CODE OF FEDERAL REGULATIONS
Published by
Office of the Federal Register
National Archives and Records
Administration
The seal of the National Archives and Records Administration (NARA) authenticates the Code of Federal Regulations (CFR) as the official codification of Federal regulations established under the Federal Register Act. Under the provisions of 44 U.S.C. 1507, the contents of the CFR, a special edition of the Federal Register, shall be judicially noticed. The CFR is prima facie evidence of the original documents published in the Federal Register (44 U.S.C. 1510).
It is prohibited to use NARA's official seal and the stylized Code of Federal Regulations logo on any republication of this material without the express, written permission of the Archivist of the United States or the Archivist's designee. Any person using NARA's official seals and logos in a manner inconsistent with the provisions of 36 CFR part 1200 is subject to the penalties specified in 18 U.S.C. 506, 701, and 1017.
This is the Official U.S. Government edition of this publication and is herein identified to certify its authenticity. Use of the 0-16 ISBN prefix is for U.S. Government Printing Office Official Editions only. The Superintendent of Documents of the U.S. Government Printing Office requests that any reprinted edition clearly be labeled as a copy of the authentic work with a new ISBN.
U . S . G O V E R N M E N T P R I N T I N G O F F I C E
U.S. Superintendent of Documents • Washington, DC 20402-0001
http://bookstore.gpo.gov
Phone: toll-free (866) 512-1800; DC area (202) 512-1800
Cite this Code:
The Code of Federal Regulations is a codification of the general and permanent rules published in the Federal Register by the Executive departments and agencies of the Federal Government. The Code is divided into 50 titles which represent broad areas subject to Federal regulation. Each title is divided into chapters which usually bear the name of the issuing agency. Each chapter is further subdivided into parts covering specific regulatory areas.
Each volume of the Code is revised at least once each calendar year and issued on a quarterly basis approximately as follows:
Title 1 through Title 16
Title 17 through Title 27
Title 28 through Title 41
Title 42 through Title 50
The appropriate revision date is printed on the cover of each volume.
The contents of the Federal Register are required to be judicially noticed (44 U.S.C. 1507). The Code of Federal Regulations is prima facie evidence of the text of the original documents (44 U.S.C. 1510).
The Code of Federal Regulations is kept up to date by the individual issues of the Federal Register. These two publications must be used together to determine the latest version of any given rule.
To determine whether a Code volume has been amended since its revision date (in this case, July 1, 2006), consult the “List of CFR Sections Affected (LSA),” which is issued monthly, and the “Cumulative List of Parts Affected,” which appears in the Reader Aids section of the daily Federal Register. These two lists will identify the Federal Register page number of the latest amendment of any given rule.
Each volume of the Code contains amendments published in the Federal Register since the last revision of that volume of the Code. Source citations for the regulations are referred to by volume number and page number of the Federal Register and date of publication. Publication dates and effective dates are usually not the same and care must be exercised by the user in determining the actual effective date. In instances where the effective date is beyond the cut-off date for the Code a note has been inserted to reflect the future effective date. In those instances where a regulation published in the Federal Register states a date certain for expiration, an appropriate note will be inserted following the text.
The Paperwork Reduction Act of 1980 (Pub. L. 96-511) requires Federal agencies to display an OMB control number with their information collection request.
Provisions that become obsolete before the revision date stated on the cover of each volume are not carried. Code users may find the text of provisions in effect on a given date in the past by using the appropriate numerical list of sections affected. For the period before January 1, 2001, consult either the List of CFR Sections Affected, 1949-1963, 1964-1972, 1973-1985, or 1986-2000, published in 11 separate volumes. For the period beginning January 1, 2001, a “List of CFR Sections Affected” is published at the end of each CFR volume.
(a) The incorporation will substantially reduce the volume of material published in the Federal Register.
(b) The matter incorporated is in fact available to the extent necessary to afford fairness and uniformity in the administrative process.
(c) The incorporating document is drafted and submitted for publication in accordance with 1 CFR part 51.
Properly approved incorporations by reference in this volume are listed in the Finding Aids at the end of this volume.
A subject index to the Code of Federal Regulations is contained in a separate volume, revised annually as of January 1, entitled CFR
An index to the text of “Title 3—The President” is carried within that volume.
The Federal Register Index is issued monthly in cumulative form. This index is based on a consolidation of the “Contents” entries in the daily Federal Register.
A List of CFR Sections Affected (LSA) is published monthly, keyed to the revision dates of the 50 CFR titles.
There are no restrictions on the republication of textual material appearing in the Code of Federal Regulations.
For a legal interpretation or explanation of any regulation in this volume, contact the issuing agency. The issuing agency's name appears at the top of odd-numbered pages.
For inquiries concerning CFR reference assistance, call 202-741-6000 or write to the Director, Office of the Federal Register, National Archives and Records Administration, Washington, DC 20408 or e-mail fedreg.info@nara.gov.
The Government Printing Office (GPO) processes all sales and distribution of the CFR. For payment by credit card, call toll-free, 866-512-1800 or DC area, 202-512-1800, M-F, 8 a.m. to 4 p.m. e.s.t. or fax your order to 202-512-2250, 24 hours a day. For payment by check, write to the Superintendent of Documents, Attn: New Orders, P.O. Box 371954, Pittsburgh, PA 15250-7954. For GPO Customer Service call 202-512-1803.
The full text of the Code of Federal Regulations, the LSA (List of CFR Sections Affected), The United States Government Manual, the Federal Register, Public Laws, Public Papers, Weekly Compilation of Presidential Documents and the Privacy Act Compilation are available in electronic format at
The Office of the Federal Register also offers a free service on the National Archives and Records Administration's (NARA) World Wide Web site for public law numbers, Federal Register finding aids, and related information. Connect to NARA's web site at
Title 40—
Chapter I—Environmental Protection Agency appears in all thirty-one volumes. An alphabetical Listing of Pesticide Chemicals Index appears in parts 150-189. Regulations issued by the Council on Environmental Quality appear in the volume containing part 790 to End. The OMB control numbers for title 40 appear in § 9.1 of this chapter.
For this volume, Robert J. Sheehan was Chief Editor. The Code of Federal Regulations publication program is under the direction of Frances D. McDonald, assisted by Alomha S. Morris.
(This book contains part 63)
Nomenclature changes to chapter I appear at 65 FR 47324, 47325, Aug. 2, 2000.
42 U.S.C. 7401
This subpart establishes national emission standards for hazardous air pollutants (NESHAP) and work practice standards for hazardous air pollutants (HAP) emitted from hydrochloric acid (HCl) production. This subpart also establishes requirements to demonstrate initial and continuous compliance with the emission limitations and work practice standards.
(a) You are subject to this subpart if you own or operate an HCl production facility that produces a liquid HCl product at a concentration of 30 weight percent or greater during its normal operations and is located at, or is part of, a major source of HAP. This does not include HCl production facilities that only produce occasionally liquid HCl product at a concentration of 30 weight percent or greater.
(1) An HCl production facility is the collection of unit operations and equipment associated with the production of liquid HCl product. The HCl production facility begins at the point where a gaseous stream containing HCl enters the HCl production unit. The HCl production facility includes all HCl storage tanks that contain liquid HCl product that is produced in the HCl production unit, with the exceptions noted in paragraph (a)(2) of this section. The HCl production facility also includes all HCl transfer operations that load HCl product produced in the HCl production unit into a tank truck, rail car, ship, or barge, along with the piping and other equipment in HCl service used to transfer liquid HCl product from the HCl production unit to the HCl storage tanks and/or HCl transfer operations. The HCl production facility ends at the point that the liquid HCl product produced in the HCl production unit is loaded into a tank truck, rail car, ship, or barge, at the point the HCl product enters another process on the plant site, or at the point the HCl product leaves the plant site via pipeline.
(2) Storage tanks that are dedicated feedstock tanks for another process and storage tanks that store HCl dedicated for use in wastewater treatment are not considered part of an HCl production facility.
(3) A major source of HAP emissions is any stationary source or group of stationary sources within a contiguous area under common control that emits or has the potential to emit any single HAP at a rate of 9.07 megagrams (10 tons) or more per year or any combination of HAP at a rate of 22.68 megagrams (25 tons) or more per year.
(b) An HCl production facility is not subject to this subpart if it is also subject to NESHAP under one of the subparts listed in paragraphs (b)(1) through (5) of this section.
(1) 40 CFR part 63, subpart S, National Emission Standards for Hazardous Air Pollutants from the Pulp and Paper Industry.
(2) 40 CFR part 63, subpart CCC, National Emission Standards for Hazardous Air Pollutants for Steel Pickling—HCl Process Facilities and Hydrochloric Acid Regeneration Plants.
(3) 40 CFR part 63, subpart MMM, National Emission Standards for Hazardous Air Pollutants for Pesticide Active Ingredient Production.
(4) 40 CFR part 63, section 63.994, subpart SS, National Emission Standards for Closed Vent Systems, Control Devices, Recovery Devices and Routing to a Fuel Gas System or a Process.
(5) 40 CFR part 63, subpart GGG, National Emission Standards for Pharmaceuticals Production.
(c) An HCl production facility is not subject to this subpart if it is located following the incineration of chlorinated waste gas streams, waste liquids, or solid wastes, and the emissions from the HCl production facility are subject to section 63.113(c), subpart G, National Emission Standards for Organic Hazardous Air Pollutants from the Synthetic Organic Chemical Manufacturing Industry for Process Vents, Storage Vessels, Transfer Operations, and Wastewater.
(d) An HCl production facility is not subject to this subpart if it produces HCl through the direct synthesis of hydrogen and chlorine and is part of a chlor-alkali facility.
(e) An HCl production facility is not subject to this subpart if it is a research and development facility.
(f) An HCl production facility is not subject to this subpart if all of the gaseous streams containing HCl and chlorine (Cl
(a) This subpart applies to each new, reconstructed, or existing affected source at an HCl production facility.
(b) The affected source is the group of one or more HCl production facilities at a plant site that are subject to this subpart, and all associated wastewater operations, which contain the collection of emission streams listed in paragraphs (b)(1) through (5) of this section.
(1) Each emission stream from an HCl process vent.
(2) Each emission stream from an HCl storage tank.
(3) Each emission stream from an HCl transfer operation.
(4) Each emission stream resulting from leaks from equipment in HCl service.
(5) Each emission stream from HCl wastewater operations. There are no emission limitations or other requirements in this subpart that apply to HCl wastewater operations.
(c) An affected source is a new affected source if you commenced construction of the affected source after September 18, 2001 and you met the applicability criteria of § 63.8985 at the time you commenced construction.
(d) An affected source is reconstructed if you meet the criteria as defined in § 63.2.
(e) An affected source is existing if it is not new or reconstructed.
(a) If you have a new or reconstructed affected source, you must comply with this subpart according to paragraphs (a)(1) or (2) of this section.
(1) If you start up your affected source before April 17, 2003, you must comply with the emission limitations and work practice standards in this subpart no later than April 17, 2003.
(2) If you start up your affected source after April 17, 2003, you must comply with the emission limitations and work practice standards in this subpart upon startup of your affected source.
(b) If you have an existing affected source, you must comply with the
(c) If you have an area source that increases its emissions or its potential to emit such that it becomes a major source of HAP, the provisions in paragraphs (c)(1) and (2) of this section apply.
(1) Any portion of the existing facility that is a new affected source or a new reconstructed source must be in compliance with this subpart upon startup.
(2) All other parts of the source must be in compliance with this subpart no later than the date 3 years after the area source becomes a major source.
(d) You must meet the notification requirements in § 63.9045 according to the schedule in § 63.9045 and in subpart A of this part. Some of the notifications must be submitted before you are required to comply with the emission limitations in this subpart.
(a) With the exceptions noted in paragraphs (c) and (d) of this section, you must meet the applicable emission limit and work practice standard in table 1 to this subpart for each emission stream listed under § 63.8990(b)(1) through (4) that is part of your affected source.
(b) With the exceptions noted in paragraph (c) of this section, you must meet the applicable operating limit in Table 2 to this subpart for each emission stream listed under § 63.8990(b)(1) through (3) that is part of your affected source.
(c) The emission streams listed in paragraphs (c)(1) through (4) of this section are exempt from the emission limitations, work practice standards, and all other requirements of this subpart.
(1) Emission streams from HCl storage tanks that never store liquid HCl product with a concentration of 30 weight percent or greater.
(2) Emission streams from HCl transfer operations that never load liquid HCl product with a concentration of 30 weight percent or greater.
(3) Emission streams from HCl wastewater operations.
(4) Emission streams from HCl process vents, HCl storage tanks, and HCl transfer operations that are also subject to 40 CFR part 63, subpart EEE, National Emission Standards for Hazardous Air Pollutants for Hazardous Waste Combustors, or 40 CFR 266.107, subpart H, Burning of Hazardous Waste in Boilers and Industrial Furnaces.
(d) The emission limits for HCl storage tanks in table 1 to this subpart do not apply during periods of planned routine maintenance of HCl storage tank control devices. Periods of planned routine maintenance of each HCl storage tank control device, during which the control device does not meet the emission limits specified in table 1 to this subpart, shall not exceed 240 hours per year.
(a) You must be in compliance with the emission limitations and work practice standards in this subpart at all times, except during periods of startup, shutdown, and malfunction.
(b) You must always operate and maintain your affected source, including air pollution control and monitoring equipment, according to the provisions in § 63.6(e)(1)(i).
(c) You must develop a written startup, shutdown, and malfunction plan according to the provisions in § 63.6(e)(3).
(d) All monitoring equipment shall be installed, calibrated, maintained, and operated according to manufacturer's specifications or other written procedures that provide adequate assurance that the equipment would reasonably be expected to monitor accurately. For each monitoring system required in this section, you must develop, implement, and submit to the Administrator a site-specific monitoring plan that addresses the installation requirements in paragraphs (d)(1) through (3) of this section, the ongoing
(1) Installation of the continuous monitoring system (CMS) sampling probe or other interface at a measurement location relative to each affected process unit such that the measurement is representative of control of the exhaust emissions (
(2) Performance and equipment specifications for the sample interface, the pollutant concentration or parametric signal analyzer, and the data collection and reduction system.
(3) Performance evaluation procedures and acceptance criteria (
(4) Ongoing operation and maintenance (O&M) procedures in accordance with the general requirements of §§ 63.8(c)(1), (3), (4)(ii), (7), and (8), and 63.9025.
(5) Ongoing data quality assurance procedures in accordance with the general requirements of § 63.8(d).
(6) Ongoing recordkeeping and reporting procedures in accordance with the general requirements of § 63.10(c) and (e)(1) and (2)(i).
(a) If you have a new or reconstructed affected source, you must conduct performance tests within 180 calendar days after the compliance date that is specified for your source in § 63.8995(a) and according to the provisions in § 63.7(a)(2).
(b) If you have an existing affected source, you must conduct performance tests within 180 calendar days after the compliance date that is specified for your existing affected source in § 63.8995(b) and according to the provisions in § 63.7(a)(2).
(c) If you commenced construction or reconstruction between September 18, 2001 and April 17, 2003, you must demonstrate initial compliance with either the proposed emission limitation or the promulgated emission limitation no later than 180 calendar days after April 17, 2003 or within 180 calendar days after startup of the source, whichever is later, according to § 63.7(a)(2)(ix).
(a) You must conduct all applicable performance tests according to the procedures in § 63.9020 on the earlier of your title V operating permit renewal or within 5 years of issuance of your title V permit. For emission points meeting the outlet concentration limits in table 1 to this subpart without the use of a control device, all applicable performance tests must also be conducted whenever process changes are made that could reasonably be expected to increase the outlet concentration. Examples of process changes include, but are not limited to, changes in production capacity, production rate, feedstock type, or catalyst type, or whenever there is replacement, removal, or addition of recovery equipment. For purposes of this paragraph, process changes do not include: process upsets and unintentional, temporary process changes.
(b) You must report the results of subsequent performance tests within 60 days after the completion of the test. This report should also verify that the operating limits for your affected source have not changed or provide documentation of revised operating limits established as specified in Table 2 to this subpart. The reports for all subsequent performance tests should include all applicable information required in § 63.9050.
(a) You must conduct each performance test in Table 3 to this subpart that applies to you as directed in paragraphs (a)(1) through (4) of this section, except as noted in paragraphs (b) and (c) of this section.
(1) You must develop a site-specific test plan according to § 63.7(c)(2) and conduct each performance test according to the site-specific test plan.
(2) You must conduct each performance test under representative conditions according to the requirements in § 63.7(e)(1) and under the specific conditions that this subpart specifies in Table 3.
(3) You may not conduct performance tests during periods of startup, shutdown, or malfunction, as specified in § 63.7(e)(1).
(4) You must conduct at least three separate test runs for each performance test required in this section, as specified in § 63.7(e)(3). Each test run must last at least 1 hour.
(b) If you are complying with a percent reduction emission limitation, you must determine the percent reduction in accordance with paragraphs (b)(1) and (2) of this section.
(1) Calculate the mass rate of either HCl or chlorine using Equations 1 and 2 of this section:
(2) Calculate the percent reduction of HCl or Cl
(c) You may prepare a design evaluation in lieu of conducting a performance test for HCl storage tanks and HCl transfer operations that are not routed to a control device that also controls HCl process vent emissions or any other continuous vent stream. The design evaluation shall include documentation demonstrating that the control technique being used achieves the required control efficiency when a liquid HCl product with a concentration of 30 weight percent or greater is being loaded into the storage tank, or a tank truck, rail car, ship, or barge.
(1) If you use a caustic scrubber control device or a water scrubber control device, the design evaluation shall address the vent stream composition, constituent concentrations, liquid-to-vapor ratio, scrubbing liquid flow rate and concentration, temperature, and the reaction kinetics of the constituents with the scrubbing liquid. The design evaluation shall establish the design exhaust vent concentration level and shall include the additional information in paragraphs (c)(1)(i) and (ii) of this section for trays and a packed column scrubber.
(i) Type and total number of theoretical and actual trays.
(ii) Type and total surface area of packing for entire column and for individual packed sections, if the column contains more than one packed section.
(2) If you use any other control device, the design evaluation shall address the composition and HAP concentration of the vent stream immediately preceding the control device, as well as other parameters necessary to demonstrate that the control technique being used achieves the required control efficiency when a liquid HCl product with a concentration of 30 weight percent or greater is being loaded into the storage tank, or a tank truck, rail car, ship, or barge.
(d) You are not required to conduct a performance test for an emission point
(e) You must establish all operating limits with which you will demonstrate continuous compliance with the applicable emission limits in Table 1 to this subpart as described in paragraphs (e)(1) through (3) of this section.
(1) If you use a caustic scrubber control device or water scrubber control device and you conduct a performance test, you must establish operating limits according to paragraphs (e)(1)(i) and (ii) of this section. If a series of control devices are used, you must establish separate operating limits for each device.
(i) You must establish the minimum value as the operating limit for scrubber inlet liquid or recirculating liquid flow rate, as appropriate. The minimum value shall be based on the scrubber inlet liquid or recirculating liquid flow rate, as appropriate, values measured during the performance test.
(ii) You must establish the minimum and maximum values as the operating limits for scrubber effluent pH. The minimum and maximum values shall be based on the scrubber effluent pH values measured during the performance test.
(2) If you use any other control device and you conduct a performance test, you must establish operating limits according to your site-specific test plan submitted in accordance with § 63.7(c)(2)(i). The operating limits shall be based on the operating parameter values measured during the performance test. If a series of control devices are used, you must establish separate operating limits for each device.
(3) If you do not conduct a performance test for a HCl storage tank or HCl transfer operation, you must use engineering assessments and/or manufacturer's recommendations to establish the operating limits specified in paragraphs (e)(1)(i) and (ii), or (e)(2), of this section.
(4) As needed in applicability determinations, you must use ASTM E224 to determine the HCl concentration in liquid products.
(a) For each operating parameter that you are required by § 63.9020(e) to monitor, you must install, operate, and maintain each CMS according to the requirements in paragraphs (a)(1) through (6) of this section.
(1) You must operate your CMS and collect data at all times the process is operating.
(2) You must collect data from at least four equally spaced periods each hour.
(3) For at least 75 percent of the operating hours in a 24-hour period, you must have valid data (as defined in your site-specific monitoring plan) for at least 4 equally spaced periods each hour.
(4) For each hour that you have valid data from at least four equally spaced periods, you must calculate the hourly average value using all valid data or, where data are collected from an automated CMS, using at least one measured value per minute if measured more frequently than once per minute.
(5) You must calculate the daily average using all of the hourly averages calculated according to paragraph (a)(4) of this section for the 24-hour period.
(6) You must record the results for each inspection, calibration, and validation check as specified in your site-specific monitoring plan.
(b) For scrubber control devices, you may request approval, in accordance with § 63.8(f), to monitor parameters other than those specified in § 63.9020(e). In accordance with § 63.8(f), you must submit a monitoring plan to the Administrator and the plan must meet the requirements in paragraphs (a) and (b)(1) through (3) of this section. You must conduct monitoring in accordance with the plan submitted to
(1) Identify the operating parameter to be monitored to ensure that the control or capture efficiency measured during the initial compliance test is maintained.
(2) Discuss why this parameter is appropriate for demonstrating ongoing compliance.
(3) Identify the specific monitoring procedures.
(c) For any other control device, you must ensure that the CMS is operated according to a monitoring plan submitted to the Administrator as required by § 63.8(f). The monitoring plan must meet the requirements in paragraphs (a) and (c)(1) through (3) of this section. You must conduct monitoring in accordance with the plan submitted to the Administrator, as amended, unless comments received from the Administrator require an alternate monitoring scheme.
(1) Identify the operating parameter to be monitored to ensure that the control or capture efficiency measured during the initial compliance test is maintained.
(2) Discuss why this parameter is appropriate for demonstrating ongoing compliance.
(3) Identify the specific monitoring procedures.
(a) You must demonstrate initial compliance with each emission limit and work practice standard that applies to you according to Table 4 to this subpart.
(b) You must establish each site-specific operating limit in Table 2 to this subpart that applies to you according to the requirements in § 63.9020 and Table 3 to this subpart.
(c) You must submit the Notification of Compliance Status containing the results of the initial compliance demonstration according to the requirements in § 63.9045(e).
(a) You must monitor and collect data according to this section.
(b) If you use a caustic scrubber or a water scrubber/absorber to meet the emission limits in Table 1 to this subpart, you must keep the records specified in paragraphs (b)(1) and (2) of this section to support your compliance demonstration.
(1) Records of daily average scrubber inlet liquid or recirculating liquid flow rate, as appropriate.
(2) Records of the daily average scrubber effluent pH.
(c) If you use any other control device to meet the emission limits in Table 1 to this subpart, you must keep records of the operating parameter values identified in your monitoring plan in § 63.9025(c) to support your compliance demonstration.
(d) Except for monitor malfunctions, associated repairs, and required quality assurance or control activities (including, as applicable, calibration checks and required zero and span adjustments), you must monitor continuously (or collect data at all required intervals) at all times that the affected source is operating. This includes periods of startup, shutdown, or malfunction when the affected source is operating. A monitoring malfunction includes, but is not limited to, any sudden, infrequent, not reasonably preventable failure of the monitoring equipment to provide valid data. Monitoring failures that are caused in part by poor maintenance or careless operation are not malfunctions.
(e) You may not use data recorded during monitoring malfunctions, associated repairs, and required quality assurance or control activities in data averages and calculations used to report emission or operating levels, nor may such data be used in fulfilling a minimum data availability requirement, if applicable. You must use all the data collected during all other periods in assessing the operation of the control device and associated control system.
(a) You must demonstrate continuous compliance with each emission limit and work practice standard in Table 1 to this subpart that applies to you according to Table 4 to this subpart.
(b) You must demonstrate continuous compliance with each operating limit in Table 2 of this subpart that applies to you according to Tables 4 and 5 to this subpart.
