface of the plating solution.

2.0   Summary of Method

2.1   During an electroplating or anodizing operation, gas bubbles generated during the process rise to the surface of the liquid and burst. Upon bursting, tiny droplets of chromic acid become entrained in ambient air. The addition of a wetting agent to the tank bath reduces the surface tension of the liquid and diminishes the formation of these droplets.

2.2   This method determines the surface tension of the bath using a stalagmometer or a tensiometer to confirm that there is sufficient wetting agent present.

3.0   Definitions [Reserved]

4.0   Interferences [Reserved]

5.0   Safety

5.1   Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method may not address all of the safety problems associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to performing this test method.

6.0   Equipment and Supplies

6.1   Stalagmometer. Any commercially available stalagmometer or equivalent surface tension measuring device may be used to measure the surface tension of the plating or anodizing tank liquid provided the procedures specified in Section 11.1.2 are followed.

6.2   Tensiometer. A tensiometer may be used to measure the surface tension of the tank liquid provided the procedures specified in ASTM Method D 1331-89, Standard Test Methods for Surface and Interfacial Tension of Solutions of Surface Active Agents (incorporated by reference—see §63.14) are followed.

7.0   Reagents and Standards [Reserved]

8.0   Sample Collection, Sample Recovery, Sample Preservation, Sample Holding Times, Storage, and Transport [Reserved]

9.0   Quality Control [Reserved]

10.0   Calibration and Standardization [Reserved]

11.0   Analytical Procedure

11.1   Procedure. The surface tension of the tank bath may be measured using a tensiometer, stalagmometer, or any other equivalent surface tension measuring device for measuring surface tension in dynes per centimeter.

11.1.1   If a tensiometer is used, the procedures specified in ASTM Method D 1331-89 must be followed.

11.1.2   If a stalagmometer is used, the procedures specified in Sections 11.1.2.1 through 11.1.2.3 must be followed.

11.1.2.1   Check the stalagmometer for visual signs of damage. If the stalagmometer appears to be chipped, cracked, or otherwise in disrepair, the instrument shall not be used.

11.1.2.2   Using distilled or deionized water and following the procedures provided by the manufacturer, count the number of drops corresponding to the distilled/deionized water liquid volume between the upper and lower etched marks on the stalagmometer. If the number of drops for the distilled/deionized water is not within ±1 drop of the number indicated on the instrument, the stalagmometer must be cleaned, using the procedures specified in Section 11.1.3 of this method, before using the instrument to measure the surface tension of the tank liquid.

11.1.2.2.1   If the stalagmometer must be cleaned, as indicated in Section 11.1.2.2, repeat the procedure specified in Section 11.1.2.2 before proceeding.

11.1.2.2.2   If, after cleaning and performing the procedure in Section 11.1.2.2, the number of drops indicated for the distilled/deionized water is not within ±1 drop of the number indicated on the instrument, either use the number of drops corresponding to the distilled/deionized water volume as the reference number of drops, or replace the instrument.

11.1.2.3   Determine the surface tension of the tank liquid using the procedures specified by the manufacturer of the stalagmometer.

11.1.3   Stalagmometer cleaning procedures. The procedures specified in Sections 11.1.3.1 through 11.1.3.10 shall be used for cleaning a stalagmometer, as required by Section 11.1.2.2.

11.1.3.1   Set up the stalagmometer on its stand in a fume hood.

11.1.3.2   Place a clean 150 (mL) beaker underneath the stalagmometer and fill the beaker with reagent grade concentrated nitric acid.

11.1.3.3   Immerse the bottom tip of the stalagmometer (approximately 1 centimeter (0.5 inches)) into the beaker.

11.1.3.4   Squeeze the rubber bulb and pinch at the arrow up (1) position to collapse.

11.1.3.5   Place the bulb end securely on top end of stalagmometer and carefully draw the nitric acid by pinching the arrow up (1) position until the level is above the top etched line.

11.1.3.6   Allow the nitric acid to remain in stalagmometer for 5 minutes, then carefully remove the bulb, allowing the acid to completely drain.

11.1.3.7   Fill a clean 150 mL beaker with distilled or deionized water.

11.1.3.8   Using the rubber bulb per the instructions in Sections 11.1.3.4 and 11.1.3.5, rinse and drain stalagmometer with deionized or distilled water.

11.1.3.9   Fill a clean 150 mL beaker with isopropyl alcohol.

11.1.3.10   Again using the rubber bulb per the instructions in Sections 11.1.3.4 and 11.1.3.5, rinse and drain stalagmometer twice with isopropyl alcohol and allow the stalagmometer to dry completely.

11.2   Frequency of Measurements.

11.2.1   Measurements of the bath surface tension are performed using a progressive system which decreases the frequency of surface tension measurements required when the proper surface tension is maintained.

11.2.1.1   Initially, following the compliance date, surface tension measurements must be conducted once every 4 hours of tank operation for the first 40 hours of tank operation.

11.2.1.2   Once there are no exceedances during a period of 40 hours of tank operation, measurements may be conducted once every 8 hours of tank operation.

11.2.1.3   Once there are no exceedances during a second period of 40 consecutive hours of tank operation, measurements may be conducted once every 40 hours of tank operation on an on-going basis, until an exceedance occurs. The maximum time interval for measurements is once every 40 hours of tank operation.

11.2.2   If a measurement of the surface tension of the solution is above the 40 dynes per centimeter limit when measured using a stalagmometer, above 33 dynes per centimeter when measured using a tensiometer, or above an alternate surface tension limit established during the performance test, the time interval shall revert back to the original monitoring schedule of once every 4 hours. A subsequent decrease in frequency would then be allowed according to Section 11.2.1.

12.0   Data Analysis and Calculations

12.1   Log Book of Surface Tension Measurements and Fume Suppressant Additions.

12.1.1   The surface tension of the plating or anodizing tank bath must be measured as specified in Section 11.2.

12.1.2   The measurements must be recorded in the log book. In addition to the record of surface tension measurements, the frequency of fume suppressant maintenance additions and the amount of fume suppressant added during each maintenance addition must be recorded in the log book.

12.1.3   The log book will be readily available for inspection by regulatory personnel.

12.2   Instructions for Apparatus Used in Measuring Surface Tension.

12.2.1   Included with the log book must be a copy of the instructions for the apparatus used for measuring the surface tension of the plating or anodizing bath.

12.2.2   If a tensiometer is used, a copy of ASTM Method D 1331-89 must be included with the log book.

13.0   Method Performance [Reserved]

14.0   Pollution Prevention [Reserved]

15.0   Waste Management [Reserved]

16.0   References [Reserved]

17.0   Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 307—Determination of Emissions From Halogenated Solvent Vapor Cleaning Machines Using a Liquid Level Procedure

1. Applicability and Principle

1.1   Applicability. This method is applicable to the determination of the halogenated solvent emissions from solvent vapor cleaners in the idling mode.

1.2   Principle. The solvent level in the solvent cleaning machine is measured using inclined liquid level indicators. The change in liquid level corresponds directly to the amount of solvent lost from the solvent cleaning machine.

2. Apparatus

Note: Mention of trade names or specific products does not constitute endorsement by the Environmental Protection Agency.

2.1   Inclined Liquid Level Indicator. A schematic of the inclined liquid level indicators used in this method is shown in figure 307-1; two inclined liquid level indicators having 0.05 centimeters divisions or smaller shall be used. The liquid level indicators shall be made of glass, Teflon, or any similar material that will not react with the solvent being used. A 6-inch by 1-inch slope is recommended; however the slope may vary depending on the size and design of the solvent cleaning machine.

Note: It is important that the inclined liquid level indicators be constructed with ease of reading in mind. The inclined liquid level indicators should also be mounted so that they can be raised or lowered if necessary to suit the solvent cleaning machine size.

eCFR graphic ec01my92.075.gif

View or download PDF

2.2   Horizontal Indicator. Device to check the inclined liquid level indicators orientation relative to horizontal.

2.3   Velocity Meter. Hotwire and vane anemometers, or other devices capable of measuring the flow rates ranging from 0 to 15.2 meters per minute across the solvent cleaning machine.

3. Procedure

3.1   Connection of the Inclined Liquid Level Indicator. Connect one of the inclined liquid level indicators to the boiling sump drain and the other inclined liquid level indicator to the immersion sump drain using Teflon tubing and the appropriate fittings. A schematic diagram is shown in figure 307-2.

eCFR graphic ec01my92.076.gif

View or download PDF

3.2   Positioning of Velocity Meter. Position the velocity meter so that it measures the flow rate of the air passing directly across the solvent cleaning machine.

3.3   Level the Inclined Liquid Level Indicators.

3.4   Initial Inclined Liquid Level Indicator Readings. Open the sump drainage valves. Allow the solvent cleaning machine to operate long enough for the vapor zone to form and the system to stabilize (check with manufacturer). Record the inclined liquid level indicators readings and the starting time on the data sheet. A sample data sheet is provided in figure 307-3.

Date
Run
Solvent type
Solvent density, g/m3 (lb/ft3)
Length of boiling sump (SB), m (ft)
Width of boiling sump (WB), m (ft)
Length of immersion sump (SI), m (ft)
Width of immersion sump (WI), m (ft)

Length of solvent vapor/air interface (SV), m (ft) ______

Width of solvent vapor/air interface (WV), m (ft) ______

Clock timeBoiling sump readingImmersion sump readingFlow rate reading
   
   
   
   
   
   

Figure 307-3. Data sheet.

3.5   Final Inclined Liquid Level Indicator Readings. At the end of the 16-hour test run, check to make sure the inclined liquid level indicators are level; if not, make the necessary adjustments. Record the final inclined liquid level indicators readings and time.

3.6   Determination of Solvent Vapor/Air Interface Area for Each Sump. Determine the area of the solvent/air interface of the individual sumps. Whenever possible, physically measure these dimensions, rather than using factory specifications. A schematic of the dimensions of a solvent cleaning machine is provided in figure 307-4.

eCFR graphic ec01my92.077.gif

View or download PDF

4. Calculations

4.1   Nomenclature.

AB = area of boiling sump interface, m2 (ft2).

AI = area of immersion sump interface, m2 (ft2).

AV = area of solvent/air interface, m2 (ft2).

E = emission rate, kg/m2-hr (lb/ft2-hr).

K = 100,000 cm . g/m . kg for metric units.

= 12 in./ft for English units.

LBF = final boiling sump inclined liquid level indicators reading, cm (in.).

LBi = initial boiling sump inclined liquid level indicators reading, cm (in.).

LIf = final immersion sump inclined liquid level indicators reading, cm (in.).

LIi = initial immersion sump inclined liquid level indicators reading, cm (in.).

SB = length of the boiling sump, m (ft).

SI = length of the immersion sump, m (ft).

SV = length of the solvent vapor/air interface, m (ft).

WB = width of the boiling sump, m (ft).

WI = width of the immersion sump, m (ft).

WV = width of the solvent vapor/air interface, m (ft).

ρ = density of solvent, g/m3 (lb/ft3).

θ = test time, hr.

4.2   Area of Sump Interfaces. Calculate the areas of the boiling and immersion sump interfaces as follows:

AB = SB WB      Eq. 307-1

AI = SI WI      Eq. 307-2

4.3   Area of Solvent/Air Interface. Calculate the area of the solvent vapor/air interface as follows:

AV = SV WV      Eq. 307-3

4.4   Emission Rate. Calculate the emission rate as follows:

eCFR graphic er02de94.007.gif

View or download PDF

Method 308—Procedure for Determination of Methanol Emission From Stationary Sources

1.0   Scope and Application

1.1   Analyte. Methanol. Chemical Abstract Service (CAS) No. 67-56-1.

1.2   Applicability. This method applies to the measurement of methanol emissions from specified stationary sources.

2.0   Summary of Method

A gas sample is extracted from the sampling point in the stack. The methanol is collected in deionized distilled water and adsorbed on silica gel. The sample is returned to the laboratory where the methanol in the water fraction is separated from other organic compounds with a gas chromatograph (GC) and is then measured by a flame ionization detector (FID). The fraction adsorbed on silica gel is extracted with an aqueous solution of n-propanol and is then separated and measured by GC/FID.

3.0   Definitions [Reserved]

4.0   Interferences [Reserved]

5.0   Safety

5.1   Disclaimer. This method may involve hazardous materials, operations, and equipment. This test method does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this test method to establish appropriate safety and health practices and to determine the applicability of regulatory limitations before performing this test method.

5.2   Methanol Characteristics. Methanol is flammable and a dangerous fire and explosion risk. It is moderately toxic by ingestion and inhalation.

6.0   Equipment and Supplies

6.1   Sample Collection. The following items are required for sample collection:

6.1.1   Sampling Train. The sampling train is shown in Figure 308-1 and component parts are discussed below.

6.1.1.1   Probe. Teflon®, approximately 6-millimeter (mm) (0.24 inch) outside diameter.

6.1.1.2   Impinger. A 30-milliliter (ml) midget impinger. The impinger must be connected with leak-free glass connectors. Silicone grease may not be used to lubricate the connectors.

6.1.1.3   Adsorbent Tube. Glass tubes packed with the required amount of the specified adsorbent.

6.1.1.4   Valve. Needle valve, to regulate sample gas flow rate.

6.1.1.5   Pump. Leak-free diaphragm pump, or equivalent, to pull gas through the sampling train. Install a small surge tank between the pump and rate meter to eliminate the pulsation effect of the diaphragm pump on the rotameter.

6.1.1.6   Rate Meter. Rotameter, or equivalent, capable of measuring flow rate to within 2 percent of the selected flow rate of up to 1000 milliliter per minute (ml/min). Alternatively, the tester may use a critical orifice to set the flow rate.

6.1.1.7   Volume Meter. Dry gas meter (DGM), sufficiently accurate to measure the sample volume to within 2 percent, calibrated at the selected flow rate and conditions actually encountered during sampling, and equipped with a temperature sensor (dial thermometer, or equivalent) capable of measuring temperature accurately to within 3 °C (5.4 °F).

6.1.1.8   Barometer. Mercury (Hg), aneroid, or other barometer capable of measuring atmospheric pressure to within 2.5 mm (0.1 inch) Hg. See the NOTE in Method 5 (40 CFR part 60, appendix A), section 6.1.2.

6.1.1.9   Vacuum Gauge and Rotameter. At least 760-mm (30-inch) Hg gauge and 0- to 40-ml/min rotameter, to be used for leak-check of the sampling train.

6.2   Sample Recovery. The following items are required for sample recovery:

6.2.1   Wash Bottles. Polyethylene or glass, 500-ml, two.

6.2.2   Sample Vials. Glass, 40-ml, with Teflon®-lined septa, to store impinger samples (one per sample).

6.2.3   Graduated Cylinder. 100-ml size.

6.3   Analysis. The following are required for analysis:

6.3.1   Gas Chromatograph. GC with an FID, programmable temperature control, and heated liquid injection port.

6.3.2   Pump. Capable of pumping 100 ml/min. For flushing sample loop.

6.3.3   Flow Meter. To monitor accurately sample loop flow rate of 100 ml/min.

6.3.4   Regulators. Two-stage regulators used on gas cylinders for GC and for cylinder standards.

6.3.5   Recorder. To record, integrate, and store chromatograms.

6.3.6   Syringes. 1.0- and 10-microliter (l) size, calibrated, for injecting samples.

6.3.7   Tubing Fittings. Stainless steel, to plumb GC and gas cylinders.

6.3.8   Vials. Two 5.0-ml glass vials with screw caps fitted with Teflon®-lined septa for each sample.

6.3.9   Pipettes. Volumetric type, assorted sizes for preparing calibration standards.

6.3.10   Volumetric Flasks. Assorted sizes for preparing calibration standards.

6.3.11   Vials. Glass 40-ml with Teflon®-lined septa, to store calibration standards (one per standard).

7.0   Reagents and Standards

Note: Unless otherwise indicated, all reagents must conform to the specifications established by the Committee on Analytical Reagents of the American Chemical Society. Where such specifications are not available, use the best available grade.

7.1   Sampling. The following are required for sampling:

7.1.1   Water. Deionized distilled to conform to the American Society for Testing and Materials (ASTM) Specification D 1193-77, Type 3. At the option of the analyst, the potassium permanganate (KMnO4) test for oxidizable organic matter may be omitted when high concentrations of organic matter are not expected to be present.

7.1.2   Silica Gel. Deactivated chromatographic grade 20/40 mesh silica gel packed in glass adsorbent tubes. The silica gel is packed in two sections. The front section contains 520 milligrams (mg) of silica gel, and the back section contains 260 mg.

7.2   Analysis. The following are required for analysis:

7.2.1   Water. Same as specified in section 7.1.1.

7.2.2   n-Propanol, 3 Percent. Mix 3 ml of n-propanol with 97 ml of water.

7.2.3   Methanol Stock Standard. Prepare a methanol stock standard by weighing 1 gram of methanol into a 100-ml volumetric flask. Dilute to 100 ml with water.

7.2.3.1   Methanol Working Standard. Prepare a methanol working standard by pipetting 1 ml of the methanol stock standard into a 100-ml volumetric flask. Dilute the solution to 100 ml with water.

7.2.3.2   Methanol Standards For Impinger Samples. Prepare a series of methanol standards by pipetting 1, 2, 5, 10, and 25 ml of methanol working standard solution respectively into five 50-ml volumetric flasks. Dilute the solutions to 50 ml with water. These standards will have 2, 4, 10, 20, and 50 µg/ml of methanol, respectively. After preparation, transfer the solutions to 40-ml glass vials capped with Teflon® septa and store the vials under refrigeration. Discard any excess solution.

7.2.3.3   Methanol Standards for Adsorbent Tube Samples. Prepare a series of methanol standards by first pipetting 10 ml of the methanol working standard into a 100-ml volumetric flask and diluting the contents to exactly 100 ml with 3 percent n-propanol solution. This standard will contain 10 µg/ml of methanol. Pipette 5, 15, and 25 ml of this standard, respectively, into four 50-ml volumetric flasks. Dilute each solution to 50 ml with 3 percent n-propanol solution. These standards will have 1, 3, and 5 µg/ml of methanol, respectively. Transfer all four standards into 40-ml glass vials capped with Teflon®-lined septa and store under refrigeration. Discard any excess solution.

7.2.4   GC Column. Capillary column, 30 meters (100 feet) long with an inside diameter (ID) of 0.53 mm (0.02 inch), coated with DB 624 to a film thickness of 3.0 micrometers, (µm) or an equivalent column. Alternatively, a 30-meter capillary column coated with polyethylene glycol to a film thickness of 1 µm such as AT-WAX or its equivalent.

7.2.5   Helium. Ultra high purity.

7.2.6   Hydrogen. Zero grade.

7.2.7   Oxygen. Zero grade.

8.0   Procedure

8.1   Sampling. The following items are required for sampling:

8.1.1   Preparation of Collection Train. Measure 20 ml of water into the midget impinger. The adsorbent tube must contain 520 mg of silica gel in the front section and 260 mg of silica gel in the backup section. Assemble the train as shown in Figure 308-1. An optional, second impinger that is left empty may be placed in front of the water-containing impinger to act as a condensate trap. Place crushed ice and water around the impinger.

eCFR graphic er15ap98.014.gif

View or download PDF

8.1.2   Leak Check. A leak check prior to the sampling run is optional; however, a leak check after the sampling run is mandatory. The leak-check procedure is as follows:

Temporarily attach a suitable (e.g., 0-to 40-ml/min) rotameter to the outlet of the DGM, and place a vacuum gauge at or near the probe inlet. Plug the probe inlet, pull a vacuum of at least 250 mm (10 inch) Hg, and note the flow rate as indicated by the rotameter. A leakage rate not in excess of 2 percent of the average sampling rate is acceptable.

Note: Carefully release the probe inlet plug before turning off the pump.

8.1.3   Sample Collection. Record the initial DGM reading and barometric pressure. To begin sampling, position the tip of the Teflon® tubing at the sampling point, connect the tubing to the impinger, and start the pump. Adjust the sample flow to a constant rate between 200 and 1000 ml/min as indicated by the rotameter. Maintain this constant rate (±10 percent) during the entire sampling run. Take readings (DGM, temperatures at DGM and at impinger outlet, and rate meter) at least every 5 minutes. Add more ice during the run to keep the temperature of the gases leaving the last impinger at 20 °C (68 °F) or less. At the conclusion of each run, turn off the pump, remove the Teflon® tubing from the stack, and record the final readings. Conduct a leak check as in section 8.1.2. (This leak check is mandatory.) If a leak is found, void the test run or use procedures acceptable to the Administrator to adjust the sample volume for the leakage.

8.2   Sample Recovery. The following items are required for sample recovery:

8.2.1   Impinger. Disconnect the impinger. Pour the contents of the midget impinger into a graduated cylinder. Rinse the midget impinger and the connecting tubes with water, and add the rinses to the graduated cylinder. Record the sample volume. Transfer the sample to a glass vial and cap with a Teflon® septum. Discard any excess sample. Place the samples in an ice chest for shipment to the laboratory.

8.2.2.   Adsorbent Tubes. Seal the silica gel adsorbent tubes and place them in an ice chest for shipment to the laboratory.

9.0   Quality Control

9.1   Miscellaneous Quality Control Measures. The following quality control measures are required:

SectionQuality control measureEffect
8.1.2, 8.1.3, 10.1Sampling equipment leak check and calibrationEnsures accurate measurement of sample volume.
10.2GC calibrationEnsures precision of GC analysis.

10.0   Calibration and Standardization

10.1   Metering System. The following items are required for the metering system:

10.1.1   Initial Calibration.

10.1.1.1   Before its initial use in the field, first leak-check the metering system (drying tube, needle valve, pump, rotameter, and DGM) as follows: Place a vacuum gauge at the inlet to the drying tube, and pull a vacuum of 250 mm (10 inch) Hg; plug or pinch off the outlet of the flow meter, and then turn off the pump. The vacuum shall remain stable for at least 30 seconds. Carefully release the vacuum gauge before releasing the flow meter end.

10.1.1.2   Next, remove the drying tube, and calibrate the metering system (at the sampling flow rate specified by the method) as follows: Connect an appropriately sized wet test meter (e.g., 1 liter per revolution (0.035 cubic feet per revolution)) to the inlet of the drying tube. Make three independent calibrations runs, using at least five revolutions of the DGM per run. Calculate the calibration factor, Y (wet test meter calibration volume divided by the DGM volume, both volumes adjusted to the same reference temperature and pressure), for each run, and average the results. If any Y-value deviates by more than 2 percent from the average, the metering system is unacceptable for use. Otherwise, use the average as the calibration factor for subsequent test runs.

10.1.2   Posttest Calibration Check. After each field test series, conduct a calibration check as in section 10.1.1 above, except for the following variations: (a) The leak check is not to be conducted, (b) three, or more revolutions of the DGM may be used, and (c) only two independent runs need be made. If the calibration factor does not deviate by more than 5 percent from the initial calibration factor (determined in section 10.1.1), then the DGM volumes obtained during the test series are acceptable. If the calibration factor deviates by more than 5 percent, recalibrate the metering system as in section 10.1.1, and for the calculations, use the calibration factor (initial or recalibration) that yields the lower gas volume for each test run.

10.1.3   Temperature Sensors. Calibrate against mercury-in-glass thermometers. An alternative mercury-free thermometer may be used if the thermometer is, at a minimum, equivalent in terms of performance or suitably effective for the specific temperature measurement application.

10.1.4   Rotameter. The rotameter need not be calibrated, but should be cleaned and maintained according to the manufacturer's instruction.

10.1.5   Barometer. Calibrate against a mercury barometer.

10.2   Gas Chromatograph. The following procedures are required for the gas chromatograph:

10.2.1   Initial Calibration. Inject 1 µl of each of the standards prepared in sections 7.2.3.3 and 7.2.3.4 into the GC and record the response. Repeat the injections for each standard until two successive injections agree within 5 percent. Using the mean response for each calibration standard, prepare a linear least squares equation relating the response to the mass of methanol in the sample. Perform the calibration before analyzing each set of samples.