(c) You must report each instance in which you did not meet an emission limit, work practice standard or operating limit in Table 1 or 2 to this subpart, respectively, that applies to you. This includes periods of startup, shutdown, and malfunction. These instances are deviations from the emission limitations in this subpart. These deviations must be reported according to the requirements in § 63.9050.
(d) [Reserved]
(e) Consistent with §§ 63.6(e) and 63.7(e)(1), deviations that occur during a period of startup, shutdown, or malfunction are not violations if you demonstrate to the Administrator's satisfaction that you were operating in accordance with § 63.6(e)(1). The Administrator will determine whether deviations that occur during a period of startup, shutdown, or malfunction are violations, according to the provisions in § 63.6(e).
(a) You must submit all of the notifications in §§ 63.7(b) and (c), 63.8(f)(4) and (6), and 63.9 (b) through (h) that apply to you by the dates specified.
(b) As specified in § 63.9(b)(2), if you start up your affected source before April 17, 2003, you must submit an Initial Notification not later than 120 calendar days after April 17, 2003.
(c) As specified in § 63.9(b)(4), if you start up your new or reconstructed affected source on or after April 17, 2003, you must submit the application for construction or reconstruction required by § 63.9(b)(1)(iii) in lieu of the initial notification.
(d) You must submit a notification of intent to conduct a performance test at least 60 calendar days before the performance test is scheduled to begin, as required in § 63.7(b)(1).
(e) [Reserved]
(f) You must submit the Notification of Compliance Status, including the performance test results, within 240 calendar days after the applicable compliance dates specified in § 63.8995.
(g) The Notification of Compliance Status must also include the information in paragraphs (g)(1) through (2) of this section that applies to you.
(1) Each operating parameter value averaged over the full period of the performance test (for example, average pH).
(2) Each operating parameter range within which HAP emissions are reduced to the level corresponding to meeting the applicable emission limits in Table 1 to this subpart.
(a) You must submit each report in Table 6 to this subpart that applies to you.
(b) Unless the Administrator has approved a different schedule for submission of reports under § 63.10(a), you must submit each report according to paragraphs (b)(1) through (5) of this section.
(1) The first compliance report must cover the period beginning on the compliance date that is specified for your affected source in § 63.8995 and ending on June 30 or December 31, whichever date is the first date following the end of the first calendar half after the compliance date that is specified for your source in § 63.8995 (i.e., June 30, 2006, for sources existing on April 17, 2006).
(2) The first compliance report must be postmarked or delivered no later than July 31 or January 31, whichever date follows the end of the first calendar half after the compliance date that is specified for your affected source in § 63.8995 (i.e., July 31, 2006, for sources existing on April 17, 2006).
(3) Each subsequent compliance report must cover the semiannual reporting period from January 1 through June 30 or the semiannual reporting period from July 1 through December 31.
(4) Each subsequent compliance report must be postmarked or delivered no later than July 31 or January 31, whichever date is the first date following the end of the semiannual reporting period.
(5) For each affected source that is subject to permitting regulations pursuant to 40 CFR part 70 or 71, and if the permitting authority has established dates for submitting semiannual reports pursuant to 40 CFR 70.6 (a)(3)(iii)(A) or 71.6 (a)(3)(iii)(A), you may submit the first and subsequent compliance reports according to the dates the permitting authority has established instead of according to the dates in paragraphs (b)(1) through (4) of this section.
(c) The compliance report must contain the following information in paragraphs (c)(1) through (10) of this section.
(1) Company name and address.
(2) Statement by a responsible official with that official's name, title, and signature, certifying the truth, accuracy, and completeness of the content of the report.
(3) Date of report and beginning and ending dates of the reporting period.
(4) If you had a startup, shutdown, or malfunction during the reporting period and you took actions consistent with your startup, shutdown, and malfunction plan, the compliance report must include the information in § 63.10(d)(5)(i).
(5) If there are no deviations from any emission limitations that apply to you, a statement that there were no deviations from the emission limitations during the reporting period.
(6) If there were no periods during which the CMS was out-of-control in accordance with the monitoring plan, a statement that there were no periods during which the CMS was out-of-control during the reporting period.
(7) Verification that you continue to use the equipment LDAR plan and information that explains any periods when the procedures in the plan were not followed and the corrective actions were not taken.
(8) If you did not make revisions to your site-specific monitoring plan and/or LDAR plan during the reporting period, a statement that you did not make any revisions to your site-specific monitoring plan and/or LDAR plan during the reporting period. If you made revisions to your site-specific monitoring plan and/or LDAR plan during the reporting period, a copy of the revised plan.
(9) If you meet the outlet concentration limit in table 1 to this subpart without the use of a control device for any emission point, verification that you have not made any process changes that could reasonably be expected to increase the outlet concentration since your most recent performance test for that emission point.
(10) The information specified in paragraphs (c)(10)(i) and (ii) of this section for those planned routine maintenance operations that caused or may cause an HCl storage tank control device not to meet the emission limits in table 1 to this subpart, as applicable.
(i) A description of the planned routine maintenance that was performed for each HCl storage tank control device during the reporting period. This description shall include the type of maintenance performed and the total number of hours during the reporting period that the HCl storage tank control device did not meet the emission limits in table 1 to this subpart, as applicable, due to planned routine maintenance.
(ii) A description of the planned routine maintenance that is anticipated to be performed for each HCl storage tank control device during the next reporting period. This description shall include the type of maintenance necessary, planned frequency of maintenance, and lengths of maintenance periods.
(d) For each deviation from an emission limitation occurring at an affected source where you are using a CMS to comply with the emission limitation in this subpart, you must include the information in paragraphs (c)(1) through (6) of this section and the following information in paragraphs (d)(1) through (9) of this section. This
(1) The date and time that each malfunction started and stopped.
(2) The date and time that each CMS was inoperative, except for zero (low-level) and high-level checks.
(3) The date, time, and duration that each CMS was out-of-control, including the information in § 63.8(c)(8).
(4) The date and time that each deviation started and stopped, and whether each deviation occurred during a period of startup, shutdown, or malfunction or during another period.
(5) A summary of the total duration of the deviation during the reporting period and the total duration as a percent of the total source operating time during that reporting period.
(6) A breakdown of the total duration of the deviations during the reporting period into those that are due to startup, shutdown, control equipment problems, process problems, other known causes, and other unknown causes.
(7) A summary of the total duration of CMS downtime during the reporting period, and the total duration of CMS downtime as a percent of the total source operating time during that reporting period.
(8) A brief description of the process units.
(9) A description of any changes in CMS, processes, or controls since the last reporting period.
(e) Each affected source that has obtained a title V operating permit pursuant to 40 CFR part 70 or 71 must report all deviations as defined in this subpart in the semiannual monitoring report required by 40 CFR 70.6(a)(3)(iii)(A) or 71.6(a)(3)(iii)(A). If an affected source submits a compliance report pursuant to Table 6 to this subpart along with, or as part of, the semiannual monitoring report required by 40 CFR 70.6(a)(3)(iii)(A) or 71.6(a)(3)(iii)(A), and the compliance report includes all required information concerning deviations from any emission limitation in this subpart, submission of the compliance report shall be deemed to satisfy any obligation to report the same deviations in the semiannual monitoring report. However, submission of a compliance report shall not otherwise affect any obligation the affected source may have to report deviations from permit requirements to the permit authority.
(f) For each startup, shutdown, or malfunction during the reporting period that is not consistent with your startup, shutdown, and malfunction plan you must submit an immediate startup, shutdown and malfunction report. Unless the Administrator has approved a different schedule for submission of reports under § 63.10(a), you must submit each report according to paragraphs (f)(1) and (2) of this section.
(1) An initial report containing a description of the actions taken for the event must be submitted by fax or telephone within 2 working days after starting actions inconsistent with the plan.
(2) A follow-up report containing the information listed in § 63.10(d)(5)(ii) must be submitted within 7 working days after the end of the event unless you have made alternative reporting arrangements with the permitting authority.
(a) You must keep a copy of each notification and report that you submitted to comply with this subpart, including all documentation supporting any Initial Notification or Notification of Compliance Status that you submitted, as required in § 63.10(b)(2)(xiv).
(b) You must also keep the following records specified in paragraphs (b)(1) through (5) of this section.
(1) The records in § 63.6(e)(3)(iii) through (v) related to startup, shutdown, and malfunction.
(2) Records of performance tests as required in § 63.10(b)(2)(viii).
(3) Records of operating parameter values that are consistent with your monitoring plan.
(4) Records of the date and time that each deviation started and stopped and whether the deviation occurred during a period of startup, shutdown, or malfunction or during another period.
(5) Copies of the current versions of the site-specific monitoring plan and the equipment LDAR plan. You also must submit copies of these plans and
(6) Records of the planned routine maintenance performed on each HCl storage tank control device including the duration of each time the control device does not meet the emission limits in table 1 to this subpart, as applicable, due to planned routine maintenance. Such a record shall include the information specified in paragraphs (b)(6)(i) and (ii) of this section.
(i) The first time of day and date the emission limits in table 1 to this subpart, as applicable, were not met at the beginning of the planned routine maintenance, and
(ii) The first time of day and date the emission limits in table 1 to this subpart, as applicable, were met at the conclusion of the planned routine maintenance.
(a) Your records must be in a form suitable and readily available for expeditious inspection and review, according to § 63.10(b)(1).
(b) As specified in § 63.10(b)(1), you must keep each record for 5 years following the date of each occurrence, measurement, maintenance, corrective action, report, or record.
(c) You must keep each record on site, or readily accessible from on site through a computer or other means, for at least 2 years after the date of each occurrence, measurement, maintenance, corrective action, report, or record, according to § 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.
(d) You must keep each previous (
(a) Table 7 to this subpart shows which parts of the General Provisions in §§ 63.1 through 63.15 apply to you.
(a) This subpart can be implemented and enforced by us, the U.S. EPA, or a delegated authority such as your State, local, or tribal agency. If the U.S. EPA Administrator has delegated authority to your State, local, or tribal agency, then that agency, as well as U.S. EPA, has the authority to implement and enforce this subpart. You should contact your U.S. 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 under section 40 CFR part 63, subpart E, the authorities contained in paragraph (c) of this section are retained by the Administrator of U.S. EPA and are not transferred to the State, local, or tribal agency.
(c) The authorities in paragraphs (c)(1) through (4) of this section that cannot be delegated to State, local, or tribal agencies are as follows.
(1) Approval of alternatives to requirements in §§ 63.8980, 63.8985, 63.8990, 63.8995, and 63.9000.
(2) Approval of major changes to test methods under § 63.7(e)(2)(ii) and (f) and as defined in § 63.90.
(3) Approval of major changes to monitoring under § 63.8(f) and as defined in § 63.90.
(4) Approval of major changes to recordkeeping and reporting under § 63.10(f) and as defined in § 63.90.
Terms used in this subpart are defined in the Clean Air Act in 40 CFR 63.2 and in this section as follows:
(1) Fails to meet any requirement or obligation established by this subpart, including but not limited to any emission limitation or work practice standard;
(2) Fails to meet any term or condition that is adopted to implement an applicable requirement in this subpart and that is included in the operating permit for any affected source required to obtain such a permit; or
(3) Fails to meet any emission limitation or work practice standard in this subpart during startup, shutdown, or malfunction, regardless of whether or not such failure is permitted by this subpart.
(1) A leak from equipment in HCl service subject to this subpart.
(2) An exit from a control device used to comply with this subpart.
(3) An HCl storage tank vent or HCl transfer operation vent subject to this subpart.
(4) A HCl wastewater operation vent subject to this subpart.
(5) A point of discharge from a relief valve.
(6) A point of discharge from an analyzer.
As stated in § 63.9000(a), you must comply with the following emission limits and work practice standards for each emission stream that is part of an affected source.
As stated in § 63.9000(b), you must comply with the following operating limits for each emission stream that is part of an affected source that is vented to a control device.
As stated in § 63.9020, you must comply with the following requirements for performance tests for HCl production for each affected source.
As stated in § 63.9030, you must comply with the following requirements to demonstrate initial compliance with the applicable emission limits for each affected source vented to a control device and each work practice standard.
As stated in § 63.9040, you must comply with the following requirements to demonstrate continuous compliance with the applicable emission limitations for each affected source vented to a control device and each work practice standard.
As stated in § 63.9050(a), you must submit a compliance report that includes the information in § 63.9050(c) through (e) as well as the information in the following table. You must also submit startup, shutdown, and malfunction (SSM) reports according to the requirements in § 63.9050(f) and the following:
As stated in § 63.9065, you must comply with the applicable General Provisions requirements according to the following:
This subpart PPPPP establishes national emission standards for hazardous air pollutants (NESHAP) for engine test cells/stands located at major sources of hazardous air pollutants (HAP) emissions. This subpart also establishes requirements to demonstrate initial and continuous compliance with the emission limitations contained in this NESHAP.
You are subject to this subpart if you own or operate an engine test cell/stand that is located at a major source of HAP emissions.
(a) An engine test cell/stand is any apparatus used for testing uninstalled stationary or uninstalled mobile (motive) engines.
(b) An uninstalled engine is an engine that is not installed in, or an integrated part of, the final product.
(c) A major source of HAP emissions is a plant site that emits or has the potential to emit any single HAP at a rate of 10 tons (9.07 megagrams) or more per year or any combination of HAP at a rate of 25 tons (22.68 megagrams) or more per year.
This subpart applies to each new, reconstructed, or existing affected source.
(a)
(1)
(2)
(3)
(b) Existing affected sources do not have to meet the requirements of this subpart and of subpart A of this part.
(c) Any portion of a new or reconstructed affected source located at a major source that is used exclusively for testing internal combustion engines with rated power of less than 25 horsepower (hp) (19 kilowatts(kW)) does not have to meet the requirements of this subpart and of subpart A of this part except for the initial notification requirements of § 63.9345(b).
(d) Any portion of a new or reconstructed affected source located at a major source that meets any of the criteria specified in paragraphs (d)(1) through (4) of this section does not have to meet the requirements of this subpart and of subpart A of this part.
(1) Any portion of the affected source used exclusively for testing combustion turbine engines.
(2) Any portion of the affected source used exclusively for testing rocket engines.
(3) Any portion of the affected source used in research and teaching activities at facilities that are not engaged in the development of engines or engine test services for commercial purposes.
(4) Any portion of the affected source operated to test or evaluate fuels (such as knock engines), transmissions, or electronics.
(a)
(2) If you start up your new or reconstructed affected source on or after May 27, 2003, you must comply with the emission limitations in this subpart upon startup.
(b)
(c) You must meet the notification requirements in § 63.9345 and in 40 CFR part 63, subpart A.
For each new or reconstructed affected source that is used in whole or in part for testing internal combustion engines with rated power of 25 hp (19 kW) or more and that is located at a major source, you must comply with the emission limitations in Table 1 to this subpart. (Tables are found at the end of this subpart.)
You may use either a continuous parameter monitoring system (CPMS) or a continuous emission monitoring system (CEMS) to demonstrate compliance with the emission limitations. Continuous monitoring systems must meet the requirements in § 63.9306 (CPMS) and § 63.9307 (CEMS).
(a) For any new or reconstructed affected source on which you use add-on controls, you must meet the operating limits specified in Table 2 to this subpart. These operating limits must be established during the performance test according to the requirements in § 63.9324. You must meet the operating limits at all times after you establish them.
(b) If you use an add-on control device other than those listed in Table 2 to this subpart, or wish to monitor an
(a) You must be in compliance with the emission limitation that applies to you at all times, except during periods of startup, shutdown, or malfunction (SSM) of your control device or associated monitoring equipment.
(b) If you must comply with the emission limitation, you must operate and maintain your engine test cell/stand, air pollution control equipment, and monitoring equipment in a manner consistent with good air pollution control practices for minimizing emissions at all times.
(c) You must develop a written SSM plan (SSMP) for emission control devices and associated monitoring equipment according to the provisions in § 63.6(e)(3). The plan will apply only to emission control devices, and not to engine test cells/stands.
(a)
(1) The CPMS must complete a minimum of one cycle of operation for each successive 15-minute period. You must have a minimum of four equally spaced successive cycles of CPMS operation in 1 hour.
(2) You must determine the average of all recorded readings for each successive 3-hour period of the emission capture system and add-on control device operation.
(3) You must record the results of each inspection, calibration, and validation check of the CPMS.
(4) You must maintain the CPMS at all times and have available necessary parts for routine repairs of the monitoring equipment.
(5) You must operate the CPMS and collect emission capture system and add-on control device parameter data at all times that an engine test cell/stand is operating, except during monitoring malfunctions, associated repairs, and required quality assurance or control activities (including, if applicable, calibration checks and required zero and span adjustments).
(6) You must not use emission capture system or add-on control device parameter data recorded during monitoring malfunctions, associated repairs, out-of-control periods, or required quality assurance or control activities when calculating data averages. You must use all the data collected during all other periods in calculating the data averages for determining compliance with the emission capture system and add-on control device operating limits.
(7) A monitoring malfunction is any sudden, infrequent, not reasonably preventable failure of the CPMS to provide valid data. Monitoring failures that are caused in part by poor maintenance or careless operation are not malfunctions. Any period for which the monitoring system is out-of-control and data are not available for required calculations is a deviation from the monitoring requirements.
(b)
(1) You must monitor or secure the valve or closure mechanism controlling the bypass line in a nondiverting position in such a way that the valve or closure mechanism cannot be opened without creating a record that the valve was opened. The method used to monitor or secure the valve or closure mechanism must meet one of the requirements specified in paragraphs (b)(1)(i) through (iv) of this section.
(i)
(ii)
(iii)
(iv)
(2) If any bypass line is opened, you must include a description of why the bypass line was opened and the length of time it remained open in the semiannual compliance reports required in § 63.9350.
(c)
(1) For a thermal oxidizer, install a gas temperature monitor in the firebox of the thermal oxidizer or in the duct immediately downstream of the firebox before any substantial heat exchange occurs.
(2) For a catalytic oxidizer, you must install a gas temperature monitor in the gas stream immediately before the catalyst bed, and if you established operating limits according to § 63.9324(b)(1) and (2), also install a gas temperature monitor in the gas stream immediately after the catalyst bed.
(i) If you establish operating limits according to § 63.9324(b)(1) and (2), then you must install the gas temperature monitors both upstream and downstream of the catalyst bed. The temperature monitors must be in the gas stream immediately before and after the catalyst bed to measure the temperature difference across the bed.
(ii) If you establish operating limits according to § 63.9324(b)(3) and (4), then you must install a gas temperature monitor upstream of the catalyst bed. The temperature monitor must be in the gas stream immediately before the catalyst bed to measure the temperature.
(3) For all thermal oxidizers and catalytic oxidizers, you must meet the requirements in paragraphs (a) and (c)(3)(i) through (vii) of this section for each gas temperature monitoring device.
(i) Locate the temperature sensor in a position that provides a representative temperature.
(ii) Use a temperature sensor with a measurement sensitivity of 4 degrees Fahrenheit or 0.75 percent of the temperature value, whichever is larger.
(iii) Shield the temperature sensor system from electromagnetic interference and chemical contaminants.
(iv) If a gas temperature chart recorder is used, it must have a measurement sensitivity in the minor division of at least 20 degrees Fahrenheit.
(v) Perform an electronic calibration at least semiannually according to the procedures in the manufacturer's owner's manual. Following the electronic calibration, you must conduct a temperature sensor validation check in
(vi) Conduct calibration and validation checks anytime the sensor exceeds the manufacturer's specified maximum operating temperature range or install a new temperature sensor.
(vii) At least monthly, inspect components for integrity and electrical connections for continuity, oxidation, and galvanic corrosion.
(d) Emission capture systems. The capture system monitoring system must comply with the applicable requirements in paragraphs (d)(1) and (2) of this section.
(1) For each flow measurement device, you must meet the requirements in paragraphs (a) and (d)(1)(i) through (iv) of this section.
(i) Locate a flow sensor in a position that provides a representative flow measurement in the duct from each capture device in the emission capture system to the add-on control device.
(ii) Reduce swirling flow or abnormal velocity distributions due to upstream and downstream disturbances.
(iii) Conduct a flow sensor calibration check at least semiannually.
(iv) At least monthly, inspect components for integrity, electrical connections for continuity, and mechanical connections for leakage.
(2) For each pressure drop measurement device, you must comply with the requirements in paragraphs (a) and (d)(2)(i) through (vi) of this section.
(i) Locate the pressure sensor(s) in or as close to a position that provides a representative measurement of the pressure drop across each opening you are monitoring.
(ii) Minimize or eliminate pulsating pressure, vibration, and internal and external corrosion.
(iii) Check pressure tap pluggage daily.
(iv) Using an inclined manometer with a measurement sensitivity of 0.0002 inch water, check gauge calibration quarterly and transducer calibration monthly.
(v) Conduct calibration checks any time the sensor exceeds the manufacturer's specified maximum operating pressure range or install a new pressure sensor.
(vi) At least monthly, inspect components for integrity, electrical connections for continuity, and mechanical connections for leakage.
(a) You must install, operate, and maintain each CEMS to monitor carbon monoxide (CO) or total hydrocarbons (THC) and oxygen (O
(b) To comply with the CO or THC percent reduction emission limitation, you may install, operate, and maintain a CEMS to monitor CO or THC and O
(c) To comply with either emission limitations, the CEMS must be installed and operated according to the requirements described in paragraphs (c)(1) through (4) of this section.
(1) You must install, operate, and maintain each CEMS according to the applicable Performance Specification (PS) of 40 CFR part 60, appendix B (PS-3 or PS-4A).
(2) You must conduct a performance evaluation of each CEMS according to the requirements in 40 CFR 63.8 and according to PS-3 of 40 CFR part 60, appendix B, using Reference Method 3A or 3B for the O
(3) As specified in § 63.8(c)(4)(ii), each CEMS must complete a minimum of one cycle of operation (sampling, analyzing, and data recording) for each successive 15-minute period. You must have at least two data points, each representing a different 15-minute period within the same hour, to have a valid hour of data.
(4) All CEMS data must be reduced as specified in § 63.8(g)(2) and recorded as CO concentration in parts per million by volume, dry basis (ppmvd), corrected to 15 percent O
(d) If you have CEMS that are subject to paragraph (a) or (b) of this section, you must properly maintain and operate the monitors continuously according to the requirements described in paragraphs (d)(1) and (2) of this section.
(1)
(2)
(i) You must conduct all monitoring in continuous operation at all times that the engine test cell/stand is operating, except for, as applicable, monitoring malfunctions, associated repairs, and required quality assurance or control activities (including, as applicable, calibration drift checks and required zero and high-level adjustments). Quality assurance or control activities must be performed according to procedure 1 of 40 CFR part 60, appendix F.
(ii) Data recorded during monitoring malfunctions, associated repairs, out-of-control periods, and required quality assurance or control activities must not be used for purposes of calculating data averages. You must use all of the data collected from all other periods in assessing compliance. A monitoring malfunction is any sudden, infrequent, not reasonably preventable failure of the monitoring equipment to provide valid data. Monitoring failures that are caused in part by poor maintenance or careless operation are not malfunctions. Any period for which the monitoring system is out-of-control and data are not available for required calculations constitutes a deviation from the monitoring requirements.
You must conduct the initial compliance demonstrations that apply to you in Table 3 to this subpart within 180 calendar days after the compliance date that is specified for your new or reconstructed affected source in § 63.9295 and according to the provisions in § 63.7(a)(2).
(a) You must conduct each initial compliance demonstration that applies to you in Table 3 to this subpart.
(b) You must conduct an initial performance evaluation of each capture and control system according to §§ 63.9321, 63.9322, 63.9323 and 63.9324, and each CEMS according to the requirements in 40 CFR 63.8 and according to the applicable Performance Specification of 40 CFR part 60, appendix B (PS-3 or PS-4A).