10.2.2   Continuing Calibration. At the beginning of each day, analyze the mid level calibration standard as described in section 10.5.1. The response from the daily analysis must agree with the response from the initial calibration within 10 percent. If it does not, the initial calibration must be repeated.

11.0   Analytical Procedure

11.1   Gas Chromatograph Operating Conditions. The following operating conditions are required for the GC:

11.1.1   Injector. Configured for capillary column, splitless, 200 °C (392 °F).

11.1.2   Carrier. Helium at 10 ml/min.

11.1.3   Oven. Initially at 45 °C for 3 minutes; then raise by 10 °C to 70 °C; then raise by 70 °C/min to 200 °C.

11.2   Impinger Sample. Inject 1 µl of the stored sample into the GC. Repeat the injection and average the results. If the sample response is above that of the highest calibration standard, either dilute the sample until it is in the measurement range of the calibration line or prepare additional calibration standards. If the sample response is below that of the lowest calibration standard, prepare additional calibration standards. If additional calibration standards are prepared, there shall be at least two that bracket the response of the sample. These standards should produce approximately 50 percent and 150 percent of the response of the sample.

11.3   Silica Gel Adsorbent Sample. The following items are required for the silica gel adsorbent samples:

11.3.1   Preparation of Samples. Extract the front and backup sections of the adsorbent tube separately. With a file, score the glass adsorbent tube in front of the first section of silica gel. Break the tube open. Remove and discard the glass wool. Transfer the first section of the silica gel to a 5-ml glass vial and stopper the vial. Remove the spacer between the first and second section of the adsorbent tube and discard it. Transfer the second section of silica gel to a separate 5-ml glass vial and stopper the vial.

11.3.2   Desorption of Samples. Add 3 ml of the 10 percent n-propanol solution to each of the stoppered vials and shake or vibrate the vials for 30 minutes.

11.3.3   Inject a 1-µl aliquot of the diluted sample from each vial into the GC. Repeat the injection and average the results. If the sample response is above that of the highest calibration standard, either dilute the sample until it is in the measurement range of the calibration line or prepare additional calibration standards. If the sample response is below that of the lowest calibration standard, prepare additional calibration standards. If additional calibration standards are prepared, there shall be at least two that bracket the response of the sample. These standards should produce approximately 50 percent and 150 percent of the response of the sample.

12.0   Data Analysis and Calculations

12.1   Nomenclature.

Caf = Concentration of methanol in the front of the adsorbent tube, µg/ml.

Cab = Concentration of methanol in the back of the adsorbent tube, µg/ml.

Ci = Concentration of methanol in the impinger portion of the sample train, µg/ml.

E=Mass emission rate of methanol, µg/hr (lb/hr).

Mtot = Total mass of methanol collected in the sample train, µg.

Pbar = Barometric pressure at the exit orifice of the DGM, mm Hg (in. Hg).

Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).

Qstd = Dry volumetric stack gas flow rate corrected to standard conditions, dscm/hr (dscf/hr).

Tm = Average DGM absolute temperature, degrees K (°R).

Tstd = Standard absolute temperature, 293 degrees K (528 °R).

Vaf = Volume of front half adsorbent sample, ml.

Vab = Volume of back half adsorbent sample, ml.

Vi = Volume of impinger sample, ml.

Vm = Dry gas volume as measured by the DGM, dry cubic meters (dcm), dry cubic feet (dcf).

Vm(std) = Dry gas volume measured by the DGM, corrected to standard conditions, dry standard cubic meters (dscm), dry standard cubic feet (dscf).

12.2   Mass of Methanol. Calculate the total mass of methanol collected in the sampling train using Equation 308-1.

eCFR graphic er15ap98.015.gif

View or download PDF

12.3   Dry Sample Gas Volume, Corrected to Standard Conditions. Calculate the volume of gas sampled at standard conditions using Equation 308-2.

eCFR graphic er15ap98.016.gif

View or download PDF

12.4   Mass Emission Rate of Methanol. Calculate the mass emission rate of methanol using Equation 308-3.

eCFR graphic er15ap98.017.gif

View or download PDF

13.0   Method Performance [Reserved]

14.0   Pollution Prevention [Reserved]

15.0   Waste Management [Reserved]

16.0   Bibliography

1. Rom, J.J. “Maintenance, Calibration, and Operation of Isokinetic Source Sampling Equipment.” Office of Air Programs, Environmental Protection Agency. Research Triangle Park, NC. APTD-0576 March 1972.

2. Annual Book of ASTM Standards. Part 31; Water, Atmospheric Analysis. American Society for Testing and Materials. Philadelphia, PA. 1974. pp. 40-42.

3. Westlin, P.R. and R.T. Shigehara. “Procedure for Calibrating and Using Dry Gas Volume Meters as Calibration Standards.” Source Evaluation Society Newsletter. 3(1) :17-30. February 1978.

4. Yu, K.K. “Evaluation of Moisture Effect on Dry Gas Meter Calibration.” Source Evaluation Society Newsletter. 5(1) :24-28. February 1980.

5. NIOSH Manual of Analytical Methods, Volume 2. U.S. Department of Health and Human Services National Institute for Occupational Safety and Health. Center for Disease Control. 4676 Columbia Parkway, Cincinnati, OH 45226. (available from the Superintendent of Documents, Government Printing Office, Washington, DC 20402.)

6. Pinkerton, J.E. “Method for Measuring Methanol in Pulp Mill Vent Gases.” National Council of the Pulp and Paper Industry for Air and Stream Improvement, Inc., New York, NY.

17.0   Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 310A—Determination of Residual Hexane Through Gas Chromatography

1.0   Scope and Application

1.1   This method is used to analyze any crumb rubber or water samples for residual hexane content.

1.2   The sample is heated in a sealed bottle with an internal standard and the vapor is analyzed by gas chromatography.

2.0   Summary of Method

2.1   This method, utilizing a capillary column gas chromatograph with a flame ionization detector, determines the concentration of residual hexane in rubber crumb samples.

3.0   Definitions

3.1   The definitions are included in the text as needed.

4.0   Interferences

4.1   There are no known interferences.

5.0   Safety

5.1   It is the responsibility of the user of this procedure to establish safety and health practices applicable to their specific operation.

6.0   Equipment and Supplies

6.1   Gas Chromatograph with a flame ionization detector and data handling station equipped with a capillary column 30 meters long.

6.2   Chromatograph conditions for Sigma 1:

6.2.1   Helium pressure: 50# inlet A, 14# aux

6.2.2   Carrier flow: 25 cc/min

6.2.3   Range switch: 100x

6.2.4   DB: 1 capillary column

6.3   Chromatograph conditions for Hewlett-Packard GC:

6.3.1   Initial temperature: 40 °C

6.3.2   Initial time: 8 min

6.3.3   Rate: 0

6.3.4   Range: 2

6.3.5   DB: 1705 capillary column

6.4   Septum bottles and stoppers

6.5   Gas Syringe—0.5 cc

7.0   Reagents and Standards

7.1   Chloroform, 99.9+%, A.S.C. HPLC grade

8.0   Sample Collection, Preservation, and Storage

8.1   A representative sample should be caught in a clean 8 oz. container with a secure lid.

8.2   The container should be labeled with sample identification, date and time.

9.0   Quality Control

9.1   The instrument is calibrated by injecting calibration solution (Section 10.2 of this method) five times.

9.2   The retention time for components of interest and relative response of monomer to the internal standard is determined.

9.3   Recovery efficiency must be determined once for each sample type and whenever modifications are made to the method.

9.3.1   Determine the percent hexane in three separate dried rubber crumb samples.

9.3.2   Weigh a portion of each crumb sample into separate sample bottles and add a known amount of hexane (10 microliters) by microliter syringe and 20 microliters of internal standard. Analyze each by the described procedure and calculate the percent recovery of the known added hexane.

9.3.3   Repeat the previous step using twice the hexane level (20 microliters), analyze and calculate the percent recovery of the known added hexane.

9.3.4   Set up two additional sets of samples using 10 microliters and 20 microliters of hexane as before, but add an amount of water equal to the dry crumb used. Analyze and calculate percent recovery to show the effect of free water on the results obtained.

9.3.5   A value of R between 0.70 and 1.30 is acceptable.

9.3.6   R shall be used to correct all reported results for each compound by dividing the measured results of each compound by the R for that compound for the same sample type.

10.0   Calibration and Instrument Settings

10.1   Calibrate the chromatograph using a standard made by injecting 10 µl of fresh hexane and 20 µl of chloroform into a sealed septum bottle. This standard will be 0.6 wt.% total hexane based on 1 gram of dry rubber.

10.2   Analyze the hexane used and calculate the percentage of each hexane isomer (2-methylpentane, 3-methylpentane, n-hexane, and methylcyclo-pentane). Enter these percentages into the method calibration table.

10.3   Heat the standard bottle for 30 minutes in a 105 °C oven.

10.4   Inject about 0.25 cc of vapor into the gas chromatograph and after the analysis is finished, calibrate according to the procedures described by the instrument manufacturer.

11.0   Procedure

11.1   Using a cold mill set at a wide roller gap (125-150 mm), mill about 250 grams of crumb two times to homogenize the sample.

11.2   Weigh about 2 grams of wet crumb into a septum bottle and cap with a septum ring. Add 20 µl of chloroform with a syringe and place in a 105 °C oven for 45 minutes.

11.3   Run the moisture content on a separate portion of the sample and calculate the grams of dry rubber put into the septum bottle.

11.4   Set up the data station on the required method and enter the dry rubber weight in the sample weight field.

11.5   Inject a 0.25 cc vapor sample into the chromatograph and push the start button.

11.6   At the end of the analysis, the data station will print a report listing the concentration of each identified component.

11.7   To analyze water samples, pipet 5 ml of sample into the septum bottle, cap and add 20 µl of chloroform. Place in a 105 °C oven for 30 minutes.

11.8   Enter 5 grams into the sample weight field.

11.9   Inject a 0.25 cc vapor sample into the chromatograph and push the start button.

11.10   At the end of the analysis, the data station will print a report listing the concentration of each identified component.

12.0   Data Analysis and Calculation

12.1   For samples that are prepared as in section 11 of this method, ppm n-hexane is read directly from the computer.

12.2   The formulas for calculation of the results are as follows:

ppmhexane = (Ahexane×Rhexane)/(Ais×Ris)

Where:

Ahexane = area of hexane

Rhexane = response of hexane

Ais = area of the internal standard

Ris = response of the internal standard

% hexane in crumb=(ppmhexane/sample amount)100

12.3   Correct the results by the value of R (as determined in sections 9.3.4, 9.3.5, and 9.3.6 of this method).

13.0   Method Performance

13.1   The test has a standard deviation of 0.14 wt% at 0.66 wt% hexane. Spike recovery of 12 samples at two levels of hexane averaged 102.3%. Note: Recovery must be determined for each type of sample. The values given here are meant to be examples of method performance.

14.0   Pollution Prevention

14.1   Waste generation should be minimized where possible. Sample size should be an amount necessary to adequately run the analysis.

15.0   Waste Management

15.1   All waste shall be handled in accordance with federal and state environmental regulations.

16.0   References and Publications

16.1   DSM Copolymer Test Method T-3380.

Method 310B—Determination of Residual Hexane Through Gas Chromatography

1.0   Scope and Application

AnalyteCAS No.MatrixMethod sensitivity (5.5g sample size)
Hexane110-54-3Rubber crumb.01 wt%.
Applicable TermonomerRubber crumb.001 wt%.

1.1   Data Quality Objectives:

In the production of ethylene-propylene terpolymer crumb rubber, the polymer is recovered from solution by flashing off the solvent with steam and hot water. The resulting water-crumb slurry is then pumped to the finishing units. Certain amounts of solvent (hexane being the most commonly used solvent) and diene monomer remain in the crumb. The analyst uses the following procedure to determine those amounts.

2.0   Summary of Method

2.1   The crumb rubber sample is dissolved in toluene to which heptane has been added as an internal standard. Acetone is then added to this solution to precipitate the crumb, and the supernatant is analyzed for hexane and diene by a gas chromatograph equipped with a flame ionization detector (FID).

3.0   Definitions

3.1   Included in text as needed.

4.0   Interferences

4.1   None known.

4.2   Benzene, introduced as a contaminant in the toluene solvent, elutes between methyl cyclopentane and cyclohexane. However, the benzene peak is completely resolved.

4.3   2,2-dimethyl pentane, a minor component of the hexane used in our process, elutes just prior to methyl cyclopentane. It is included as “hexane” in the analysis whether it is integrated separately or included in the methyl cyclopentane peak.

5.0   Safety

5.1   This procedure does not purport to address all of the safety concerns associated with its use. It is the responsibility of the user of this procedure to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

5.2   Chemicals used in this analysis are flammable and hazardous (see specific toxicity information below). Avoid contact with sources of ignition during sample prep. All handling should be done beneath a hood. Playtex or nitrile gloves recommended.

5.3   Hexane is toxic by ingestion and inhalation. Vapor inhalation causes irritation of nasal and respiratory passages, headache, dizziness, nausea, central nervous system depression. Chronic overexposure can cause severe nerve damage. May cause irritation on contact with skin or eyes. May cause damage to kidneys.

5.4   Termonomer may be harmful by inhalation, ingestion, or skin absorption. Vapor or mist is irritating to the eyes, mucous membranes, and upper respiratory tract. Causes skin irritation.

5.5   Toluene is harmful or fatal if swallowed. Vapor harmful if inhaled. Symptoms: headache, dizziness, hallucinations, distorted perceptions, changes in motor activity, nausea, diarrhea, respiratory irritation, central nervous system depression, unconsciousness, liver, kidney and lung damage. Contact can cause severe eye irritation. May cause skin irritation. Causes irritation of eyes, nose, and throat.

5.6   Acetone, at high concentrations or prolonged overexposure, may cause headache, dizziness, irritation of eyes and respiratory tract, loss of strength, and narcosis. Eye contact causes severe irritation; skin contact may cause mild irritation. Concentrations of 20,000 ppm are immediately dangerous to life and health.

5.7   Heptane is harmful if inhaled or swallowed. May be harmful if absorbed through the skin. Vapor or mist is irritating to the eyes, mucous membranes, and upper respiratory tract. Prolonged or repeated exposure to skin causes defatting and dermatitis.

5.8   The steam oven used to dry the polymer in this procedure is set at 110 °C. Wear leather gloves when removing bottles from the oven.

6.0   Equipment and Supplies

6.1   4000-ml volumetric flask

6.2   100-ml volumetric pipette

6.3   1000-ml volumetric flask

6.4   8-oz. French Square sample bottles with plastic-lined caps

6.5   Top-loading balance

6.6   Laboratory shaker

6.7   Laboratory oven set at 110 °C (steam oven)

6.8   Gas chromatograph, Hewlett-Packard 5890A, or equivalent, interfaced with HP 7673A (or equivalent) autosampler (equipped with nanoliter adapter and robotic arm), and HP 3396 series II or 3392A (or equivalent) integrator/controller.

6.9   GC column, capillary type, 50m × 0.53mm, methyl silicone, 5 micron film thickness, Quadrex, or equivalent.

6.10   Computerized data acquisition system, such as CIS/CALS

6.11   Crimp-top sample vials and HP p/n 5181-1211 crimp caps, or screw-top autosampler vials and screw tops.

6.12   Glass syringes, 5-ml, with “Luer-lock” fitting

6.13   Filters, PTFE, .45 µm pore size, Gelman Acrodisc or equivalent, to fit on Luer-lock syringes (in 6.12, above).

7.0   Reagents and Standards

7.1   Reagent toluene, EM Science Omnisolv (or equivalent)

Purity Check: Prior to using any bottle of reagent toluene, analyze it according to section 11.2 of this method. Use the bottle only if hexane, heptane, and termonomer peak areas are less than 15 each (note that an area of 15 is equivalent to less than 0.01 wt% in a 10g sample).

7.2   Reagent acetone, EM Science Omnisolv HR-GC (or equivalent)

Purity Check: Prior to using any bottle of reagent acetone, analyze it according to section 11.2 of this method. Use the bottle only if hexane, heptane, and termonomer peak areas are less than 15 each.

7.3   Reagent heptane, Aldrich Chemical Gold Label, Cat #15,487-3 (or equivalent)

Purity Check: Prior to using any bottle of reagent heptane, analyze it according to section 11.2 of this method. Use the bottle only if hexane and termonomer peak areas are less than 5 each.

7.4   Internal standard solution—used as a concentrate for preparation of the more dilute Polymer Dissolving Solution. It contains 12.00g heptane/100ml of solution which is 120.0g per liter.

Preparation of internal standard solution (polymer dissolving stock solution):

ActionNotes
7.4.1   Tare a clean, dry 1-liter volumetric flask on the balance. Record the weight to three placesIf the 1-liter volumetric flask is too tall to fit in the balance case, you can shield the flask from drafts by inverting a paint bucket with a hole cut in the bottom over the balance cover. Allow the neck of the flask to project through the hole in the bucket.
7.4.2   Weigh 120.00 g of n-heptane into the flask. Record the total weight of the flask and heptane as well as the weight of heptane addedUse 99+% n-heptane from Aldrich or Janssen Chimica.
7.4.3   Fill the flask close to the mark with toluene, about 1 to 2 below the markUse EM Science Omnisolve toluene, Grade TX0737-1, or equivalent.
7.4.4   Shake the flask vigorously to mix the contentsAllow any bubbles to clear before proceeding to the next step.
7.4.5   Top off the flask to the mark with toluene. Shake vigorously, as in section 7.4.4 of this method, to mix well
7.4.6   Weigh the flask containing the solution on the three place balance record the weight
7.4.7 Transfer the contents of the flask to a 1 qt Boston round bottleDiscard any excess solution
7.4.8   Label the bottle with the identity of the contents, the weights of heptane and toluene used, the date of preparation and the preparer's nameBe sure to include the words “Hexane in Crumb Polymer Dissolving Stock Solution” on the label.
7.4.9   Refrigerate the completed blend for the use of the routine Technicians

7.5   Polymer Dissolving Solution (“PDS”)—Heptane (as internal standard) in toluene. This solution contains 0.3g of heptane internal standard per 100 ml of solution.

7.5.1   Preparation of Polymer Dissolving Solution. Fill a 4,000-ml volumetric flask about 34 full with toluene.

7.5.2   Add 100 ml of the internal standard solution (section 7.4 of this method) to the flask using the 100ml pipette.

7.5.3   Fill the flask to the mark with toluene. Discard any excess.

7.5.4   Add a large magnetic stirring bar to the flask and mix by stirring.

7.5.5   Transfer the polymer solvent solution to the one-gallon labeled container with 50ml volumetric dispenser attached.

7.5.6   Purity Check: Analyze according to section 11.2. NOTE: You must “precipitate” the sample with an equal part of acetone (thus duplicating actual test conditions—see section 11.1 of this method, sample prep) before analyzing. Analyze the reagent 3 times to quantify the C6 and termonomer interferences. Inspect the results to ensure good agreement among the three runs (within 10%).

7.5.7   Tag the bottle with the following information:

   POLYMER DISSOLVING SOLUTION FOR C6 IN CRUMB ANALYSIS

   PREPARER'S NAME

   DATE

   CALS FILE ID'S OF THE THREE ANALYSES FOR PURITY (from section 7.5.6 of this method)

7.6   Quality Control Solution: the quality control solution is prepared by adding specific amounts of mixed hexanes (barge hexane), n-nonane and termonomer to some polymer dissolving solution. Nonane elutes in the same approximate time region as termonomer and is used to quantify in that region because it has a longer shelf life. Termonomer, having a high tendency to polymerize, is used in the QC solution only to ensure that both termonomer isomers elute at the proper time.

First, a concentrated stock solution is prepared; the final QC solution can then be prepared by diluting the stock solution.

7.6.1   In preparation of stock solution, fill a 1-liter volumetric flask partially with polymer dissolving solution (PDS)—see section 7.5 of this method. Add 20.0 ml barge hexane, 5.0 ml n-nonane, and 3 ml termonomer. Finish filling the volumetric to the mark with PDS.

7.6.2   In preparation of quality control solution, dilute the quality control stock solution (above) precisely 1:10 with PDS, i.e. 10 ml of stock solution made up to 100 ml (volumetric flask) with PDS. Pour the solution into a 4 oz. Boston round bottle and store in the refrigerator.

8.0   Sample Collection, Preservation and Storage

8.1   Line up facility to catch crumb samples. The facility is a special facility where the sample is drawn.

8.1.1   Ensure that the cock valve beneath facility is closed.

8.1.2   Line up the system from the slurry line cock valve to the cock valve at the nozzle on the stripper.

8.1.3   Allow the system to flush through facility for a period of 30 seconds.

8.2   Catch a slurry crumb sample.

8.2.1   Simultaneously close the cock valves upstream and downstream of facility.

8.2.2   Close the cock valve beneath the slurry line in service.

8.2.3   Line up the cooling tower water through the sample bomb water jacket to the sewer for a minimum of 30 minutes.

8.2.4   Place the sample catching basket beneath facility and open the cock valve underneath the bomb to retrieve the rubber crumb.

8.2.5   If no rubber falls by gravity into the basket, line up nitrogen to the bleeder upstream of the sample bomb and force the rubber into the basket.

8.2.6   Close the cock valve underneath the sample bomb.

8.3   Fill a plastic “Whirl-pak” sample bag with slurry crumb and send it to the lab immediately.

8.4   Once the sample reaches the lab, it should be prepped as soon as possible to avoid hexane loss through evaporation. Samples which have lain untouched for more than 30 minutes should be discarded.

9.0   Quality Control

Quality control is monitored via a computer program that tracks analyses of a prepared QC sample (from section 7.6.2 of this method). The QC sample result is entered daily into the program, which plots the result as a data point on a statistical chart. If the data point does not satisfy the “in-control” criteria (as defined by the lab quality facilitator), an “out-of-control” flag appears, mandating corrective action.

In addition, the area of the n-heptane peak is monitored so that any errors in making up the polymer dissolving solution will be caught and corrected. Refer to section 12.4 of this method.

9.1   Fill an autosampler vial with the quality control solution (from section 7.6.2 of this method) and analyze on the GC as normal (per section 11 of this method).

9.2   Add the concentrations of the 5 hexane isomers as they appear on the CALS printout. Also include the 2,2-dimethyl-pentane peak just ahead of the methyl cyclopentane (the fourth major isomer) peak in the event that the peak integration split this peak out. Do not include the benzene peak in the sum. Note the nonane concentration. Record both results (total hexane and nonane) in the QC computer program. If out of control, and GC appears to be functioning within normal parameters, reanalyze a fresh control sample. If the fresh QC is not in control, check stock solution for contaminants or make up a new QC sample with the toluene currently in use. If instrument remains out-of-control, more thorough GC troubleshooting may be needed.

Also, verify that the instrument has detected both isomers of termonomer (quantification not necessary—see section 7.0 of this method).

9.3   Recovery efficiency must be determined for high ethylene concentration, low ethylene concentration, E-P terpolymer, or oil extended samples and whenever modifications are made to the method. Recovery shall be between 70 and 130 percent. All test results must be corrected by the recovery efficiency value (R).

9.3.1   Approximately 10 grams of wet EPDM crumb (equivalent to about 5 grams of dry rubber) shall be added to six sample bottles containing 100 ml of hexane in crumb polymer dissolving solution (toluene containing 0.3 gram n-heptane/100 ml solution). The polymer shall be dissolved by agitating the bottles on a shaker for 4 hours. The polymer shall be precipitated using 100 ml acetone.

9.3.2   The supernatant liquid shall be decanted from the polymer. Care shall be taken to remove as much of the liquid phase from the sample as possible to minimize the effect of retained liquid phase upon the next cycle of the analysis. The supernatant liquid shall be analyzed by gas chromatography using an internal standard quantitation method with heptane as the internal standard.