(c) The initial demonstration of compliance with the carbon monoxide (CO) or total hydrocarbon (THC) concentration limitation consists of the first 4-hour rolling average CO or THC concentration recorded after completion of the CEMS performance evaluation. You must correct the CO or THC concentration at the outlet of the engine test cell/stand or the emission control device to a dry basis and to 15 percent O
(d) The initial demonstration of compliance with the CO or THC percent reduction emission limitation consists of
(1) Correct the CO or THC concentrations at the inlet and outlet of the emission control device to a dry basis and to 15 percent O
(2) Calculate the percent reduction in CO or THC using Equation 2 of this section:
(a) You must conduct each performance test required by § 63.9310 according to the requirements in § 63.7(e)(1) and under the conditions in this section unless you obtain a waiver of the performance test according to the provisions in § 63.7(h).
(1)
(2)
(b) You must conduct each performance test of an emission capture system according to the requirements in § 63.9322. You must conduct each performance test of an add-on control device according to the requirements in § 63.9323.
You must use the procedures and test methods in this section to determine capture efficiency as part of the performance test required by § 63.9310.
(a)
(1) The capture system meets the criteria in Method 204 of appendix M to 40 CFR part 51 for a potential to emit (PTE) and directs all the exhaust gases from the enclosure to an add-on control device.
(2) All engine test operations creating exhaust gases for which the test is applicable are conducted within the capture system.
(b)
(c)
(1) Either use a building enclosure or construct an enclosure around the engine test cell/stand and all areas where emissions from the engine testing subsequently occur. The enclosure must meet the applicable definition of a temporary total enclosure or building enclosure in Method 204 of appendix M to 40 CFR part 51.
(2) Use Method 204B or 204C of appendix M to 40 CFR part 51 to measure the total mass, kg, of TVH emissions captured by the emission capture system during each capture efficiency test run as measured at the inlet to the add-on control device. To make the measurement, substitute TVH for each occurrence of the term VOC in the methods.
(i) The sampling points for the Method 204B or 204C of appendix M to 40 CFR part 51 measurement must be upstream from the add-on control device and must represent total emissions routed from the capture system and entering the add-on control device.
(ii) If multiple emission streams from the capture system enter the add-on control device without a single common duct, then the emissions entering the add-on control device must be simultaneously measured in each duct, and the total emissions entering the add-on control device must be determined.
(3) Use Method 204D or 204E of appendix M to 40 CFR part 51 to measure the total mass, kg, of TVH emissions that are not captured by the emission capture system; they are measured as they exit the temporary total enclosure or building enclosure during each capture efficiency test run. To make the measurement, substitute TVH for each occurrence of the term VOC in the methods.
(i) Use Method 204D of appendix M to 40 CFR part 51 if the enclosure is a temporary total enclosure.
(ii) Use Method 204E of appendix M to 40 CFR part 51 if the enclosure is a building enclosure. During the capture efficiency measurement, all organic compound emitting operations inside the building enclosure, other than the engine test cell/stand operation for which capture efficiency is being determined, must be shut down, but all fans and blowers must be operating normally.
(4) For each capture efficiency test run, determine the percent capture efficiency of the emission capture system using Equation 1 of this section:
(5) Determine the capture efficiency the emission capture system as the average of the capture efficiencies measured in the three test runs.
(d)
You must use the procedures and test methods in this section to determine the add-on control device emission destruction or removal efficiency as part of the performance test required by § 63.9310. You must conduct three test runs as specified in § 63.7(e)(3), and each test run must last at least 1 hour.
(a) For all types of add-on control devices, use the test methods specified in paragraphs (a)(1) through (5) of this section.
(1) Use Method 1 or 1A of appendix A to 40 CFR part 60, as appropriate, to select sampling sites and velocity traverse points.
(2) Use Method 2, 2A, 2C, 2D, 2F, or 2G of appendix A to 40 CFR part 60, as appropriate, to measure gas volumetric flow rate.
(3) Use Method 3, 3A, or 3B of appendix A to 40 CFR part 60, as appropriate, for gas analysis to determine dry molecular weight. The ANSI/ASME PTC 19.10-1981 Part 10 is an acceptable alternative to Method 3B (incorporated by reference, see § 63.14).
(4) Use Method 4 of appendix A to 40 CFR part 60, to determine stack gas moisture.
(5) Methods for determining gas volumetric flow rate, dry molecular weight, and stack gas moisture must be performed, as applicable, during each test run.
(b) Measure total gaseous organic mass emissions as carbon at the inlet and outlet of the add-on control device simultaneously, using either Method 25 or 25A of appendix A to 40 CFR part 60, as specified in paragraphs (b)(1) through (3) of this section. You must use the same method for both the inlet and outlet measurements.
(1) Use Method 25 of appendix A to 40 CFR part 60 if the add-on control device is an oxidizer, and you expect the total gaseous organic concentration as carbon to be more than 50 parts per million at the control device outlet.
(2) Use Method 25A of appendix A to 40 CFR part 60 if the add-on control device is an oxidizer, and you expect the total gaseous organic concentration as carbon to be 50 ppm or less at the control device outlet.
(c) For each test run, determine the total gaseous organic emissions mass flow rates for the inlet and the outlet of the add-on control device, using Equation 1 of this section. If there is more than one inlet or outlet to the add-on control device, you must calculate the total gaseous organic mass flow rate using Equation 1 of this section for each inlet and each outlet and then total all of the inlet emissions and total all of the outlet emissions.
(d) For each test run, determine the add-on control device organic emissions destruction or removal efficiency, using Equation 2 of this section:
(e) Determine the emission destruction or removal efficiency of the add-on control device as the average of the efficiencies determined in the three test runs and calculated in Equation 2 of this section.
During the performance test required by § 63.9310, you must establish the operating limits required by § 63.9302 according to this section, unless you have received approval for alternative monitoring and operating limits under § 63.8(f) as specified in § 63.9302.
(a)
(1) During the performance test, you must monitor and record the combustion temperature at least once every 15 minutes during each of the three test runs. You must monitor the temperature in the firebox of the thermal oxidizer or immediately downstream of the firebox before any substantial heat exchange occurs.
(2) Use the data collected during the performance test to calculate and record the average combustion temperature maintained during the performance test. This average combustion temperature is the minimum operating limit for your thermal oxidizer.
(b)
(1) During the performance test, you must monitor and record the temperature just before the catalyst bed and the temperature difference across the catalyst bed at least once every 15 minutes during each of the three test runs.
(2) Use the data collected during the performance test to calculate and record the average temperature just before the catalyst bed and the average temperature difference across the catalyst bed maintained during the performance test. These are the minimum operating limits for your catalytic oxidizer.
(3) As an alternative to monitoring the temperature difference across the catalyst bed, you may monitor the temperature at the inlet to the catalyst bed and implement a site-specific inspection and maintenance plan for your catalytic oxidizer as specified in paragraph (b)(4) of this section. During the performance test, you must monitor and record the temperature just before the catalyst bed at least once every 15 minutes during each of the three test runs. Use the data collected during the performance test to calculate and record the average temperature just before the catalyst bed during the performance test. This is the minimum operating limit for your catalytic oxidizer.
(4) You must develop and implement an inspection and maintenance plan for your catalytic oxidizer(s) for which you elect to monitor according to paragraph (b)(3) of this section. The plan must address, at a minimum, the elements specified in paragraphs (b)(4)(i) through (iii) of this section.
(i) Annual sampling and analysis of the catalyst activity (
(ii) Monthly inspection of the oxidizer system, including the burner assembly and fuel supply lines for problems and, as necessary, adjust the equipment to assure proper air-to-fuel mixtures.
(iii) Annual internal and monthly external visual inspection of the catalyst bed to check for channeling, abrasion, and settling. If problems are found, you must take corrective action consistent with the manufacturer's recommendation and conduct a new performance test to determine destruction efficiency according to § 63.9323.
(c)
(1) During the capture efficiency determination required by § 63.9310, you must monitor and record either the gas volumetric flow rate or the duct static pressure for each separate capture device in your emission capture system at least once every 15 minutes during each of the three test runs at a point in the duct between the capture device and the add-on control device inlet.
(2) Calculate and record the average gas volumetric flow rate or duct static pressure for the three test runs for each capture device. This average gas volumetric flow rate or duct static pressure is the minimum operating limit for that specific capture device.
(a) You must demonstrate initial compliance with the emission limitation that applies to you according to Table 3 to this subpart.
(b) You must submit the Notification of Compliance Status containing results of the initial compliance demonstration according to the requirements in § 63.9345(c).
(a) Except for monitor malfunctions, associated repairs, and required quality assurance or quality control activities (including, as applicable, calibration drift checks and required zero and high-level adjustments of the monitoring system), you must conduct all monitoring in continuous operation at all times the engine test cell/stand is operating.
(b) Do not use data recorded during monitor malfunctions, associated repairs, and required quality assurance or quality control activities for meeting the requirements of this subpart, including data averages and calculations. You must use all the data collected during all other periods in assessing the performance of the emission control device or in assessing emissions from the new or reconstructed affected source.
(a) You must demonstrate continuous compliance with the emission limitation in Table 1 to this subpart that applies to you according to methods specified in Table 5 to this subpart.
(b) You must report each instance in paragraphs (b)(1) and (2) of this section. These instances are deviations from the emission limitation in this subpart and must be reported according to the requirements in § 63.9350.
(1) You must report each instance in which you did not meet the emission limitation that applies to you.
(2) You must report each instance in which you did not meet the requirements in Table 7 to this subpart that apply to you.
(c)
(2) The Administrator will determine whether deviations that occur during a period of SSM of control devices and associated monitoring equipment are violations, according to the provisions in § 63.6(e).
(a) You must submit all of the notifications in §§ 63.8(e), 63.8(f)(4) and (6), and 63.9(b), (g)(1), (g)(2) and (h) that apply to you by the dates specified.
(b) If you own or operate a new or reconstructed test cell/stand used for testing internal combustion engines, you are required to submit an Initial Notification as specified in paragraphs (b)(1) through (3) of this section.
(1) As specified in § 63.9(b)(2), if you start up your new or reconstructed affected source before the effective date of this subpart, you must submit an Initial Notification not later than 120 calendar days after May 27, 2003.
(2) As specified in § 63.9(b), if you start up your new or reconstructed affected source on or after the effective date of this subpart, you must submit an Initial Notification not later than 120 calendar days after you become subject to this subpart.
(3) If you are required to submit an Initial Notification but are otherwise not affected by the requirements of this subpart, in accordance with § 63.9290(c), your notification should include the information in § 63.9(b)(2)(i) through (v) and a statement that your new or reconstructed engine test cell/stand has no additional requirements and explain the basis of the exclusion (for example, that the test cell/stand is used exclusively for testing internal combustion engines with rated power of less than 25 hp (19 kW)).
(c) If you are required to comply with the emission limitations in Table 1 to this subpart, you must submit a Notification of Compliance Status according to § 63.9(h)(2)(ii). For each initial compliance demonstration with the emission limitation, you must submit the Notification of Compliance Status before the close of business on the 30th calendar day following the completion of the initial compliance demonstration.
(d) You must submit a notification of initial performance evaluation of your CEMS or performance testing of your control device at least 60 calendar days before the performance testing/evaluation is scheduled to begin as required in § 63.8(e)(2).
(a) If you own or operate a new or reconstructed affected source that must meet the emission limitation, you must submit a semiannual compliance report according to Table 6 to this subpart by the applicable dates specified in paragraphs (a)(1) through (6) of this section, unless the Administrator has approved a different schedule.
(1) The first semiannual compliance report must cover the period beginning on the compliance date specified in § 63.9295 and ending on June 30 or December 31, whichever date is the first date following the end of the first calendar half after the compliance date specified in § 63.9295.
(2) The first semiannual compliance report must be postmarked or delivered no later than July 31 or January 31, whichever date follows the end of the first calendar half after the compliance date that is specified in § 63.9295.
(3) Each subsequent semiannual compliance report must cover the semiannual reporting period from January 1 through June 30 or the semiannual reporting period from July 1 through December 31.
(4) Each subsequent semiannual compliance report must be postmarked or delivered no later than July 31 or January 31, whichever date is the first date following the end of the semiannual reporting period.
(5) For each new or reconstructed engine test cell/stand that is subject to permitting regulations pursuant to 40 CFR part 70 or 71, and if the permitting authority has established the date for submitting semiannual reports pursuant to 40 CFR 70.6(a)(3)(iii)(A) or 40 CFR 71.6(a)(3)(iii)(A), you may submit the first and subsequent compliance reports according to the dates the permitting authority has established instead of according to the dates in paragraphs (a)(1) through (4) of this section.
(6) If you had an SSM of a control device or associated monitoring equipment during the reporting period and you took actions consistent with your SSMP, the compliance report must include the information in paragraphs § 63.10(d)(5)(i).
(b) If there is no deviation from the applicable emission limitation and the CEMS or CPMS was not out-of-control, according to § 63.8(c)(7), the semiannual compliance report must contain the information described in paragraphs (b)(1) through (4) of this section.
(1) Company name and address.
(2) Statement by a responsible official, with that official's name, title, and signature, certifying the truth, accuracy, and completeness of the content of the report.
(3) Date of report and beginning and ending dates of the reporting period.
(4) A statement that no deviation from the emission limit occurred during the reporting period and that no
(c) For each deviation from an emission limit, the semiannual compliance report must include the information in paragraphs (b)(1) through (3) of this section and the information included in paragraphs (c)(1) through (4) of this section.
(1) The date and time that each deviation started and stopped.
(2) The total operating time of each new or reconstructed engine test cell/stand during the reporting period.
(3) A summary of the total duration of the deviation during the reporting period (recorded in 4-hour periods), and the total duration as a percent of the total operating time during that reporting period.
(4) A breakdown of the total duration of the deviations during the reporting period into those that are due to control equipment problems, process problems, other known causes, and other unknown causes.
(d) For each CEMS or CPMS deviation, the semiannual compliance report must include the information in paragraphs (b)(1) through (3) of this section and the information included in paragraphs (d)(1) through (10) of this section.
(1) The date and time that each CEMS or CPMS was inoperative except for zero (low-level) and high-level checks.
(2) The date and time that each CEMS or CPMS was out-of-control including the information in § 63.8(c)(8).
(3) A summary of the total duration of CEMS or CPMS downtime during the reporting period (reported in 4-hour periods), and the total duration of CEMS or CPMS downtime as a percent of the total engine test cell/stand operating time during that reporting period.
(4) A breakdown of the total duration of CEMS or CPMS downtime during the reporting period into periods that are due to monitoring equipment malfunctions, nonmonitoring equipment malfunctions, quality assurance/quality control calibrations, other known causes and other unknown causes.
(5) The monitoring equipment manufacturer(s) and model number(s) of each monitor.
(6) The date of the latest CEMS or CPMS certification or audit.
(7) The date and time period of each deviation from an operating limit in Table 2 to this subpart; date and time period of any bypass of the add-on control device; and whether each deviation occurred during a period of SSM or during another period.
(8) A summary of the total duration of each deviation from an operating limit in Table 2 to this subpart, each bypass of the add-on control device during the semiannual reporting period, and the total duration as a percent of the total source operating time during that semiannual reporting period.
(9) A breakdown of the total duration of the deviations from the operating limits in Table 2 to this subpart and bypasses of the add-on control device during the semiannual reporting period by identifying deviations due to startup, shutdown, control equipment problems, process problems, other known causes, and other unknown causes.
(10) A description of any changes in CEMS, CPMS, or controls since the last reporting period.
(e) If you had an SSM of a control device or associated monitoring equipment during the semiannual reporting period that was not consistent with your SSMP, you must submit an immediate SSM report according to the requirements in § 63.10(d)(5)(ii).
(a) You must keep the records as described in paragraphs (a)(1) through (5) of this section.
(1) A copy of each notification and report that you submitted to comply with this subpart, including all documentation supporting any Initial Notification or Notification of Compliance Status that you submitted, according to the requirements in § 63.10(b)(2)(xiv).
(2) Records of performance evaluations as required in § 63.10(b)(2)(viii).
(3) Records of the occurrence and duration of each malfunction of the air pollution control equipment, if applicable, as required in § 63.10(b)(2)(ii).
(4) Records of all maintenance on the air pollution control equipment, if applicable, as required in § 63.10(b)(iii).
(5) The calculation of the mass of organic HAP emission reduction by emission capture systems and add-on control devices.
(b) For each CPMS, you must keep the records as described in paragraphs (b)(1) through (7) of this section.
(1) For each deviation, a record of whether the deviation occurred during a period of SSM of the control device and associated monitoring equipment.
(2) The records in § 63.6(e)(3)(iii) through (v) related to SSM.
(3) The records required to show continuous compliance with each operating limit specified in Table 2 to this subpart that applies to you.
(4) For each capture system that is a PTE, the data and documentation you used to support a determination that the capture system meets the criteria in Method 204 of appendix M to 40 CFR part 51 for a PTE and has a capture efficiency of 100 percent, as specified in § 63.9322(a).
(5) For each capture system that is not a PTE, the data and documentation you used to determine capture efficiency according to the requirements specified in §§ 63.9321 and 63.9322(b) through (e), including the records specified in paragraphs (b)(5)(i) and (ii) of this section that apply to you.
(i) Records for a gas-to-gas protocol using a temporary total enclosure or a building enclosure. Records of the mass of TVH emissions captured by the emission capture system as measured by Method 204B or C of appendix M to 40 CFR part 51 at the inlet to the add-on control device, including a copy of the test report. Records of the mass of TVH emissions not captured by the capture system that exited the temporary total enclosure or building enclosure during each capture efficiency test run as measured by Method 204D or E of appendix M to 40 CFR part 51, including a copy of the test report. Records documenting that the enclosure used for the capture efficiency test met the criteria in Method 204 of appendix M to 40 CFR part 51 for either a temporary total enclosure or a building enclosure.
(ii) Records for an alternative protocol. Records needed to document a capture efficiency determination using an alternative method or protocol as specified in § 63.9322(e), if applicable.
(6) The records specified in paragraphs (b)(6)(i) and (ii) of this section for each add-on control device organic HAP destruction or removal efficiency determination as specified in § 63.9323.
(i) Records of each add-on control device performance test conducted according to §§ 63.9321, 63.9322, and 63.9323.
(ii) Records of the engine testing conditions during the add-on control device performance test showing that the performance test was conducted under representative operating conditions.
(7) Records of the data and calculations you used to establish the emission capture and add-on control device operating limits as specified in § 63.9324 and to document compliance with the operating limits as specified in Table 2 to this subpart.
(c) For each CEMS, you must keep the records as described in paragraphs (c)(1) through (4) of this section.
(1) Records described in § 63.10(b)(2)(vi) through (xi).
(2) Previous (
(3) Request for alternatives to the relative accuracy test for CEMS as required in § 63.8(f)(6)(i), if applicable.
(4) The records in § 63.6(e)(3)(iii) through (v) related to SSM of the control device and associated monitoring equipment.
(d) You must keep the records required in Table 5 to this subpart to show continuous compliance with each emission limitation that applies to you.
(a) You must maintain all applicable records in such a manner that they can be readily accessed and are suitable for inspection according to § 63.10(b)(1).
(b) As specified in § 63.10(b)(1), you must keep each records for 5 years following the date of each occurrence, measurement, maintenance, corrective action, report, or record.
(c) You must retain your records of the most recent 2 years on site, or your records must be accessible on site. Your records of the remaining 3 years may be retained off site.
Table 7 to this subpart shows which parts of the General Provisions in §§ 63.1 through 63.15 apply to you.
(a) This subpart can be implemented and enforced by us, the U.S. EPA, or a delegated authority such as your State, local, or tribal agency. If the U.S. EPA Administrator has delegated authority to your State, local, or tribal agency, then that agency, in addition to the U.S. EPA, has the authority to implement and enforce this subpart. You should contact your U.S. EPA Regional Office to find out if implementation and enforcement of 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 under section 40 CFR part 63, subpart E, the authorities contained in paragraph (c) of this section are retained by the Administrator of U.S. EPA and are not transferred to the State, local, or tribal agency.
(c) The authorities that cannot be delegated to State, local, or tribal agencies are described in paragraphs (c)(1) through (4) of this section.
(1) Approval of alternatives to the emission limitations in § 63.9300 under § 63.6(g).
(2) Approval of major changes to test methods under § 63.7(e)(2)(ii) and (f) and as defined in § 63.90.
(3) Approval of major changes to monitoring under § 63.8(f) and as defined in § 63.90.
(4) Approval of major changes to recordkeeping and reporting under § 63.10(f) and as defined in § 63.90.
Terms used in this subpart are defined in the CAA; in 40 CFR 63.2, and in this section:
(1) Fails to meet any requirement or obligation established by this subpart, including but not limited to any emission limitations;
(2) Fails to meet any term or condition that is adopted to implement an applicable requirement in this subpart and that is included in the operating permit for any affected source required to obtain such a permit; or
(3) Fails to meet any emission limitation in this subpart during malfunction, regardless or whether or not such failure is permitted by this subpart.
You must comply with the emission limits that apply to your affected source in the following table as required by § 63.9300.
If you are required to comply with operating limits in § 63.9302, you must comply with the applicable operating limits in the following table:
As stated in § 63.9321, you must demonstrate initial compliance with each emission limitation that applies to you according to the following table:
As stated in § 63.9330, you must demonstrate initial compliance with each emission limitation that applies to you according to the following table:
As stated in § 63.9340, you must demonstrate continuous compliance with each emission limitation that applies to you according to the following table:
As stated in § 63.9350, you must submit each report that applies to you according to the following table:
As stated in 63.9365, you must comply with the General Provisions in §§ 63.1 through 63.15 that apply to you according to the following table:
This subpart establishes national emission standards for hazardous air pollutants (NESHAP) for friction materials manufacturing facilities that use a solvent-based process. This subpart also establishes requirements to demonstrate initial and continuous compliance with all applicable emission limitations in this subpart.
(a) You are subject to this subpart if you own or operate a friction materials manufacturing facility (as defined in § 63.9565) that is (or is part of) a major source of hazardous air pollutants (HAP) emissions on the first compliance date that applies to you, as specified in § 63.9495. Your friction materials manufacturing facility is a major source of HAP if it emits or has the potential to emit any single HAP at a rate of 9.07 megagrams (10 tons) or more per year or any combination of HAP at a rate of 22.68 megagrams (25 tons) or more per year.
(b) The requirements in this subpart do not apply to research and development facilities, as defined in section 112(c)(7) of the Clean Air Act.
(a) This subpart applies to each new, reconstructed, or existing affected source at your friction materials manufacturing facility.
(b) The affected source covered by this subpart is each new, reconstructed, or existing solvent mixer (as defined in § 63.9565) at your friction materials manufacturing facility.
(c) A solvent mixer at your friction materials manufacturing facility is new if you commence construction of the solvent mixer after October 18, 2002. An affected source is reconstructed if it meets the definition of “reconstruction” in § 63.2, and reconstruction is commenced after October 18, 2002.
(d) A solvent mixer at your friction materials manufacturing facility is existing if it is not new or reconstructed.
(a) If you have an existing solvent mixer, you must comply with each of the requirements for existing sources no later than October 18, 2005.
(b) If you have a new or reconstructed solvent mixer and its initial startup date is after October 18, 2002, you must comply with the requirements for new and reconstructed sources upon initial startup.
(c) If your friction materials manufacturing facility is an area source that increases its emissions or its potential to emit such that it becomes a (or part of a) major source of HAP emissions, then paragraphs (c)(1) and (2) of this section apply.
(1) For any portion of the area source that becomes a new or reconstructed affected source, you must comply with the requirements for new and reconstructed sources upon startup or no later than October 18, 2002, whichever is later.
(2) For any portion of the area source that becomes an existing affected source, you must comply with the requirements for existing sources no later than 1 year after the area source becomes a major source or no later than October 18, 2005, whichever is later.
(d) You must meet the notification and schedule requirements in § 63.9535. Several of the notifications must be submitted before the compliance date for your affected source.
(a) For each new, reconstructed, or existing large solvent mixer at your friction materials manufacturing facility, you must limit HAP solvent emissions to the atmosphere to no more than 30 percent of that which would otherwise be emitted in the absence of solvent recovery and/or solvent substitution, based on a 7-day block average.
(b) For each new, reconstructed, or existing small solvent mixer at your friction materials manufacturing facility, you must limit HAP solvent emissions to the atmosphere to no more than 15 percent of that which would otherwise be emitted in the absence of solvent recovery and/or solvent substitution, based on a 7-day block average.
(a) You must be in compliance with the emission limitation in this subpart at all times, except during periods of startup, shutdown, or malfunction.
(b) You must always operate and maintain your affected source, including air pollution control and monitoring equipment, according to the provisions in § 63.6(e)(1)(i).
(c) You must develop a written startup, shutdown, and malfunction plan according to the provisions in § 63.6(e)(3).
(a) If you use a solvent recovery system and/or solvent substitution, you must conduct your initial compliance demonstration within 7 calendar days after the compliance date that is specified for your source in § 63.9495.
(b) If you use a control technique other than a solvent recovery system and/or solvent substitution, you must comply with the provisions in § 63.9570.
(a) You have demonstrated initial compliance for each new, reconstructed, or existing large solvent mixer subject to the emission limitation in § 63.9500(a) if the HAP solvent discharged to the atmosphere during the first 7 days after the compliance date, determined according to the provisions in § 63.9520, does not exceed a 7-day block average of 30 percent of that which would otherwise be emitted in the absence of solvent recovery and/or solvent substitution.
(b) You have demonstrated initial compliance for each new, reconstructed, or existing small solvent mixer subject to the emission limitation in § 63.9500(b) if the HAP solvent discharged to the atmosphere during the first 7 days after the compliance date, determined according to the provisions in § 63.9520, does not exceed a 7-day block average of 15 percent of that which would otherwise be emitted in the absence of solvent recovery and/or solvent substitution.
(c) You must submit a notification of compliance status containing the results of the initial compliance demonstration according to § 63.9535(e).
(a) If you use a solvent recovery system, you must use the procedures in paragraphs (a)(1) through (8) of this section to demonstrate initial compliance with the emission limitations in § 63.9500(a) and (b).
(1) Record the date and time of each mix batch.
(2) Record the identity of each mix batch using a unique batch ID, as defined in § 63.9565.
(3) Measure and record the weight of HAP solvent loaded into the solvent mixer for each mix batch.
(4) Measure and record the weight of HAP solvent recovered for each mix batch.
(5) If you use a solvent recovery system, you must determine the percent of HAP solvent discharged to the atmosphere for each mix batch according to Equation 1 of this section as follows:
(6) If you use solvent substitution for a mix batch, you must record the use of a non-HAP material as a substitute for a HAP solvent for that mix batch and assign a value of 0 percent to the percent of HAP solvent discharged to the atmosphere for that mix batch (Pb).
(7) Determine the 7-day block average percent of HAP solvent discharged to the atmosphere according to Equation 2 of this section as follows:
(8) Have valid data for at least 90 percent of the mix batches over the 7-day averaging period.
(b) If you use a control technique other than a solvent recovery system and/or solvent substitution, you may apply to EPA for approval to use an alternative method of demonstrating compliance with the emission limitations for solvent mixers in § 63.9500(a) and (b), as provided in § 63.9570.
(a) If you use a solvent recovery system, you must install, operate, and maintain a weight measurement device to measure the weight of HAP solvent loaded into the solvent mixer and the weight of HAP solvent recovered for each mix batch.
(b) For each weight measurement device required by this section, you must develop and submit for approval a site-specific monitoring plan that addresses the requirements of paragraphs (b)(1) through (6) of this section:
(1) Procedures for installing the weight measurement device;
(2) The minimum accuracy of the weight measurement device in pounds and as a percent of the average weight of solvent to be loaded into the solvent mixer;
(3) Site-specific procedures for how the measurements will be made;
(4) How the measurement data will be recorded, reduced, and stored;
(5) Procedures and acceptance criteria for calibration of the weight measurement device; and
(6) How the measurement device will be maintained, including a routine maintenance schedule and spare parts inventory list.
(c) The site-specific monitoring plan required in paragraph (b) of this section must include, at a minimum, the requirements of paragraphs (c)(1) through (3) of this section:
(1) The weight measurement device must have a minimum accuracy of ±0.05 kilograms (±0.1 pounds) or ±1 percent of the average weight of solvent to be loaded into the solvent mixer, whichever is greater.
(2) An initial multi-point calibration of the weight measurement device must be made using 5 points spanning the expected range of weight measurements before the weight measurement device can be used. The manufacturer's calibration results can be used to meet this requirement.
(3) Once per day, an accuracy audit must be made using a single Class F calibration weight that corresponds to 20 to 80 percent of the average weight of solvent to be loaded into the solvent mixer. If the weight measurement device cannot reproduce the value of the calibration weight within ±0.05 kilograms (0.1 pounds) or ±1 percent of the average weight of solvent to be loaded into the solvent mixer, whichever is greater, the scale must be recalibrated before being used again. The recalibration must be performed with at least five Class F calibration weights spanning the expected range of weight measurements.
(d) You must operate and maintain the weight measurement device according to the site-specific monitoring plan.
(e) You must maintain records of all maintenance activities, calibrations, and calibration audits.
(a) If you use a solvent recovery system and/or solvent substitution, you must demonstrate continuous compliance with the emission limitations for solvent mixers in § 63.9500(a) and (b) according to the provisions in paragraphs (a)(1) through (3) of this section.
(1) Except for during malfunctions of your weight measurement device and associated repairs, you must collect and record the information required in § 63.9520(a)(1) through (8) at all times that the affected source is operating and record all information needed to document conformance with these requirements.
(2) For new, reconstructed, or existing large solvent mixers, maintain the 7-day block average percent of HAP solvent discharged to the atmosphere at or below 30 percent of that which would otherwise be emitted in the absence of solvent recovery and/or solvent substitution.
(3) For new, reconstructed, or existing small solvent mixers, maintain the 7-day block average percent of HAP solvent discharged to the atmosphere at or below 15 percent of that which would otherwise be emitted in the absence of solvent recovery and/or solvent substitution.
(b) If you use a control technique other than a solvent recovery system and/or solvent substitution, you must demonstrate continuous compliance with the emission limitations for solvent mixers in § 63.9500(a) and (b) according to the provisions in § 63.9570.
(c) You must report each instance in which you did not meet the emission limitations for solvent mixers in § 63.9500(a) and (b). This includes periods of startup, shutdown, or malfunction. These instances are deviations
(d) [Reserved]
(e) Consistent with §§ 63.6(e) and 63.7(e)(1), deviations that occur during a period of startup, shutdown, or malfunction are not violations if you demonstrate to the Administrator's satisfaction that you were operating in accordance with § 63.6(e)(1). The Administrator will determine whether deviations that occur during a period of startup, shutdown, or malfunction are violations, according to the provisions in § 63.6(e).
(a) You must submit all of the notifications in §§ 63.8(f)(4) and 63.9(b), (c), (d), and (h) that apply to you by the specified dates.
(b) If you use a control technique other than a solvent recovery system and/or solvent substitution, you must comply with the provisions in § 63.9570.
(c) As specified in § 63.9(b)(2), if you start up your affected source before October 18, 2002, you must submit your initial notification no later than 120 calendar days after October 18, 2002.
(d) As specified in § 63.9(b)(3), if you start up your new affected source on or after October 18, 2002, you must submit your initial notification no later than 120 calendar days after you become subject to this subpart.
(e) You must submit a notification of compliance status according to § 63.9(h)(2)(ii). You must submit the notification of compliance status before the close of business on the 30th calendar day following the completion of the initial compliance demonstration.
(a) Unless the Administrator has approved a different schedule, you must submit each semiannual compliance report according to the requirements in paragraphs (a)(1) through (5) of this section.
(1) The first compliance report must cover the period beginning on the compliance date that is specified for your affected source in § 63.9495 and ending on June 30 or December 31, whichever date comes first after the compliance date that is specified for your source in § 63.9495.
(2) The first compliance report must be postmarked or delivered no later than July 31 or January 31, whichever date comes first after your first compliance report is due.
(3) Each subsequent compliance report must cover the semiannual reporting period from January 1 through June 30 or the semiannual reporting period from July 1 through December 31.
(4) Each subsequent compliance report must be postmarked or delivered no later than July 31 or January 31, whichever date comes first after the end of the semiannual reporting period.
(5) For each affected source that is subject to permitting regulations pursuant to 40 CFR part 70 or 71 of this chapter, and if the permitting authority has established dates for submitting semiannual reports pursuant to 40 CFR 70.6(a)(3)(iii)(A) or 40 CFR 71.6(a)(3)(iii)(A) of this chapter, you may submit the first and subsequent compliance reports according to the dates the permitting authority has established instead of according to the dates in paragraphs (a)(1) through (4) of this section.
(b) Each compliance report must include the information in paragraphs (b)(1) through (3) of this section, and if applicable, paragraphs (b)(4) through (6) of this section.
(1) Company name and address.
(2) Statement by a responsible official, with the official's name, title, and signature, certifying that, based on information and belief formed after reasonable inquiry, the statements and information in the report are true, accurate, and complete.
(3) Date of report and beginning and ending dates of the reporting period.
(4) If you had a startup, shutdown, or malfunction during the reporting period and you took actions consistent with your startup, shutdown, and malfunction plan, the compliance report
(5) If there were no deviations from the emission limitations for solvent mixers in § 63.9500(a) and (b), a statement that there were no deviations from the emission limitations during the reporting period.
(6) If there were no periods during which a monitoring system was out-of-control as specified in § 63.8(c)(7), a statement that there were no periods during which a monitoring system was out-of-control during the reporting period.
(c) For each deviation from an emission limitation occurring at an affected source, you must include the information in paragraphs (b)(1) through (4) and (c)(1) and (2) of this section. This includes periods of startup, shutdown, or malfunction.
(1) The total operating time of each affected source during the reporting period.
(2) Information on the number, duration, and cause of deviations (including unknown cause, if applicable), as applicable, and the corrective action taken.
(d) If you had a startup, shutdown, or malfunction during the semiannual reporting period that was not consistent with your startup, shutdown, and malfunction plan, you must submit an immediate startup, shutdown, and malfunction report according to the requirements in § 63.10(d)(5)(ii).
(e) If you have obtained a title V operating permit for an affected source pursuant to 40 CFR part 70 or 71 of this chapter, you must report all deviations as defined in this subpart in the semiannual monitoring report required by 40 CFR 70.6(a)(3)(iii)(A) or 40 CFR 71.6(a)(3)(iii)(A) of this chapter. If you submit a compliance report for an affected source along with, or as part of, the semiannual monitoring report required by 40 CFR 70.6(a)(3)(iii)(A) or 40 CFR 71.6(a)(3)(iii)(A) of this chapter, and the compliance report includes all the required information concerning deviations from any emission limitation in this subpart, then submission of the compliance report satisfies any obligation to report the same deviations in the semiannual monitoring report. However, submission of a compliance report does not otherwise affect any obligation you may have to report deviations from permit requirements to your permitting authority.
(a) You must keep the records in paragraphs (a)(1) and (2) of this section that apply to you.
(1) A copy of each notification and report that you submitted to comply with this subpart, including all documentation supporting any initial notification or notification of compliance status that you submitted, according to the requirements in § 63.10(b)(2)(xiv).
(2) The records in § 63.6(e)(3)(iii) through (v) related to startup, shutdown, or malfunction.
(b) You must keep the records required in § 63.9525 to show proper operation and maintenance of the weight measurement device.
(c) You must keep the records required in § 63.9530 to show continuous compliance with the emission limitations for solvent mixers in § 63.9500(a) and (b).
(a) You must keep your records in a form suitable and readily available for expeditious review, according to § 63.10(b)(1).
(b) As specified in § 63.10(b)(1), you must keep each record for 5 years following the date of each occurrence, measurement, maintenance, corrective action, report, or record.
(c) You must keep each record on site for at least 2 years after the date of each occurrence, measurement, maintenance, corrective action, report, or record, according to § 63.10(b)(1). You can keep the records offsite for the remaining 3 years.
Table 1 to this subpart shows which parts of the General Provisions in §§ 63.1 through 63.15 apply to you.
(a) This subpart can be implemented and enforced by the U.S. EPA, or a delegated authority such as your State, local, or tribal agency. If the U.S. EPA Administrator has delegated authority to your State, local, or tribal agency, then that agency, in addition to the U.S. EPA, has the authority to implement and enforce this subpart. You should contact your U.S. 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 under 40 CFR part 63, subpart E, the authorities contained in paragraphs (c)(1) through (4) of this section are retained by the Administrator of the U.S. EPA and are not transferred to the State, local, or tribal agency.
(c) The authorities that cannot be delegated to State, local or tribal agencies are as follows:
(1) Approval of alternatives to the emission limitations in § 63.9500(a) and (b) under § 63.6(g).
(2) Approval of major alternatives to test methods under § 63.7(e)(2)(ii) and (f) and as defined in § 63.90.
(3) Approval of major alternatives to monitoring under § 63.8(f) and as defined in § 63.90.
(4) Approval of major alternatives to recordkeeping and reporting under § 63.10(f) and as defined in § 63.90.
Terms used in this subpart are defined in the Clean Air Act, in § 63.2, and in this section as follows:
(1) Fails to meet any requirement or obligation established by this subpart, including, but not limited to, any emission limitation (including any operating limit);
(2) Fails to meet any term or condition that is adopted to implement an applicable requirement in this subpart and that is included in the operating permit for any affected source required to obtain such a permit; or
(3) Fails to meet any emission limitation (including any operating limit) in this subpart during startup, shutdown, or malfunction, regardless of whether or not such failure is permitted by this subpart.
(a) If you use a control technique other than a solvent recovery system and/or solvent substitution, you may request approval to use an alternative method of demonstrating compliance with the emission limitations in § 63.9500(a) and (b) according to the procedures in this section.
(b) You can request approval to use an alternative method of demonstrating compliance in the initial notification for existing sources, the notification of construction or reconstruction for new sources, or at any time.
(c) You must submit a description of the proposed testing, monitoring, recordkeeping, and reporting that will be used and the proposed basis for demonstrating compliance.
(1) If you have not previously performed testing, you must submit a proposed test plan. If you are seeking permission to use an alternative method of compliance based on previously performed testing, you must submit the results of testing, a description of the procedures followed in testing, and a description of pertinent conditions during testing.
(2) You must submit a monitoring plan that includes a description of the control technique, test results verifying the performance of the control technique, the appropriate operating parameters that will be monitored, and the frequency of measuring and recording to establish continuous compliance with the emission limitations in § 63.9500(a) and (b). You must also include the proposed performance specifications and quality assurance procedures for the monitors. The monitoring plan is subject to the Administrator's approval. You must install, calibrate, operate, and maintain the monitors in accordance with the monitoring plan approved by the Administrator.
(d) Use of the alternative method of demonstrating compliance must not begin until approval is granted by the Administrator.
As required in § 63.9505, you must comply with each applicable General Provisions requirement according to the following table:
This subpart establishes national emission standards for hazardous air pollutants (NESHAP) for taconite iron ore processing. This subpart also establishes requirements to demonstrate initial and continuous compliance with all applicable emission limitations (emission limits and operating limits), work practice standards, and operation and maintenance requirements in this subpart.
You are subject to this subpart if you own or operate a taconite iron ore processing plant that is (or is part of) a major source of hazardous air pollutant (HAP) emissions on the first compliance date that applies to you. Your taconite iron ore processing plant is a major source of HAP if it emits or has the potential to emit any single HAP at a rate of 10 tons or more per year or any combination of HAP at a rate of 25 tons or more per year.
(a) This subpart applies to each new and existing affected source at your taconite iron ore processing plant.
(b) The affected sources are each new or existing ore crushing and handling operation, ore dryer, indurating furnace, and finished pellet handling operation at your taconite iron ore processing plant, as defined in § 63.9652.
(c) This subpart covers emissions from ore crushing and handling emission units, ore dryer stacks, indurating furnace stacks, finished pellet handling emission units, and fugitive dust emissions.
(d) An ore crushing and handling operation, ore dryer, indurating furnace, or finished pellet handling operation at your taconite iron ore processing plant is existing if you commenced construction or reconstruction of the affected source before December 18, 2002.
(e) An ore crushing and handling operation, ore dryer, indurating furnace, or finished pellet handling operation at your taconite iron ore processing plant is new if you commence construction or reconstruction of the affected source on or after December 18, 2002. An affected source is reconstructed if it meets the definition of reconstruction in § 63.2.
(a) If you have an existing affected source, you must comply with each emission limitation, work practice standard, and operation and maintenance requirement in this subpart that applies to you no later than October 30, 2006.
(b) If you have a new affected source and its initial startup date is on or before October 30, 2003, you must comply with each emission limitation, work practice standard, and operation and maintenance requirement in this subpart that applies to you by October 30, 2003.
(c) If you have a new affected source and its initial startup date is after October 30, 2003, you must comply with each emission limitation, work practice standard, and operation and maintenance requirement in this subpart that applies to you upon initial startup.
(d) If your taconite iron ore processing plant is an area source that becomes a major source of HAP, the compliance dates in paragraphs (d)(1) and (2) of this section apply to you.
(1) Any portion of the taconite iron ore processing plant that is a new affected source or a new reconstructed source must be in compliance with this subpart upon startup.
(2) All other parts of the taconite iron ore processing plant must be in compliance with this subpart no later than 3 years after the plant becomes a major source.
(e) You must meet the notification and schedule requirements in § 63.9640. Several of these notifications must be submitted before the compliance date for your affected source.
(a) You must meet each emission limit in Table 1 to this subpart that applies to you.
(b) You must meet each operating limit for control devices in paragraphs (b)(1) through (5) of this section that applies to you.
(1) Except as provided in paragraph (b)(2) of this section, for each wet scrubber applied to meet any particulate matter emission limit in Table 1 to this subpart, you must maintain the daily average pressure drop and daily average scrubber water flow rate at or above the minimum levels established during the initial performance test.
(2) For each dynamic wet scrubber applied to meet any particulate matter emission limit in Table 1 to this subpart, you must maintain the daily average scrubber water flow rate and either the daily average fan amperage (a surrogate for fan speed as revolutions per minute) or the daily average pressure drop at or above the minimum levels established during the initial performance test.
(3) For each dry electrostatic precipitator applied to meet any particulate matter emission limit in Table 1 to this subpart, you must meet the operating limits in paragraph (b)(3)(i) or (ii) of this section.
(i) Maintain the 6-minute average opacity of emissions exiting the control device stack at or below the level established during the initial performance test.
(ii) Maintain the daily average secondary voltage and daily average secondary current for each field at or above the minimum levels established during the initial performance test.
(4) For each wet electrostatic precipitator applied to meet any particulate matter emission limit in Table 1 to this subpart, you must meet the operating limits in paragraphs (b)(4)(i) through (iii) of this section.
(i) Maintain the daily average secondary voltage for each field at or above the minimum levels established during the initial performance test.
(ii) Maintain the daily average stack outlet temperature at or below the maximum levels established during the initial performance test.
(iii) Maintain the daily average water flow rate at or above the minimum levels established during the initial performance test.
(5) If you use any air pollution control device other than a baghouse, wet scrubber, dynamic scrubber, dry electrostatic precipitator, or wet electrostatic precipitator, you must submit a site-specific monitoring plan in accordance with § 63.9631(f).
(c) You may petition the Administrator for approval of alternatives to the monitoring requirements in paragraphs (b)(1) through (4) of this section as allowed under § 63.8(f) and as defined in § 63.90.
(a) You must prepare, and at all times operate according to, a fugitive dust emissions control plan that describes in detail the measures that will be put in place to control fugitive dust emissions from the locations listed in paragraphs (a)(1) through (6) of this section.
(1) Stockpiles (includes, but is not limited to, stockpiles of uncrushed ore, crushed ore, or finished pellets);
(2) Material transfer points;
(3) Plant roadways;
(4) Tailings basin;
(5) Pellet loading areas; and
(6) Yard areas.
(b) A copy of your fugitive dust emissions control plan must be submitted for approval to the Administrator on or before the applicable compliance date for the affected source as specified in § 63.9583. The requirement for the plant to operate according to the fugitive dust emissions control plan must be incorporated by reference in the operating permit for the plant that is issued by the designated permitting authority under 40 CFR part 70 or 40 CFR part 71.
(c) You can use an existing fugitive dust emissions control plan provided it meets the requirements in paragraphs (c)(1) through (3) of this section.
(1) The plan satisfies the requirements of paragraph (a) of this section.
(2) The plan describes the current measures to control fugitive dust emission sources.
(3) The plan has been approved as part of a State implementation plan or title V permit.
(d) You must maintain a current copy of the fugitive dust emissions control plan onsite, and it must be available for inspection upon request. You must keep the plan for the life of the affected source or until the affected source is no longer subject to the requirements of this subpart.
(a) As required by § 63.6(e)(1)(i), you must always operate and maintain your affected source, including air pollution control and monitoring equipment, in a manner consistent with good air pollution control practices for minimizing emissions at least to the levels required by this subpart.
(b) You must prepare, and at all times operate according to, a written operation and maintenance plan for each control device applied to meet any particulate matter emission limit in Table 1 to this subpart and to meet the requirement of each indurating furnace subject to good combustion practices (GCP). Each site-specific operation and maintenance plan must be submitted to the Administrator on or before the compliance date that is specified in § 63.9583 for your affected source. The plan you submit must explain why the chosen practices (
(1) Preventative maintenance for each control device, including a preventative maintenance schedule that is consistent with the manufacturer's instructions for routine and long-term maintenance.
(2) Corrective action procedures for bag leak detection systems. In the event a bag leak detection system alarm is triggered, you must initiate corrective action to determine the cause of the alarm within 1 hour of the alarm, initiate corrective action to correct the cause of the problem within 24 hours of the alarm, and complete the corrective action as soon as practicable. Corrective actions may include, but are not limited to, the actions listed in paragraphs (b)(2)(i) through (vi) of this section.
(i) Inspecting the baghouse for air leaks, torn or broken bags or filter media, or any other condition that may cause an increase in emissions.
(ii) Sealing off defective bags or filter media.
(iii) Replacing defective bags or filter media or otherwise repairing the control device.
(iv) Sealing off a defective baghouse compartment.
(v) Cleaning the bag leak detection system probe, or otherwise repairing the bag leak detection system.
(vi) Adjusting the process operation producing the particulate emissions.
(3) Corrective action procedures for continuous parameter monitoring systems (CPMS) for all air pollution control devices except for baghouses. In the event you exceed an established operating limit for an air pollution control device except for a baghouse, you
(4) Good combustion practices for indurating furnaces. You must identify and implement a set of site-specific GCP for each type of indurating furnace at your plant. These GCP should correspond to your standard operating procedures for maintaining the proper and efficient combustion within each indurating furnace. Good combustion practices include, but are not limited to, the elements listed in paragraphs (b)(4)(i) through (v) of this section.
(i) Proper operating conditions for each indurating furnace (
(ii) Routine inspection and preventative maintenance and corresponding schedules of each indurating furnace.
(iii) Performance analyses of each indurating furnace.
(iv) Keeping applicable operator logs.
(v) Keeping applicable records to document compliance with each element.
(a) You must be in compliance with the requirements in paragraphs (a)(1) through (6) in this section at all times, except during periods of startup, shutdown, and malfunction. The terms startup, shutdown, and malfunction are defined in § 63.2.
(1) The emission limitations in § 63.9590.
(2) The work practice standards in § 63.9591.
(3) The operation and maintenance requirements in § 63.9600.
(4) The notification requirements in § 63.9640.