9.3.3   The precipitated polymer from the steps described above shall be redissolved using toluene as the solvent. No heptane shall be added to the sample in the second dissolving step. The toluene solvent and acetone precipitant shall be determined to be free of interfering compounds.

9.3.4   The rubber which was dissolved in the toluene shall be precipitated with acetone as before, and the supernatant liquid decanted from the precipitated polymer. The liquid shall be analyzed by gas chromatography and the rubber phase dried in a steam-oven to determine the final polymer weight.

9.3.5   The ratios of the areas of the hexane peaks and of the heptane internal standard peak shall be calculated for each of the six samples in the two analysis cycles outlined above. The area ratios of the total hexane to heptane (R1) shall be determined for the two analysis cycles of the sample set. The ratio of the values of R1 from the second analysis cycle to the first cycle shall be determined to give a second ratio (R2).

10.0   Calibration and Standardization

The procedure for preparing a Quality Control sample with the internal standard in it is outlined in section 7.6 of this method.

10.1   The relative FID response factors for n-heptane, the internal standard, versus the various hexane isomers and termonomer are relatively constant and should seldom need to be altered. However Baseline construction is a most critical factor in the production of good data. For this reason, close attention should be paid to peak integration. Procedures for handling peak integration will depend upon the data system used.

10.2   If recalibration of the analysis is needed, make up a calibration blend of the internal standard and the analytes as detailed below and analyze it using the analytical method used for the samples.

10.2.1   Weigh 5 g heptane into a tared scintillation vial to five places.

10.2.2   Add 0.2 ml termonomer to the vial and reweigh.

10.2.3   Add 0.5 ml hexane to the vial and reweigh.

10.2.4   Cap, and shake vigorously to mix.

10.2.5   Calculate the weights of termonomer and of hexane added and divide their weights by the weight of the n-heptane added. The result is the known of given value for the calibration.

10.2.6   Add 0.4 ml of this mixture to a mixture of 100 ml toluene and 100 ml of acetone. Cap and shake vigorously to mix.

10.2.7   Analyze the sample.

10.2.8   Divide the termonomer area and the total areas of the hexane peaks by the n-heptane area. This result is the “found” value for the calibration.

10.2.9   Divide the appropriate “known” value from 10.2.5 by the found value from 10.2.8. The result is the response factor for the analyte in question. Previous work has shown that the standard deviation of the calibration method is about 1% relative.

11.0   Procedure

11.1   SAMPLE PREPARATION

11.1.1   Tare an 8oz sample bottle—Tag attached, cap off; record weight and sample ID on tag in pencil.

11.1.2   Place crumb sample in bottle: RLA-3: 10 g (gives a dry wt. of 5.5 g).

11.1.3   Dispense 100ml of PDS into each bottle. SAMPLE SHOULD BE PLACED INTO SOLUTION ASAP TO AVOID HEXANE LOSS—Using “Dispensette” pipettor. Before dispensing, “purge” the dispensette (25% of its volume) into a waste bottle to eliminate any voids.

11.1.4   Tightly cap bottles and load samples into shaker.

11.1.5   Insure that “ON-OFF” switch on the shaker itself is “ON.”

11.1.6   Locate shaker timer. Insure that toggle switch atop timer control box is in the middle (“off”) position. If display reads “04:00” (4 hours), move toggle switch to the left position. Shaker should begin operating.

11.1.7   After shaker stops, add 100 ml acetone to each sample to precipitate polymer. Shake minimum of 5 minutes on shaker—Vistalon sample may not have fully dissolved; nevertheless, for purposes of consistency, 4 hours is the agreed-upon dissolving time.

11.1.8   Using a 5-ml glass Luer-lock syringe and Acrodisc filter, filter some of the supernatant liquid into an autosampler vial; crimp the vial and load it into the GC autosampler for analysis (section 11.2 of this method)—The samples are filtered to prevent polymer buildup in the GC. Clean the syringes in toluene.

11.1.9   Decant remaining supernatant into a hydrocarbon waste sink, being careful not to discard any of the polymer. Place bottle of precipitate into the steam oven and dry for six hours—Some grades of Vistalon produce very small particles in the precipitate, thus making complete decanting impossible without discarding some polymer. In this case, decant as much as possible and put into the oven as is, allowing the oven to drive off remaining supernatant (this practice is avoided for environmental reasons). WARNING: OVEN IS HOT—110 °C (230 °F).

11.1.10   Cool, weigh and record final weight of bottle.

11.2   GC ANALYSIS

11.2.1   Initiate the CALS computer channel.

11.2.2   Enter the correct instrument method into the GC's integrator.

11.2.3   Load sample vial(s) into autosampler.

11.2.4   Start the integrator.

11.2.5   When analysis is complete, plot CALS run to check baseline skim.

12.0 Data Analysis and Calculations

12.1   Add the concentrations of the hexane peaks as they appear on the CALS printout. Do not include the benzene peak in the sum.

12.2   Subtract any hexane interferences found in the PDS (see section 7.5.6 of this method); record the result.

12.3   Note the termonomer concentration on the CALS printout. Subtract any termonomer interference found in the PDS and record this result in a “% termonomer by GC” column in a logbook.

12.4   Record the area (from CALS printout) of the heptane internal standard peak in a “C7 area” column in the logbook. This helps track instrument performance over the long term.

12.5   After obtaining the final dry weight of polymer used (Section 11.1.10 of this method), record that result in a “dry wt.” column of the logbook (for oil extended polymer, the amount of oil extracted is added to the dry rubber weight).

12.6   Divide the %C6 by the dry weight to obtain the total PHR hexane in crumb. Similarly, divide the % termonomer by the dry weight to obtain the total PHR termonomer in crumb. Note that PHR is an abbreviation for “parts per hundred”. Record both the hexane and termonomer results in the logbook.

12.7   Correct all results by the recovery efficiency value (R).

13.0   Method Performance

13.1   The method has been shown to provide 100% recovery of the hexane analyte. The method was found to give a 6% relative standard deviation when the same six portions of the same sample were carried through the procedure. Note: These values are examples; each sample type, as specified in Section 9.3, must be tested for sample recovery.

14.0   Pollution Prevention

14.1   Dispose of all hydrocarbon liquids in the appropriate disposal sink system; never pour hydrocarbons down a water sink.

14.2   As discussed in section 11.1.9 of this method, the analyst can minimize venting hydrocarbon vapor to the atmosphere by decanting as much hydrocarbon liquid as possible before oven drying.

15.0   Waste Management

15.1   The Technician conducting the analysis should follow the proper waste management practices for their laboratory location.

16.0   References

16.1   Baton Rouge Chemical Plant Analytical Procedure no. BRCP 1302

16.2   Material Safety Data Sheets (from chemical vendors) for hexane, ENB, toluene, acetone, and heptane

Method 310C—Determination of Residual N-Hexane in EPDM Rubber Through Gas Chromatography

1.0   Scope and Application

1.1   This method describes a procedure for the determination of residual hexane in EPDM wet crumb rubber in the 0.01—2% range by solvent extraction of the hexane followed by gas chromatographic analysis where the hexane is detected by flame ionization and quantified via an internal standard.

1.2   This method may involve hazardous materials operations and equipment. This method does not purport to address all the safety problems associated with it use, if any. It is the responsibility of the user to consult and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

2.0   Summary

2.1   Residual hexane contained in wet pieces of EPDM polymer is extracted with MIBK. A known amount of an internal standard (IS) is added to the extract which is subsequently analyzed via gas chromatography where the hexane and IS are separated and detected utilizing a megabore column and flame ionization detection (FID). From the response to the hexane and the IS, the amount of hexane in the EPDM polymer is calculated.

3.0   Definitions

3.1   Hexane—refers to n-hexane

3.2   Heptane—refers to n-heptane

3.3   MIBK—methyl isobutyl ketone (4 methyl 2—Pentanone)

4.0   Interferences

4.1   Material eluting at or near the hexane and/or the IS will cause erroneous results. Prior to extraction, solvent blanks must be analyzed to confirm the absence of interfering peaks.

5.0   Safety

5.1   Review Material Safety Data Sheets of the chemicals used in this method.

6.0   Equipment and Supplies

6.1   4 oz round glass jar with a wide mouth screw cap lid.

6.2   Vacuum oven.

6.3   50 ml pipettes.

6.4   A gas chromatograph with an auto sampler and a 50 meter, 0.53 ID, methyl silicone column with 5 micron phase thickness.

6.5   Shaker, large enough to hold 10, 4 oz. jars.

6.6   1000 and 4000 ml volumetric flasks.

6.7   Electronic integrator or equivalent data system.

6.8   GC autosampler vials.

6.9   50 uL syringe.

7.0   Reagents and Standards

7.1   Reagent grade Methyl-Iso-Butyl-Ketone (MIBK)

7.2   n-heptane, 99% + purity

7.3   n-hexane, 99% + purity

8.0   Sample Collection

8.1   Trap a sample of the EPDM crumb slurry in the sampling apparatus. Allow the crumb slurry to circulate through the sampling apparatus for 5 minutes; then close off the values at the bottom and top of the sampling apparatus, trapping the crumb slurry. Run cooling water through the water jacket for a minimum of 30 minutes. Expel the cooled crumb slurry into a sample catching basket. If the crumb does not fall by gravity, force it out with demineralized water or nitrogen. Send the crumb slurry to the lab for analysis.

9.0   Quality Control

9.1   The Royalene crumb sample is extracted three times with MIBK containing an internal standard. The hexane from each extraction is added together to obtain a total hexane content. The percent hexane in the first extraction is then calculated and used as the recovery factor for the analysis.

9.2   Follow this test method through section 11.4 of the method. After removing the sample of the first extraction to be run on the gas chromatograph, drain off the remainder of the extraction solvent, retaining the crumb sample in the sample jar. Rinse the crumb with demineralized water to remove any MIBK left on the surface of the crumb. Repeat the extraction procedure with fresh MIBK with internal standard two more times.

9.3   After the third extraction, proceed to section 11.5 of this method and obtain the percent hexane in each extraction. Use the sample weight obtained in section 12.1 of this method to calculate the percent hexane in each of the extracts.

9.4   Add the percent hexane obtained from the three extractions for a total percent hexane in the sample.

9.5   Use the following equations to determine the recovery factor (R):

% Recovery of the first extraction=(% hexane in the first extract/total % hexane)×100

Recovery Factor (R)=(% Hexane Recovered in the first extract)/100

10.0   Calibration

10.1   Preparation of Internal Standard (IS) solution:

Accuracy weigh 30 grams of n-heptane into a 1000 ml volumetric flask. Dilute to the mark with reagent grade MIBK. Label this Solution “A”. Pipette 100 mls. of Solution A into a 4 liter volumetric flask. Fill the flask to the mark with reagent MIBK. Label this Solution “B”. Solution “B” will have a concentration of 0.75 mg/ml of heptane.

10.2   Preparation of Hexane Standard Solution (HS):

Using a 50 uL syringe, weigh by difference, 20 mg of n-hexane into a 50 ml volumetric flask containing approximately 40 ml of Solution B. Fill the flask to the mark with Solution B and mix well.

10.3   Conditions for GC analysis of standards and samples:

Temperature:

Initial=40 °C

Final=150 °C

Injector=160 °C

Detector=280 °C

Program Rate=5.0 °C/min

Initial Time=5 minutes Final Time=6 minutes

Flow Rate=5.0 ml/min

Sensitivity=detector response must be adjusted to keep the hexane and IS on scale.

10.4   Fill an autosampler vial with the HS, analyze it three times and calculate a Hexane Relative Response Factor (RF) as follows:

RF=(AIS × CHS × PHS)/(AHS × CIS × PIS)      (1)

Where:

AIS = Area of IS peak (Heptane)

AHS = Area of peak (Hexane Standard)

CHS = Mg of Hexane/50 ml HS

CIS = Mg of Heptane/50 ml IS Solution B

PIS = Purity of the IS n-heptane

PHS = Purity of the HS n-hexane

11.0   Procedure

11.1   Weight 10 grams of wet crumb into a tared (W1), wide mouth 4 oz. jar.

11.2   Pipette 50 ml of Solution B into the jar with the wet crumb rubber.

11.3   Screw the cap on tightly and place it on a shaker for 4 hours.

11.4   Remove the sample from the shaker and fill an autosampler vial with the MIBK extract.

11.5   Analyze the sample two times.

11.6   Analyze the HS twice, followed by the samples. Inject the HS twice at the end of each 10 samples or at the end of the run.

12.0   Calculations

12.1   Drain off the remainder of the MIBK extract from the polymer in the 4 oz. jar. Retain all the polymer in the jar. Place the uncovered jar and polymer in a heated vacuum oven until the polymer is dry. Reweigh the jar and polymer (W2) and calculate the dried sample weight of the polymer as follows:

Dried SW=W2—W1 (2)

12.2   Should the polymer be oil extended, pipette 10 ml of the MIBK extract into a tared evaporating dish (W1) and evaporate to dryness on a steam plate.

Reweigh the evaporating dish containing the extracted oil (W2). Calculate the oil content of the polymer as follows:

Gram of oil extracted =5 (W2—W1)   (3)

% Hexane in polymer=(As×RF×CIS×PIS)/(AIS×SW)   (4)

Where:

As = Area of sample hexane sample peak.

AIS = Area of IS peak in sample.

CIS = Concentration of IS in 50 ml.

PIS = Purity of IS.

SW=Weight of dried rubber after extraction. (For oil extended polymer, the amount of oil extracted is added to the dry rubber weight).

% Corrected Hexane=(% Hexane in Polymer)/R (5)

R=Recovery factor determined in section 9 of this method.

13.0   Method Performance

13.1   Performance must be determined for each sample type by following the procedures in section 9 of this method.

14.0   Waste Generation

14.1   Waste generation should be minimized where possible.

15.0   Waste Management

15.1   All waste shall be handled in accordance with Federal and State environmental regulations.

16.0   References [Reserved]

Method 311—Analysis of Hazardous Air Pollutant Compounds in Paints and Coatings by Direct Injection Into a Gas Chromatograph

1. Scope and Application

1.1   Applicability. This method is applicable for determination of most compounds designated by the U.S. Environmental Protection Agency as volatile hazardous air pollutants (HAP's) (See Reference 1) that are contained in paints and coatings. Styrene, ethyl acrylate, and methyl methacrylate can be measured by ASTM D 4827-93 or ASTM D 4747-87. Formaldehyde can be measured by ASTM PS 9-94 or ASTM D 1979-91. Toluene diisocyanate can be measured in urethane prepolymers by ASTM D 3432-89. Method 311 applies only to those volatile HAP's which are added to the coating when it is manufactured, not to those which may form as the coating cures (reaction products or cure volatiles). A separate or modified test procedure must be used to measure these reaction products or cure volatiles in order to determine the total volatile HAP emissions from a coating. Cure volatiles are a significant component of the total HAP content of some coatings. The term “coating” used in this method shall be understood to mean paints and coatings.

1.2   Principle. The method uses the principle of gas chromatographic separation and quantification using a detector that responds to concentration differences. Because there are many potential analytical systems or sets of operating conditions that may represent useable methods for determining the concentrations of the compounds cited in Section 1.1 in the applicable matrices, all systems that employ this principle, but differ only in details of equipment and operation, may be used as alternative methods, provided that the prescribed quality control, calibration, and method performance requirements are met. Certified product data sheets (CPDS) may also include information relevant to the analysis of the coating sample including, but not limited to, separation column, oven temperature, carrier gas, injection port temperature, extraction solvent, and internal standard.

2. Summary of Method

Whole coating is added to dimethylformamide and a suitable internal standard compound is added. An aliquot of the sample mixture is injected onto a chromatographic column containing a stationary phase that separates the analytes from each other and from other volatile compounds contained in the sample. The concentrations of the analytes are determined by comparing the detector responses for the sample to the responses obtained using known concentrations of the analytes.

3. Definitions [Reserved]

4. Interferences

4.1   Coating samples of unknown composition may contain the compound used as the internal standard. Whether or not this is the case may be determined by following the procedures of Section 11 and deleting the addition of the internal standard specified in Section 11.5.3. If necessary, a different internal standard may be used.

4.2   The GC column and operating conditions developed for one coating formulation may not ensure adequate resolution of target analytes for other coating formulations. Some formulations may contain nontarget analytes that coelute with target analytes. If there is any doubt about the identification or resolution of any gas chromatograph (GC) peak, it may be necessary to analyze the sample using a different GC column or different GC operating conditions.

4.3   Cross-contamination may occur whenever high-level and low-level samples are analyzed sequentially. The order of sample analyses specified in Section 11.7 is designed to minimize this problem.

4.4   Cross-contamination may also occur if the devices used to transfer coating during the sample preparation process or for injecting the sample into the GC are not adequately cleaned between uses. All such devices should be cleaned with acetone or other suitable solvent and checked for plugs or cracks before and after each use.

5. Safety

5.1   Many solvents used in coatings are hazardous. Precautions should be taken to avoid unnecessary inhalation and skin or eye contact. This method may involve hazardous materials, operations, and equipment. This test method does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this test method to establish appropriate safety and health practices and to determine the applicability of regulatory limitations in regards to the performance of this test method.

5.2   Dimethylformamide is harmful if inhaled or absorbed through the skin. The user should obtain relevant health and safety information from the manufacturer. Dimethylformamide should be used only with adequate ventilation. Avoid contact with skin, eyes, and clothing. In case of contact, immediately flush skin or eyes with plenty of water for at least 15 minutes. If eyes are affected, consult a physician. Remove and wash contaminated clothing before reuse.

5.3   User's manuals for the gas chromatograph and other related equipment should be consulted for specific precautions to be taken related to their use.

6. Equipment and Supplies

Note: Certified product data sheets (CPDS) may also include information relevant to the analysis of the coating sample including, but not limited to, separation column, oven temperature, carrier gas, injection port temperature, extraction solvent, and internal standard.

6.1   Sample Collection.

6.1.1   Sampling Containers. Dual-seal sampling containers, four to eight fluid ounce capacity, should be used to collect the samples. Glass sample bottles or plastic containers with volatile organic compound (VOC) impermeable walls must be used for corrosive substances (e.g., etch primers and certain coating catalysts such as methyl ethyl ketone (MEK) peroxide). Sample containers, caps, and inner seal liners must be inert to the compounds in the sample and must be selected on a case-by-case basis.

6.1.1.1   Other routine sampling supplies needed include waterproof marking pens, tubing, scrappers/spatulas, clean rags, paper towels, cooler/ice, long handle tongs, and mixing/stirring paddles.

6.1.2   Personal safety equipment needed includes eye protection, respiratory protection, a hard hat, gloves, steel toe shoes, etc.

6.1.3   Shipping supplies needed include shipping boxes, packing material, shipping labels, strapping tape, etc.

6.1.4   Data recording forms and labels needed include coating data sheets and sample can labels.

Note: The actual requirements will depend upon the conditions existing at the source sampled.

6.2   Laboratory Equipment and Supplies.

6.2.1   Gas Chromatograph (GC). Any instrument equipped with a flame ionization detector and capable of being temperature programmed may be used. Optionally, other types of detectors (e.g., a mass spectrometer), and any necessary interfaces, may be used provided that the detector system yields an appropriate and reproducible response to the analytes in the injected sample. Autosampler injection may be used, if available.

6.2.2   Recorder. If available, an electronic data station or integrator may be used to record the gas chromatogram and associated data. If a strip chart recorder is used, it must meet the following criteria: A 1 to 10 millivolt (mV) linear response with a full scale response time of 2 seconds or less and a maximum noise level of ±0.03 percent of full scale. Other types of recorders may be used as appropriate to the specific detector installed provided that the recorder has a full scale response time of 2 seconds or less and a maximum noise level of ±0.03 percent of full scale.

6.2.3   Column. The column must be constructed of materials that do not react with components of the sample (e.g., fused silica, stainless steel, glass). The column should be of appropriate physical dimensions (e.g., length, internal diameter) and contain sufficient suitable stationary phase to allow separation of the analytes. DB-5, DB-Wax, and FFAP columns are commonly used for paint analysis; however, it is the responsibility of each analyst to select appropriate columns and stationary phases.

6.2.4   Tube and Tube Fittings. Supplies to connect the GC and gas cylinders.

6.2.5   Pressure Regulators. Devices used to regulate the pressure between gas cylinders and the GC.

6.2.6   Flow Meter. A device used to determine the carrier gas flow rate through the GC. Either a digital flow meter or a soap film bubble meter may be used to measure gas flow rates.

6.2.7   Septa. Seals on the GC injection port through which liquid or gas samples can be injected using a syringe.

6.2.8   Liquid Charging Devices. Devices used to inject samples into the GC such as clean and graduated 1, 5, and 10 microliter (µl) capacity syringes.

6.2.9   Vials. Containers that can be sealed with a septum in which samples may be prepared or stored. The recommended size is 25 ml capacity. Mininert® valves have been found satisfactory and are available from Pierce Chemical Company, Rockford, Illinois.

6.2.10   Balance. Device used to determine the weights of standards and samples. An analytical balance capable of accurately weighing to 0.0001 g is required.

7. Reagents and Standards

7.1   Purity of Reagents. Reagent grade chemicals shall be used in all tests. Unless otherwise specified, all reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available. Other grades may be used provided it is first ascertained that the reagent is of sufficient purity to permit its use without lessening the accuracy of determination.

7.2   Carrier Gas. Helium carrier gas shall have a purity of 99.995 percent or higher. High purity nitrogen may also be used. Other carrier gases that are appropriate for the column system and analyte may also be used. Ultra-high purity grade hydrogen gas and zero-grade air shall be used for the flame ionization detector.

7.3   Dimethylformamide (DMF). Solvent for all standards and samples. Some other suitable solvent may be used if DMF is not compatible with the sample or coelutes with a target analyte.

Note: DMF may coelute with ethylbenzene or p-xylene under the conditions described in the note under Section 6.2.3.

7.4   Internal Standard Materials. The internal standard material is used in the quantitation of the analytes for this method. It shall be gas chromatography spectrophotometric quality or, if this grade is not available, the highest quality available. Obtain the assay for the internal standard material and maintain at that purity during use. The recommended internal standard material is 1-propanol; however, selection of an appropriate internal standard material for the particular coating and GC conditions used is the responsibility of each analyst.

7.5   Reference Standard Materials. The reference standard materials are the chemicals cited in Section 1.1 which are of known identity and purity and which are used to assist in the identification and quantification of the analytes of this method. They shall be the highest quality available. Obtain the assays for the reference standard materials and maintain at those purities during use.

7.6   Stock Reference Standards. Stock reference standards are dilutions of the reference standard materials that may be used on a daily basis to prepare calibration standards, calibration check standards, and quality control check standards. Stock reference standards may be prepared from the reference standard materials or purchased as certified solutions.

7.6.1   Stock reference standards should be prepared in dimethylformamide for each analyte expected in the coating samples to be analyzed. The concentrations of analytes in the stock reference standards are not specified but must be adequate to prepare the calibration standards required in the method. A stock reference standard may contain more than one analyte provided all analytes are chemically compatible and no analytes coelute. The actual concentrations prepared must be known to within 0.1 percent (e.g., 0.1000 ±0.0001 g/g solution). The following procedure is suggested. Place about 35 ml of dimethylformamide into a tared ground-glass stoppered 50 ml volumetric flask. Weigh the flask to the nearest 0.1 mg. Add 12.5 g of the reference standard material and reweigh the flask. Dilute to volume with dimethylformamide and reweigh. Stopper the flask and mix the contents by inverting the flask several times. Calculate the concentration in grams per gram of solution from the net gain in weights, correcting for the assayed purity of the reference standard material.

Note: Although a glass-stoppered volumetric flask is convenient, any suitable glass container may be used because stock reference standards are prepared by weight.

7.6.2   Transfer the stock reference standard solution into one or more Teflon-sealed screw-cap bottles. Store, with minimal headspace, at −10 °C to 0 °C and protect from light.