(5) The reporting requirements in § 63.9641.
(6) The recordkeeping requirements in § 63.9642.
(b) During the period between the compliance date specified for your affected source in § 63.9583 and the date upon which continuous monitoring systems have been installed and certified and any applicable operating limits have been set, you must maintain a log detailing the operation and maintenance of the process and emissions control equipment. This includes the daily monitoring and recordkeeping of air pollution control device operating parameters as specified in § 63.9590(b).
(c) You must develop a written startup, shutdown, and malfunction plan according to the provisions in § 63.6(e)(3).
(a) For each ore crushing and handling affected source, you must demonstrate initial compliance with the emission limits in Table 1 to this subpart by conducting an initial performance test for particulate matter as specified in paragraphs (a)(1) and (2) of this section.
(1) Except as provided in paragraph (e) of this section, an initial performance test must be performed on all stacks associated with ore crushing and handling.
(2) Initial performance tests must be completed no later than 180 calendar days after the compliance date specified in § 63.9583. Performance tests conducted between October 30, 2003 and no later than 180 days after the corresponding compliance date can be used for initial compliance demonstration, provided the tests meet the initial performance testing requirements of this subpart.
(b) For each indurating furnace affected source, you must demonstrate initial compliance with the emission limits in Table 1 to this subpart by conducting an initial performance test for particulate matter as specified in paragraphs (b)(1) and (2) of this section.
(1) An initial performance test must be performed on all stacks associated with each indurating furnace.
(2) Initial performance tests must be completed no later than 180 calendar days after the compliance date specified in § 63.9583. Performance tests conducted between October 30, 2003 and no later than 180 days after the corresponding compliance date can be used for initial compliance demonstration, provided the tests meet the initial performance testing requirements of this subpart. For indurating furnaces with multiple stacks, the performance tests for all stacks must be completed within a reasonable period of time, such that the indurating furnace operating characteristics remain representative for the duration of the stack tests.
(c) For each finished pellet handling affected source, you must demonstrate initial compliance with the emission limits in Table 1 to this subpart by conducting an initial performance test for particulate matter as specified in paragraphs (c)(1) and (2) of this section.
(1) Except as provided in paragraph (e) of this section, an initial performance test must be performed on all stacks associated with finished pellet handling.
(2) Initial performance tests must be completed no later than 180 calendar days after the compliance date specified in § 63.9583. Performance tests conducted between October 30, 2003 and no later than 180 days after the corresponding compliance date can be used for initial compliance demonstration, provided the tests meet the initial compliance testing requirements of this subpart.
(d) For each ore dryer affected source, you must demonstrate initial compliance with the emission limits in Table 1 to this subpart by conducting an initial performance test for particulate matter as specified in paragraphs (d)(1) and (2) of this section.
(1) An initial performance test must be performed on all stacks associated with each ore dryer.
(2) Initial performance tests must be completed no later than 180 calendar days after the compliance date specified in § 63.9583. Performance tests conducted between October 30, 2003 and no later than 180 days after the corresponding compliance date can be used for initial compliance demonstration, provided the tests meet the initial compliance testing requirements of this subpart. For ore dryers with multiple stacks, the performance tests for all stacks must be completed within a reasonable period of time, such that the ore dryer operating characteristics remain representative for the duration of the stack tests.
(e) For ore crushing and handling affected sources and finished pellet handling affected sources, in lieu of conducting initial performance tests for particulate matter on all stacks, you may elect to group a maximum of six similar emission units together and conduct an initial compliance test on one representative emission unit within each group of similar emission units. The determination of whether emission units are similar must meet the criteria in paragraph (f) of this section. If you decide to test representative emission units, you must prepare and submit a testing plan as described in paragraph (g) of this section.
(f) If you elect to test representative emission units as provided in paragraph (e) of this section, the units that are grouped together as similar units must meet the criteria in paragraphs (f)(1) through (3) of this section.
(1) All emission units within a group must be of the same process type (
(2) All emission units within a group must also have the same type of air pollution control device (
(3) The site-specific operating limits established for the emission unit selected as representative of a group of similar emission units will be used as
(g) If you plan to conduct initial performance tests on representative emission units within an ore crushing and handling affected source or a finished pellet handling affected source, you must submit a testing plan for initial performance tests. This testing plan must be submitted to the Administrator or delegated authority no later than 90 days prior to the first scheduled initial performance test. The testing plan must contain the information specified in paragraphs (g)(1) through (3) of this section.
(1) A list of all emission units. This list must clearly identify all emission units that have been grouped together as similar emission units. Within each group of emission units, you must identify the emission unit that will be the representative unit for that group and subject to initial performance testing.
(2) A list of the process type and type of air pollution control device on each emission unit.
(3) A schedule indicating when you will conduct an initial performance test for particulate matter for each representative emission unit.
(h) For each work practice standard and operation and maintenance requirement that applies to you where initial compliance is not demonstrated using a performance test, you must demonstrate initial compliance within 30 calendar days after the compliance date that is specified for your affected source in § 63.9583.
(i) If you commenced construction or reconstruction of an affected source between December 18, 2002 and October 30, 2003 , you must demonstrate initial compliance with either the proposed emission limit or the promulgated emission limit no later than 180 calendar days after October 30, 2003 or no later than 180 calendar days after startup of the source, whichever is later, according to § 63.7(a)(2)(ix).
(j) If you commenced construction or reconstruction of an affected source between December 18, 2002 and October 30, 2003, and you chose to comply with the proposed emission limit when demonstrating initial compliance, you must conduct a second performance test to demonstrate compliance with the promulgated emission limit by 3 years and 180 calendar days after October 30, 2003, or after startup of the source, whichever is later, according to § 63.7(a)(2)(ix).
(a) You must conduct each performance test that applies to your affected source according to the requirements in § 63.7(e)(1) and paragraphs (b) and (c) of this section.
(b) For each ore crushing and handling affected source and each finished pellet handling affected source, you must determine compliance with the applicable emission limit for particulate matter in Table 1 to this subpart by following the test methods and procedures in paragraphs (b)(1) through (3) of this section.
(1) Except as provided in § 63.9620(e), determine the concentration of particulate matter in the stack gas for each emission unit according to the test methods in appendix A to part 60 of this chapter. The applicable test methods are listed in paragraphs (b)(1)(i) through (v) of this section.
(i) Method 1 or 1A to select sampling port locations and the number of traverse points. Sampling ports must be located at the outlet of the control device and prior to any releases to the atmosphere.
(ii) Method 2, 2A, 2C, 2D, 2F, or 2G, as applicable, to determine the volumetric flow rate of the stack gas.
(iii) Method 3, 3A, or 3B to determine the dry molecular weight of the stack gas.
(iv) Method 4 to determine the moisture content of the stack gas.
(v) Method 5, 5D, or 17 to determine the concentration of particulate matter.
(2) Each Method 5, 5D, or 17 performance test must consist of three separate runs. Each run must be conducted for a minimum of 2 hours. The average particulate matter concentration from
(3) For each ore crushing and handling affected source and each finished pellet handling affected source, you must determine the flow-weighted mean concentration of particulate matter emissions from all emission units in each affected source following the procedure in paragraph (b)(3)(i) or (ii) of this section.
(i) If an initial performance test is conducted on all emission units within an affected source, calculate the flow-weighted mean concentration of particulate matter emissions from the affected source using Equation 2 of this section.
(ii) If you are grouping similar emission units together in accordance with § 63.9620(e), you must follow the procedures in paragraphs (b)(3)(ii)(A) through (C) of this section.
(A) Assign the average particulate matter concentration measured from the representative unit, as determined from Equation 1 of this section, to each emission unit within the corresponding group of similar units.
(B) Establish the maximum operating volumetric flow rate of exhaust gas from each emission unit within each group of similar units.
(C) Using the data from paragraphs (b)(3)(ii)(A) and (B) of this section, calculate the flow-weighted mean concentration of particulate matter emissions from the affected source using Equation 3 of this section.
(c) For each ore dryer affected source and each indurating furnace affected source, you must determine compliance with the applicable emission limit for particulate matter in Table 1 to this subpart by following the test methods and procedures in paragraphs (c)(1) through (3) of this section.
(1) Determine the concentration of particulate matter for each stack according to the test methods in 40 CFR part 60, appendix A. The applicable test methods are listed in paragraphs (c)(1)(i) through (v) of this section.
(i) Method 1 or 1A to select sampling port locations and the number of traverse points. Sampling ports must be
(ii) Method 2, 2A, 2C, 2D, 2F, or 2G, as applicable, to determine the volumetric flow rate of the stack gas.
(iii) Method 3, 3A, or 3B to determine the dry molecular weight of the stack gas.
(iv) Method 4 to determine the moisture content of the stack gas.
(v) Method 5, 5D, or 17 to determine the concentration of particulate matter.
(2) Each Method 5, 5D, or 17 performance test must consist of three separate runs. Each run must be conducted for a minimum of 2 hours. The average particulate matter concentration from the three runs will be used to determine compliance, as shown in Equation 1 of this section.
(3) For each ore dryer and each indurating furnace with multiple stacks, calculate the flow-weighted mean concentration of particulate matter emissions using Equation 4 of this section.
(a) For wet scrubbers subject to performance testing in § 63.9620 and operating limits for pressure drop and scrubber water flow rate in § 63.9590(b)(1), you must establish site-specific operating limits according to the procedures in paragraphs (a)(1) through (3) of this section.
(1) Using the CPMS required in § 63.9631(b), measure and record the pressure drop and scrubber water flow rate every 15 minutes during each run of the particulate matter performance test.
(2) Calculate and record the average pressure drop and scrubber water flow rate for each individual test run. Your operating limits are established as the lowest average pressure drop and the lowest average scrubber water flow rate corresponding to any of the three test runs.
(3) If a rod-deck venturi scrubber is applied to an indurating furnace to meet any particulate matter emission limit in Table 1 to this subpart, you may establish a lower average pressure drop operating limit by using historical average pressure drop data from a certified performance test completed on or after December 18, 2002 instead of using the average pressure drop value determined during the initial performance test, as specified in paragraph (a)(2) of this section. If historical average pressure drop data are used to establish an operating limit (
(b) For dynamic wet scrubbers subject to performance testing in § 63.9620 and operating limits for scrubber water flow rate and either fan amperage or pressure drop in § 63.9590(b)(2), you must establish site-specific operating limits according to the procedures in paragraphs (b)(1) and (2) of this section.
(1) Using the CPMS required in § 63.9631(b), measure and record the scrubber water flow rate and either the fan amperage or pressure drop every 15 minutes during each run of the particulate matter performance test.
(2) Calculate and record the average scrubber water flow rate and either the average fan amperage or average pressure drop for each individual test run. Your operating limits are established
(c) For a dry electrostatic precipitator subject to performance testing in § 63.9620 and operating limits in § 63.9590(b)(3), you must establish a site-specific operating limit according to the procedures in paragraphs (c)(1) or (2) of this section.
(1) If the operating limit for your dry electrostatic precipitator is a 6-minute average opacity of emissions value, then you must follow the requirements in paragraphs (c)(1)(i) through (iii) of this section.
(i) Using the continuous opacity monitoring system (COMS) required in § 63.9631(d)(1), measure and record the opacity of emissions from each control device stack during the particulate matter performance test.
(ii) Compute and record the 6-minute opacity averages from 24 or more data points equally spaced over each 6-minute period (
(iii) Using the opacity measurements from a performance test that meets the emission limit, determine the opacity value corresponding to the 99 percent upper confidence level of a normal distribution of the 6-minute opacity averages.
(2) If the operating limit for your dry electrostatic precipitator is the daily average secondary voltage and daily average secondary current for each field, then you must follow the requirements in paragraphs (c)(2)(i) and (ii) of this section.
(i) Using the CPMS required in § 63.9631(d)(2), measure and record the secondary voltage and secondary current for each dry electrostatic precipitator field every 15 minutes during each run of the particulate matter performance test.
(ii) Calculate and record the average secondary voltage and secondary current for each dry electrostatic precipitator field for each individual test run. Your operating limits are established as the lowest average secondary voltage and secondary current value for each dry electrostatic precipitator field corresponding to any of the three test runs.
(d) For a wet electrostatic precipitator subject to performance testing in § 63.9620 and operating limit in § 63.9590(b)(4), you must establish a site-specific operating limit according to the procedures in paragraphs (d)(1) and (2) of this section.
(1) Using the CPMS required in § 63.9631(e), measure and record the parametric values in paragraphs (d)(1)(i) through (iii) of this section for each wet electrostatic precipitator field every 15 minutes during each run of the particulate matter performance test.
(i) Secondary voltage;
(ii) Water flow rate; and
(iii) Stack outlet temperature.
(2) For each individual test run, calculate and record the average value for each operating parameter in paragraphs (d)(1)(i) through (iii) of this section for each wet electrostatic precipitator field. Your operating limits are established as the lowest average value for each operating parameter corresponding to any of the three test runs.
(e) If you use an air pollution control device other than a wet scrubber, dynamic wet scrubber, dry electrostatic precipitator, wet electrostatic precipitator, or baghouse, and it is subject to performance testing in § 63.9620, you must submit a site-specific monitoring plan in accordance with § 63.9631(f). The site-specific monitoring plan must include the site-specific procedures for demonstrating initial and continuous compliance with the corresponding operating limits.
(f) You may change the operating limits for any air pollution control device as long as you meet the requirements in paragraphs (f)(1) through (3) of this section.
(1) Submit a written notification to the Administrator of your request to conduct a new performance test to revise the operating limit.
(2) Conduct a performance test to demonstrate compliance with the applicable emission limitation in Table 1 to this subpart.
(3) Establish revised operating limits according to the applicable procedures
(a) For each affected source subject to an emission limit in Table 1 to this subpart, you must demonstrate initial compliance by meeting the emission limit requirements in paragraphs (a)(1) through (4) of this section.
(1) For ore crushing and handling, the flow-weighted mean concentration of particulate matter, determined according to the procedures in §§ 63.9620(a) and 63.9621(b), must not exceed the emission limits in Table 1 to this subpart.
(2) For indurating furnaces, the flow-weighted mean concentration of particulate matter, determined according to the procedures in §§ 63.9620(b) and 63.9621(c), must not exceed the emission limits in Table 1 to this subpart.
(3) For finished pellet handling, the flow-weighted mean concentration of particulate matter, determined according to the procedures in §§ 63.9620(c) and 63.9621(b), must not exceed the emission limits in Table 1 to this subpart.
(4) For ore dryers, the flow-weighted mean concentration of particulate matter, determined according to the procedures in §§ 63.9620(d) and 63.9621(c), must not exceed the emission limits in Table 1 to this subpart.
(b) For each affected source subject to an emission limit in Table 1 to this subpart, you must demonstrate initial compliance by meeting the operating limit requirements in paragraphs (b)(1) through (5) of this section.
(1) For each wet scrubber subject to performance testing in § 63.9620 and operating limits for pressure drop and scrubber water flow rate in § 63.9590(b)(1), you have established appropriate site-specific operating limits and have a record of the pressure drop and scrubber water flow rate measured during the performance test in accordance with § 63.9622(a).
(2) For each dynamic wet scrubber subject to performance testing in § 63.9620 and operating limits for scrubber water flow rate and either fan amperage or pressure drop in § 63.9590(b)(2), you have established appropriate site-specific operating limits and have a record of the scrubber water flow rate and either the fan amperage or pressure drop value, measured during the performance test in accordance with § 63.9622(b).
(3) For each dry electrostatic precipitator subject to performance testing in § 63.9620 and one of the operating limits in § 63.9590(b)(3), you must meet the requirements in paragraph (b)(3)(i) or (ii) of this section.
(i) If you are subject to the operating limit for opacity in § 63.9590(b)(3)(i), you have established appropriate site-specific operating limits and have a record of the opacity measured during the performance test in accordance with § 63.9622(c)(1).
(ii) If you are subject to the operating limit for secondary voltage and secondary current in § 63.9590(b)(3)(ii), you have established appropriate site-specific operating limits and have a record of the secondary voltage and secondary current measured during the performance test in accordance with § 63.9622(c)(2).
(4) For each wet electrostatic precipitator subject to performance testing in § 63.9620 and operating limits for secondary voltage, water flow rate, and stack outlet temperature in § 63.9590(b)(4), you have established appropriate site-specific operating limits and have a record of the secondary voltage, water flow rate, and stack outlet temperature measured during the performance test in accordance with § 63.9622(d).
(5) For other air pollution control devices subject to performance testing in § 63.9620 and operating limits in accordance with § 63.9590(b)(5), you have submitted a site-specific monitoring plan in accordance with § 63.9631(f) and have a record of the site-specific operating limits as measured during the performance test in accordance with § 63.9622(e).
(c) For each emission limitation and operating limit that applies to you, you must submit a notification of compliance status according to § 63.9640(e).
You must demonstrate initial compliance with the work practice standards by meeting the requirements in paragraphs (a) through (c) of this section.
(a) You must prepare a fugitive dust emissions control plan in accordance with the requirements in § 63.9591.
(b) You must submit to the Administrator the fugitive dust emissions control plan in accordance with the requirements in § 63.9591.
(c) You must implement each control practice according to the procedures specified in your fugitive dust emissions control plan.
For each air pollution control device subject to operating limits in § 63.9590(b), you have demonstrated initial compliance if you meet all of the requirements in paragraphs (a) through (d) of this section.
(a) You have prepared the operation and maintenance plan for air pollution control devices in accordance with § 63.9600(b).
(b) You have operated each air pollution control device according to the procedures in the operation and maintenance plan.
(c) You have submitted a notification of compliance status according to the requirements in § 63.9640(e).
(d) You have prepared a site-specific monitoring plan in accordance with § 63.9632(b).
(a) You must conduct subsequent performance tests to demonstrate continued compliance with the ore crushing and handling emission limits in Table 1 to this subpart according to the schedule developed by your permitting authority and shown in your title V permit. If a title V permit has not been issued, you must submit a testing plan and schedule, containing the information specified in paragraph (e) of this section, to the permitting authority for approval.
(b) You must conduct subsequent performance tests on all stacks associated with indurating furnaces to demonstrate continued compliance with the indurating furnace emission limits in Table 1 to this subpart according to the schedule developed by your permitting authority and shown in your title V permit, but no less frequent than twice per 5-year permit term. If a title V permit has not been issued, you must submit a testing plan and schedule, containing the information specified in paragraph (e) of this section, to the permitting authority for approval. For indurating furnaces with multiple stacks, the performance tests for all stacks associated with that indurating furnace must be conducted within a reasonable period of time, such that the indurating furnace operating characteristics remain representative for the duration of the stack tests.
(c) You must conduct subsequent performance tests to demonstrate continued compliance with the finished pellet handling emission limits in Table 1 to this subpart according to the schedule developed by your permitting authority and shown in your title V permit. If a title V permit has not been issued, you must submit a testing plan and schedule, containing the information specified in paragraph (e) of this section, to the permitting authority for approval.
(d) You must conduct subsequent performance tests on all stacks associated with ore dryers to demonstrate continued compliance with the ore dryer emission limits in Table 1 to this subpart according to the schedule developed by your permitting authority and shown in your title V permit. If a title V permit has not been issued, you must submit a testing plan and schedule, containing the information specified in paragraph (e) of this section, to the permitting authority for approval. For ore dryers with multiple stacks, the performance tests for all stacks associated with an ore dryer must be conducted within a reasonable period of time, such that the ore dryer operating characteristics remain representative for the duration of the stack tests.
(e) If your plant does not have a title V permit, you must submit a testing plan for subsequent performance tests as required in paragraphs (a) through (d) of this section. This testing plan must be submitted to the Administrator on or before the compliance date that is specified in § 63.9583. The testing plan must contain the information specified in paragraphs (e)(1) and (2) of this section. You must maintain a current copy of the testing plan onsite, and it must be available for inspection upon request. You must keep the plan for the life of the affected source or until the affected source is no longer subject to the requirements of this subpart.
(1) A list of all emission units.
(2) A schedule indicating when you will conduct subsequent performance tests for particulate matter for each of the emission units.
(a) For each baghouse applied to meet any particulate matter emission limit in Table 1 to this subpart, you must install, operate, and maintain a bag leak detection system to monitor the relative change in particulate matter loadings according to the requirements in § 63.9632(a), and conduct inspections at their specified frequencies according to the requirements in paragraphs (a)(1) through (8) of this section.
(1) Monitor the pressure drop across each baghouse cell each day to ensure pressure drop is within the normal operating range.
(2) Confirm that dust is being removed from hoppers through weekly visual inspections or other means of ensuring the proper functioning of removal mechanisms.
(3) Check the compressed air supply of pulse-jet baghouses each day.
(4) Monitor cleaning cycles to ensure proper operation using an appropriate methodology.
(5) Check bag cleaning mechanisms for proper functioning through monthly visual inspections or equivalent means.
(6) Make monthly visual checks of bag tension on reverse air and shaker-type baghouses to ensure that bags are not kinked (kneed or bent) or lying on their sides. You do not have to make this check for shaker-type baghouses that have self-tensioning (spring-loaded) devices.
(7) Confirm the physical integrity of the baghouse through quarterly visual inspections of the baghouse interior for air leaks.
(8) Inspect fans for wear, material buildup, and corrosion through quarterly visual inspections, vibration detectors, or equivalent means.
(b) Except as provided in paragraph (c) of this section, for each wet scrubber subject to the operating limits for pressure drop and scrubber water flow rate in § 63.9590(b)(1), you must install, operate, and maintain a CPMS according to the requirements in § 63.9632(b) through (e) and monitor the daily average pressure drop and daily average scrubber water flow rate according to the requirements in § 63.9633.
(c) For each dynamic wet scrubber subject to the scrubber water flow rate and either the fan amperage or pressure drop operating limits in § 63.9590(b)(2), you must install, operate, and maintain a CPMS according to the requirements in § 63.9632(b) through (e) and monitor the daily average scrubber water flow rate and either the daily average fan amperage or the daily average pressure drop according to the requirements in § 63.9633.
(d) For each dry electrostatic precipitator subject to the operating limits in § 63.9590(b)(3), you must follow the monitoring requirements in paragraph (d)(1) or (2) of this section.
(1) If the operating limit you choose to monitor is the 6-minute average opacity of emissions in accordance with § 63.9590(b)(3)(i), you must install, operate, and maintain a COMS according to the requirements in § 63.9632(f) and monitor the 6-minute average opacity of emissions exiting each control device stack according to the requirements in § 63.9633.
(2) If the operating limit you choose to monitor is average secondary voltage and average secondary current for each dry electrostatic precipitator field in accordance with § 63.9590(b)(3)(ii), you must install, operate, and maintain a CPMS according to the requirements in § 63.9632(b) through
(e) For each wet electrostatic precipitator subject to the operating limits in § 63.9590(b)(4), you must install, operate, and maintain a CPMS according to the requirements in § 63.9632(b) through (e) and monitor the daily average secondary voltage, daily average stack outlet temperature, and daily average water flow rate according to the requirements in § 63.9633.
(f) If you use any air pollution control device other than a baghouse, wet scrubber, dry electrostatic precipitator, or wet electrostatic precipitator, you must submit a site-specific monitoring plan that includes the information in paragraphs (f)(1) through (4) of this section. The monitoring plan is subject to approval by the Administrator. You must maintain a current copy of the monitoring plan onsite, and it must be available for inspection upon request. You must keep the plan for the life of the affected source or until the affected source is no longer subject to the requirements of this subpart.
(1) A description of the device.
(2) Test results collected in accordance with § 63.9621 verifying the performance of the device for reducing emissions of particulate matter to the atmosphere to the levels required by this subpart.
(3) A copy of the operation and maintenance plan required in § 63.9600(b).
(4) Appropriate operating parameters that will be monitored to maintain continuous compliance with the applicable emission limitation(s).
(a) For each negative pressure baghouse or positive pressure baghouse equipped with a stack, applied to meet any particulate emission limit in Table 1 to this subpart, you must install, operate, and maintain a bag leak detection system according to the requirements in paragraphs (a)(1) through (8) of this section.
(1) The system must be certified by the manufacturer to be capable of detecting emissions of particulate matter at concentrations of 10 milligrams per actual cubic meter (0.0044 grains per actual cubic foot) or less.
(2) The system must provide output of relative changes in particulate matter loadings.
(3) The system must be equipped with an alarm that will sound when an increase in relative particulate loadings is detected over the alarm level set point established according to paragraph (a)(4) of this section. The alarm must be located such that it can be heard by the appropriate plant personnel.
(4) For each bag leak detection system, you must develop and submit to the Administrator for approval, a site-specific monitoring plan that addresses the items identified in paragraphs (a)(4)(i) through (v) of this section. For each bag leak detection system that operates based on the triboelectric effect, the monitoring plan shall be consistent with the recommendations contained in the U.S. Environmental Protection Agency (U.S. EPA) guidance document, “Fabric Filter Bag Leak Detection Guidance” (EPA-454/R-98-015). This document is available on the EPA's Technology Transfer Network at
(i) Installation of the bag leak detection system.
(ii) Initial and periodic adjustment of the bag leak detection system including how the alarm set-point will be established.
(iii) Operation of the bag leak detection system including quality assurance procedures.
(iv) How the bag leak detection system will be maintained including a routine maintenance schedule and spare parts inventory list.
(v) How the bag leak detection system output shall be recorded and stored.
(5) To make the initial adjustment of the system, establish the baseline output by adjusting the sensitivity (range) and the averaging period of the device. Then, establish the alarm set points and the alarm delay time (if applicable).
(6) Following initial adjustment, do not adjust averaging period, alarm set point, or alarm delay time, without approval from the Administrator except as provided for in paragraph (a)(6)(i) of this section.
(i) Once per quarter, you may adjust the sensitivity of the bag leak detection system to account for seasonal effects, including temperature and humidity, according to the procedures identified in the site-specific monitoring plan required under paragraph (a)(4) of this section.
(ii) [Reserved]
(7) Where multiple detectors are required, the system's instrumentation and alarm may be shared among detectors.
(8) The bag leak detector sensor must be installed downstream of the baghouse and upstream of any wet scrubber.
(b) For each CPMS required in § 63.9631, you must develop and make available for inspection upon request by the permitting authority a site-specific monitoring plan that addresses the requirements in paragraphs (b)(1) through (7) of this section.
(1) Installation of the CPMS sampling probe or other interface at a measurement location relative to each affected emission unit such that the measurement is representative of control of the exhaust emissions (
(2) Performance and equipment specifications for the sample interface, the parametric signal analyzer, and the data collection and reduction system.
(3) Performance evaluation procedures and acceptance criteria (
(4) Ongoing operation and maintenance procedures in accordance with the general requirements of § 63.8(c)(1), (3), (4)(ii), (7), and (8).
(5) Ongoing data quality assurance procedures in accordance with the general requirements of § 63.8(d).
(6) Ongoing recordkeeping and reporting procedures in accordance with the general requirements of § 63.10(c), (e)(1), and (e)(2)(i).
(7) Corrective action procedures that you will follow in the event an air pollution control device, except for a baghouse, exceeds an established operating limit as required in § 63.9600(b)(3).
(c) Unless otherwise specified, each CPMS must meet the requirements in paragraphs (c)(1) and (2) of this section.
(1) Each CPMS must complete a minimum of one cycle of operation for each successive 15-minute period and must have valid data for at least 95 percent of every daily averaging period.
(2) Each CPMS must determine and record the daily average of all recorded readings.
(d) You must conduct a performance evaluation of each CPMS in accordance with your site-specific monitoring plan.
(e) You must operate and maintain the CPMS in continuous operation according to the site-specific monitoring plan.
(f) For each dry electrostatic precipitator subject to the opacity operating limit in § 63.9590(b)(3)(i), you must install, operate, and maintain each COMS according to the requirements in paragraphs (f)(1) through (4) of this section.
(1) You must install each COMS and conduct a performance evaluation of each COMS according to § 63.8 and Performance Specification 1 in appendix B to 40 CFR part 60.
(2) You must develop and implement a quality control program for operating and maintaining each COMS according to § 63.8. At a minimum, the quality control program must include a daily calibration drift assessment, quarterly performance audit, and annual zero alignment of each COMS.
(3) You must operate and maintain each COMS according to § 63.8(e) and your quality control program. You must also identify periods the COMS is out of control, including any periods that the COMS fails to pass a daily calibration drift assessment, quarterly
(4) You must determine and record the 6-minute average opacity for periods during which the COMS is not out of control.
(a) Except for monitoring malfunctions, associated repairs, and required quality assurance or control activities (including as applicable, calibration checks and required zero and span adjustments), you must monitor continuously (or collect data at all required intervals) at all times an affected source is operating.
(b) You may not use data recorded during monitoring malfunctions, associated repairs, and required quality assurance or control activities in data averages and calculations used to report emission or operating levels, or to fulfill a minimum data availability requirement. You must use all the data collected during all other periods in assessing compliance.
(c) A monitoring malfunction is any sudden, infrequent, not reasonably preventable failure of the monitoring system to provide valid data. Monitoring failures that are caused in part by poor maintenance or careless operation are not considered malfunctions.
(a) For each affected source subject to an emission limit in Table 1 to this subpart, you must demonstrate continuous compliance by meeting the requirements in paragraphs (b) through (f) of this section.
(b) For ore crushing and handling affected sources and finished pellet handling affected sources, you must demonstrate continuous compliance by meeting the requirements in paragraphs (b)(1) through (3) of this section.
(1) The flow-weighted mean concentration of particulate matter for all ore crushing and handling emission units and for all finished pellet handling emission units must be maintained at or below the emission limits in Table 1 to this subpart.
(2) You must conduct subsequent performance tests for emission units in the ore crushing and handling and finished pellet handling affected sources following the schedule in your title V permit. If a title V permit has not been issued, you must conduct subsequent performance tests according to a testing plan approved by the Administrator or delegated authority.
(3) For emission units not selected for initial performance testing and defined within a group of similar emission units in accordance with § 63.9620(e), you must calculate the daily average value of each operating parameter for the similar air pollution control device applied to each similar emission unit within a defined group using Equation 1 of this section.
(c) For ore dryers and indurating furnaces, you must demonstrate continuous compliance by meeting the requirements in paragraphs (c)(1) and (2) of this section.
(1) The flow-weighted mean concentration of particulate matter for all stacks from the ore dryer or indurating furnace must be maintained at or below the emission limits in Table 1 to this subpart.
(2) For ore dryers, you must conduct subsequent performance tests following the schedule in your title V permit. For indurating furnaces, you must conduct subsequent performance tests following the schedule in your title V permit, but no less frequent than twice per 5-year permit term. If a title V permit has not been issued, you must conduct subsequent performance tests according to a testing plan approved by
(d) For each baghouse applied to meet any particulate emission limit in Table 1 to this subpart, you must demonstrate continuous compliance by completing the requirements in paragraphs (d)(1) and (2) of this section.
(1) Maintaining records of the time you initiated corrective action in the event of a bag leak detection system alarm, the corrective action(s) taken, and the date on which corrective action was completed.
(2) Inspecting and maintaining each baghouse according to the requirements in § 63.9631(a)(1) through (8) and recording all information needed to document conformance with these requirements. If you increase or decrease the sensitivity of the bag leak detection system beyond the limits specified in your site-specific monitoring plan, you must include a copy of the required written certification by a responsible official in the next semiannual compliance report.
(e) Except as provided in paragraph (f) of this section, for each wet scrubber subject to the operating limits for pressure drop and scrubber water flow rate in § 63.9590(b)(1), you must demonstrate continuous compliance by completing the requirements of paragraphs (e)(1) through (4) of this section.
(1) Maintaining the daily average pressure drop and daily average scrubber water flow rate at or above the minimum levels established during the initial or subsequent performance test.
(2) Operating and maintaining each wet scrubber CPMS according to § 63.9632(b) and recording all information needed to document conformance with these requirements.
(3) Collecting and reducing monitoring data for pressure drop and scrubber water flow rate according to § 63.9632(c) and recording all information needed to document conformance with these requirements.
(4) If the daily average pressure drop or daily average scrubber water flow rate is below the operating limits established for a corresponding emission unit or group of similar emission units, you must then follow the corrective action procedures in paragraph (j) of this section.
(f) For each dynamic wet scrubber subject to the operating limits for scrubber water flow rate and either the fan amperage or pressure drop in § 63.9590(b)(2), you must demonstrate continuous compliance by completing the requirements of paragraphs (f)(1) through (4) of this section.
(1) Maintaining the daily average scrubber water flow rate and either the daily average fan amperage or the daily average pressure drop at or above the minimum levels established during the initial or subsequent performance test.
(2) Operating and maintaining each dynamic wet scrubber CPMS according to § 63.9632(b) and recording all information needed to document conformance with these requirements.
(3) Collecting and reducing monitoring data for scrubber water flow rate and either fan amperage or pressure drop according to § 63.9632(c) and recording all information needed to document conformance with these requirements.
(4) If the daily average scrubber water flow rate, daily average fan amperage, or daily average pressure drop is below the operating limits established for a corresponding emission unit or group of similar emission units, you must then follow the corrective action procedures in paragraph (j) of this section.
(g) For each dry electrostatic precipitator subject to operating limits in § 63.9590(b)(3), you must demonstrate continuous compliance by completing the requirements of paragraph (g)(1) or (2) of this section.
(1) If the operating limit for your dry electrostatic precipitator is a 6-minute average opacity of emissions value, then you must follow the requirements in paragraphs (g)(1)(i) through (iii) of this section.
(i) Maintaining the 6-minute average opacity of emissions at or below the maximum level established during the initial or subsequent performance test.
(ii) Operating and maintaining each COMS and reducing the COMS data according to § 63.9632(f).
(iii) If the 6-minute average opacity of emissions is above the operating limits established for a corresponding emission unit, you must then follow
(2) If the operating limit for your dry electrostatic precipitator is the daily average secondary voltage and daily average secondary current for each field, then you must follow the requirements in paragraphs (g)(2)(i) through (iv) of this section.
(i) Maintaining the daily average secondary voltage or daily average secondary current for each field at or above the minimum levels established during the initial or subsequent performance test.
(ii) Operating and maintaining each dry electrostatic precipitator CPMS according to § 63.9632(b) and recording all information needed to document conformance with these requirements.
(iii) Collecting and reducing monitoring data for secondary voltage or secondary current for each field according to § 63.9632(c) and recording all information needed to document conformance with these requirements.
(iv) If the daily average secondary voltage or daily average secondary current for each field is below the operating limits established for a corresponding emission unit, you must then follow the corrective action procedures in paragraph (j) of this section.
(h) For each wet electrostatic precipitator subject to the operating limits for secondary voltage, stack outlet temperature, and water flow rate in § 63.9590(b)(4), you must demonstrate continuous compliance by completing the requirements of paragraphs (h)(1) through (4) of this section.
(1) Maintaining the daily average secondary voltage, daily average secondary current, and daily average scrubber water flow rate for each field at or above the minimum levels established during the initial or subsequent performance test. Maintaining the daily average stack outlet temperature at or below the maximum levels established during the initial or subsequent performance test.
(2) Operating and maintaining each wet electrostatic precipitator CPMS according to § 63.9632(b) and recording all information needed to document conformance with these requirements.
(3) Collecting and reducing monitoring data for secondary voltage, stack outlet temperature, and water flow rate according to § 63.9632(c) and recording all information needed to document conformance with these requirements.
(4) If the daily average secondary voltage, stack outlet temperature, or water flow rate does not meet the operating limits established for a corresponding emission unit, you must then follow the corrective action procedures in paragraph (j) of this section.
(i) If you use an air pollution control device other than a wet scrubber, dynamic wet scrubber, dry electrostatic precipitator, wet electrostatic precipitator, or baghouse, you must submit a site-specific monitoring plan in accordance with § 63.9631(f). The site-specific monitoring plan must include the site-specific procedures for demonstrating initial and continuous compliance with the corresponding operating limits.
(j) If the daily average operating parameter value for an emission unit or group of similar emission units does not meet the corresponding established operating limit, you must then follow the procedures in paragraphs (j)(1) through (4) of this section.
(1) You must initiate and complete initial corrective action within 10 calendar days and demonstrate that the initial corrective action was successful. During any period of corrective action, you must continue to monitor and record all required operating parameters for equipment that remains in operation. After 10 calendar days, measure and record the daily average operating parameter value for the emission unit or group of similar emission units on which corrective action was taken. After the initial corrective action, if the daily average operating parameter value for the emission unit or group of similar emission units meets the operating limit established for the corresponding unit or group, then the corrective action was successful and the emission unit or group of similar emission units is in compliance with the established operating limits.
(2) If the initial corrective action required in paragraph (j)(1) of this section was not successful, then you must complete additional corrective action
(3) If the second attempt at corrective action required in paragraph (j)(2) of this section was not successful, then you must repeat the procedures of paragraph (j)(2) of this section until the corrective action is successful. If the third attempt at corrective action is unsuccessful, you must conduct another performance test in accordance with the procedures in § 63.9622(f) and report to the Administrator as a deviation the third unsuccessful attempt at corrective action.
(4) After the third unsuccessful attempt at corrective action, you must submit to the Administrator the written report required in paragraph (j)(3) of this section within 5 calendar days after the third unsuccessful attempt at corrective action. This report must notify the Administrator that a deviation has occurred and document the types of corrective measures taken to address the problem that resulted in the deviation of established operating parameters and the resulting operating limits.
(a) You must demonstrate continuous compliance with the work practice standard requirements in § 63.9591 by operating in accordance with your fugitive dust emissions control plan at all times.
(b) You must maintain a current copy of the fugitive dust emissions control plan required in § 63.9591 onsite and it must be available for inspection upon request. You must keep the plan for the life of the affected source or until the affected source is no longer subject to the requirements of this subpart.
(a) For each control device subject to an operating limit in § 63.9590(b), you must demonstrate continuous compliance with the operation and maintenance requirements in § 63.9600(b) by completing the requirements of paragraphs (a)(1) through (4) of this section.
(1) Performing preventative maintenance for each control device in accordance with § 63.9600(b)(1) and recording all information needed to document conformance with these requirements;
(2) Initiating and completing corrective action for a bag leak detection system alarm in accordance with § 63.9600(b)(2) and recording all information needed to document conformance with these requirements;
(3) Initiating and completing corrective action for a CPMS when you exceed an established operating limit for an air pollution control device except for a baghouse in accordance with § 63.9600(b)(3) and recording all information needed to document conformance with these requirements; and
(4) Implementing and maintaining site-specific good combustion practices for each indurating furnace in accordance with § 63.9600(b)(4) and recording all information needed to document conformance with these requirements.
(b) You must maintain a current copy of the operation and maintenance plan required in § 63.9600(b) onsite, and it must be available for inspection upon request. You must keep the plan for the life of the affected source or until the affected source is no longer subject to the requirements of this subpart.
(a)
(b)
(2) The Administrator will determine whether deviations that occur during a period of startup, shutdown, or malfunction are violations, according to the provisions in § 63.6(e).
(a) You must submit all of the notifications in §§ 63.7(b) and (c), 63.8(f)(4), and 63.9(b) through (h) that apply to you by the specified dates.
(b) As specified in § 63.9(b)(2), if you start up your affected source before October 30, 2003, you must submit your initial notification no later than 120 calendar days after October 30, 2003.
(c) As specified in § 63.9(b)(3), if you start up your new affected source on or after October 30, 2003, you must submit your initial notification no later than 120 calendar days after you become subject to this subpart.
(d) If you are required to conduct a performance test, you must submit a notification of intent to conduct a performance test at least 60 calendar days before the performance test is scheduled to begin, as required in § 63.7(b)(1).
(e) If you are required to conduct a performance test or other initial compliance demonstration, you must submit a notification of compliance status according to § 63.9(h)(2)(ii). The initial notification of compliance status must be submitted by the dates specified in paragraphs (e)(1) and (2) of this section.
(1) For each initial compliance demonstration that does not include a performance test, you must submit the notification of compliance status before the close of business on the 30th calendar day following completion of the initial compliance demonstration.
(2) For each initial compliance demonstration that does include a performance test, you must submit the notification of compliance status, including the performance test results, before the close of business on the 60th calendar day following the completion of the performance test according to § 63.10(d)(2).
(a)
(1) The first compliance report must cover the period beginning on the compliance date that is specified for your affected source in § 63.9583 and ending on June 30 or December 31, whichever date comes first after the compliance date that is specified for your source in § 63.9583.
(2) The first compliance report must be postmarked or delivered no later than July 31 or January 31, whichever date comes first after your first compliance report is due.
(3) Each subsequent compliance report must cover the semiannual reporting period from January 1 through June 30 or the semiannual reporting period from July 1 through December 31.
(4) Each subsequent compliance report must be postmarked or delivered
(5) For each affected source that is subject to permitting regulations pursuant to 40 CFR part 70 or 40 CFR part 71, and if the permitting authority has established dates for submitting semiannual reports pursuant to 40 CFR 70.6(a)(3)(iii)(A) or 40 CFR 71.6(a)(3)(iii)(A), you may submit the first and subsequent compliance reports according to the dates the permitting authority has established instead of according to the dates in paragraphs (a)(1) through (4) of this section.
(b)
(1) Company name and address.
(2) Statement by a responsible official, with the official's name, title, and signature, certifying the truth, accuracy, and completeness of the content of the report.
(3) Date of report and beginning and ending dates of the reporting period.
(4) If you had a startup, shutdown, or malfunction during the reporting period and you took actions consistent with your startup, shutdown, and malfunction plan, the compliance report must include the information in § 63.10(d)(5)(i).
(5) If there were no deviations from the continuous compliance requirements in §§ 63.9634 through 63.9636 that apply to you, then provide a statement that there were no deviations from the emission limitations, work practice standards, or operation and maintenance requirements during the reporting period.
(6) If there were no periods during which a continuous monitoring system (including a CPMS or COMS) was out-of-control as specified in § 63.8(c)(7), then provide a statement that there were no periods during which a continuous monitoring system was out-of-control during the reporting period.
(7) For each deviation from an emission limitation in Table 1 to this subpart that occurs at an affected source where you are not using a continuous monitoring system (including a CPMS or COMS) to comply with an emission limitation in this subpart, the compliance report must contain the information in paragraphs (b)(1) through (4) of this section and the information in paragraphs (b)(7)(i) and (ii) of this section. This includes periods of startup, shutdown, and malfunction.
(i) The total operating time of each affected source during the reporting period.
(ii) Information on the number, duration, and cause of deviations (including unknown cause) as applicable, and the corrective action taken.
(8) For each deviation from an emission limitation occurring at an affected source where you are using a continuous monitoring system (including a CPMS or COMS) to comply with the emission limitation in this subpart, you must include the information in paragraphs (b)(1) through (4) of this section and the information in paragraphs (b)(8)(i) through (xi) of this section. This includes periods of startup, shutdown, and malfunction.
(i) The date and time that each malfunction started and stopped.
(ii) The date and time that each continuous monitoring system was inoperative, except for zero (low-level) and high-level checks.
(iii) The date, time, and duration that each continuous monitoring system was out-of-control, including the information in § 63.8(c)(8).
(iv) The date and time that each deviation started and stopped, and whether each deviation occurred during a period of startup, shutdown, or malfunction or during another period.
(v) A summary of the total duration of the deviation during the reporting period and the total duration as a percent of the total source operating time during that reporting period.
(vi) A breakdown of the total duration of the deviations during the reporting period including those that are due to startup, shutdown, control equipment problems, process problems, other known causes, and other unknown causes.
(vii) A summary of the total duration of continuous monitoring system downtime during the reporting period and the total duration of continuous
(viii) A brief description of the process units.
(ix) A brief description of the continuous monitoring system.
(x) The date of the latest continuous monitoring system certification or audit.
(xi) A description of any changes in continuous monitoring systems, processes, or controls since the last reporting period.
(c)
(d)
(e)
(a) You must keep the records listed in paragraphs (a)(1) through (3) of this section.
(1) A copy of each notification and report that you submitted to comply with this subpart, including all documentation supporting any initial notification or notification of compliance status that you submitted, according to the requirements in § 63.10(b)(2)(xiv).
(2) The records in § 63.6(e)(3)(iii) through (v) related to startup, shutdown, and malfunction.
(3) Records of performance tests and performance evaluations as required in § 63.10(b)(2)(viii).
(b) For each COMS, you must keep the records specified in paragraphs (b)(1) through (4) of this section.
(1) Records described in § 63.10(b)(2)(vi) through (xi).
(2) Monitoring data for COMS during a performance evaluation as required in § 63.6(h)(7)(i) and (ii).
(3) Previous (that is, superceded) versions of the performance evaluation plan as required in § 63.8(d)(3).
(4) Records of the date and time that each deviation started and stopped, and whether the deviation occurred during a period of startup, shutdown, or malfunction or during another period.
(c) You must keep the records required in §§ 63.9634 through 63.9636 to show continuous compliance with each emission limitation, work practice standard, and operation and maintenance requirement that applies to you.
(a) Your records must be in a form suitable and readily available for expeditious review, according to § 63.10(b)(1).
(b) As specified in § 63.10(b)(1), you must keep each record for 5 years following the date of each occurrence, measurement, maintenance, corrective action, report, or record.
(c) You must keep each record on site for at least 2 years after the date of each occurrence, measurement, maintenance, corrective action, report, or record according to § 63.10(b)(1). You can keep the records offsite for the remaining 3 years.
Table 2 to this subpart shows which parts of the General Provisions in §§ 63.1 through 63.15 apply to you.
(a) This subpart can be implemented and enforced by us, the EPA, or a delegated authority such as your State, local, or tribal agency. If the EPA Administrator has delegated authority to your State, local, or tribal agency, then that agency 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 under subpart E of this part, the authorities contained in paragraph (c) of this section are retained by the Administrator of the EPA and are not transferred to the State, local, or tribal agency.
(c) The authorities that will not be delegated to State, local, or tribal agencies are specified in paragraphs (c)(1) through (4) of this section.
(1) Approval of non-opacity emission limitations and work practice standards under § 63.6(h)(9) and as defined in § 63.90.
(2) Approval of major alternatives to test methods under § 63.7(e)(2)(ii) and (f) and as defined in § 63.90.
(3) Approval of major alternatives to monitoring under § 63.8(f) and as defined in § 63.90.
(4) Approval of major alternatives to recordkeeping and reporting under § 63.10(f) and as defined in § 63.90.
Terms used in this subpart are defined in the Clean Air Act, in § 63.2, and in this section as follows.
(1) Fails to meet any requirement or obligation established by this subpart, including but not limited to any emission limitation (including operating limits) or operation and maintenance requirement;
(2) Fails to meet any term or condition that is adopted to implement an applicable requirement in this subpart and that is included in the operating permit for any affected source required to obtain such a permit; or
(3) Fails to meet any emission limitation in this subpart during startup, shutdown, or malfunction, regardless
(1) Stockpiles (includes, but is not limited to, stockpiles of uncrushed ore, crushed ore, or finished pellets);
(2) Material transfer points;
(3) Plant roadways;
(4) Tailings basins;
(5) Pellet loading areas; and
(6) Yard areas.
As required in § 63.9590(a), you must comply with each applicable emission limit in the following table:
As required in § 63.9650, you must comply with the requirements of the NESHAP General Provisions (40 CFR part 63, subpart A) shown in the following table:
This subpart establishes national emission standards for hazardous air pollutants (NESHAP) for refractory products manufacturing facilities. This subpart also establishes requirements to demonstrate initial and continuous compliance with the emission limitations.