7.6.3   Prepare fresh stock reference standards every six months, or sooner if analysis results from daily calibration check standards indicate a problem. Fresh stock reference standards for very volatile HAP's may have to be prepared more frequently.

7.7   Calibration Standards. Calibration standards are used to determine the response of the detector to known amounts of reference material. Calibration standards must be prepared at a minimum of three concentration levels from the stock reference standards (see Section 7.6). Prepare the calibration standards in dimethylformamide (see Section 7.3). The lowest concentration standard should contain a concentration of analyte equivalent either to a concentration of no more than 0.01% of the analyte in a coating or to a concentration that is lower than the actual concentration of the analyte in the coating, whichever concentration is higher. The highest concentration standard should contain a concentration of analyte equivalent to slightly more than the highest concentration expected for the analyte in a coating. The remaining calibration standard should contain a concentration of analyte roughly at the midpoint of the range defined by the lowest and highest concentration calibration standards. The concentration range of the standards should thus correspond to the expected range of analyte concentrations in the prepared coating samples (see Section 11.5). Each calibration standard should contain each analyte for detection by this method expected in the actual coating samples (e.g., some or all of the compounds listed in Section 1.1 may be included). Each calibration standard should also contain an appropriate amount of internal standard material (response for the internal standard material is within 25 to 75 percent of full scale on the attenuation setting for the particular reference standard concentration level). Calibration Standards should be stored for 1 week only in sealed vials with minimal headspace. If the stock reference standards were prepared as specified in Section 7.6, the calibration standards may be prepared by either weighing each addition of the stock reference standard or by adding known volumes of the stock reference standard and calculating the mass of the standard reference material added. Alternative 1 (Section 7.7.1) specifies the procedure to be followed when the stock reference standard is added by volume. Alternative 2 (Section 7.7.2) specifies the procedure to be followed when the stock reference standard is added by weight.

Note: To assist with determining the appropriate amount of internal standard to add, as required here and in other sections of this method, the analyst may find it advantageous to prepare a curve showing the area response versus the amount of internal standard injected into the GC.

7.7.1   Preparation Alternative 1. Determine the amount of each stock reference standard and dimethylformamide solvent needed to prepare approximately 25 ml of the specific calibration concentration level desired. To a tared 25 ml vial that can be sealed with a crimp-on or Mininert® valve, add the total amount of dimethylformamide calculated to be needed. As quickly as practical, add the calculated amount of each stock reference standard using new pipets (or pipet tips) for each stock reference standard. Reweigh the vial and seal it. Using the known weights of the standard reference materials per ml in the stock reference standards, the volumes added, and the total weight of all reagents added to the vial, calculate the weight percent of each standard reference material in the calibration standard prepared. Repeat this process for each calibration standard to be prepared.

7.7.2   Preparation Alternative 2. Determine the amount of each stock reference standard and dimethylformamide solvent needed to prepare approximately 25 ml of the specific calibration concentration level desired. To a tared 25 ml vial that can be sealed with a crimp-on or Mininert® valve, add the total amount of dimethylformamide calculated to be needed. As quickly as practical, add the calculated amount of a stock reference standard using a new pipet (or pipet tip) and reweigh the vial. Repeat this process for each stock reference standard to be added. Seal the vial after obtaining the final weight. Using the known weight percents of the standard reference materials in the stock reference standards, the weights of the stock reference standards added, and the total weight of all reagents added to the vial, calculate the weight percent of each standard reference material in the calibration standard prepared. Repeat this process for each calibration standard to be prepared.

8. Sample Collection, Preservation, Transport, and Storage

8.1   Copies of material safety data sheets (MSDS's) for each sample should be obtained prior to sampling. The MSDS's contain information on the ingredients, and physical and chemical properties data. The MSDS's also contain recommendations for proper handling or required safety precautions. Certified product data sheets (CPDS) may also include information relevant to the analysis of the coating sample including, but not limited to, separation column, oven temperature, carrier gas, injection port temperature, extraction solvent, and internal standard.

8.2   A copy of the blender's worksheet can be requested to obtain data on the exact coating being sampled. A blank coating data sheet form (see Section 18) may also be used. The manufacturer's formulation information from the product data sheet should also be obtained.

8.3   Prior to sample collection, thoroughly mix the coating to ensure that a representative, homogeneous sample is obtained. It is preferred that this be accomplished using a coating can shaker or similar device; however, when necessary, this may be accomplished using mechanical agitation or circulation systems.

8.3.1   Water-thinned coatings tend to incorporate or entrain air bubbles if stirred too vigorously; mix these types of coatings slowly and only as long as necessary to homogenize.

8.3.2   Each component of multicomponent coatings that harden when mixed must be sampled separately. The component mix ratios must be obtained at the facility at the time of sampling and submitted to the analytical laboratory.

8.4   Sample Collection. Samples must be collected in a manner that prevents or minimizes loss of volatile components and that does not contaminate the coating reservoir. A suggested procedure is as follows. Select a sample collection container which has a capacity at least 25 percent greater than the container in which the sample is to be transported. Make sure both sample containers are clean and dry. Using clean, long-handled tongs, turn the sample collection container upside down and lower it into the coating reservoir. The mouth of the sample collection container should be at approximately the midpoint of the reservoir (do not take the sample from the top surface). Turn the sample collection container over and slowly bring it to the top of the coating reservoir. Rapidly pour the collected coating into the sample container, filling it completely. It is important to fill the sample container completely to avoid any loss of volatiles due to volatilization into the headspace. Return any unused coating to the reservoir or dispose as appropriate.

Note: If a company requests a set of samples for its own analysis, a separate set of samples, using new sample containers, should be taken at the same time.

8.5   Once the sample is collected, place the sample container on a firm surface and insert the inner seal in the container by placing the seal inside the rim of the container, inverting a screw cap, and pressing down on the screw cap which will evenly force the inner seal into the container for a tight fit. Using clean towels or rags, remove all residual coating material from the outside of the sample container after inserting the inner seal. Screw the cap onto the container.

8.5.1   Affix a sample label (see Section 18) clearly identifying the sample, date collected, and person collecting the sample.

8.5.2   Prepare the sample for transportation to the laboratory. The sample should be maintained at the coating's recommended storage temperature specified on the Material Safety Data Sheet, or, if no temperature is specified, the sample should be maintained within the range of 5 °C to 38 °C.

8.9   The shipping container should adhere to U.S. Department of Transportation specification DOT 12-B. Coating samples are considered hazardous materials; appropriate shipping procedures should be followed.

9. Quality Control

9.1   Laboratories using this method should operate a formal quality control program. The minimum requirements of the program should consist of an initial demonstration of laboratory capability and an ongoing analysis of blanks and quality control samples to evaluate and document quality data. The laboratory must maintain records to document the quality of the data generated. When results indicate atypical method performance, a quality control check standard (see Section 9.4) must be analyzed to confirm that the measurements were performed in an in-control mode of operation.

9.2   Before processing any samples, the analyst must demonstrate, through analysis of a reagent blank, that there are no interferences from the analytical system, glassware, and reagents that would bias the sample analysis results. Each time a set of analytical samples is processed or there is a change in reagents, a reagent blank should be processed as a safeguard against chronic laboratory contamination. The blank samples should be carried through all stages of the sample preparation and measurement steps.

9.3   Required instrument quality control parameters are found in the following sections:

9.3.1   Baseline stability must be demonstrated to be ≤5 percent of full scale using the procedures given in Section 10.1.

9.3.2   The GC calibration is not valid unless the retention time (RT) for each analyte at each concentration is within ±0.05 min of the retention time measured for that analyte in the stock standard.

9.3.3   The retention time (RT) of any sample analyte must be within ±0.05 min of the average RT of the analyte in the calibration standards for the analyte to be considered tentatively identified.

9.3.4   The GC system must be calibrated as specified in Section 10.2.

9.3.5   A one-point daily calibration check must be performed as specified in Section 10.3.

9.4   To establish the ability to generate results having acceptable accuracy and precision, the analyst must perform the following operations.

9.4.1   Prepare a quality control check standard (QCCS) containing each analyte expected in the coating samples at a concentration expected to result in a response between 25 percent and 75 percent of the limits of the calibration curve when the sample is prepared as described in Section 11.5. The QCCS may be prepared from reference standard materials or purchased as certified solutions. If prepared in the laboratory, the QCCS must be prepared independently from the calibration standards.

9.4.2   Analyze three aliquots of the QCCS according to the method beginning in Section 11.5.3 and calculate the weight percent of each analyte using Equation 1, Section 12.

9.4.3   Calculate the mean weight percent (X̅) for each analyte from the three results obtained in Section 9.4.2.

9.4.4   Calculate the percent accuracy for each analyte using the known concentrations (Ti) in the QCCS using Equation 3, Section 12.

9.4.5   Calculate the percent relative standard deviation (percent RSD) for each analyte using Equation 7, Section 12, substituting the appropriate values for the relative response factors (RRF's) in said equation.

9.4.6   If the percent accuracy (Section 9.4.4) for all analytes is within the range 90 percent to 110 percent and the percent RSD (Section 9.4.5) for all analytes is ≤20 percent, system performance is acceptable and sample analysis may begin. If these criteria are not met for any analyte, then system performance is not acceptable for that analyte and the test must be repeated for those analytes only. Repeated failures indicate a general problem with the measurement system that must be located and corrected. In this case, the entire test, beginning at Section 9.4.1, must be repeated after the problem is corrected.

9.5   Great care must be exercised to maintain the integrity of all standards. It is recommended that all standards be stored at −10 °C to 0 °C in screw-cap amber glass bottles with Teflon liners.

9.6   Unless otherwise specified, all weights are to be recorded within 0.1 mg.

10. Calibration and Standardization.

10.1   Column Baseline Drift. Before each calibration and series of determinations and before the daily calibration check, condition the column using procedures developed by the laboratory or as specified by the column supplier. Operate the GC at initial (i.e., before sample injection) conditions on the lowest attenuation to be used during sample analysis. Adjust the recorder pen to zero on the chart and obtain a baseline for at least one minute. Initiate the GC operating cycle that would be used for sample analysis. On the recorder chart, mark the pen position at the end of the simulated sample analysis cycle. Baseline drift is defined as the absolute difference in the pen positions at the beginning and end of the cycle in the direction perpendicular to the chart movement. Calculate the percent baseline drift by dividing the baseline drift by the chart width representing full-scale deflection and multiply the result by 100.

10.2   Calibration of GC. Bring all stock standards and calibration standards to room temperature while establishing the GC at the determined operating conditions.

10.2.1   Retention Times (RT's) for Individual Compounds.

Note: The procedures of this subsection are required only for the initial calibration. However, it is good laboratory practice to follow these procedures for some or all analytes before each calibration. The procedures were written for chromatograms output to a strip chart recorder. More modern instruments (e.g., integrators and electronic data stations) determine and print out or display retention times automatically.

The RT for each analyte should be determined before calibration. This provides a positive identification for each peak observed from the calibration standards. Inject an appropriate volume (see note in Section 11.5.2) of one of the stock reference standards into the gas chromatograph and record on the chart the pen position at the time of the injection (see Section 7.6.1). Dilute an aliquot of the stock reference standard as required in dimethylformamide to achieve a concentration that will result in an on-scale response. Operate the gas chromatograph according to the determined procedures. Select the peak(s) that correspond to the analyte(s) [and internal standard, if used] and measure the retention time(s). If a chart recorder is used, measure the distance(s) on the chart from the injection point to the peak maxima. These distances, divided by the chart speed, are defined as the RT's of the analytes in question. Repeat this process for each of the stock reference standard solutions.

Note: If gas chromatography with mass spectrometer detection (GC-MS) is used, a stock reference standard may contain a group of analytes, provided all analytes are adequately separated during the analysis. Mass spectral library matching can be used to identify the analyte associated with each peak in the gas chromatogram. The retention time for the analyte then becomes the retention time of its peak in the chromatogram.

10.2.2   Calibration. The GC must be calibrated using a minimum of three concentration levels of each potential analyte. (See Section 7.7 for instructions on preparation of the calibration standards.) Beginning with the lowest concentration level calibration standard, carry out the analysis procedure as described beginning in Section 11.7. Repeat the procedure for each progressively higher concentration level until all calibration standards have been analyzed.

10.2.2.1   Calculate the RT's for the internal standard and for each analyte in the calibration standards at each concentration level as described in Section 10.2.1. The RT's for the internal standard must not vary by more than 0.10 minutes. Identify each analyte by comparison of the RT's for peak maxima to the RT's determined in Section 10.2.1.

10.2.2.2   Compare the retention times (RT's) for each potential analyte in the calibration standards for each concentration level to the retention times determined in Section 10.2.1. The calibration is not valid unless all RT's for all analytes meet the criteria given in Section 9.3.2.

10.2.2.3   Tabulate the area responses and the concentrations for the internal standard and each analyte in the calibration standards. Calculate the response factor for the internal standard (RFis) and the response factor for each compound relative to the internal standard (RRF) for each concentration level using Equations 5 and 6, Section 12.

10.2.2.4   Using the RRF's from the calibration, calculate the percent relative standard deviation (percent RSD) for each analyte in the calibration standard using Equation 7, Section 12. The percent RSD for each individual calibration analyte must be less than 15 percent. This criterion must be met in order for the calibration to be valid. If the criterion is met, the mean RRF's determined above are to be used until the next calibration.

10.3   Daily Calibration Checks. The calibration curve (Section 10.2.2) must be checked and verified at least once each day that samples are analyzed. This is accomplished by analyzing a calibration standard that is at a concentration near the midpoint of the working range and performing the checks in Sections 10.3.1, 10.3.2, and 10.3.3.

10.3.1   For each analyte in the calibration standard, calculate the percent difference in the RRF from the last calibration using Equation 8, Section 12. If the percent difference for each calibration analyte is less than 10 percent, the last calibration curve is assumed to be valid. If the percent difference for any analyte is greater than 5 percent, the analyst should consider this a warning limit. If the percent difference for any one calibration analyte exceeds 10 percent, corrective action must be taken. If no source of the problem can be determined after corrective action has been taken, a new three-point (minimum) calibration must be generated. This criterion must be met before quantitative analysis begins.

10.3.2   If the RFis for the internal standard changes by more than ±20 percent from the last daily calibration check, the system must be inspected for malfunctions and corrections made as appropriate.

10.3.3   The retention times for the internal standard and all calibration check analytes must be evaluated. If the retention time for the internal standard or for any calibration check analyte changes by more than 0.10 min from the last calibration, the system must be inspected for malfunctions and corrections made as required.

11. Procedure

11.1   All samples and standards must be allowed to warm to room temperature before analysis. Observe the given order of ingredient addition to minimize loss of volatiles.

11.2   Bring the GC system to the determined operating conditions and condition the column as described in Section 10.1.

Note: The temperature of the injection port may be an especially critical parameter. Information about the proper temperature may be found on the CPDS.

11.3   Perform the daily calibration checks as described in Section 10.3. Samples are not to be analyzed until the criteria in Section 10.3 are met.

11.4   Place the as-received coating sample on a paint shaker, or similar device, and shake the sample for a minimum of 5 minutes to achieve homogenization.

11.5   Note: The steps in this section must be performed rapidly and without interruption to avoid loss of volatile organics. These steps must be performed in a laboratory hood free from solvent vapors. All weights must be recorded to the nearest 0.1 mg.

11.5.1   Add 16 g of dimethylformamide to each of two tared vials (A and B) capable of being septum sealed.

11.5.2   To each vial add a weight of coating that will result in the response for the major constituent being in the upper half of the linear range of the calibration curve.

Note: The magnitude of the response obviously depends on the amount of sample injected into the GC as specified in Section 11.8. This volume must be the same as used for preparation of the calibration curve, otherwise shifts in compound retention times may occur. If a sample is prepared that results in a response outside the limits of the calibration curve, new samples must be prepared; changing the volume injected to bring the response within the calibration curve limits is not permitted.

11.5.3   Add a weight of internal standard to each vial (A and B) that will result in the response for the internal standard being between 25 percent and 75 percent of the linear range of the calibration curve.

11.5.4   Seal the vials with crimp-on or Mininert® septum seals.

11.6   Shake the vials containing the prepared coating samples for 60 seconds. Allow the vials to stand undisturbed for ten minutes. If solids have not settled out on the bottom after 10 minutes, then centrifuge at 1,000 rpm for 5 minutes. The analyst also has the option of injecting the sample without allowing the solids to settle.

11.7   Analyses should be conducted in the following order: daily calibration check sample, method blank, up to 10 injections from sample vials (i.e., one injection each from up to five pairs of vials, which corresponds to analysis of 5 coating samples).

11.8   Inject the prescribed volume of supernatant from the calibration check sample, the method blank, and the sample vials onto the chromatographic column and record the chromatograms while operating the system under the specified operating conditions.

Note: The analyst has the option of injecting the unseparated sample.

12. Data Analysis and Calculations

12.1 Qualitative Analysis. An analyte (e.g., those cited in Section 1.1) is considered tentatively identified if two criteria are satisfied: (1) elution of the sample analyte within ±0.05 min of the average GC retention time of the same analyte in the calibration standard; and (2) either (a) confirmation of the identity of the compound by spectral matching on a gas chromatograph equipped with a mass selective detector or (b) elution of the sample analyte within ±0.05 min of the average GC retention time of the same analyte in the calibration standard analyzed on a dissimilar GC column.

12.1.1 The RT of the sample analyte must meet the criteria specified in Section 9.3.3.

12.1.2 When doubt exists as to the identification of a peak or the resolution of two or more components possibly comprising one peak, additional confirmatory techniques (listed in Section 12.1) must be used.

12.2 Quantitative Analysis. When an analyte has been identified, the quantification of that compound will be based on the internal standard technique.

12.2.1 A single analysis consists of one injection from each of two sample vials (A and B) prepared using the same coating. Calculate the concentration of each identified analyte in the sample as follows:

eCFR graphic er07de95.003.gif

View or download PDF

12.2.2 Report results for duplicate analysis (sample vials A and B) without correction.

12.3 Precision Data. Calculate the percent difference between the measured concentrations of each analyte in vials A and B as follows.

12.3.1 Calculate the weight percent of the analyte in each of the two sample vials as described in Section 12.2.1.

12.3.2 Calculate the percent difference for each analyte as:

eCFR graphic er07de95.004.gif

View or download PDF

where Ai and Bi are the measured concentrations of the analyte in vials A and B.

12.4 Calculate the percent accuracy for analytes in the QCCS (See Section 9.4) as follows:

eCFR graphic er07de95.005.gif

View or download PDF

where Xx is the mean measured value and Tx is the known true value of the analyte in the QCCS.

12.5 Obtain retention times (RT's) from data station or integrator or, for chromatograms from a chart recorder, calculate the RT's for analytes in the calibration standards (See Section 10.2.2.2) as follows:

eCFR graphic er07de95.006.gif

View or download PDF

12.6 Calculate the response factor for the internal standard (See Section 10.2.2.3) as follows:

eCFR graphic er07de95.007.gif

View or download PDF

where:

Ais = Area response of the internal standard.

Cis = Weight percent of the internal standard.

12.7 Calculate the relative response factors for analytes in the calibration standards (See Section 10.2.2.3) as follows:

where:

eCFR graphic er07de95.008.gif

View or download PDF

RRFx = Relative response factor for an individual analyte.

Ax = Area response of the analyte being measured.

Cx = Weight percent of the analyte being measured.

12.8 Calculate the percent relative standard deviation of the relative response factors for analytes in the calibration standards (See Section 10.2.2.4) as follows:

eCFR graphic er07de95.009.gif

View or download PDF

12.9 Calculate the percent difference in the relative response factors between the calibration curve and the daily calibration checks (See Section 10.3) as follows:

eCFR graphic er07de95.010.gif

View or download PDF

13. Measurement of Reaction Byproducts That are HAP [Reserved]

14. Method Performance [Reserved]

15. Pollution Prevention [Reserved]

16. Waste Management

16.1 The coating samples and laboratory standards and reagents may contain compounds which require management as hazardous waste. It is the laboratory's responsibility to ensure all wastes are managed in accordance with all applicable laws and regulations.

16.2 To avoid excessive laboratory waste, obtain only enough sample for laboratory analysis.

16.3 It is recommended that discarded waste coating solids, used rags, used paper towels, and other nonglass or nonsharp waste materials be placed in a plastic bag before disposal. A separate container, designated “For Sharp Objects Only,” is recommended for collection of discarded glassware and other sharp-edge items used in the laboratory. It is recommended that unused or excess samples and reagents be placed in a solvent-resistant plastic or metal container with a lid or cover designed for flammable liquids. This container should not be stored in the area where analytical work is performed. It is recommended that a record be kept of all compounds placed in the container for identification of the contents upon disposal.

17. References

1. Clean Air Act Amendments, Public Law 101-549, Titles I-XI, November, 1990.

2. Standard Test Method for Water Content of Water-Reducible Paints by Direct Injection into a Gas Chromatograph. ASTM Designation D3792-79.

3. Standard Practice for Sampling Liquid Paints and Related Pigment Coatings. ASTM Designation D3925-81.

4. Standard Test Method for Determination of Dichloromethane and 1,1,1-Trichloroethane in Paints and Coatings by Direct Injection into a Gas Chromatograph. ASTM Designation D4457-85.

5. Standard Test Method for Determining the Unreacted Monomer Content of Latexes Using Capillary Column Gas Chromatography. ASTM Designation D4827-93.

6. Standard Test Method for Determining Unreacted Monomer Content of Latexes Using Gas-Liquid Chromatography. ASTM Designation D 4747-87.

7. Method 301—“Field Validation of Pollutant Measurement Methods from Various Waste Media,” 40 CFR 63, Appendix A.

8. “Reagent Chemicals, American Chemical Society Specifications,” American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see “Reagent Chemicals and Standards” by Joseph Rosin, D. Van Nostrand Co., Inc., New York, NY and the “United States Pharmacopeia.”

18. Tables, Diagrams, Flowcharts, and Validation Data

Agency:
Inspector:
Date/Time:
Sample ID#:
Source ID:
Coating Name/Type:
Plant Witness:
Type Analysis Required:
Special Handling:

Sample Container Label

Coating Data

Date:
Source:
DataSample ID No.Sample ID No.
Coating:
Supplier Name
Name and Color of Coating
Type of Coating (primer, clearcoat, etc.)
Identification Number for Coating
Coating Density (lbs/gal)
Total Volatiles Content (wt percent)
Water Content (wt percent)
Exempt Solvents Content (wt percent)
VOC Content (wt percent)
Solids Content (vol percent)
Diluent Properties:
Name
Identification Number
Diluent Solvent Density (lbs/gal)
VOC Content (wt percent)
Water Content (wt percent)
Exempt Solvent Content (wt percent)
Diluent/Solvent Ratio (gal diluent solvent/gal coating)

Stock Reference Standard

Name of Reference Material:
Supplier Name:
Lot Number:
Purity:
Name of Solvent Material: Dimethylformamide
Supplier Name:
Lot Number:
Purity:
Date Prepared:
Prepared By:
Notebook/page no.:

Preparation Information

1. Weight Empty Flask____,g
2. Weight Plus DMF____,g
3. Weight Plus Reference Material____,g
4. Weight After Made to Volume____,g
5. Weight DMF (lines 2-1+3-4)____,g
6. Weight Ref. Material (lines 3-2)____,g
7. Corrected Weight of Reference Material (line 6 times purity)____,g
8. Fraction Reference Material in Standard (Line 7 ÷ Line 5) soln____,g/g
9. Total Volume of Standard Solution____, ml
10. Weight Reference Material per ml of Solution (Line 7 ÷ Line 9)____,g/ml
Laboratory ID No. for this Standard____
Expiration Date for this Standard____

CALIBRATION STANDARD

Date Prepared:
Date Expires:
Prepared By:
Notebook/page:

Calibration Standard Identification No.:

 

Preparation Information

Final Weight Flask Plus Reagents____, g
Weight Empty Flask____, g
Total Weight Of Reagents____, g
Analyte nameaStock reference standard ID No.Amount of stock reference standard added (by volume or by weight)Calculated weight analyte added, gWeight percent analyte in calibration standardb
Volume added, mlAmount in standard, g/mlWeight added, gAmount in standard, g/g soln

aInclude internal standard(s).

bWeight percent = weight analyte added ÷ total weight of reagents.