You are subject to this subpart if you own or operate a refractory products manufacturing facility that is, is located at, or is part of, a major source of hazardous air pollutant (HAP) emissions according to the criteria in paragraphs (a) and (b) of this section.
(a) A refractory products manufacturing facility is a plant site that manufactures refractory products (refractory bricks, refractory shapes, monolithics, kiln furniture, crucibles, and other materials used for lining furnaces and other high temperature process units), as defined in § 63.9824. Refractory products manufacturing facilities typically process raw material by crushing, grinding, and screening; mixing the processed raw materials with binders and other additives; forming
(b) A major source of HAP is a plant site that emits or has the potential to emit any single HAP at a rate of 9.07 megagrams (10 tons) or more per year or any combination of HAP at a rate of 22.68 megagrams (25 tons) or more per year.
(a) This subpart applies to each new, reconstructed, or existing affected source at a refractory products manufacturing facility.
(b) The existing affected sources are shape dryers, curing ovens, and kilns that are used to manufacture refractory products that use organic HAP; shape preheaters, pitch working tanks, defumers, and coking ovens that are used to produce pitch-impregnated refractory products; kilns that are used to manufacture chromium refractory products; and kilns that are used to manufacture clay refractory products.
(c) The new or reconstructed affected sources are shape dryers, curing ovens, and kilns that are used to manufacture refractory products that use organic HAP; shape preheaters, pitch working tanks, defumers, and coking ovens used to produce pitch-impregnated refractory products; kilns that are used to manufacture chromium refractory products; and kilns that are used to manufacture clay refractory products.
(d) Shape dryers, curing ovens, kilns, coking ovens, defumers, shape preheaters, and pitch working tanks that are research and development (R&D) process units are not subject to the requirements of this subpart. (See definition of
(e) A source is a new affected source if you began construction of the affected source after June 20, 2002, and you met the applicability criteria at the time you began construction.
(f) An affected source is reconstructed if you meet the criteria as defined in § 63.2.
(g) An affected source is existing if it is not new or reconstructed.
(a) If you have a new or reconstructed affected source, you must comply with this subpart according to paragraphs (a)(1) and (2) of this section.
(1) If the initial startup of your affected source is before April 16, 2003, then you must comply with the emission limitations for new and reconstructed sources in this subpart no later than April 16, 2003.
(2) If the initial startup of your affected source is after April 16, 2003, then you must comply with the emission limitations for new and reconstructed sources in this subpart upon initial startup of your affected source.
(b) If you have an existing affected source, you must comply with the emission limitations for existing sources no later than April 17, 2006.
(c) You must be in compliance with this subpart when you conduct a performance test on an affected source.
(d) If you have an existing area source that increases its emissions or its potential to emit such that it becomes a major source of HAP, you must be in compliance with this subpart according to paragraphs (d)(1) and (2) of this section.
(1) Any portion of the existing facility that is a new affected source or a new reconstructed source must be in compliance with this subpart upon startup.
(2) All other parts of the existing facility must be in compliance with this subpart by 3 years after the date the area source becomes a major source.
(e) If you have a new area source (
(f) You must meet the notification requirements in § 63.9812 according to the schedule in § 63.9812 and in 40 CFR part 63, subpart A. Some of the notifications must be submitted before you are required to comply with the emission limitations in this subpart.
(a) You must meet each emission limit in Table 1 to this subpart that applies to you.
(b) You must meet each operating limit in Table 2 to this subpart that applies to you.
(c) You must meet each work practice standard in Table 3 to this subpart that applies to you.
To meet the emission limits in Table 1 to this subpart, you must use one or both of the options listed in paragraphs (a) and (b) of this section.
(a)
(b)
(a) You must be in compliance with the emission limitations (including operating limits and work practice standards) in this subpart at all times, except during periods specified in paragraphs (a)(1) and (2) of this section.
(1) Periods of startup, shutdown, and malfunction.
(2) Periods of scheduled maintenance on a control device that is used on an affected continuous kiln, as specified in paragraph (e) of this section.
(b) Except as specified in paragraph (e) of this section, you must always operate and maintain your affected source, including air pollution control and monitoring equipment, according to the provisions in § 63.6(e)(1)(i). During the period between the compliance date specified for your affected source in § 63.9786 and the date upon which continuous monitoring systems have been installed and validated and any applicable operating limits have been established, you must maintain a log detailing the operation and maintenance of the process and emissions control equipment.
(c) You must develop a written startup, shutdown, and malfunction plan (SSMP) according to the provisions in § 63.6(e)(3).
(d) You must prepare and implement a written operation, maintenance, and monitoring (OM&M) plan according to the requirements in § 63.9794.
(e) If you own or operate an affected continuous kiln and must perform scheduled maintenance on the control device for that kiln, you may bypass the kiln control device and continue operating the kiln upon approval by the Administrator, provided you satisfy the conditions listed in paragraphs (e)(1) through (3) of this section.
(1) You must request approval from the Administrator to bypass the control device while the scheduled maintenance is performed. You must submit a separate request each time you plan to bypass the control device, and your request must include the information specified in paragraphs (e)(1)(i) through (vi) of this section.
(i) Reason for the scheduled maintenance.
(ii) Explanation for why the maintenance cannot be performed when the kiln is shut down.
(iii) Detailed description of the maintenance activities.
(iv) Time required to complete the maintenance.
(v) How you will minimize HAP emissions from the kiln during the period when the control device is out of service.
(vi) How you will minimize the time when the kiln is operating and the control device is out of service for scheduled maintenance.
(2) You must minimize HAP emissions during the period when the kiln is operating and the control device is out of service.
(3) You must minimize the time period during which the kiln is operating and the control device is out of service.
(f) You must be in compliance with the provisions of subpart A of this part, except as noted in Table 11 to this subpart.
(a) For each continuous parameter monitoring system (CPMS) required by this subpart, you must develop, implement, make available for inspection, and revise, as necessary, an OM&M plan that includes the information in paragraphs (a)(1) through (13) of this section.
(1) A list and identification of each process and add-on APCD that is required by this subpart to be monitored, the type of monitoring device that will be used, and the operating parameters that will be monitored.
(2) Specifications for the sensor, signal analyzer, and data collection system.
(3) A monitoring schedule that specifies the frequency that the parameter values will be determined and recorded.
(4) The operating limits for each parameter that represent continuous compliance with the emission limitations in § 63.9788, based on values of the monitored parameters recorded during performance tests.
(5) Procedures for installing the CPMS at a measurement location relative to each process unit or APCD such that measurement is representative of control of emissions.
(6) Procedures for the proper operation and routine and long-term maintenance of each process unit and APCD, including a maintenance and inspection schedule that is consistent with the manufacturer's recommendations.
(7) Procedures for the proper operation and maintenance of monitoring equipment consistent with the requirements in §§ 63.8(c)(1), (3), (4)(ii), (7), and (8), and 63.9804.
(8) Ongoing data quality assurance procedures in accordance with the general requirements of § 63.8(d).
(9) Procedures for evaluating the performance of each CPMS.
(10) Procedures for responding to operating parameter deviations, including the procedures in paragraphs (a)(10)(i) through (iii) of this section:
(i) Procedures for determining the cause of the operating parameter deviation.
(ii) Actions for correcting the deviation and returning the operating parameters to the allowable limits.
(iii) Procedures for recording the times that the deviation began and ended, and when corrective actions were initiated and completed.
(11) Procedures for keeping records to document compliance and reporting in accordance with the requirements of § 63.10(c), (e)(1), and (e)(2)(i).
(12) If you operate a kiln that is subject to the limits on the type of fuel used, as specified in items 3 and 4 of Table 3 to subpart SSSSS, procedures for using alternative fuels.
(13) If you operate an affected continuous kiln and you plan to take the kiln control device out of service for scheduled maintenance, as specified in § 63.9792(e), the procedures specified in paragraphs (a)(13)(i) and (ii) of this section.
(i) Procedures for minimizing HAP emissions from the kiln during periods of scheduled maintenance of the kiln control device when the kiln is operating and the control device is out of service.
(ii) Procedures for minimizing any period of scheduled maintenance on the kiln control device when the kiln is operating and the control device is out of service.
(b) Changes to the operating limits in your OM&M plan require a new performance test. If you are revising an operating limit parameter value, you must meet the requirements in paragraphs (b)(1) and (2) of this section.
(1) Submit a Notification of Performance Test to the Administrator as specified in § 63.7(b).
(2) After completing the performance tests to demonstrate that compliance
(c) If you are revising the inspection and maintenance procedures in your OM&M plan, you do not need to conduct a new performance test.
You must conduct performance tests within 180 calendar days after the compliance date that is specified for your source in § 63.9786 and according to the provisions in § 63.7(a)(2).
(a) You must conduct a performance test every 5 years following the initial performance test, as part of renewing your 40 CFR part 70 or 40 CFR part 71 operating permit.
(b) You must conduct a performance test when you want to change the parameter value for any operating limit specified in your OM&M plan.
(c) If you own or operate a source that is subject to the emission limits specified in items 2 through 9 of Table 1 to this subpart, you must conduct a performance test on the source(s) listed in paragraphs (c)(1) and (2) of this section before you start production of any refractory product for which the organic HAP processing rate is likely to exceed by more than 10 percent the maximum organic HAP processing rate established during the most recent performance test on that same source.
(1) Each affected shape dryer or curing oven that is used to process the refractory product with the higher organic HAP processing rate.
(2) Each affected kiln that follows an affected shape dryer or curing oven and is used to process the refractory product with the higher organic HAP processing rate.
(d) If you own or operate a kiln that is subject to the emission limits specified in item 5 or 9 of Table 1 to this subpart, you must conduct a performance test on the affected kiln following any process changes that are likely to increase organic HAP emissions from the kiln (
(e) If you own or operate a clay refractory products kiln that is subject to the emission limits specified in item 10 or 11 of Table 1 to this subpart and is controlled with a dry limestone adsorber (DLA), you must conduct a performance test on the affected kiln following any change in the source of limestone used in the DLA.
(a) You must conduct each performance test in Table 4 to this subpart that applies to you.
(b) Before conducting the performance test, you must install and validate all monitoring equipment.
(c) Each performance test must be conducted according to the requirements in § 63.7 and under the specific conditions in Table 4 to this subpart.
(d) You may not conduct performance tests during periods of startup, shutdown, or malfunction, as specified in § 63.7(e)(1).
(e) You must conduct separate test runs for at least the duration specified for each performance test required in this section, as specified in § 63.7(e)(3) and Table 4 to this subpart.
(f) For batch process sources, you must satisfy the requirements specified in paragraphs (f)(1) through (5) of this section.
(1) You must conduct at least two test runs.
(2) Each test run must last an entire batch cycle unless you develop an emissions profile, as specified in items 8(a)(i)(4) and 17(b)(i)(4) of Table 4 to this subpart, or you satisfy the conditions for terminating a test run prior to the completion of a batch cycle as specified in item 8(a)(i)(5) of Table 4 to this subpart.
(3) Each test run must be performed over a separate batch cycle unless you satisfy the conditions for conducting both test runs over a single batch
(i) You do not produce the product that corresponds to the maximum organic HAP processing rate for that batch process source in consecutive batch cycles.
(ii) To produce that product in two consecutive batch cycles would disrupt production of other refractory products.
(4) If you want to conduct a performance test over a single batch cycle, you must include in your Notification of Performance Test the rationale for testing over a single batch cycle.
(5) If you are granted approval to conduct a performance test over a single batch cycle, you must use paired sampling trains and collect two sets of emissions data. Each set of data can be considered a separate test run.
(g) You must use the data gathered during the performance test and the equations in paragraphs (g)(1) through (3) of this section to determine compliance with the emission limitations.
(1) To determine compliance with the total hydrocarbon (THC) emission concentration limit listed in Table 1 to this subpart, you must calculate your emission concentration corrected to 18 percent oxygen for each test run using Equation 1 of this section:
(2) To determine compliance with any of the emission limits based on percentage reduction across an emissions control system specified in Table 1 to this subpart, you must calculate the percentage reduction for each test run using Equation 2 of this section:
(3) To determine compliance with production-based hydrogen fluoride (HF) and hydrogen chloride (HCl) emission limits in Table 1 to this subpart, you must calculate your mass emissions per unit of uncalcined clay processed for each test run using Equation 3 of this section:
(h) You must establish each site-specific operating limit in Table 2 to this subpart that applies to you, as specified in Table 4 to this subpart.
(i) For each affected source that is equipped with an add-on APCD that is not addressed in Table 2 to this subpart or that is using process changes as a means of meeting the emission limits in Table 1 to this subpart, you must meet the requirements in § 63.8(f) and paragraphs (i)(1) through (3) of this section.
(1) For sources subject to the THC concentration limit specified in item 3 or 7 of Table 1 to this subpart, you must satisfy the requirements specified in paragraphs (i)(1)(i) through (iii) of this section.
(i) You must install a THC continuous emissions monitoring system (CEMS) at the outlet of the control device or in the stack of the affected source.
(ii) You must meet the requirements specified in Performance Specification (PS) 8 of 40 CFR part 60, appendix B.
(iii) You must meet the requirements specified in Procedure 1 of 40 CFR part 60, appendix F.
(2) For sources subject to the emission limits specified in item 3, 4, 7, or 8 of Table 1 to this subpart, you must submit a request for approval of alternative monitoring methods to the Administrator no later than the submittal date for the Notification of Performance Test, as specified in § 63.9812(d). The request must contain the information specified in paragraphs (i)(2)(i) through (v) of this section.
(i) Description of the alternative add-on APCD or process changes.
(ii) Type of monitoring device or method that will be used, including the sensor type, location, inspection procedures, quality assurance and quality control measures, and data recording device.
(iii) Operating parameters that will be monitored.
(iv) Frequency that the operating parameter values will be determined and recorded to establish continuous compliance with the operating limits.
(v) Averaging time.
(3) You must establish site-specific operating limits during the performance test based on the information included in the approved alternative monitoring methods request and, as applicable, as specified in Table 4 to this subpart.
If you decide to develop an emissions profile for an affected batch process source; as indicated in item 8(a)(i)(4) or 17(b)(i)(4) of Table 4 to this subpart, you must measure and record mass emissions of the applicable pollutant throughout a complete batch cycle of the affected batch process source according to the procedures described in paragraph (a) or (b) of this section.
(a) If your affected batch process source is subject to the THC concentration limit specified in item 6(a), 7(a), 8, or 9 of Table 1 to this subpart or the THC percentage reduction limit specified in item 6(b) or 7(b) of Table 1 to this subpart, you must measure and record the THC mass emissions rate at the inlet to the control device using the test methods, averaging periods, and procedures specified in items 10(a) and (b) of Table 4 to this subpart for each complete hour of the batch process cycle.
(b) If your affected batch process source is subject to the HF and HCl percentage reduction emission limits in item 11 of Table 1 to this subpart, you must measure and record the HF mass emissions rate at the inlet to the control device through a series of 1-hour test runs according to the test method specified in item 14(a) of Table 4 to this subpart for each complete hour of the batch process cycle.
(a) You must install, operate, and maintain each CPMS required by this subpart according to your OM&M plan and the requirements in paragraphs (a)(1) through (15) of this section.
(1) You must satisfy all applicable requirements of performance specifications for CPMS specified in 40 CFR part 60, appendix B, upon promulgation of such performance specifications.
(2) You must satisfy all applicable requirements of quality assurance (QA) procedures for CPMS specified in 40 CFR part 60, appendix F, upon promulgation of such QA procedures.
(3) You must install each sensor of your CPMS in a location that provides representative measurement of the appropriate parameter over all operating conditions, taking into account the manufacturer's guidelines.
(4) You must use a CPMS that is capable of measuring the appropriate parameter over a range that extends from a value of at least 20 percent less than the lowest value that you expect your CPMS to measure, to a value of at least 20 percent greater than the highest value that you expect your CPMS to measure.
(5) You must use a data acquisition and recording system that is capable of recording values over the entire range specified in paragraph (a)(4) of this section.
(6) You must use a signal conditioner, wiring, power supply, and data acquisition and recording system that are compatible with the output signal of the sensors used in your CPMS.
(7) You must perform an initial calibration of your CPMS based on the procedures specified in the manufacturer's owner's manual.
(8) You must use a CPMS that is designed to complete a minimum of one cycle of operation for each successive 15-minute period. To have a valid hour of data, you must have at least three of four equally-spaced data values (or at least 75 percent of the total number of values if you collect more than four data values per hour) for that hour (not including startup, shutdown, malfunction, or out-of-control periods).
(9) You must record valid data from at least 90 percent of the hours during which the affected source or process operates.
(10) You must determine and record the 15-minute block averages of all measurements, calculated after every 15 minutes of operation as the average of the previous 15 operating minutes (not including periods of startup, shutdown, or malfunction).
(11) You must determine and record the 3-hour block averages of all 15-minute recorded measurements, calculated after every 3 hours of operation as the average of the previous 3 operating hours (not including periods of startup, shutdown, or malfunction).
(12) You must record the results of each inspection, calibration, initial validation, and accuracy audit.
(13) At all times, you must maintain your CPMS including, but not limited to, maintaining necessary parts for routine repairs of the CPMS.
(14) You must perform an initial validation of your CPMS under the conditions specified in paragraphs (14)(i) and (ii) of this section.
(i) Prior to the initial performance test on the affected source for which the CPMS is required.
(ii) Within 180 days of your replacing or relocating one or more of the sensors of your CPMS.
(15) Except for redundant sensors, as defined in § 63.9824, any device that you use to conduct an initial validation or accuracy audit of your CPMS must meet the accuracy requirements specified in paragraphs (15)(i) and (ii) of this section.
(i) The device must have an accuracy that is traceable to National Institute of Standards and Technology (NIST) standards.
(ii) The device must be at least three times as accurate as the required accuracy for the CPMS.
(b) For each temperature CPMS that is used to monitor the combustion chamber temperature of a thermal oxidizer or the catalyst bed inlet temperature of a catalytic oxidizer, you must meet the requirements in paragraphs (a) and (b)(1) through (6) of this section.
(1) Use a temperature CPMS with a minimum accuracy of ±1.0 percent of the temperature value or 2.8 degrees Celsius (°C) (5 degrees Fahrenheit (°F)), whichever is greater.
(2) Use a data recording system with a minimum resolution of one-half or better of the required CPMS accuracy specified in paragraph (b)(1) of this section.
(3) Perform an initial validation of your CPMS according to the requirements in paragraph (3)(i) or (ii) of this section.
(i) Place the sensor of a calibrated temperature measurement device adjacent to the sensor of your temperature CPMS in a location that is subject to the same environment as the sensor of your temperature CPMS. The calibrated temperature measurement device must satisfy the accuracy requirements of paragraph (a)(15) of this section. While the process and control device that is monitored by your CPMS are operating normally, record concurrently and compare the temperatures measured by your temperature CPMS and the calibrated temperature measurement device. Using the calibrated temperature measurement device as the reference, the temperature measured by your CPMS must be within the accuracy specified in paragraph (b)(1) of this section.
(ii) Perform any of the initial validation methods for temperature CPMS specified in performance specifications for CPMS established in 40 CFR part 60, appendix B.
(4) Perform an accuracy audit of your temperature CPMS at least quarterly, according to the requirements in paragraph (b)(4)(i), (ii), or (iii) of this section.
(i) If your temperature CPMS includes a redundant temperature sensor, record three pairs of concurrent temperature measurements within a 24-hour period. Each pair of concurrent measurements must consist of a temperature measurement by each of the two temperature sensors. The minimum time interval between any two such pairs of consecutive temperature measurements is 1 hour. The measurements must be taken during periods when the process and control device that is monitored by your temperature CPMS are operating normally. Calculate the mean of the three values for each temperature sensor. The mean values must agree within the required overall accuracy of the CPMS, as specified in paragraph (b)(1) of this section.
(ii) If your temperature CPMS does not include a redundant temperature sensor, place the sensor of a calibrated temperature measurement device adjacent to the sensor of your temperature CPMS in a location that is subject to the same environment as the sensor of your temperature CPMS. The calibrated temperature measurement device must satisfy the accuracy requirements of paragraph (a)(15) of this section. While the process and control device that is monitored by your temperature CPMS are operating normally, record concurrently and compare the temperatures measured by your CPMS and the calibrated temperature measurement device. Using the calibrated temperature measurement device as the reference, the temperature measured by your CPMS must be within the accuracy specified in paragraph (b)(1) of this section.
(iii) Perform any of the accuracy audit methods for temperature CPMS specified in QA procedures for CPMS established in 40 CFR part 60, appendix F.
(5) Conduct an accuracy audit of your CPMS following any 24-hour period throughout which the temperature measured by your CPMS exceeds the manufacturer's specified maximum operating temperature range, or install a new temperature sensor.
(6) If your CPMS is not equipped with a redundant temperature sensor, perform at least quarterly a visual inspection of all components of the CPMS for integrity, oxidation, and galvanic corrosion.
(c) For each pressure CPMS that is used to monitor the pressure drop across a DLA or wet scrubber, you must meet the requirements in paragraphs (a) and (c)(1) through (7) of this section.
(1) Use a pressure CPMS with a minimum accuracy of ±5.0 percent or 0.12 kilopascals (kPa) (0.5 inches of water column (in. w.c.)), whichever is greater.
(2) Use a data recording system with a minimum resolution of one-half the required CPMS accuracy specified in paragraph (c)(1) of this section, or better.
(3) Perform an initial validation of your pressure CPMS according to the requirements in paragraph (c)(3)(i) or (ii) of this section.
(i) Place the sensor of a calibrated pressure measurement device adjacent to the sensor of your pressure CPMS in a location that is subject to the same environment as the sensor of your pressure CPMS. The calibrated pressure measurement device must satisfy the accuracy requirements of paragraph (a)(15) of this section. While the process and control device that is monitored by your CPMS are operating normally, record concurrently and compare the pressure measured by your CPMS and the calibrated pressure measurement device. Using the calibrated pressure measurement device as the reference, the pressure measured by your CPMS must be within the accuracy specified in paragraph (c)(1) of this section.
(ii) Perform any of the initial validation methods for pressure CPMS specified in performance specifications for CPMS established in 40 CFR part 60, appendix B.
(4) Perform an accuracy audit of your pressure CPMS at least quarterly, according to the requirements in paragraph (c)(4)(i), (ii), or (iii) of this section.
(i) If your pressure CPMS includes a redundant pressure sensor, record three pairs of concurrent pressure measurements within a 24-hour period. Each pair of concurrent measurements must consist of a pressure measurement by each of the two pressure sensors. The minimum time interval between any two such pairs of consecutive pressure
(ii) If your pressure CPMS does not include a redundant pressure sensor, place the sensor of a calibrated pressure measurement device adjacent to the sensor of your pressure CPMS in a location that is subject to the same environment as the sensor of your pressure CPMS. The calibrated pressure measurement device must satisfy the accuracy requirements of paragraph (a)(15) of this section. While the process and control device that is monitored by your pressure CPMS are operating normally, record concurrently and compare the pressure measured by your CPMS and the calibrated pressure measurement device. Using the calibrated pressure measurement device as the reference, the pressure measured by your CPMS must be within the accuracy specified in paragraph (c)(1) of this section.
(iii) Perform any of the accuracy audit methods for pressure CPMS specified in QA procedures for CPMS established in 40 CFR part 60, appendix F.
(5) Conduct an accuracy audit of your CPMS following any 24-hour period throughout which the pressure measured by your CPMS exceeds the manufacturer's specified maximum operating pressure range, or install a new pressure sensor.
(6) At least monthly, check all mechanical connections on your CPMS for leakage.
(7) If your CPMS is not equipped with a redundant pressure sensor, perform at least quarterly a visual inspection of all components of the CPMS for integrity, oxidation, and galvanic corrosion.
(d) For each liquid flow rate CPMS that is used to monitor the liquid flow rate in a wet scrubber, you must meet the requirements in paragraphs (a) and (d)(1) through (7) of this section.