Quality Control Check Standard

Date Prepared:
Date Expires:
Prepared By:
Notebook/page:

Quality Control Check Standard Identification No.:

 

Preparation Information

Final Weight Flask Plus Reagents____,g
Weight Empty Flask____,g
Total Weight Of Reagents____,g
Analyte nameaStock reference standard ID No.Amount of stock reference standard added (by volume or by weight)Calculated weight analyte added, gWeight percent analyte in QCC standardb
Volume added, mlAmount in standard, g/mlWeight added, gAmount in standard, g/g soln

aInclude internal Standard(s).

bWeight percent=weight analyte added ÷ total weight of reagents.

Quality Control Check Standard Analysis

Date OCCS Analyzed:
OCCS Identification No.
Analyst:
QCC Expiration Date:

Analysis Results

AnalyteWeight percent determinedMean Wt percentPercent accuracxPercent RSDMeets criteria in Section 9.4.6
Run 1Run 2Run 3Percent
accuracy
Percent RSD

Calibration of Gas Chromatograph

Calibration Date:
Calibrated By:

Part 1—Retention Times for Individual Analytes

AnalyteStock standard. ID No.Recorder chart speedDistance from injection point to peak maximumRetention time, minutesa
Inches/min.cm/min.InchesCentimeters

aRetention time=distance to peak maxima÷chart speed.

CALIBRATION OF GAS CHROMATOGRAPH

Calibration Date:
Calibrated By:

Part 2—Analysis of Calibration Standards

AnalyteCalib. STD ID No. Calib. STD ID No. Calib. STD ID No.
Name:
Conc. in STD
Area Response
RT
Name:
Conc. in STD
Area Response
RT
Name:
Conc. in STD
Area Response
RT
Name:
Conc. in STD
Area Response
RT
Name:
Conc. in STD
Area Response
RT
Name:
Conc. in STD
Area Response
RT
Name:
Conc. in STD
Area Response
RT
Name:
Conc. in STD
Area Response
RT
Internal Standard Name:
Conc. in STD
Area Response
RT

Calibration of Gas Chromatograph

Calibration Date:
Calibrated By:

Part 3—Data Analysis for Calibration Standards

AnalyteCalib. STD IDCalib. STD IDCalib. STD IDMeanpercent RSD of RFIs RT within ±0.05 min of RT for stock? (Y/N)Is percent RSD <30% (Y/N)
Name:
RT
RF
Name:
RT
RF
Name:
RT
RF
Name:
RT
RF
Name:
RT
RF
Name:
RT
RF
Name:
RT
RF

Daily Calibration Check

Date:
Analyst:

Calibration Check Standard ID No.:

Expiration Date:
AnalyteRetention Time (RT)Response Factor (RF)
Last This DifferenceaLast This Differenceb

aRetention time (RT) change (difference) must be less than ±0.10 minutes.

bResponse factor (RF) change (difference) must be less than 20 percent for each analyte and for the internal standard.

Sample Analysis

Vial A ID No.:
Vial B ID No.:
Analyzed By:
Date:
Sample preparation informationVial A (g)Vial B (g)
Measured:
wt empty via
wt plus DMF
wt plus sample
wt plus internal
standard
Calculated:
wt DMF
wt sample
wt internal standard

Analysis Results: Duplicate Samples

AnalyteArea responseRFWt percent in sample
Vial AVial BVial AVial BAverage
   
   
   
   
   
   
   
   
   
   
   
   
   
Internal Standard

Method 312A—Determination of Styrene in Latex Styrene-Butadiene Rubber, Through Gas Chromatography

1. Scope and Application

1.1 This method describes a procedure for determining parts per million (ppm) styrene monomer (CAS No. 100-42-5) in aqueous samples, including latex samples and styrene stripper water.

1.2 The sample is separated in a gas chromatograph equipped with a packed column and a flame ionization detector.

2.0 Summary of Method

2.1 This method utilizes a packed column gas chromatograph with a flame ionization detector to determine the concentration of residual styrene in styrene butadiene rubber (SBR) latex samples.

3.0 Definitions

3.1 The definitions are included in the text as needed.

4.0 Interferences

4.1 In order to reduce matrix effects and emulsify the styrene, similar styrene free latex is added to the internal standard. There are no known interferences.

4.2 The operating parameters are selected to obtain resolution necessary to determine styrene monomer concentrations in latex.

5.0 Safety

5.1 It is the responsibility of the user of this procedure to establish appropriate safety and health practices.

6.0 Equipment and Supplies

6.1 Adjustable bottle-top dispenser, set to deliver 3 ml. (for internal standard), Brinkmann Dispensette, or equivalent.

6.2 Pipettor, set to 10 ml., Oxford Macro-set, or equivalent.

6.3 Volumetric flask, 100-ml, with stopper.

6.4 Hewlett Packard Model 5710A dual channel gas chromatograph equipped with flame ionization detector.

6.4.1 11 ft. × 18 in. stainless steel column packed with 10% TCEP on 100/120 mesh Chromosorb P, or equivalent.

6.4.2 Perkin Elmer Model 023 strip chart recorder, or equivalent.

6.5 Helium carrier gas, zero grade.

6.6 Liquid syringe, 25-µl.

6.7 Digital MicroVAX 3100 computer with VG Multichrom software, or equivalent data handling system.

6.6 Wire Screens, circular, 70-mm, 80-mesh diamond weave.

6.7 DEHA—(N,N-Diethyl hydroxylamine), 97+% purity, CAS No. 3710-84-7

6.8 p-Dioxane, CAS No. 123-91-1

7.0 Reagents and Standards

7.1 Internal standard preparation.

7.1.1 Pipette 5 ml p-dioxane into a 1000-ml volumetric flask and fill to the mark with distilled water and mix thoroughly.

7.2 Calibration solution preparation.

7.2.1 Pipette 10 ml styrene-free latex (eg: NBR latex) into a 100-ml volumetric flask.

7.2.2 Add 3 ml internal standard (section 7.1.1 of this method).

7.2.3 Weigh exactly 10 µl fresh styrene and record the weight.

7.2.4 Inject the styrene into the flask and mix well.

7.2.5 Add 2 drops of DEHA, fill to the mark with water and mix well again.

7.2.6 Calculate concentration of the calibration solution as follows:

mg/l styrene=(mg styrene added)/0.1 L

8.0 Sample Collection, Preservation, and Storage

8.1 A representative SBR emulsion sample should be caught in a clean, dry 6-oz. teflon lined glass container. Close it properly to assure no sample leakage.

8.2 The container should be labeled with sample identification, date and time.

9.0 Quality Control

9.1 The instrument is calibrated by injecting calibration solution (Section 7.2 of this method) five times.

9.2 The retention time for components of interest and relative response of monomer to the internal standard is determined.

9.3 Recovery efficiency must be determined once for each sample type and whenever modifications are made to the method.

9.3.1 A set of six latex samples shall be collected. Two samples shall be prepared for analysis from each sample. Each sample shall be analyzed in duplicate.

9.3.2 The second set of six latex samples shall be analyzed in duplicate before spiking each sample with approximately 1000 ppm styrene. The spiked samples shall be analyzed in duplicate.

9.3.3 For each hydrocarbon, calculate the average recovery efficiency (R) using the following equations:

where:

R=Σ(Rn)/6

where:

Rn = (cns−cv)/Sn

n=sample number

cns = concentration of compound measured in spiked sample number n.

cnu = concentration of compound measured in unspiked sample number n.

Sn = theoretical concentration of compound spiked into sample n.

9.3.4 A value of R between 0.70 and 1.30 is acceptable.

9.3.5 R is used to correct all reported results for each compound by dividing the measured results of each compound by the R for that compound for the same sample type.

10.0 Calibration and Instrument Settings

10.1 Injection port temperature, 250 °C.

10.2 Oven temperature, 110 °C, isothermal.

10.3 Carrier gas flow, 25 cc/min.

10.4 Detector temperature, 250 °C.

10.5 Range, 1X.

11.0 Procedure

11.1 Turn on recorder and adjust baseline to zero.

11.2 Prepare sample.

11.2.1 For latex samples, add 3 ml Internal Standard (section 7.1 of this method) to a 100-ml volumetric flask. Pipet 10 ml sample into the flask using the Oxford pipettor, dilute to the 100-ml mark with water, and shake well.

11.2.2 For water samples, add 3 ml Internal Standard (section 7.1 of this method) to a 100-ml volumetric flask and fill to the mark with sample. Shake well.

11.3 Flush syringe with sample.

11.4 Carefully inject 2 µl of sample into the gas chromatograph column injection port and press the start button.

11.5 When the run is complete the computer will print a report of the analysis.

12.0 Data Analysis and Calculation

12.1 For samples that are prepared as in section 11.2.1 of this method:

ppm styrene = A×D

Where:

A = “ppm” readout from computer

D = dilution factor (10 for latex samples)

12.2 For samples that are prepared as in section 11.2.2 of this method, ppm styrene is read directly from the computer.

13.0 Method Performance

13.1 This test has a standard deviation (1) of 3.3 ppm at 100 ppm styrene. The average Spike Recovery from six samples at 1000 ppm Styrene was 96.7 percent. The test method was validated using 926 ppm styrene standard. Six analysis of the same standard provided average 97.7 percent recovery. Note: These are example recoveries and do not replace quality assurance procedures in this method.

14.0 Pollution Prevention

14.1 Waste generation should be minimized where possible. Sample size should be an amount necessary to adequately run the analysis.

15.0 Waste Management

15.1 All waste shall be handled in accordance with Federal and State environmental regulations.

16.0 References and Publications

16.1 40 CFR 63 Appendix A—Method 301 Test Methods Field Validation of Pollutant Measurement

16.2 DSM Copolymer Test Method T-3060, dated October 19, 1995, entitled: Determination of Residual Styrene in Latex, Leonard, C.D., Vora, N.M.et al

Method 312B—Determination of Residual Styrene in Styrene-Butadiene (SBR) Rubber Latex by Capillary Gas Chromatography

1.0 Scope

1.1 This method is applicable to SBR latex solutions.

1.2 This method quantitatively determines residual styrene concentrations in SBR latex solutions at levels from 80 to 1200 ppm.

2.0 Principle of Method

2.1 A weighed sample of a latex solution is coagulated with an ethyl alcohol (EtOH) solution containing a specific amount of alpha-methyl styrene (AMS) as the internal standard. The extract of this coagulation is then injected into a gas chromatograph and separated into individual components. Quantification is achieved by the method of internal standardization.

3.0 Definitions

3.1 The definitions are included in the text as needed.

4.0 Interferences [Reserved]

5.0 Safety

5.1 This method may involve hazardous materials, operations, and equipment. This method does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this method to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

6.0 Equipment and Supplies

6.1 Analytical balance, 160 g capacity, and 0.1 mg resolution

6.2 Bottles, 2-oz capacity, with poly-cap screw lids

6.3 Mechanical shaker

6.4 Syringe, 10-ul capacity

6.5 Gas chromatograph, Hewlett Packard model 5890A, or equivalent, configured with FID with a megabore jet, splitless injector packed with silanized glass wool.

6.5.1 Establish the following gas chromatographic conditions, and allow the system to thoroughly equilibrate before use.

Injection technique = Splitless

Injector temperature = 225 deg C

Oven temperature = 70 deg C (isothermal)

Detector: temperature = 300 deg C

range = 5

attenuation = 0

Carrier gas: helium = 47 ml/min

Detector gases: hydrogen = 30 ml/min

air = 270 ml/min

make-up = 0 ml/min

Analysis time: = 3.2 min at the specified carrier gas flow rate and column temperature.

6.6 Gas chromatographic column, DB-1, 30 M X 0.53 ID, or equivalent, with a 1.5 micron film thickness.

6.7 Data collection system, Perkin-Elmer/Nelson Series Turbochrom 4 Series 900 Interface, or equivalent.

6.8 Pipet, automatic dispensing, 50-ml capacity, and 2-liter reservoir.

6.9 Flasks, volumetric, class A, 100-ml and 1000-ml capacity.

6.10 Pipet, volumetric delivery, 10-ml capacity, class A.

7.0 Chemicals and Reagents

CHEMICALS:

7.1 Styrene, C8H8, 99+%, CAS 100-42-5

7.2 Alpha methyl styrene, C9H10, 99%, CAS 98-83-9

7.3 Ethyl alcohol, C2H5OH, denatured formula 2B, CAS 64-17-5

REAGENTS:

7.4 Internal Standard Stock Solution: 5.0 mg/ml AMS in ethyl alcohol.

7.4.1 Into a 100-ml volumetric flask, weigh 0.50 g of AMS to the nearest 0.1 mg.

7.4.2 Dilute to the mark with ethyl alcohol. This solution will contain 5.0 mg/ml AMS in ethyl alcohol and will be labeled the AMS STOCK SOLUTION.

7.5 Internal Standard Working Solution: 2500 ug/50 ml of AMS in ethyl alcohol.

7.5.1 Using a 10 ml volumetric pipet, quantitatively transfer 10.0 ml of the AMS STOCK SOLUTION into a 1000-ml volumetric flask.

7.5.2 Dilute to the mark with ethyl alcohol. This solution will contain 2500 ug/50ml of AMS in ethyl alcohol and will be labeled the AMS WORKING SOLUTION.

7.5.3 Transfer the AMS WORKING SOLUTION to the automatic dispensing pipet reservoir.

7.6 Styrene Stock Solution: 5.0 mg/ml styrene in ethyl alcohol.

7.6.1 Into a 100-ml volumetric flask, weigh 0.50 g of styrene to the nearest 0.1 mg.

7.6.2 Dilute to the mark with ethyl alcohol. This solution will contain 5.0 mg/ml styrene in ethyl alcohol and will be labeled the STYRENE STOCK SOLUTION.

7.7 Styrene Working Solution: 5000 ug/10 ml of styrene in ethyl alcohol.

7.7.1 Using a 10-ml volumetric pipet, quantitatively transfer 10.0 ml of the STYRENE STOCK SOLUTION into a 100-ml volumetric flask.

7.7.2 Dilute to the mark with ethyl alcohol. This solution will contain 5000 ug/10 ml of styrene in ethyl alcohol and will be labeled the STYRENE WORKING SOLUTION.

8.0 Sample Collection, Preservation and Storage

8.1 Label a 2-oz sample poly-cap lid with the identity, date and time of the sample to be obtained.

8.2 At the sample location, open sample valve for at least 15 seconds to ensure that the sampling pipe has been properly flushed with fresh sample.

8.3 Fill the sample jar to the top (no headspace) with sample, then cap it tightly.

8.4 Deliver sample to the Laboratory for testing within one hour of sampling.

8.5 Laboratory testing will be done within two hours of the sampling time.

8.6 No special storage conditions are required unless the storage time exceeds 2 hours in which case refrigeration of the sample is recommended.

9.0 Quality Control

9.1 For each sample type, 12 samples of SBR latex shall be obtained from the process for the recovery study. Half the vials and caps shall be tared, labeled “spiked”, and numbered 1 through 6. The other vials are labeled “unspiked” and need not be tared, but are also numbered 1 through 6.

9.2 The six vials labeled “spiked” shall be spiked with an amount of styrene to approximate 50% of the solution's expected residual styrene level.

9.3 The spiked samples shall be shaken for several hours and allowed to cool to room temperature before analysis.

9.4 The six samples of unspiked solution shall be coagulated and a mean styrene value shall be determined, along with the standard deviation, and the percent relative standard deviation.

9.5 The six samples of the spiked solution shall be coagulated and the results of the analyses shall be determined using the following equations:

Mr = Ms−Mu

R=Mr/S

where:

Mu = Mean value of styrene in the unspiked sample

Ms = Measured amount of styrene in the spiked sample

Mr = Measured amount of the spiked compound

S=Amount of styrene added to the spiked sample

R=Fraction of spiked styrene recovered

9.6 A value of R between 0.70 and 1.30 is acceptable.

9.7 R is used to correct all reported results for each compound by dividing the measured results of each compound by the R for that compound for the same sample type.

10.0 Calibration

10.1 Using a 10-ml volumetric pipet, quantitatively transfer 10.0 ml of the STYRENE WORKING SOLUTION (section 7.7.2 of this method) into a 2-oz bottle.

10.2 Using the AMS WORKING SOLUTION equipped with the automatic dispensing pipet (section 7.5.3 of this method), transfer 50.0 ml of the internal standard solution into the 2-oz bottle.

10.3 Cap the 2-oz bottle and swirl. This is the calibration standard, which contains 5000 µg of styrene and 2500 µg of AMS.

10.4 Using the conditions prescribed (section 6.5 of this method), chromatograph 1 µl of the calibration standard.

10.5 Obtain the peak areas and calculate the relative response factor as described in the calculations section (section 12.1 of this method).

11.0 Procedure

11.1 Into a tared 2-oz bottle, weigh 10.0 g of latex to the nearest 0.1 g.

11.2 Using the AMS WORKING SOLUTION equipped with the automatic dispensing pipet (section 7.5.3 of this method), transfer 50.0 ml of the internal standard solution into the 2-oz bottle.

11.3 Cap the bottle. Using a mechanical shaker, shake the bottle for at least one minute or until coagulation of the latex is complete as indicated by a clear solvent.

11.4 Using the conditions prescribed (section 6.5 of this method), chromatograph 1 ul of the liquor.

11.5 Obtain the peak areas and calculate the concentration of styrene in the latex as described in the calculations section (Section 12.2 of this method).

12.0 Calculations

12.1 Calibration:

RF=(Wx×Ais) / (Wis×Ax)

where:

RF=the relative response factor for styrene

Wx = the weight (ug) of styrene

Ais = the area of AMS

Wis = the weight (ug) of AMS

Ax = the area of styrene

12.2 Procedure:

ppmstyrene = (Ax RF×Wis) / (Ais×Ws)

where:

ppmstyrene = parts per million of styrene in the latex

Ax = the area of styrene

RF=the response factor for styrene

Wis = the weight (ug) of AMS

Ais = the area of AMS

Ws = the weight (g) of the latex sample

12.3 Correct for recovery (R) as determined by section 9.0 of this method.

13.0 Precision

13.1 Precision for the method was determined at the 80, 144, 590, and 1160 ppm levels. The standard deviations were 0.8, 1.5, 5 and 9 ppm respectively. The percent relative standard deviations (%RSD) were 1% or less at all levels. Five degrees of freedom were used for all precision data except at the 80 ppm level, where nine degrees of freedom were used. Note: These are example results and do not replace quality assurance procedures in this method.

14.0 Pollution Prevention

14.1 Waste generation should be minimized where possible. Sample size should be an amount necessary to adequately run the analysis.

15.0 Waste Management

15.1 Discard liquid chemical waste into the chemical waste drum.

15.2 Discard latex sample waste into the latex waste drum.

15.3 Discard polymer waste into the polymer waste container.

16.0 References

16.1 This method is based on Goodyear Chemical Division Test Method E-889.

Method 312C—Determination of Residual Styrene in SBR Latex Produced by Emulsion Polymerization

1.0 Scope

1.1 This method is applicable for determining the amount of residual styrene in SBR latex as produced in the emulsion polymerization process.

2.0 Principle of Method

2.1 A weighed sample of latex is coagulated in 2-propanol which contains alpha-methyl styrene as an Internal Standard. The extract from the coagulation will contain the alpha-methyl styrene as the Internal Standard and the residual styrene from the latex. The extract is analyzed by a Gas Chromatograph. Percent styrene is calculated by relating the area of the styrene peak to the area of the Internal Standard peak of known concentration.

3.0 Definitions

3.1 The definitions are included in the text as needed.

4.0 Interferences [Reserved]

5.0 Safety

5.1 When using solvents, avoid contact with skin and eyes. Wear hand and eye protection. Wash thoroughly after use.

5.2 Avoid overexposure to solvent vapors. Handle only in well ventilated areas.

6.0 Equipment and Supplies

6.1 Gas Chromatograph—Hewlett Packard 5890, Series II with flame ionization detector, or equivalent.

Column—HP 19095F-123, 30m × 0.53mm, or equivalent. Substrate HP FFAP (cross-linked) film thickness 1 micrometer. Glass injector port liners with silanized glass wool plug.

Integrator—HP 3396, Series II, or equivalent.

6.2 Wrist action shaker

6.3 Automatic dispenser

6.4 Automatic pipet, calibrated to deliver 5.0 ±0.01 grams of latex

6.5 Four-ounce wide-mouth bottles with foil lined lids

6.6 Crimp cap vials, 2ml, teflon lined septa

6.7 Disposable pipets

6.8 Qualitative filter paper

6.9 Cap crimper

6.10 Analytical balance

6.11 10ml pipette

6.12 Two-inch funnel

7.0 Reagents and Standards

7.1 2-Propanol (HP2C grade)

7.2 Alpha methyl styrene (99+% purity)

7.3 Styrene (99+% purity)

7.4 Zero air

7.5 Hydrogen (chromatographic grade)

7.6 Helium

7.7 Internal Standard preparation

7.7.1 Weigh 5.000-5.005 grams of alpha-methyl styrene into a 100ml volumetric flask and bring to mark with 2-propanol to make Stock “A” Solution.

Note: Shelf life—6 months.

7.7.2 Pipette 10ml of Stock “A” Solution into a 100ml volumetric flask and bring to mark with 2-propanol to prepare Stock “B” Solution.

7.7.3 Pipette 10ml of the Stock “B” solution to a 1000ml volumetric flask and bring to the mark with 2-propanol. This will be the Internal Standard Solution (0.00005 grams/ml).

7.8 Certification of Internal Standard—Each batch of Stock “B” Solution will be certified to confirm concentration.

7.8.1 Prepare a Standard Styrene Control Solution in 2-propanol by the following method:

7.8.1.1 Weigh 5.000 ±.005g of styrene to a 100ml volumetric flask and fill to mark with 2-propanol to make Styrene Stock “A” Solution.

7.8.1.2 Pipette 10ml of Styrene Stock “A” Solution to a 100ml volumetric flask and fill to mark with 2-propanol to make Styrene Stock “B” Solution.

7.8.1.3 Pipette 10ml of Styrene Stock “B” soluion to a 250ml volumtric flask and fill to mark wtih 2-propanol to make the Certification Solution.

7.8.2 Certify Alpha-Methyl Styrene Stock “B” Solution.

7.8.2.1 Pipette 5ml of the Certification Solution and 25ml of the Alpha Methyl Styrene Internal Standard Solution to a 4-oz. bottle, cap and shake well.

7.8.2.2 Analyze the resulting mixture by GC using the residual styrene method. (11.4-11.6 of this method)

7.8.2.3 Calculate the weight of alpha methyl styrene present in the 25ml aliquat of the new Alpha Methyl Styrene Standard by the following equation:

Wx = Fx xWis(Ax/Ais)

Where

Ax = Peak area of alpha methyl styrene

Ais = Peak area of styrene

Wx = Weight of alpha methyl styrene

Wis = Weight of styrene (.00100)

Fx = Analyzed response factor = 1

The Alpha Methyl Styrene Stock Solution used to prepare the Internal Standard Solution may be considered certified if the weight of alpha methyl styrene analyzed by this method is within the range of .00121g to .00129g.

8.0 Sampling

8.1 Collect a latex sample in a capped container. Cap the bottle and identify the sample as to location and time.

8.2 Deliver sample to Laboratory for testing within one hour.

8.3 Laboratory will test within two hours.

8.4 No special storage conditions are required.

9.0 Quality Control

9.1 The laboratory is required to operate a formal quality control program. This consists of an initial demonstration of the capability of the method as well as ongoing analysis of standards, blanks, and spiked samples to demonstrate continued performance.

9.1.1 When the method is first set up, a calibration is run and the recovery efficiency for each type of sample must be determined.

9.1.2 If new types of samples are being analyzed, then recovery efficiency for each new type of sample must be determined. New type includes any change, such as polymer type, physical form or a significant change in the composition of the matrix.

9.2 Recovery efficiency must be determined once for each sample type and whenever modifications are made to the method.

9.2.1 In determining the recovery efficiency, the quadruplet sampling system shall be used. Six sets of samples (for a total of 24) shall be taken. In each quadruplet set, half of the samples (two out of the four) shall be spiked with styrene.

9.2.2 Prepare the samples as described in section 8 of this method. To the vials labeled “spiked”, add a known amount of styrene that is expected to be present in the latex.

9.2.3 Run the spiked and unspiked samples in the normal manner. Record the concentrations of styrene reported for each pair of spiked and unspiked samples with the same vial number.

9.2.4 For each hydrocarbon, calculate the average recovery efficiency (R) using the following equation:

R=Σ(Rn)/12

Where: n = sample number

Rn = (Ms−Mu)/S

Ms = total mass of compound (styrene) measured in spiked sample (µg)

Mu = total mass of compound (styrene) measured in unspiked sample (µg)

S=theoretical mass of compound (styrene) spiked into sample (µg)

R=fraction of spiked compound (styrene) recovered

9.2.5 A different R value should be obtained for each sample type. A value of R between 0.70 and 1.30 is acceptable.

9.2.6 R is used to correct all reported results for each compound by dividing the measured results of each compound by the R for that compound for the same sample type.

10.0 Calibration

A styrene control sample will be tested weekly to confirm the FID response and calibration.

10.1 Using the Styrene Certification Solution prepared in 7.8.1, perform test analysis as described in 7.8.2 using the equation in 7.8.2.3 to calculate results.

10.2 Calculate the weight of styrene in the styrene control sample using the following equation:

Wsty = (Fx xAsty xWis)Ais

The instrument can be considered calibrated if the weight of the styrene analyzed is within range of 0.00097-0.00103gms.

11.0 Procedure

11.1 Using an auto pipet, add 25ml of Internal Standard Solution to a 4 oz. wide-mouth bottle.

11.2 Using a calibrated auto pipet, add 5.0 ±0.01g latex to the bottle containing the 25ml of Internal Standard Solution.

11.3 Cap the bottle and place on the wrist action shaker. Shake the sample for a minimum of five minutes using the timer on the shaker. Remove from shaker.

11.4 Using a disposable pipet, fill the 2ml sample vial with the clear alcohol extract. (If the extract is not clear, it should be filtered using a funnel and filter paper.) Cap and seal the vial.

11.5 Place the sample in the autosampler tray and start the GC and Integrator. The sample will be injected into the GC by the auto-injector, and the Integrator will print the results.

11.6 Gas Chromatograph Conditions

Oven Temp—70 °C

Injector Temp—225 °C

Detector Temp—275 °C

Helium Pressure—500 KPA

Column Head Pressure—70 KPA

Makeup Gas—30 ml/min.

Column—HP 19095F—123, 30m×0.53mm Substrate: HP—FFAP (cross-linked) 1 micrometer film thickness

12.0 Calculations

12.1 The integrator is programmed to do the following calculation at the end of the analysis:

%ResidualStyrene=(Ax XWis)/(Ais XWx)XFx X100

Where:

Ax = Peak area of styrene

Ais = Peak area of internal standard

Wx = Weight of sample = 5g

Wis = Weight of internal std. = 0.00125g

Fx = Analyzed response factor = 1.0

12.2 The response factor is determined by analyzing a solution of 0.02g of styrene and 0.02g of alpha methyl styrene in 100ml of 2-propanol. Calculate the factor by the following equation:

Fx = (Wx xAis)/(Wis xAx)

Where:

Wx = Weight of styrene

Ax = Peak area of styrene

Wis = Weight of alpha methyl styrene

Ais = Peak area of alpha methyl styrene

13.0 Method Performance

13.1 Performance must be determined for each sample type by following the procedures in section 9 of this method.

14.0 Waste Generation

14.1 Waste generation should be minimized where possible.

15.0 Waste Management

15.1 All waste shall be handled in accordance with Federal and State environmental regulations.

16.0 References [Reserved]

Method 313A—Determination of Residual Hydrocarbons in Rubber Crumb

1.0 Scope and Application

1.1 This method determines residual toluene and styrene in stripper crumb of the of the following types of rubber: polybutadiene (PBR) and styrene/butadiene rubber (SBR), both derived from solution polymerization processes that utilize toluene as the polymerization solvent.

1.2 The method is applicable to a wide range of concentrations of toluene and styrene provided that calibration standards cover the desired range. It is applicable at least over the range of 0.01 to 10.0 % residual toluene and from 0.1 to 3.0 % residual styrene. It is probably applicable over a wider range, but this must be verified prior to use.

1.3 The method may also be applicable to other process samples as long as they are of a similar composition to stripper crumb. See section 3.1 of this method for a description of stripper crumb.

2.0 Summary of Method

2.1 The wet crumb is placed in a sealed vial and run on a headspace sampler which heats the vial to a specified temperature for a specific time and then injects a known volume of vapor into a capillary GC. The concentration of each component in the vapor is proportional to the level of that component in the crumb sample and does not depend on water content of the crumb.

2.2 Identification of each component is performed by comparing the retention times to those of known standards.

2.3 Results are calculated by the external standard method since injections are all performed in an identical manner. The response for each component is compared with that obtained from dosed samples of crumb.

2.4 Measured results of each compound are corrected by dividing each by the average recovery efficiency determined for the same compound in the same sample type.

3.0 Definitions

3.1 Stripper crumb refers to pieces of rubber resulting from the steam stripping of a toluene solution of the same polymer in a water slurry. The primary component of this will be polymer with lesser amounts of entrained water and residual toluene and other hydrocarbons. The amounts of hydrocarbons present must be such that the crumb is a solid material, generally less that 10 % of the dry rubber weight.

4.0 Interferences

4.1 Contamination is not normally a problem since samples are sealed into vials immediately on sampling.

4.2 Cross contamination in the headspace sampler should not be a problem if the correct sampler settings are used. This should be verified by running a blank sample immediately following a normal or high sample. Settings may be modified if necessary if this proves to be a problem, or a blank sample may be inserted between samples.

4.3 Interferences may occur if volatile hydrocarbons are present which have retention times close to that of the components of interest. Since the solvent makeup of the processes involved are normally fairly well defined this should not be a problem. If it is found to be the case, switching to a different chromatographic column will probably resolve the situation.

5.0 Safety

5.1 The chemicals specified in this method should all be handled according to standard laboratory practices as well as any special precautions that may be listed in the MSDS for that compound.

5.2 Sampling of strippers or other process streams may involve high pressures and temperatures or may have the potential for exposure to chemical fumes. Only personnel who have been trained in the specific sampling procedures required for that process should perform this operation. An understanding of the process involved is necessary. Proper personal protective equipment should be worn. Any sampling devices should be inspected prior to use. A detailed sampling procedure which specifies exactly how to obtain the sample must be written and followed.

6.0 Equipment and Supplies

6.1 Hewlett Packard (HP) 7694 Headspace sampler, or equivalent, with the following conditions:

Times (min.): GC cycle time 6.0 , vial equilibration 30.0 , pressurization 0.25 , loop fill 0.25, loop equilibration 0.05 , inject 0.25

Temperatures (deg C): oven 70, loop 80, transfer line 90

Pressurization gas: He @ 16 psi

6.2 HP 5890 Series II capillary gas chromatograph, or equivalent, with the following conditions:

Column: Supelco SPB-1, or equivalent, 15m × .25mm × .25 µ film

Carrier: He @ 6 psi

Run time: 4 minutes

Oven: 70 deg C isothermal

Injector: 200 deg C split ratio 50:1

Detector: FID @ 220 deg C

6.3 HP Chemstation consisting of computer, printer and Chemstation software, or an equivalent chromatographic data system.

6.4 20 ml headspace vials with caps and septa.

6.5 Headspace vial crimper.

6.6 Microliter pipetting syringes.

6.7 Drying oven at 100 deg C vented into cold trap or other means of trapping hydrocarbons released.

6.8 Laboratory shaker or tumbler suitable for the headspace vials.

6.9 Personal protective equipment required for sampling the process such as rubber gloves and face and eye protection.

7.0 Reagents and Standards

7.1 Toluene, 99.9+% purity, HPLC grade.

7.2 Styrene, 99.9+% purity, HPLC grade.

7.3 Dry rubber of same type as the stripper crumb samples.

8.0 Sample Collection, Preservation and Storage

8.1 Collect a sample of crumb in a manner appropriate for the process equipment being sampled.

8.1.1 If conditions permit, this may be done by passing a stream of the crumb slurry through a strainer, thus separating the crumb from the water. Allow the water to drain freely, do not attempt to squeeze any water from the crumb. Results will not depend on the exact water content of the samples. Immediately place several pieces of crumb directly into a headspace vial. This should be done with rubber gloves to protect the hands from both the heat and from contact with residual hydrocarbons. The vial should be between 14 and 13 full. Results do not depend on sample size as long as there is sufficient sample to reach an equilibrium vapor pressure in the headspace of the vial. Cap and seal the vial. Prepare each sample at least in duplicate. This is to minimize the effect of the variation that naturally occurs in the composition of non homogeneous crumb. The free water is not analyzed by this method and should be disposed of appropriately along with any unused rubber crumb.

8.1.2 Alternatively the process can be sampled in a specially constructed sealed bomb which can then be transported to the laboratory. The bomb is then cooled to ambient temperature by applying a stream of running water. The bomb can then be opened and the crumb separated from the water and the vials filled as described in section 8.1.1 of this method. The bomb may be stored up to 8 hours prior to transferring the crumb into vials.

8.2 The sealed headspace vials may be run immediately or may be stored up to 72 hours prior to running. It is possible that even longer storage times may be acceptable, but this must be verified for the particular type of sample being analyzed (see section 9.2.3 of this method). The main concern here is that some types of rubber eventually may flow, thus compacting the crumb so that the surface area is reduced. This may have some effect on the headspace equilibration.

9.0 Quality Control

9.1 The laboratory is required to operate a formal quality control program. This consists of an initial demonstration of the capability of the method as well as ongoing analysis of standards, blanks and spiked samples to demonstrate continued performance.

9.1.1 When the method is first set up a calibration is run (described in section 10 of this method) and an initial demonstration of method capability is performed (described in section 9.2 of this method). Also recovery efficiency for each type of sample must be determined (see section 9.4 of this method).

9.1.2 It is permissible to modify this method in order to improve separations or make other improvements, provided that all performance specifications are met. Each time a modification to the method is made it is necessary to repeat the calibration (section 10 of this method), the demonstration of method performance (section 9.2 of this method) and the recovery efficiency for each type of sample (section 9.4 of this method).

9.1.3 Ongoing performance should be monitored by running a spiked rubber standard. If this test fails to demonstrate that the analysis is in control, then corrective action must be taken. This method is described in section 9.3 of this method.

9.1.4 If new types of samples are being analyzed then recovery efficiency for each new type of sample must be determined. New type includes any change, such as polymer type, physical form or a significant change in the composition of the matrix.

9.2 Initial demonstration of method capability to establish the accuracy and precision of the method. This is to be run following the calibration described in section 10 of this method.

9.2.1 Prepare a series of identical spiked rubber standards as described in section 9.3 of this method. A sufficient number to determine statistical information on the test should be run. Ten may be a suitable number, depending on the quality control methodology used at the laboratory running the tests. These are run in the same manner as unknown samples (see section 11 of this method).

9.2.2 Determine mean and standard deviation for the results. Use these to determine the capability of the method and to calculate suitable control limits for the ongoing performance check which will utilize the same standards.

9.2.3 Prepare several additional spiked rubber standards and run 2 each day to determine the suitability of storage of the samples for 24, 48 and 72 hours or longer if longer storage times are desired.

9.3 A spiked rubber standard should be run on a regular basis to verify system performance. This would probably be done daily if samples are run daily. This is prepared in the same manner as the calibration standards (section 10.1 of this method), except that only one concentration of toluene and styrene is prepared. Choose concentrations of toluene and styrene that fall in the middle of the range expected in the stripper crumb and then do not change these unless there is a major change in the composition of the unknowns. If it becomes necessary to change the composition of this standard the initial performance demonstration must be repeated with the new standard (section 9.2 of this method).

9.3.1 Each day prepare one spiked rubber standard to be run the following day. The dry rubber may be prepared in bulk and stored for any length of time consistent with the shelf life of the product. The addition of water and hydrocarbons must be performed daily and all the steps described under section 10.1 of this method must be followed.

9.3.2 Run the spiked rubber standard prepared the previous day. Record the results and plot on an appropriate control chart or other means of determining statistical control.

9.3.3 If the results for the standard indicate that the test is out of control then corrective action must be taken. This may include a check on procedures, instrument settings, maintenance or recalibration. Samples may be stored (see section 8.2 of this method) until compliance is demonstrated.

9.4 Recovery efficiency must be determined once for each sample type and whenever modifications are made to the method.

9.4.1 For each sample type collect 12 samples from the process (section 8.1 of this method). This should be done when the process is operating in a normal manner and residual hydrocarbon levels are in the normal range. Half the vials and caps should be tared, labeled “spiked” and numbered 1 through 6. The other vials are labeled “unspiked” and need not be tared but are also numbered 1 through 6. Immediately on sampling, the vials should be capped to prevent loss of volatiles. Allow all the samples to cool completely to ambient temperature. Reweigh each of the vials labeled “spiked” to determine the weight of wet crumb inside.

9.4.2 The dry weight of rubber present in the wet crumb is estimated by multiplying the weight of wet crumb by the fraction of nonvolatiles typical for the sample. If this is not known, an additional quantity of crumb may be sampled, weighed, dried in an oven and reweighed to determine the fraction of volatiles and nonvolatiles prior to starting this procedure.

9.4.3 To the vials labeled “spiked” add an amount of a mixture of toluene and styrene that is between 40 and 60 % of the amount expected in the crumb. This is done by removing the cap, adding the mixture by syringe, touching the tip of the needle to the sample in order to remove the drop and then immediately recapping the vials. The mixture is not added through the septum, because a punctured septum may leak and vent vapors as the vial is heated. The weights of toluene and styrene added may be calculated from the volumes of the mixture added, its composition and density, or may be determined by the weight of the vials and caps prior to and after addition. The exact dry weight of rubber present and the concentration of residual toluene and styrene are not known at this time so an exact calculation of the concentration of hydrocarbons is not possible until the test is completed.

9.4.4 Place all the vials onto a shaker or tumbler for 24 ±2 hours. This is essential in order for the hydrocarbons to be evenly distributed and completely absorbed into the rubber. If this is not followed the toluene and styrene will be mostly at the surface of the rubber and high results will be obtained.

9.4.5 Remove the vials from the shaker and tap them so that all the crumb settles to the bottom of the vials. Allow them to stand for 1 hour prior to analysis to allow any liquid to drain fully to the bottom.

9.4.6 Run the spiked and unspiked samples in the normal manner. Record the concentrations of toluene and styrene reported for each pair of spiked and unspiked samples with the same vial number.

9.4.7 Open each of the vials labeled “spiked”, remove all the rubber crumb and place it into a tarred drying pan. Place in a 100 deg C oven for two hours, cool and reweigh. Subtract the weight of the tare to give the dry weight of rubber in each spiked vial. Calculate the concentration of toluene and styrene spiked into each vial as percent of dry rubber weight. This will be slightly different for each vial since the weights of dry rubber will be different.

9.4.8 For each hydrocarbon calculate the average recovery efficiency (R) using the following equations:

R=R_Σ(Pn)/6 (average of the 6 individual Rn values)

Where:

Rn = (Cns—Cnu) / Sn

Where:

n=vial number

Cns=concentration of compound measured in spiked sample number n.

Cnu=concentration of compound measured in unspiked sample number n.

Sn=theoretical concentration of compound spiked into sample n calculated in step 9.4.7

9.4.9 A different R value should be obtained for each compound (styrene and toluene) and for each sample type.

9.4.10 A value of R between 0.70 and 1.30 is acceptable.

9.4.11 R is used to correct all reported results for each compound by dividing the measured results of each compound by the R for that compound for the same sample type (see section 12.2 of this method.)

10.0 Calibration

10.1 Calibration standards are prepared by dosing known amounts of the hydrocarbons of interest into vials containing known amounts of rubber and water.

10.1.1 Cut a sufficient quantity of dry rubber of the same type as will be analyzed into pieces about the same size as that of the crumb. Place these in a single layer on a piece of aluminum foil or other suitable surface and place into a forced air oven at 100 °C for four hours. This is to remove any residual hydrocarbons that may be present. This step may be performed in advance.

10.1.2 Into each of a series of vials add 3.0 g of the dry rubber.

10.1.3 Into each vial add 1.0 ml distilled water or an amount that is close to the amount that will be present in the unknowns. The exact amount of water present does not have much effect on the analysis, but it is necessary to have a saturated environment. The water will also aid in the uniform distribution of the spiked hydrocarbons over the surface of the rubber after the vials are placed on the shaker (in step 10.1.5 of this method).

10.1.4 Into each vial add varying amounts of toluene and styrene by microliter syringe and cap the vials immediately to prevent loss. The tip of the needle should be carefully touched to the rubber in order to transfer the last drop to the rubber. Toluene and styrene may first be mixed together in suitable proportions and added together if desired. The weights of toluene and styrene added may be calculated from the volumes of the mixture added, its composition and density, or may be determined by the weight of the vials and caps prior to and after addition. Concentrations of added hydrocarbons are calculated as percent of the dry rubber weight. At least 5 standards should be prepared with the amounts of hydrocarbons added being calculated to cover the entire range possible in the unknowns. Retain two samples with no added hydrocarbons as blanks.

10.1.5 Place all the vials onto a shaker or tumbler for 24 ±2 hours. This is essential in order for the hydrocarbons to be evenly distributed and completely absorbed into the rubber. If this is not followed the toluene and styrene will be mostly at the surface of the rubber and high results will be obtained.

10.1.6 Remove the vials from the shaker and tap them so that all the crumb settles to the bottom of the vials. Allow them to stand for 1 hour prior to analysis to allow any liquid to drain fully to the bottom.

10.2 Run the standards and blanks in the same manner as described for unknowns (section 11 of this method), starting with a blank, then in order of increasing hydrocarbon content and ending with the other blank.

10.3 Verify that the blanks are sufficiently free from toluene and styrene or any interfering hydrocarbons.

10.3.1 It is possible that trace levels may be present even in dry product. If levels are high enough that they will interfere with the calibration then the drying procedure in section 10.1.1 of this method should be reviewed and modified as needed to ensure that suitable standards can be prepared.

10.3.2 It is possible that the final blank is contaminated by the previous standard. If this is the case review and modify the sampler parameters as needed to eliminate this problem. If necessary it is possible to run blank samples between regular samples in order to reduce this problem, though it should not be necessary if the sampler is properly set up.

10.4 Enter the amounts of toluene and styrene added to each of the samples (as calculated in section 10.1.4 of this method) into the calibration table and perform a calibration utilizing the external standard method of analysis.

10.5 At low concentrations the calibration should be close to linear. If a wide range of levels are to be determined it may be desirable to apply a nonlinear calibration to get the best fit.

11.0 Procedure

11.1 Place the vials in the tray of the headspace sampler. Enter the starting and ending positions through the console of the sampler. For unknown samples each is run in duplicate to minimize the effect of variations in crumb composition. If excessive variation is noted it may be desirable to run more than two of each sample.

11.2 Make sure the correct method is loaded on the Chemstation. Turn on the gas flows and light the FID flame.

11.3 Start the sequence on the Chemstation. Press the START button on the headspace unit. The samples will be automatically injected after equilibrating for 30 minutes in the oven. As each sample is completed the Chemstation will calculate and print out the results as percent toluene and styrene in the crumb based on the dry weight of rubber.

12.0 Data Analysis and Calculations

12.1 For each set of duplicate samples calculate the average of the measured concentration of toluene and styrene. If more than two replicates of each sample are run calculate the average over all replicates.

12.2 For each sample correct the measured amounts of toluene and styrene using the following equation:

Corrected Result = Cm/R

Where:

Cm = Average measured concentration for that compound.

R = Recovery efficiency for that compound in the same sample type (see section 9.4 of this method)

12.3 Report the recovery efficiency (R) and the corrected results of toluene and styrene for each sample.

13.0 Method Performance

13.1 This method can be very sensitive and reproducible. The actual performance depends largely on the exact nature of the samples being analyzed. Actual performance must be determined by each laboratory for each sample type.

13.2 The main source of variation is the actual variation in the composition of non homogeneous crumb in a stripping system and the small sample sizes employed here. It therefore is the responsibility of each laboratory to determine the optimum number of replicates of each sample required to obtain accurate results.

14.0 Pollution Prevention

14.1 Samples should be kept sealed when possible in order to prevent evaporation of hydrocarbons.

14.2 When drying of samples is required it should be done in an oven which vents into a suitable device that can trap the hydrocarbons released.

14.3 Dispose of samples as described in section 15.

15.0 Waste Management

15.1 Excess stripper crumb and water as well as the contents of the used sample vials should be properly disposed of in accordance with local and federal regulations.

15.2 Preferably this will be accomplished by having a system of returning unused and spent samples to the process.

16.0 References

16.1 “HP 7694 Headspace Sampler—Operating and Service Manual”, Hewlett-Packard Company, publication number G1290-90310, June 1993.

Method 313B—The Determination of Residual Hydrocarbon in Solution Polymers by Capillary Gas Chromatography

1.0 Scope

1.1 This method is applicable to solution polymerized polybutadiene (PBD).

1.2 This method quantitatively determines n-hexane in wet crumb polymer at levels from 0.08 to 0.15% by weight.

1.3 This method may be extended to the determination of other hydrocarbons in solution produced polymers with proper experimentation and documentation.

2.0 Principle of Method

2.1 A weighed sample of polymer is dissolved in chloroform and the cement is coagulated with an isopropyl alcohol solution containing a specific amount of alpha-methyl styrene (AMS) as the internal standard. The extract of this coagulation is then injected into a gas chromatograph and separated into individual components. Quantification is achieved by the method of internal standardization.

3.0 Definitions

3.1 The definitions are included in the text as needed.

4.0 Interferences [Reserved]

5.0 Safety

5.1 This method may involve hazardous materials, operations, and equipment. This method does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this method to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

6.0 Equipment and Supplies

6.1 Analytical balance, 160 g capacity, 0.1 mg resolution

6.2 Bottles, 2-oz capacity with poly-cap screw lids

6.3 Mechanical shaker

6.4 Syringe, 10-ul capacity

6.5 Syringe, 2.5-ml capacity, with 22 gauge 1.25 inch needle, PP/PE material, disposable

6.6 Gas chromatograph, Hewlett-Packard model 5890, or equivalent, configured with FID, split injector packed with silanized glass wool.

6.6.1 Establish the following gas chromatographic conditions, and allow the system to thoroughly equilibrate before use.

6.6.2 Injector parameters:

Injection technique=Split

Injector split flow=86 ml/min

Injector temperature=225 deg C

6.6.3 Oven temperature program:

Initial temperature=40 deg C

Initial time=6 min

Program rate=10 deg C/min

Upper limit temperature=175 deg C

Upper limit interval=10 min

6.6.4 Detector parameters:

Detector temperature=300 deg C

Hydrogen flow=30 ml/min

Air flow=350 ml/min

Nitrogen make up=26 ml/min

6.7 Gas chromatographic columns: SE-54 (5%-phenyl) (1%-vinyl)-methylpolysiloxane, 15 M×0.53 mm ID with a 1.2 micron film thickness, and a Carbowax 20M (polyethylene glycol), 15 M×0.53 mm ID with a 1.2 micron film thickness.

6.7.1 Column assembly: using a 0.53 mm ID butt connector union, join the 15 M×0.53 mm SE-54 column to the 15 M×0.53 mm Carbowax 20M. The SE-54 column will be inserted into the injector and the Carbowax 20M inserted into the detector after they have been joined.

6.7.2 Column parameters:

Helium flow=2.8 ml/min

Helium headpressure=2 psig

6.8 Centrifuge

6.9 Data collection system, Hewlett-Packard Model 3396, or equivalent

6.10 Pipet, 25-ml capacity, automatic dispensing, and 2 liter reservoir

6.11 Pipet, 2-ml capacity, volumetric delivery, class A

6.12 Flasks, 100 and 1000-ml capacity, volumetric, class A

6.13 Vial, serum, 50-ml capacity, red rubber septa and crimp ring seals

6.14 Sample collection basket fabricated out of wire mesh to allow for drainage

7.0 Chemicals and Reagents

CHEMICALS:

7.1 alpha-Methyl Styrene, C9H10, 99+% purity, CAS 98-83-9

7.2 n-Hexane, C6H14, 99+% purity, CAS 110-54-3

7.3 Isopropyl alcohol, C3H8O 99.5+% purity, reagent grade, CAS 67-63-0

7.4 Chloroform, CHCl3, 99% min., CAS 67-66-3

REAGENTS:

7.5 Internal Standard Stock Solution: 10 mg/25 ml AMS in isopropyl alcohol.

7.5.1 Into a 25-ml beaker, weigh 0.4 g of AMS to the nearest 0.1 mg.

7.5.2 Quantitatively transfer this AMS into a 1-L volumetric flask. Dilute to the mark with isopropyl alcohol.

7.5.3 Transfer this solution to the automatic dispensing pipet reservoir. This will be labeled the AMS STOCK SOLUTION.

7.6 n-Hexane Stock Solution: 13mg/2ml hexane in isopropyl alcohol.

7.6.1 Into a 100-ml volumetric flask, weigh 0.65 g of n-hexane to the nearest 0.1 mg.

7.6.2 Dilute to the mark with isopropyl alcohol. This solution will be labeled the n-HEXANE STOCK SOLUTION.

8.0 Sample Collection, Preservation and Storage

8.1 A sampling device similar to Figure 1 is used to collect a non-vented crumb rubber sample at a location that is after the stripping operation but before the sample is exposed to the atmosphere.

8.2 The crumb rubber is allowed to cool before opening the sampling device and removing the sample.

8.3 The sampling device is opened and the crumb rubber sample is collected in the sampling basket.

8.4 One pound of crumb rubber sample is placed into a polyethylene bag. The bag is labeled with the time, date and sample location.

8.5 The sample should be delivered to the laboratory for testing within one hour of sampling.

8.6 Laboratory testing will be done within 3 hours of the sampling time.

8.7 No special storage conditions are required unless the storage time exceeds 3 hours in which case refrigeration of the samples is recommended.

9.0 Quality Control

9.1 For each sample type, 12 samples shall be obtained from the process for the recovery study. Half of the vials and caps shall be tared, labeled “spiked”, and numbered 1 through 6. The other vials shall be labeled “unspiked” and need not be tared, but are also numbered 1 through 6.

9.2 Determine the % moisture content of the crumb sample. After determining the % moisture content, the correction factor for calculating the dry crumb weight can be determined by using the equation in section 12.2 of this method.

9.3 Run the spiked and unspiked samples in the normal manner. Record the concentrations of the n-hexane content of the mixed hexane reported for each pair of spiked and unspiked samples.

9.4 For the recovery study, each sample of crumb shall be dissolved in chloroform containing a known amount of mixed hexane solvent.

9.5 For each hydrocarbon, calculate the recovery efficiency (R) using the following equations:

Mr = Ms−Mu

R=Mr/S

Where:

Mu = Measured amount of compound in the unspiked sample

Ms = Measured amount of compound in the spiked sample

Mr = Measured amount of the spiked compound

S=Amount of compound added to the spiked sample

R=Fraction of spiked compound recovered

9.6 Normally a value of R between 0.70 and 1.30 is acceptable.

9.7 R is used to correct all reported results for each compound by dividing the measured results of each compound by the R for that compound for the same sample type.

10.0 Calibration

10.1 Using the AMS STOCK SOLUTION equipped with the automatic dispensing pipet (7.5.3 of this method), transfer 25.0 ml of the internal standard solution into an uncapped 50-ml serum vial.

10.2 Using a 2.0 ml volumetric pipet, quantitatively transfer 2.0 ml of the n-HEXANE STOCK SOLUTION (7.6.2 of this method) into the 50-ml serum vial and cap. This solution will be labeled the CALIBRATION SOLUTION.

10.3 Using the conditions prescribed (6.6 of this method), inject 1 µl of the supernate.

10.4 Obtain the peak areas and calculate the response factor as described in the calculations section (12.1 of this method).

11.0 Procedure

11.1 Determination of Dry Polymer Weight

11.1.1 Remove wet crumb from the polyethylene bag and place on paper towels to absorb excess surface moisture.

11.1.2 Cut small slices or cubes from the center of the crumb sample to improve sample uniformity and further eliminate surface moisture.

11.1.3 A suitable gravimetric measurement should be made on a sample of this wet crumb to determine the correction factor needed to calculate the dry polymer weight.

11.2 Determination of n-Hexane in Wet Crumb

11.2.1 Remove wet crumb from the polyethylene bag and place on paper towels to absorb excess surface moisture.

11.2.2 Cut small slices or cubes from the center of the crumb sample to improve sample uniformity and further eliminate surface moisture.

11.2.3 Into a tared 2 oz bottle, weigh 1.5 g of wet polymer to the nearest 0.1 mg.

11.2.4 Add 25 ml of chloroform to the 2 oz bottle and cap.

11.2.5 Using a mechanical shaker, shake the bottle until the polymer dissolves.

11.2.6 Using the autodispensing pipet, add 25.0 ml of the AMS STOCK SOLUTION (7.5.3 of this method) to the dissolved polymer solution and cap.

11.2.7 Using a mechanical shaker, shake the bottle for 10 minutes to coagulate the dissolved polymer.

11.2.8 Centrifuge the sample for 3 minutes at 2000 rpm.

11.2.9 Using the conditions prescribed (6.6 of this method), chromatograph 1 µl of the supernate.

11.2.10 Obtain the peak areas and calculate the concentration of the component of interest as described in the calculations (12.2 of this method).

12.0 Calculations

12.1 Calibration:

RFx = (Wx × Ais) / (Wis × Ax)

Where:

RFx = the relative response factor for n-hexane

Wx = the weight (g) of n-hexane in the CALIBRATION

SOLUTION

Ais = the area of AMS

Wis = the weight (g) of AMS in the CALIBRATION SOLUTION

Ax = the area of n-hexane

12.2 Procedure:

12.2.1 Correction Factor for calculating dry crumb weight.

F=1—(% moisture / 100)

Where:

F=Correction factor for calculating dry crumb weight

% moisture determined by appropriate method

12.2.2 Moisture adjustment for chromatographic determination.

Ws = F × Wc

Where:

Ws = the weight (g) of the dry polymer corrected for moisture

F=Correction factor for calculating dry crumb weight

Wc = the weight (g) of the wet crumb in section 9.6

12.2.3 Concentration (ppm) of hexane in the wet crumb.

ppmx = (Ax * RFx * Wis * 10000) / (Ais * Ws)

Where:

ppmx = parts per million of n-hexane in the polymer

Ax = the area of n-hexane

RFx = the relative response factor for n-hexane

Wis = the weight (g) of AMS in the sample solution

Ais = the area of AMS

Ws = the weight (g) of the dry polymer corrected for moisture

13.0 Method Performance

13.1 Precision for the method was determined at the 0.08% level.

The standard deviation was 0.01 and the percent relative standard deviation (RSD) was 16.3 % with five degrees of freedom.

14.0 Waste Generation

14.1 Waste generation should be minimized where possible.

15.0 Waste Management

15.1 Discard liquid chemical waste into the chemical waste drum.

15.2 Discard polymer waste into the polymer waste container.

16.0 References

16.1 This method is based on Goodyear Chemical Division Test Method E-964.

Method 315—Determination of Particulate and Methylene Chloride Extractable Matter (MCEM) From Selected Sources at Primary Aluminum Production Facilities

Note: This method does not include all of the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and analytical) essential to its performance. Some material is incorporated by reference from other methods in this part. Therefore, to obtain reliable results, persons using this method should have a thorough knowledge of at least the following additional test methods: Method 1, Method 2, Method 3, and Method 5 of 40 CFR part 60, appendix A.

1.0 Scope and Application

1.1 Analytes. Particulate matter (PM). No CAS number assigned. Methylene chloride extractable matter (MCEM). No CAS number assigned.

1.2 Applicability. This method is applicable for the simultaneous determination of PM and MCEM when specified in an applicable regulation. This method was developed by consensus with the Aluminum Association and the U.S. Environmental Protection Agency (EPA) and has limited precision estimates for MCEM; it should have similar precision to Method 5 for PM in 40 CFR part 60, appendix A since the procedures are similar for PM.

1.3 Data quality objectives. Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.

2.0 Summary of Method

Particulate matter and MCEM are withdrawn isokinetically from the source. PM is collected on a glass fiber filter maintained at a temperature in the range of 120 ±14 °C (248 ±25 °F) or such other temperature as specified by an applicable subpart of the standards or approved by the Administrator for a particular application. The PM mass, which includes any material that condenses on the probe and is subsequently removed in an acetone rinse or on the filter at or above the filtration temperature, is determined gravimetrically after removal of uncombined water. MCEM is then determined by adding a methylene chloride rinse of the probe and filter holder, extracting the condensable hydrocarbons collected in the impinger water, adding an acetone rinse followed by a methylene chloride rinse of the sampling train components after the filter and before the silica gel impinger, and determining residue gravimetrically after evaporating the solvents.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

This method may involve hazardous materials, operations, and equipment. This method does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this method to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to performing this test method.

6.0 Equipment and Supplies

Note: Mention of trade names or specific products does not constitute endorsement by the EPA.

6.1 Sample collection. The following items are required for sample collection:

6.1.1   Sampling train. A schematic of the sampling train used in this method is shown in Figure 5-1, Method 5, 40 CFR part 60, appendix A-3. Complete construction details are given in APTD-0581 (Reference 2 in section 17.0 of this method); commercial models of this train are also available. For changes from APTD-0581 and for allowable modifications of the train shown in Figure 5-1, Method 5, 40 CFR part 60, appendix A-3, see the following subsections.

Note: The operating and maintenance procedures for the sampling train are described in APTD-0576 (Reference 3 in section 17.0 of this method). Since correct usage is important in obtaining valid results, all users should read APTD-0576 and adopt the operating and maintenance procedures outlined in it, unless otherwise specified herein. Alternative mercury-free thermometers may be used if the thermometers are, at a minimum, equivalent in terms of performance or suitably effective for the specific temperature measurement application. The use of grease for sealing sampling train components is not recommended because many greases are soluble in methylene chloride. The sampling train consists of the following components:

6.1.1.1 Probe nozzle. Glass or glass lined with sharp, tapered leading edge. The angle of taper shall be ≤30 °, and the taper shall be on the outside to preserve a constant internal diameter. The probe nozzle shall be of the button-hook or elbow design, unless otherwise specified by the Administrator. Other materials of construction may be used, subject to the approval of the Administrator. A range of nozzle sizes suitable for isokinetic sampling should be available. Typical nozzle sizes range from 0.32 to 1.27 cm ( 18 to 12 in.) inside diameter (ID) in increments of 0.16 cm (1/16 in.). Larger nozzle sizes are also available if higher volume sampling trains are used. Each nozzle shall be calibrated according to the procedures outlined in section 10.0 of this method.

6.1.1.2 Probe liner. Borosilicate or quartz glass tubing with a heating system capable of maintaining a probe gas temperature at the exit end during sampling of 120 ±14 °C (248±25 °F), or such other temperature as specified by an applicable subpart of the standards or approved by the Administrator for a particular application. Because the actual temperature at the outlet of the probe is not usually monitored during sampling, probes constructed according to APTD-0581 and using the calibration curves of APTD-0576 (or calibrated according to the procedure outlined in APTD-0576) will be considered acceptable. Either borosilicate or quartz glass probe liners may be used for stack temperatures up to about 480 °C (900 °F); quartz liners shall be used for temperatures between 480 and 900 °C (900 and 1,650 °F). Both types of liners may be used at higher temperatures than specified for short periods of time, subject to the approval of the Administrator. The softening temperature for borosilicate glass is 820 °C (1,500 °F) and for quartz glass it is 1,500 °C (2,700 °F).

6.1.1.3 Pitot tube. Type S, as described in section 6.1 of Method 2, 40 CFR part 60, appendix A, or other device approved by the Administrator. The pitot tube shall be attached to the probe (as shown in Figure 5-1 of Method 5, 40 CFR part 60, appendix A) to allow constant monitoring of the stack gas velocity. The impact (high pressure) opening plane of the pitot tube shall be even with or above the nozzle entry plane (see Method 2, Figure 2-6b, 40 CFR part 60, appendix A) during sampling. The Type S pitot tube assembly shall have a known coefficient, determined as outlined in section 10.0 of Method 2, 40 CFR part 60, appendix A.

6.1.1.4 Differential pressure gauge. Inclined manometer or equivalent device (two), as described in section 6.2 of Method 2, 40 CFR part 60, appendix A. One manometer shall be used for velocity head (Dp) readings, and the other, for orifice differential pressure readings.

6.1.1.5 Filter holder. Borosilicate glass, with a glass frit filter support and a silicone rubber gasket. The holder design shall provide a positive seal against leakage from the outside or around the filter. The holder shall be attached immediately at the outlet of the probe (or cyclone, if used).

6.1.1.6 Filter heating system. Any heating system capable of maintaining a temperature around the filter holder of 120 ±14 °C (248 ±25 °F) during sampling, or such other temperature as specified by an applicable subpart of the standards or approved by the Administrator for a particular application. Alternatively, the tester may opt to operate the equipment at a temperature lower than that specified. A temperature gauge capable of measuring temperature to within 3 °C (5.4 °F) shall be installed so that the temperature around the filter holder can be regulated and monitored during sampling. Heating systems other than the one shown in APTD-0581 may be used.

6.1.1.7 Temperature sensor. A temperature sensor capable of measuring temperature to within ±3 °C (5.4 °F) shall be installed so that the sensing tip of the temperature sensor is in direct contact with the sample gas, and the temperature around the filter holder can be regulated and monitored during sampling.

6.1.1.8 Condenser. The following system shall be used to determine the stack gas moisture content: four glass impingers connected in series with leak-free ground glass fittings. The first, third, and fourth impingers shall be of the Greenburg-Smith design, modified by replacing the tip with a 1.3 cm (1/2 in.) ID glass tube extending to about 1.3 cm (1/2 in.) from the bottom of the flask. The second impinger shall be of the Greenburg-Smith design with the standard tip. The first and second impingers shall contain known quantities of water (section 8.3.1 of this method), the third shall be empty, and the fourth shall contain a known weight of silica gel or equivalent desiccant. A temperature sensor capable of measuring temperature to within 1 °C (2 °F) shall be placed at the outlet of the fourth impinger for monitoring.

6.1.1.9 Metering system. Vacuum gauge, leak-free pump, temperature sensors capable of measuring temperature to within 3 °C (5.4 °F), dry gas meter (DGM) capable of measuring volume to within 2 percent, and related equipment, as shown in Figure 5-1 of Method 5, 40 CFR part 60, appendix A. Other metering systems capable of maintaining sampling rates within 10 percent of isokinetic and of determining sample volumes to within 2 percent may be used, subject to the approval of the Administrator. When the metering system is used in conjunction with a pitot tube, the system shall allow periodic checks of isokinetic rates.

6.1.1.10 Sampling trains using metering systems designed for higher flow rates than that described in APTD-0581 or APTD-0576 may be used provided that the specifications of this method are met.

6.1.2 Barometer. Mercury, aneroid, or other barometer capable of measuring atmospheric pressure to within 2.5 mm (0.1 in.) Hg.

Note: The barometric reading may be obtained from a nearby National Weather Service station. In this case, the station value (which is the absolute barometric pressure) shall be requested and an adjustment for elevation differences between the weather station and sampling point shall be made at a rate of minus 2.5 mm (0.1 in) Hg per 30 m (100 ft) elevation increase or plus 2.5 mm (0.1 in) Hg per 30 m (100 ft) elevation decrease.

6.1.3 Gas density determination equipment. Temperature sensor and pressure gauge, as described in sections 6.3 and 6.4 of Method 2, 40 CFR part 60, appendix A, and gas analyzer, if necessary, as described in Method 3, 40 CFR part 60, appendix A. The temperature sensor shall, preferably, be permanently attached to the pitot tube or sampling probe in a fixed configuration, such that the tip of the sensor extends beyond the leading edge of the probe sheath and does not touch any metal. Alternatively, the sensor may be attached just prior to use in the field. Note, however, that if the temperature sensor is attached in the field, the sensor must be placed in an interference-free arrangement with respect to the Type S pitot tube openings (see Method 2, Figure 2-4, 40 CFR part 60, appendix A). As a second alternative, if a difference of not more than 1 percent in the average velocity measurement is to be introduced, the temperature sensor need not be attached to the probe or pitot tube. (This alternative is subject to the approval of the Administrator.)

6.2 Sample recovery. The following items are required for sample recovery:

6.2.1 Probe-liner and probe-nozzle brushes. Nylon or Teflon® bristle brushes with stainless steel wire handles. The probe brush shall have extensions (at least as long as the probe) constructed of stainless steel, nylon, Teflon®, or similarly inert material. The brushes shall be properly sized and shaped to brush out the probe liner and nozzle.

6.2.2 Wash bottles. Glass wash bottles are recommended. Polyethylene or tetrafluoroethylene (TFE) wash bottles may be used, but they may introduce a positive bias due to contamination from the bottle. It is recommended that acetone not be stored in polyethylene or TFE bottles for longer than a month.

6.2.3 Glass sample storage containers. Chemically resistant, borosilicate glass bottles, for acetone and methylene chloride washes and impinger water, 500 ml or 1,000 ml. Screw-cap liners shall either be rubber-backed Teflon® or shall be constructed so as to be leak-free and resistant to chemical attack by acetone or methylene chloride. (Narrow-mouth glass bottles have been found to be less prone to leakage.) Alternatively, polyethylene bottles may be used.

6.2.4 Petri dishes. For filter samples, glass, unless otherwise specified by the Administrator.

6.2.5 Graduated cylinder and/or balance. To measure condensed water, acetone wash and methylene chloride wash used during field recovery of the samples, to within 1 ml or 1 g. Graduated cylinders shall have subdivisions no greater than 2 ml. Most laboratory balances are capable of weighing to the nearest 0.5 g or less. Any such balance is suitable for use here and in section 6.3.4 of this method.

6.2.6 Plastic storage containers. Air-tight containers to store silica gel.

6.2.7 Funnel and rubber policeman. To aid in transfer of silica gel to container; not necessary if silica gel is weighed in the field.

6.2.8 Funnel. Glass or polyethylene, to aid in sample recovery.

6.3 Sample analysis. The following equipment is required for sample analysis:

6.3.1 Glass or Teflon® weighing dishes.

6.3.2 Desiccator. It is recommended that fresh desiccant be used to minimize the chance for positive bias due to absorption of organic material during drying.

6.3.3 Analytical balance. To measure to within 0.l mg.

6.3.4 Balance. To measure to within 0.5 g.

6.3.5 Beakers. 250 ml.

6.3.6 Hygrometer. To measure the relative humidity of the laboratory environment.

6.3.7 Temperature sensor. To measure the temperature of the laboratory environment.

6.3.8 Buchner fritted funnel. 30 ml size, fine (<50 micron)-porosity fritted glass.

6.3.9 Pressure filtration apparatus.

6.3.10 Aluminum dish. Flat bottom, smooth sides, and flanged top, 18 mm deep and with an inside diameter of approximately 60 mm.

7.0 Reagents and Standards

7.l Sample collection. The following reagents are required for sample collection:

7.1.1 Filters. Glass fiber filters, without organic binder, exhibiting at least 99.95 percent efficiency (<0.05 percent penetration) on 0.3 micron dioctyl phthalate smoke particles. The filter efficiency test shall be conducted in accordance with ASTM Method D 2986-95A (incorporated by reference in §63.841 of this part). Test data from the supplier's quality control program are sufficient for this purpose. In sources containing S02 or S03, the filter material must be of a type that is unreactive to S02 or S03. Reference 10 in section 17.0 of this method may be used to select the appropriate filter.

7.1.2 Silica gel. Indicating type, 6 to l6 mesh. If previously used, dry at l75 °C (350 °F) for 2 hours. New silica gel may be used as received. Alternatively, other types of desiccants (equivalent or better) may be used, subject to the approval of the Administrator.

7.1.3 Water. When analysis of the material caught in the impingers is required, deionized distilled water shall be used. Run blanks prior to field use to eliminate a high blank on test samples.

7.1.4 Crushed ice.

7.1.5 Stopcock grease. Acetone-insoluble, heat-stable silicone grease. This is not necessary if screw-on connectors with Teflon” sleeves, or similar, are used. Alternatively, other types of stopcock grease may be used, subject to the approval of the Administrator. [Caution: Many stopcock greases are methylene chloride-soluble. Use sparingly and carefully remove prior to recovery to prevent contamination of the MCEM analysis.]

7.2 Sample recovery. The following reagents are required for sample recovery:

7.2.1 Acetone. Acetone with blank values <1 ppm, by weight residue, is required. Acetone blanks may be run prior to field use, and only acetone with low blank values may be used. In no case shall a blank value of greater than 1E-06 of the weight of acetone used be subtracted from the sample weight.

Note: This is more restrictive than Method 5, 40 CFR part 60, appendix A. At least one vendor (Supelco Incorporated located in Bellefonte, Pennsylvania) lists <1 mg/l as residue for its Environmental Analysis Solvents.

7.2.2 Methylene chloride. Methylene chloride with a blank value <1.5 ppm, by weight, residue. Methylene chloride blanks may be run prior to field use, and only methylene chloride with low blank values may be used. In no case shall a blank value of greater than 1.6E-06 of the weight of methylene chloride used be subtracted from the sample weight.

Note: A least one vendor quotes <1 mg/l for Environmental Analysis Solvents-grade methylene chloride.

7.3 Sample analysis. The following reagents are required for sample analysis:

7.3.l Acetone. Same as in section 7.2.1 of this method.

7.3.2 Desiccant. Anhydrous calcium sulfate, indicating type. Alternatively, other types of desiccants may be used, subject to the approval of the Administrator.

7.3.3 Methylene chloride. Same as in section 7.2.2 of this method.

8.0 Sample Collection, Preservation, Storage, and Transport

Note: The complexity of this method is such that, in order to obtain reliable results, testers should be trained and experienced with the test procedures.

8.1   Pretest preparation. It is suggested that sampling equipment be maintained according to the procedures described in APTD-0576. Alternative mercury-free thermometers may be used if the thermometers are at a minimum equivalent in terms of performance or suitably effective for the specific temperature measurement application.

8.1.1 Weigh several 200 g to 300 g portions of silica gel in airtight containers to the nearest 0.5 g. Record on each container the total weight of the silica gel plus container. As an alternative, the silica gel need not be preweighed but may be weighed directly in its impinger or sampling holder just prior to train assembly.

8.1.2 A batch of glass fiber filters, no more than 50 at a time, should placed in a soxhlet extraction apparatus and extracted using methylene chloride for at least 16 hours. After extraction, check filters visually against light for irregularities, flaws, or pinhole leaks. Label the shipping containers (glass or plastic petri dishes), and keep the filters in these containers at all times except during sampling and weighing.

8.1.3 Desiccate the filters at 20 ±5.6 °C (68 ±10 °F) and ambient pressure for at least 24 hours and weigh at intervals of at least 6 hours to a constant weight, i.e., <0.5 mg change from previous weighing; record results to the nearest 0.1 mg. During each weighing the filter must not be exposed to the laboratory atmosphere for longer than 2 minutes and a relative humidity above 50 percent. Alternatively (unless otherwise specified by the Administrator), the filters may be oven-dried at 104 °C (220 °F) for 2 to 3 hours, desiccated for 2 hours, and weighed. Procedures other than those described, which account for relative humidity effects, may be used, subject to the approval of the Administrator.

8.2 Preliminary determinations.

8.2.1 Select the sampling site and the minimum number of sampling points according to Method 1, 40 CFR part 60, appendix A or as specified by the Administrator. Determine the stack pressure, temperature, and the range of velocity heads using Method 2, 40 CFR part 60, appendix A; it is recommended that a leak check of the pitot lines (see section 8.1 of Method 2, 40 CFR part 60, appendix A) be performed. Determine the moisture content using Approximation Method 4 (section 1.2 of Method 4, 40 CFR part 60, appendix A) or its alternatives to make isokinetic sampling rate settings. Determine the stack gas dry molecular weight, as described in section 8.6 of Method 2, 40 CFR part 60, appendix A; if integrated Method 3 sampling is used for molecular weight determination, the integrated bag sample shall be taken simultaneously with, and for the same total length of time as, the particulate sample run.

8.2.2 Select a nozzle size based on the range of velocity heads such that it is not necessary to change the nozzle size in order to maintain isokinetic sampling rates. During the run, do not change the nozzle size. Ensure that the proper differential pressure gauge is chosen for the range of velocity heads encountered (see section 8.2 of Method 2, 40 CFR part 60, appendix A).

8.2.3 Select a suitable probe liner and probe length such that all traverse points can be sampled. For large stacks, consider sampling from opposite sides of the stack to reduce the required probe length.

8.2.4 Select a total sampling time greater than or equal to the minimum total sampling time specified in the test procedures for the specific industry such that: (1) The sampling time per point is not less than 2 minutes (or some greater time interval as specified by the Administrator); and (2) the sample volume taken (corrected to standard conditions) will exceed the required minimum total gas sample volume. The latter is based on an approximate average sampling rate.

8.2.5 The sampling time at each point shall be the same. It is recommended that the number of minutes sampled at each point be an integer or an integer plus one-half minute, in order to eliminate timekeeping errors.

8.2.6 In some circumstances (e.g., batch cycles), it may be necessary to sample for shorter times at the traverse points and to obtain smaller gas sample volumes. In these cases, the Administrator's approval must first be obtained.

8.3 Preparation of sampling train.

8.3.1 During preparation and assembly of the sampling train, keep all openings where contamination can occur covered until just prior to assembly or until sampling is about to begin. Place l00 ml of water in each of the first two impingers, leave the third impinger empty, and transfer approximately 200 to 300 g of preweighed silica gel from its container to the fourth impinger. More silica gel may be used, but care should be taken to ensure that it is not entrained and carried out from the impinger during sampling. Place the container in a clean place for later use in the sample recovery. Alternatively, the weight of the silica gel plus impinger may be determined to the nearest 0.5 g and recorded.

8.3.2 Using a tweezer or clean disposable surgical gloves, place a labeled (identified) and weighed filter in the filter holder. Be sure that the filter is properly centered and the gasket properly placed so as to prevent the sample gas stream from circumventing the filter. Check the filter for tears after assembly is completed.

8.3.3 When glass liners are used, install the selected nozzle using a Viton A 0-ring when stack temperatures are less than 260 °C (500 °F) and an asbestos string gasket when temperatures are higher. See APTD-0576 for details. Mark the probe with heat-resistant tape or by some other method to denote the proper distance into the stack or duct for each sampling point.

8.3.4 Set up the train as in Figure 5-1 of Method 5, 40 CFR part 60, appendix A, using (if necessary) a very light coat of silicone grease on all ground glass joints, greasing only the outer portion (see APTD-0576) to avoid possibility of contamination by the silicone grease. Subject to the approval of the Administrator, a glass cyclone may be used between the probe and filter holder when the total particulate catch is expected to exceed 100 mg or when water droplets are present in the stack gas.

8.3.5 Place crushed ice around the impingers.

8.4 Leak-check procedures.

8.4.1 Leak check of metering system shown in Figure 5-1 of Method 5, 40 CFR part 60, appendix A. That portion of the sampling train from the pump to the orifice meter should be leak-checked prior to initial use and after each shipment. Leakage after the pump will result in less volume being recorded than is actually sampled. The following procedure is suggested (see Figure 5-2 of Method 5, 40 CFR part 60, appendix A): Close the main valve on the meter box. Insert a one-hole rubber stopper with rubber tubing attached into the orifice exhaust pipe. Disconnect and vent the low side of the orifice manometer. Close off the low side orifice tap. Pressurize the system to 13 to 18 cm (5 to 7 in.) water column by blowing into the rubber tubing. Pinch off the tubing, and observe the manometer for 1 minute. A loss of pressure on the manometer indicates a leak in the meter box; leaks, if present, must be corrected.

8.4.2 Pretest leak check. A pretest leak-check is recommended but not required. If the pretest leak-check is conducted, the following procedure should be used.

8.4.2.1 After the sampling train has been assembled, turn on and set the filter and probe heating systems to the desired operating temperatures. Allow time for the temperatures to stabilize. If a Viton A 0-ring or other leak-free connection is used in assembling the probe nozzle to the probe liner, leak-check the train at the sampling site by plugging the nozzle and pulling a 380 mm (15 in.) Hg vacuum.

Note: A lower vacuum may be used, provided that it is not exceeded during the test.

8.4.2.2 If an asbestos string is used, do not connect the probe to the train during the leak check. Instead, leak-check the train by first plugging the inlet to the filter holder (cyclone, if applicable) and pulling a 380 mm (15 in.) Hg vacuum. (See NOTE in section 8.4.2.1 of this method). Then connect the probe to the train and perform the leak check at approximately 25 mm (1 in.) Hg vacuum; alternatively, the probe may be leak-checked with the rest of the sampling train, in one step, at 380 mm (15 in.) Hg vacuum. Leakage rates in excess of 4 percent of the average sampling rate or 0.00057 m3/min (0.02 cfm), whichever is less, are unacceptable.

8.4.2.3 The following leak check instructions for the sampling train described in APTD-0576 and APTD-058l may be helpful. Start the pump with the bypass valve fully open and the coarse adjust valve completely closed. Partially open the coarse adjust valve and slowly close the bypass valve until the desired vacuum is reached. Do not reverse the direction of the bypass valve, as this will cause water to back up into the filter holder. If the desired vacuum is exceeded, either leak-check at this higher vacuum or end the leak check as shown below and start over.

8.4.2.4 When the leak check is completed, first slowly remove the plug from the inlet to the probe, filter holder, or cyclone (if applicable) and immediately turn off the vacuum pump. This prevents the water in the impingers from being forced backward into the filter holder and the silica gel from being entrained backward into the third impinger.

8.4.3 Leak checks during sample run. If, during the sampling run, a component (e.g., filter assembly or impinger) change becomes necessary, a leak check shall be conducted immediately before the change is made. The leak check shall be done according to the procedure outlined in section 8.4.2 of this method, except that it shall be done at a vacuum equal to or greater than the maximum value recorded up to that point in the test. If the leakage rate is found to be no greater than 0.00057 m3/min (0.02 cfm) or 4 percent of the average sampling rate (whichever is less), the results are acceptable, and no correction will need to be applied to the total volume of dry gas metered; if, however, a higher leakage rate is obtained, either record the leakage rate and plan to correct the sample volume as shown in section 12.3 of this method or void the sample run.

Note: Immediately after component changes, leak checks are optional; if such leak checks are done, the procedure outlined in section 8.4.2 of this method should be used.

8.4.4 Post-test leak check. A leak check is mandatory at the conclusion of each sampling run. The leak check shall be performed in accordance with the procedures outlined in section 8.4.2 of this method, except that it shall be conducted at a vacuum equal to or greater than the maximum value reached during the sampling run. If the leakage rate is found to be no greater than 0.00057 m3/min (0.02 cfm) or 4 percent of the average sampling rate (whichever is less), the results are acceptable, and no correction need be applied to the total volume of dry gas metered. If, however, a higher leakage rate is obtained, either record the leakage rate and correct the sample volume, as shown in section 12.4 of this method, or void the sampling run.

8.5 Sampling train operation. During the sampling run, maintain an isokinetic sampling rate (within l0 percent of true isokinetic unless otherwise specified by the Administrator) and a temperature around the filter of 120 14 °C (248 25 °F), or such other temperature as specified by an applicable subpart of the standards or approved by the Administrator.

8.5.1 For each run, record the data required on a data sheet such as the one shown in Figure 5-2 of Method 5, 40 CFR part 60, appendix A. Be sure to record the initial reading. Record the DGM readings at the beginning and end of each sampling time increment, when changes in flow rates are made, before and after each leak-check, and when sampling is halted. Take other readings indicated by Figure 5-2 of Method 5, 40 CFR part 60, appendix A at least once at each sample point during each time increment and additional readings when significant changes (20 percent variation in velocity head readings) necessitate additional adjustments in flow rate. Level and zero the manometer. Because the manometer level and zero may drift due to vibrations and temperature changes, make periodic checks during the traverse.

8.5.2 Clean the portholes prior to the test run to minimize the chance of sampling deposited material. To begin sampling, remove the nozzle cap and verify that the filter and probe heating systems are up to temperature and that the pitot tube and probe are properly positioned. Position the nozzle at the first traverse point with the tip pointing directly into the gas stream. Immediately start the pump and adjust the flow to isokinetic conditions. Nomographs are available, which aid in the rapid adjustment of the isokinetic sampling rate without excessive computations. These nomographs are designed for use when the Type S pitot tube coefficient (Cp) is 0.85 # 0.02 and the stack gas equivalent density (dry molecular weight) is 29 ±4. APTD-0576 details the procedure for using the nomographs. If Cp and Md are outside the above-stated ranges, do not use the nomographs unless appropriate steps (see Reference 7 in section 17.0 of this method) are taken to compensate for the deviations.

8.5.3 When the stack is under significant negative pressure (height of impinger stem), close the coarse adjust valve before inserting the probe into the stack to prevent water from backing into the filter holder. If necessary, the pump may be turned on with the coarse adjust valve closed.

8.5.4 When the probe is in position, block off the openings around the probe and porthole to prevent unrepresentative dilution of the gas stream.

8.5.5 Traverse the stack cross-section, as required by Method 1, 40 CFR part 60, appendix A or as specified by the Administrator, being careful not to bump the probe nozzle into the stack walls when sampling near the walls or when removing or inserting the probe through the portholes; this minimizes the chance of extracting deposited material.

8.5.6 During the test run, make periodic adjustments to keep the temperature around the filter holder at the proper level; add more ice and, if necessary, salt to maintain a temperature of less than 20 °C (68 °F) at the condenser/silica gel outlet. Also, periodically check the level and zero of the manometer.

8.5.7 If the pressure drop across the filter becomes too high, making isokinetic sampling difficult to maintain, the filter may be replaced in the midst of the sample run. It is recommended that another complete filter assembly be used rather than attempting to change the filter itself. Before a new filter assembly is installed, conduct a leak check (see section 8.4.3 of this method). The total PM weight shall include the summation of the filter assembly catches.

8.5.8 A single train shall be used for the entire sample run, except in cases where simultaneous sampling is required in two or more separate ducts or at two or more different locations within the same duct, or in cases where equipment failure necessitates a change of trains. In all other situations, the use of two or more trains will be subject to the approval of the Administrator.

Note: When two or more trains are used, separate analyses of the front-half and (if applicable) impinger catches from each train shall be performed, unless identical nozzle sizes were used in all trains, in which case the front-half catches from the individual trains may be combined (as may the impinger catches) and one analysis of the front-half catch and one analysis of the impinger catch may be performed.

8.5.9 At the end of the sample run, turn off the coarse adjust valve, remove the probe and nozzle from the stack, turn off the pump, record the final DGM reading, and then conduct a post-test leak check, as outlined in section 8.4.4 of this method. Also leak-check the pitot lines as described in section 8.1 of Method 2, 40 CFR part 60, appendix A. The lines must pass this leak check in order to validate the velocity head data.

8.6 Calculation of percent isokinetic. Calculate percent isokinetic (see Calculations, section 12.12 of this method) to determine whether a run was valid or another test run should be made. If there was difficulty in maintaining isokinetic rates because of source conditions, consult the Administrator for possible variance on the isokinetic rates.

8.7 Sample recovery.

8.7.1 Proper cleanup procedure begins as soon as the probe is removed from the stack at the end of the sampling period. Allow the probe to cool.

8.7.2 When the probe can be safely handled, wipe off all external PM near the tip of the probe nozzle and place a cap over it to prevent losing or gaining PM. Do not cap off the probe tip tightly while the sampling train is cooling down. This would create a vacuum in the filter holder, thus drawing water from the impingers into the filter holder.

8.7.3 Before moving the sample train to the cleanup site, remove the probe from the sample train, wipe off the silicone grease, and cap the open outlet of the probe. Be careful not to lose any condensate that might be present. Wipe off the silicone grease from the filter inlet where the probe was fastened and cap it. Remove the umbilical cord from the last impinger and cap the impinger. If a flexible line is used between the first impinger or condenser and the filter holder, disconnect the line at the filter holder and let any condensed water or liquid drain into the impingers or condenser. After wiping off the silicone grease, cap off the filter holder outlet and impinger inlet. Ground-glass stoppers, plastic caps, or serum caps may be used to close these openings.

8.7.4 Transfer the probe and filter-impinger assembly to the cleanup area. This area should be clean and protected from the wind so that the chances of contaminating or losing the sample will be minimized.

8.7.5 Save a portion of the acetone and methylene chloride used for cleanup as blanks. Take 200 ml of each solvent directly from the wash bottle being used and place it in glass sample containers labeled “acetone blank” and “methylene chloride blank,” respectively.

8.7.6 Inspect the train prior to and during disassembly and note any abnormal conditions. Treat the samples as follows:

8.7.6.1 Container No. 1. Carefully remove the filter from the filter holder, and place it in its identified petri dish container. Use a pair of tweezers and/or clean disposable surgical gloves to handle the filter. If it is necessary to fold the filter, do so such that the PM cake is inside the fold. Using a dry nylon bristle brush and/or a sharp-edged blade, carefully transfer to the petri dish any PM and/or filter fibers that adhere to the filter holder gasket. Seal the container.

8.7.6.2 Container No. 2. Taking care to see that dust on the outside of the probe or other exterior surfaces does not get into the sample, quantitatively recover PM or any condensate from the probe nozzle, probe fitting, probe liner, and front half of the filter holder by washing these components with acetone and placing the wash in a glass container. Perform the acetone rinse as follows:

8.7.6.2.1 Carefully remove the probe nozzle and clean the inside surface by rinsing with acetone from a wash bottle and brushing with a nylon bristle brush. Brush until the acetone rinse shows no visible particles, after which make a final rinse of the inside surface with acetone.

8.7.6.2.2 Brush and rinse the inside parts of the Swagelok fitting with acetone in a similar way until no visible particles remain.

8.7.6.2.3 Rinse the probe liner with acetone by tilting and rotating the probe while squirting acetone into its upper end so that all inside surfaces are wetted with acetone. Let the acetone drain from the lower end into the sample container. A funnel (glass or polyethylene) may be used to aid in transferring liquid washes to the container. Follow the acetone rinse with a probe brush. Hold the probe in an inclined position, squirt acetone into the upper end as the probe brush is being pushed with a twisting action through the probe, hold a sample container under the lower end of the probe, and catch any acetone and PM that is brushed from the probe. Run the brush through the probe three times or more until no visible PM is carried out with the acetone or until none remains in the probe liner on visual inspection. With stainless steel or other metal probes, run the brush through in the above-described manner at least six times, since metal probes have small crevices in which PM can be entrapped. Rinse the brush with acetone and quantitatively collect these washings in the sample container. After the brushing, make a final acetone rinse of the probe as described above.

8.7.6.2.4 It is recommended that two people clean the probe to minimize sample losses. Between sampling runs, keep brushes clean and protected from contamination.

8.7.6.2.5 After ensuring that all joints have been wiped clean of silicone grease, clean the inside of the front half of the filter holder by rubbing the surfaces with a nylon bristle brush and rinsing with acetone. Rinse each surface three times or more if needed to remove visible particulate. Make a final rinse of the brush and filter holder. Carefully rinse out the glass cyclone also (if applicable).

8.7.6.2.6 After rinsing the nozzle, probe, and front half of the filter holder with acetone, repeat the entire procedure with methylene chloride and save in a separate No. 2M container.

8.7.6.2.7 After acetone and methylene chloride washings and PM have been collected in the proper sample containers, tighten the lid on the sample containers so that acetone and methylene chloride will not leak out when it is shipped to the laboratory. Mark the height of the fluid level to determine whether leakage occurs during transport. Label each container to identify clearly its contents.

8.7.6.3 Container No. 3. Note the color of the indicating silica gel to determine whether it has been completely spent, and make a notation of its condition. Transfer the silica gel from the fourth impinger to its original container and seal the container. A funnel may make it easier to pour the silica gel without spilling. A rubber policeman may be used as an aid in removing the silica gel from the impinger. It is not necessary to remove the small amount of dust particles that may adhere to the impinger wall and are difficult to remove. Since the gain in weight is to be used for moisture calculations, do not use any water or other liquids to transfer the silica gel. If a balance is available in the field, follow the procedure for Container No. 3 in section 11.2.3 of this method.

8.7.6.4 Impinger water. Treat the impingers as follows:

8.7.6.4.1 Make a notation of any color or film in the liquid catch. Measure the liquid that is in the first three impingers to within 1 ml by using a graduated cylinder or by weighing it to within 0.5 g by using a balance (if one is available). Record the volume or weight of liquid present. This information is required to calculate the moisture content of the effluent gas.

8.7.6.4.2 Following the determination of the volume of liquid present, rinse the back half of the train with water, add it to the impinger catch, and store it in a container labeled 3W (water).

8.7.6.4.3 Following the water rinse, rinse the back half of the train with acetone to remove the excess water to enhance subsequent organic recovery with methylene chloride and quantitatively recover to a container labeled 3S (solvent) followed by at least three sequential rinsings with aliquots of methylene chloride. Quantitatively recover to the same container labeled 3S. Record separately the amount of both acetone and methylene chloride used to the nearest 1 ml or 0.5g.

Note: Because the subsequent analytical finish is gravimetric, it is okay to recover both solvents to the same container. This would not be recommended if other analytical finishes were required.

8.8 Sample transport. Whenever possible, containers should be shipped in such a way that they remain upright at all times.

9.0 Quality Control

9.1 Miscellaneous quality control measures.

SectionQuality control measureEffect
8.4, 10.1-10.6Sampling and equipment leak check and calibrationEnsure accurate measurement of stack gas flow rate, sample volume.

9.2 Volume metering system checks. The following quality control procedures are suggested to check the volume metering system calibration values at the field test site prior to sample collection. These procedures are optional.

9.2.1 Meter orifice check. Using the calibration data obtained during the calibration procedure described in section 10.3 of this method, determine the ΔHa for the metering system orifice. The ΔHa is the orifice pressure differential in units of in. H20 that correlates to 0.75 cfm of air at 528 °R and 29.92 in. Hg. The ΔHa is calculated as follows:

eCFR graphic er07oc97.008.gif

View or download PDF

Where

0.0319 = (0.0567 in. Hg/ °R)(0.75 cfm)2;

ΔH = Average pressure differential across the orifice meter, in. H20;

Tm = Absolute average DGM temperature, °R;

Θ = Total sampling time, min;

Pbar = Barometric pressure, in. Hg;

Y = DGM calibration factor, dimensionless;

Vm = Volume of gas sample as measured by DGM, dcf.

9.2.1.1 Before beginning the field test (a set of three runs usually constitutes a field test), operate the metering system (i.e., pump, volume meter, and orifice) at the ΔHa pressure differential for 10 minutes. Record the volume collected, the DGM temperature, and the barometric pressure. Calculate a DGM calibration check value, Yc, as follows:

eCFR graphic er07oc97.009.gif

View or download PDF

Where

Yc = DGM calibration check value, dimensionless;

10 = Run time, min.

9.2.1.2 Compare the Yc value with the dry gas meter calibration factor Y to determine that: 0.97 Y <Yc <1.03Y. If the Yc value is not within this range, the volume metering system should be investigated before beginning the test.

9.2.2 Calibrated critical orifice. A calibrated critical orifice, calibrated against a wet test meter or spirometer and designed to be inserted at the inlet of the sampling meter box, may be used as a quality control check by following the procedure of section 16.2 of this method.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Probe nozzle. Probe nozzles shall be calibrated before their initial use in the field. Using a micrometer, measure the ID of the nozzle to the nearest 0.025 mm (0.001 in.). Make three separate measurements using different diameters each time, and obtain the average of the measurements. The difference between the high and low numbers shall not exceed 0.1 mm (0.004 in.). When nozzles become nicked, dented, or corroded, they shall be reshaped, sharpened, and recalibrated before use. Each nozzle shall be permanently and uniquely identified.

10.2 Pitot tube assembly. The Type S pitot tube assembly shall be calibrated according to the procedure outlined in section 10.1 of Method 2, 40 CFR part 60, appendix A.

10.3 Metering system.

10.3.1 Calibration prior to use. Before its initial use in the field, the metering system shall be calibrated as follows: Connect the metering system inlet to the outlet of a wet test meter that is accurate to within 1 percent. Refer to Figure 5-5 of Method 5, 40 CFR part 60, appendix A. The wet test meter should have a capacity of 30 liters/revolution (1 ft3/rev). A spirometer of 400 liters (14 ft3) or more capacity, or equivalent, may be used for this calibration, although a wet test meter is usually more practical. The wet test meter should be periodically calibrated with a spirometer or a liquid displacement meter to ensure the accuracy of the wet test meter. Spirometers or wet test meters of other sizes may be used, provided that the specified accuracies of the procedure are maintained. Run the metering system pump for about 15 minutes with the orifice manometer indicating a median reading, as expected in field use, to allow the pump to warm up and to permit the interior surface of the wet test meter to be thoroughly wetted. Then, at each of a minimum of three orifice manometer settings, pass an exact quantity of gas through the wet test meter and note the gas volume indicated by the DGM. Also note the barometric pressure and the temperatures of the wet test meter, the inlet of the DGM, and the outlet of the DGM. Select the highest and lowest orifice settings to bracket the expected field operating range of the orifice. Use a minimum volume of 0.15 m3 (5 cf) at all orifice settings. Record all the data on a form similar to Figure 5-6 of Method 5, 40 CFR part 60, appendix A, and calculate Y (the DGM calibration factor) and ΔHa (the orifice calibration factor) at each orifice setting, as shown on Figure 5-6 of Method 5, 40 CFR part 60, appendix A. Allowable tolerances for individual Y and ΔHa values are given in Figure 5-6 of Method 5, 40 CFR part 60, appendix A. Use the average of the Y values in the calculations in section 12 of this method.

10.3.1.1 Before calibrating the metering system, it is suggested that a leak check be conducted. For metering systems having diaphragm pumps, the normal leak check procedure will not detect leakages within the pump. For these cases the following leak check procedure is suggested: make a 10-minute calibration run at 0.00057 m3/min (0.02 cfm); at the end of the run, take the difference of the measured wet test meter and DGM volumes; divide the difference by 10 to get the leak rate. The leak rate should not exceed 0.00057 m3/min (0.02 cfm).

10.3.2 Calibration after use. After each field use, the calibration of the metering system shall be checked by performing three calibration runs at a single, intermediate orifice setting (based on the previous field test) with the vacuum set at the maximum value reached during the test series. To adjust the vacuum, insert a valve between the w