(1) Use a flow rate CPMS with a minimum accuracy of ±5.0 percent or 1.9 liters per minute (L/min) (0.5 gallons per minute (gal/min)), whichever is greater.
(2) Use a data recording system with a minimum resolution of one-half the required CPMS accuracy specified in paragraph (d)(1) of this section, or better.
(3) Perform an initial validation of your CPMS according to the requirements in paragraph (3)(i) or (ii) of this section.
(i) Use a calibrated flow rate measurement system to measure the liquid flow rate in a location that is adjacent to the measurement location for your flow rate CPMS and is subject to the same environment as your flow rate CPMS. The calibrated flow rate measurement device must satisfy the accuracy requirements of paragraph (a)(15) of this section. While the process and control device that is monitored by your flow rate CPMS are operating normally, record concurrently and compare the flow rates measured by your flow rate CPMS and the calibrated flow rate measurement device. Using the calibrated flow rate measurement device as the reference, the flow rate measured by your CPMS must be within the accuracy specified in paragraph (d)(1) of this section.
(ii) Perform any of the initial validation methods for liquid flow rate CPMS specified in performance specifications for CPMS established in 40 CFR part 60, appendix B.
(4) Perform an accuracy audit of your flow rate CPMS at least quarterly, according to the requirements in paragraph (d)(4)(i), (ii), or (iii) of this section.
(i) If your flow rate CPMS includes a redundant sensor, record three pairs of concurrent flow rate measurements within a 24-hour period. Each pair of concurrent measurements must consist of a flow rate measurement by each of the two flow rate sensors. The minimum time interval between any two such pairs of consecutive flow rate measurements is 1 hour. The measurements must be taken during periods when the process and control device that is monitored by your flow rate CPMS are operating normally. Calculate the mean of the three flow rate measurement values for each flow rate
(ii) If your flow rate CPMS does not include a redundant flow rate sensor, place the sensor of a calibrated flow rate measurement device adjacent to the sensor of your flow rate CPMS in a location that is subject to the same environment as the sensor of your flow rate CPMS. The calibrated flow rate measurement device must satisfy the accuracy requirements of paragraph (a)(15) of this section. While the process and control device that is monitored by your flow rate CPMS are operating normally, record concurrently and compare the flow rate measured by your pressure CPMS and the calibrated flow rate measurement device. Using the calibrated flow rate measurement device as the reference, the flow rate measured by your CPMS must be within the accuracy specified in paragraph (d)(1) of this section.
(iii) Perform any of the accuracy audit methods for liquid flow rate CPMS specified in QA procedures for CPMS established in 40 CFR part 60, appendix F.
(5) Conduct an accuracy audit of your flow rate CPMS following any 24-hour period throughout which the flow rate measured by your CPMS exceeds the manufacturer's specified maximum operating range, or install a new flow rate sensor.
(6) At least monthly, check all mechanical connections on your CPMS for leakage.
(7) If your CPMS is not equipped with a redundant flow rate sensor, perform at least quarterly a visual inspection of all components of the CPMS for integrity, oxidation, and galvanic corrosion.
(e) For each pH CPMS that is used to monitor the pH of a wet scrubber liquid, you must meet the requirements in paragraphs (a) and (e)(1) through (5) of this section.
(1) Use a pH CPMS with a minium accuracy of ±0.2 pH units.
(2) Use a data recording system with a minimum resolution of 0.1 pH units, or better.
(3) Perform an initial validation of your pH CPMS according to the requirements in paragraph (e)(3)(i) or (ii) of this section.
(i) Perform a single-point calibration using an NIST-certified buffer solution that is accurate to within ±0.02 pH units at 25 °C (77 °F). If the expected pH of the liquid that is monitored lies in the acidic range (less than 7 pH), use a buffer solution with a pH value of 4.00. If the expected pH of the liquid that is monitored is neutral or lies in the basic range (equal to or greater than 7 pH), use a buffer solution with a pH value of 10.00. Place the electrode of your pH CPMS in the container of buffer solution. Record the pH measured by your CPMS. Using the certified buffer solution as the reference, the pH measured by your CPMS must be within the accuracy specified in paragraph (e)(1) of this section.
(ii) Perform any of the initial validation methods for pH CPMS specified in performance specifications for CPMS established in 40 CFR part 60, appendix B.
(4) Perform an accuracy audit of your pH CPMS at least weekly, according to the requirements in paragraph (e)(4)(i), (ii), or (iii) of this section.
(i) If your pH CPMS includes a redundant pH sensor, record the pH measured by each of the two pH sensors. The measurements must be taken during periods when the process and control device that is monitored by your pH CPMS are operating normally. The two pH values must agree within the required overall accuracy of the CPMS, as specified in paragraph (e)(1) of this section.
(ii) If your pH CPMS does not include a redundant pH sensor, perform a single point calibration using an NIST-certified buffer solution that is accurate to within ±0.02 pH units at 25 °C (77 °F). If the expected pH of the liquid that is monitored lies in the acidic range (less than 7 pH), use a buffer solution with a pH value of 4.00. If the expected pH of the liquid that is monitored is neutral or lies in the basic range (equal to or greater than 7 pH), use a buffer solution with a pH value of 10.00. Place the electrode of the pH CPMS in the container of buffer solution. Record the pH measured by your CPMS. Using the certified buffer solution as the reference, the pH measured
(iii) Perform any of the accuracy audit methods for pH CPMS specified in QA procedures for CPMS established in 40 CFR part 60, appendix F.
(5) If your CPMS is not equipped with a redundant pH sensor, perform at least monthly a visual inspection of all components of the CPMS for integrity, oxidation, and galvanic corrosion.
(f) For each bag leak detection system, you must meet the requirements in paragraphs (f)(1) through (11) of this section.
(1) Each triboelectric bag leak detection system must be installed, calibrated, operated, and maintained according to the “Fabric Filter Bag Leak Detection Guidance” (EPA-454/R-98-015, September 1997). That document is available from the U.S. EPA; Office of Air Quality Planning and Standards; Emissions, Monitoring and Analysis Division; Emission Measurement Center (D205-02), Research Triangle Park, NC 27711. It is also available on the Technology Transfer Network (TTN) at the following address:
(2) The bag leak detection system must be certified by the manufacturer to be capable of detecting particulate matter (PM) emissions at concentrations of 10 milligrams per actual cubic meter (0.0044 grains per actual cubic foot) or less.
(3) The bag leak detection system sensor must provide an output of relative PM loadings.
(4) The bag leak detection system must be equipped with a device to continuously record the output signal from the sensor.
(5) The bag leak detection system must be equipped with an alarm system that will be engaged automatically when an increase in relative PM emissions over a preset level is detected. The alarm must be located where it is easily recognized by plant operating personnel.
(6) For positive pressure fabric filter systems, a bag leak detector must be installed in each baghouse compartment or cell.
(7) For negative pressure or induced air fabric filters, the bag leak detector must be installed downstream of the fabric filter.
(8) Where multiple detectors are required, the system's instrumentation and alarm may be shared among detectors.
(9) The baseline output must be established by adjusting the range and the averaging period of the device and establishing the alarm set points and the alarm delay time according to section 5.0 of the “Fabric Filter Bag Leak Detection Guidance.”
(10) Following initial adjustment of the system, the owner or operator must not adjust the sensitivity or range, averaging period, alarm set points, or alarm delay time except as detailed in the OM&M plan. In no case may the sensitivity be increased by more than 100 percent or decreased by more than 50 percent over a 365-day period unless such adjustment follows a complete fabric filter inspection that demonstrates that the fabric filter is in good operating condition. You must record each adjustment of your bag leak detection system.
(11) Record the results of each inspection, calibration, and validation check.
(g) For each lime feed rate measurement device that is used to monitor the lime feed rate of a dry injection fabric filter (DIFF) or dry lime scrubber/fabric filter (DLS/FF), or the chemical feed rate of a wet scrubber, you must meet the requirements in paragraph (a) of this section.
(h) For each affected source that is subject to the emission limit specified in item 3, 4, 7, or 8 of Table 1 to this subpart, you must satisfy the requirements of paragraphs (h)(1) through (3) of this section.
(1) Install a THC CEMS at the outlet of the control device or in the stack of the affected source.
(2) Meet the requirements of PS-8 of 40 CFR part 60, appendix B.
(3) Meet the requirements of Procedure 1 of 40 CFR part 60, appendix F.
(i) Requests for approval of alternate monitoring methods must meet the requirements in §§ 63.9800(i)(2) and 63.8(f).
(a) You must demonstrate initial compliance with each emission limit that applies to you according to the requirements specified in Table 5 to this subpart.
(b) You must establish each site-specific operating limit in Table 2 to this subpart that applies to you according to the requirements specified in § 63.9800 and Table 4 to this subpart.
(c) You must demonstrate initial compliance with each work practice standard that applies to you according to the requirements specified in Table 6 to this subpart.
(d) You must submit the Notification of Compliance Status containing the results of the initial compliance demonstration according to the requirements in § 63.9812(e).
(a) You must monitor and collect data according to this section.
(b) At all times, you must maintain your monitoring systems including, but not limited to, maintaining necessary parts for routine repairs of the monitoring equipment.
(c) Except for, as applicable, monitoring system malfunctions, associated repairs, and required quality assurance or quality control activities, you must monitor continuously whenever your affected process unit is operating. For purposes of calculating data averages, you must not use data recorded during monitoring system malfunctions, associated repairs, and required quality assurance or quality control activities. You must use all the data collected during all other periods in assessing compliance. A monitoring system malfunction is any sudden, infrequent, not reasonably preventable failure of the monitoring system to provide valid data. Monitoring system malfunctions include out of control continuous monitoring systems (CMS), such as a CPMS. Any averaging period for which you do not have valid monitoring data as a result of a monitoring system malfunction and for which such data are required constitutes a deviation, and you must notify the Administrator in accordance with § 63.9814(e). Monitoring system failures are different from monitoring system malfunctions in that they are caused in part by poor maintenance or careless operation. Any period for which there is a monitoring system failure and data are not available for required calculations constitutes a deviation and you must notify the Administrator in accordance with § 63.9814(e).
(a) You must demonstrate continuous compliance with each emission limit specified in Table 1 to this subpart that applies to you according to the requirements specified in Table 7 to this subpart.
(b) You must demonstrate continuous compliance with each operating limit specified in Table 2 to this subpart that applies to you according to the requirements specified in Table 8 to this subpart.
(c) You must demonstrate continuous compliance with each work practice standard specified in Table 3 to this subpart that applies to you according to the requirements specified in Table 9 to this subpart.
(d) For each affected source that is equipped with an add-on APCD that is not addressed in Table 2 to this subpart or that is using process changes as a means of meeting the emission limits in Table 1 to this subpart, you must demonstrate continuous compliance with each emission limit in Table 1 to this subpart and each operating limit established as required in § 63.9800(i)(3) according to the methods specified in your approved alternative monitoring methods request as described in § 63.9800(i)(2).
(e) You must report each instance in which you did not meet each emission limit and each operating limit in this
(1) [Reserved]
(2) Consistent with §§ 63.6(e) and 63.7(e)(1), deviations that occur during a period of startup, shutdown, or malfunction are not violations if you demonstrate to the Administrator's satisfaction that you were operating in accordance with § 63.6(e)(1) and your OM&M plan. The Administrator will determine whether deviations that occur during a period of startup, shutdown, or malfunction are violations, according to the provisions in § 63.6(e).
(a) You must submit all of the notifications in §§ 63.7(b) and (c), 63.8(f)(4), and 63.9 (b) through (e) and (h) that apply to you by the dates specified.
(b) As specified in § 63.9(b)(2) and (3), if you start up your affected source before April 16, 2003, you must submit an Initial Notification not later than 120 calendar days after April 16, 2003.
(c) As specified in § 63.9(b)(3), if you start up your new or reconstructed affected source on or after April 16, 2003, you must submit an Initial Notification not later than 120 calendar days after you become subject to this subpart.
(d) If you are required to conduct a performance test, you must submit a Notification of Performance Test at least 60 calendar days before the performance test is scheduled to begin, as required in § 63.7(b)(1).
(e) If you are required to conduct a performance test, you must submit a Notification of Compliance Status as specified in § 63.9(h) and paragraphs (e)(1) and (2) of this section.
(1) For each compliance demonstration that includes a performance test conducted according to the requirements in Table 4 to this subpart, you must submit the Notification of Compliance Status, including the performance test results, before the close of business on the 60th calendar day following the completion of the performance test, according to § 63.10(d)(2).
(2) In addition to the requirements in § 63.9(h)(2)(i), you must include the information in paragraphs (e)(2)(i) through (iv) of this section in your Notification of Compliance Status.
(i) The operating limit parameter values established for each affected source with supporting documentation and a description of the procedure used to establish the values.
(ii) Design information and analysis with supporting documentation demonstrating conformance with requirements for capture/collection systems in Table 2 to this subpart.
(iii) A description of the methods used to comply with any applicable work practice standard.
(iv) For each APCD that includes a fabric filter, analysis and supporting documentation demonstrating conformance with EPA guidance and specifications for bag leak detection systems in § 63.9804(f).
(f) If you operate a clay refractory products kiln or a chromium refractory products kiln that is subject to the work practice standard specified in item 3 or 4 of Table 3 to this subpart, and you intend to use a fuel other than natural gas or equivalent to fire the affected kiln, you must submit a notification of alternative fuel use within 48 hours of the declaration of a period of natural gas curtailment or supply interruption, as defined in § 63.9824. The notification must include the information specified in paragraphs (f)(1) through (5) of this section.
(1) Company name and address.
(2) Identification of the affected kiln.
(3) Reason you are unable to use natural gas or equivalent fuel, including the date when the natural gas curtailment was declared or the natural gas supply interruption began.
(4) Type of alternative fuel that you intend to use.
(5) Dates when the alternative fuel use is expected to begin and end.
(g) If you own or operate an affected continuous kiln and must perform scheduled maintenance on the control device for that kiln, you must request
(a) You must submit each report in Table 10 to this subpart that applies to you.
(b) Unless the Administrator has approved a different schedule for submission of reports under § 63.10(a), you must submit each report by the date in Table 10 to this subpart and as specified in paragraphs (b)(1) through (5) of this section.
(1) The first compliance report must cover the period beginning on the compliance date that is specified for your affected source in § 63.9786 and ending on June 30 or December 31 and lasting at least 6 months but less than 12 months. For example, if your compliance date is March 1, then the first semiannual reporting period would begin on March 1 and end on December 31.
(2) The first compliance report must be postmarked or delivered no later than July 31 or January 31 for compliance periods ending on June 30 and December 31, respectively.
(3) Each subsequent compliance report must cover the semiannual reporting period from January 1 through June 30 or the semiannual reporting period from July 1 through December 31.
(4) Each subsequent compliance report must be postmarked or delivered no later than July 31 or January 31 for compliance periods ending on June 30 and December 31, respectively.
(5) For each affected source that is subject to permitting regulations pursuant to 40 CFR part 70 or 40 CFR part 71 and, if the permitting authority has established dates for submitting semiannual reports pursuant to 40 CFR 70.6(a)(3)(iii)(A) or 40 CFR 71.6(a)(3)(iii)(A), you may submit the first and subsequent compliance reports according to the dates the permitting authority has established instead of according to the dates in paragraphs (b)(1) through (4) of this section. In such cases, you must notify the Administrator of this change.
(c) The compliance report must contain the information in paragraphs (c)(1) through (6) of this section.
(1) Company name and address.
(2) Statement by a responsible official with that official's name, title, and signature, certifying that, based on information and belief formed after reasonable inquiry, the statements and information in the report are true, accurate, and complete.
(3) Date of report and beginning and ending dates of the reporting period.
(4) If you had a startup, shutdown, or malfunction during the reporting period, and you took actions consistent with your SSMP and OM&M plan, the compliance report must include the information specified in § 63.10(d)(5)(i).
(5) If there are no deviations from any emission limitations (emission limit, operating limit, or work practice standard) that apply to you, the compliance report must include a statement that there were no deviations from the emission limitations during the reporting period.
(6) If there were no periods during which any affected CPMS was out of control as specified in § 63.8(c)(7), the compliance report must include a statement that there were no periods during which the CPMS was out of control during the reporting period.
(d) For each deviation from an emission limitation (emission limit, operating limit, or work practice standard) that occurs at an affected source where you are not using a CPMS to comply with the emission limitations in this subpart, the compliance report must contain the information in paragraphs (c)(1) through (4) and (d)(1) and (2) of this section. This includes periods of startup, shutdown, and malfunction.
(1) The compliance report must include the total operating time of each affected source during the reporting period.
(2) The compliance report must include information on the number, duration, and cause of deviations (including unknown cause, if applicable) and the corrective action taken.
(e) For each deviation from an emission limitation (emission limit, operating limit, or work practice standard)
(1) The total operating time of each affected source during the reporting period.
(2) The date and time that each startup, shutdown, or malfunction started and stopped.
(3) The date, time, and duration that each CPMS was inoperative.
(4) The date, time and duration that each CPMS was out of control, including the information in § 63.8(c)(8), as required by your OM&M plan.
(5) The date and time that each deviation from an emission limitation (emission limit, operating limit, or work practice standard) started and stopped, and whether each deviation occurred during a period of startup, shutdown, or malfunction.
(6) A description of corrective action taken in response to a deviation.
(7) A summary of the total duration of the deviations during the reporting period and the total duration as a percentage of the total source operating time during that reporting period.
(8) A breakdown of the total duration of the deviations during the reporting period into those that are due to startup, shutdown, control equipment problems, process problems, other known causes, and other unknown causes.
(9) A summary of the total duration of CPMS downtime during the reporting period and the total duration of CPMS downtime as a percentage of the total source operating time during that reporting period.
(10) A brief description of the process units.
(11) A brief description of the CPMS.
(12) The date of the latest CPMS initial validation or accuracy audit.
(13) A description of any changes in CPMS, processes, or controls since the last reporting period.
(f) If you have obtained a title V operating permit pursuant to 40 CFR part 70 or 40 CFR part 71, you must report all deviations as defined in this subpart in the semiannual monitoring report required by 40 CFR 70.6(a)(3)(iii)(A) or 40 CFR 71.6(a)(3)(iii)(A). If you submit a compliance report according to Table 10 to this subpart along with, or as part of, the semiannual monitoring report required by 40 CFR 70.6(a)(3)(iii)(A) or 40 CFR 71.6(a)(3)(iii)(A), and the compliance report includes all required information concerning deviations from any emission limitation (including any operating limit), then submitting the compliance report will satisfy any obligation to report the same deviations in the semiannual monitoring report. However, submitting a compliance report will not otherwise affect any obligation you may have to report deviations from permit requirements to the permit authority.
(g) If you operate a clay refractory products kiln or a chromium refractory products kiln that is subject to the work practice standard specified in item 3 or 4 of Table 3 to this subpart, and you use a fuel other than natural gas or equivalent to fire the affected kiln, you must submit a report of alternative fuel use within 10 working days after terminating the use of the alternative fuel. The report must include the information in paragraphs (g)(1) through (6) of this section.
(1) Company name and address.
(2) Identification of the affected kiln.
(3) Reason for using the alternative fuel.
(4) Type of alternative fuel used to fire the affected kiln.
(5) Dates that the use of the alternative fuel started and ended.
(6) Amount of alternative fuel used.
(a) You must keep the records listed in paragraphs (a)(1) through (3) of this section.
(1) A copy of each notification and report that you submitted to comply with this subpart, including all documentation supporting any Initial Notification or Notification of Compliance Status that you submitted, according to the requirements in § 63.10(b)(2)(xiv).
(2) The records in § 63.6(e)(3)(iii) through (v) related to startup, shutdown, and malfunction.
(3) Records of performance tests as required in § 63.10(b)(2)(viii).
(b) You must keep the records required in Tables 7 through 9 to this subpart to show continuous compliance with each emission limitation that applies to you.
(c) You must also maintain the records listed in paragraphs (c)(1) through (10) of this section.
(1) Records of emission data used to develop an emissions profile, as indicated in items 8(a)(i)(4) and 17(b)(i)(4) of Table 4 to this subpart.
(2) Records that document how you comply with any applicable work practice standard.
(3) For each bag leak detection system, records of each alarm, the time of the alarm, the time corrective action was initiated and completed, and a brief description of the cause of the alarm and the corrective action taken.
(4) For each kiln controlled with a DLA, records that document the source of limestone used.
(5) For each deviation of an operating limit parameter value, the date, time, and duration of the deviation, a brief explanation of the cause of the deviation and the corrective action taken, and whether the deviation occurred during a period of startup, shutdown, or malfunction.
(6) For each affected source, records of production rate on a process throughput basis (either feed rate to the process unit or discharge rate from the process unit).
(7) Records of any approved alternative monitoring method(s) or test procedure(s).
(8) Records of maintenance activities and inspections performed on control devices, including all records associated with the scheduled maintenance of continuous kiln control devices, as specified in § 63.9792(e).
(9) If you operate a source that is subject to the THC emission limits specified in item 2, 3, 6, or 7 of Table 1 to this subpart and is controlled with a catalytic oxidizer, records of annual checks of catalyst activity levels and subsequent corrective actions.
(10) Current copies of the SSMP and the OM&M plan, including any revisions and records documenting conformance with those revisions.
(a) Your records must be in a form suitable and readily available for expeditious review, according to § 63.10(b)(1).
(b) As specified in § 63.10(b)(1), you must keep each record for 5 years following the date of each occurrence, measurement, maintenance, corrective action, report, or record.
(c) You must keep each record onsite for at least 2 years after the date of each occurrence, measurement, maintenance, corrective action, report, or record, according to § 63.10(b)(1). You may keep the records offsite for the remaining 3 years.
Table 11 to this subpart shows which parts of the General Provisions specified in §§ 63.1 through 63.15 apply to you.
(a) This subpart can be implemented and enforced by us, the U.S. Environmental Protection Agency (U.S. EPA), or a delegated authority such as your State, local, or tribal agency. If the U.S. EPA Administrator has delegated authority to your State, local, or tribal agency, then that agency, in addition to the U.S. EPA, has the authority to implement and enforce this subpart. You should contact your U.S. EPA Regional Office to find out if implementation and enforcement to this subpart is delegated to your State, local, or tribal agency.
(b) In delegating implementation and enforcement authority to this subpart to a State, local, or tribal agency under 40 CFR part 63, subpart E, the authorities contained in paragraph (c) of this section are retained by the Administrator of the U.S. EPA and are not transferred to the State, local, or tribal agency.
(c) The authorities that cannot be delegated to State, local, or tribal agencies are as specified in paragraphs (c)(1) through (4) of this section.
(1) Approval of alternatives to the applicability requirements in §§ 63.9782 and 63.9784, the compliance date requirements in § 63.9786, and the emission limitations in § 63.9788.
(2) Approval of major changes to test methods under § 63.7(e)(2)(ii) and (f) and as defined in § 63.90.
(3) Approval of major changes to monitoring under § 63.8(f) and as defined in § 63.90.
(4) Approval of major changes to recordkeeping and reporting under § 63.10(f) and as defined in § 63.90.
Terms used in this subpart are defined in the Clean Air Act, in 40 CFR 63.2, the General Provisions of this part, and in this section as follows:
(1) Fails to meet any requirement or obligation established by this subpart including, but not limited to, any emission limitation (emission limit, operating limit, or work practice standard);
(2) Fails to meet any term or condition that is adopted to implement an applicable requirement in this subpart for any affected source required to obtain such a permit; or
(3) Fails to meet any emission limitation (emission limit, operating limit, or work practice standard) in this subpart during startup, shutdown, or malfunction, regardless of whether or not such failure is permitted by this subpart.
(1) The 3-hour peak THC emissions period is the period of 3 consecutive hours over which the sum of the hourly THC mass emissions rates is greater than the sum of the hourly THC mass emissions rates for any other period of 3 consecutive hours during the same batch process cycle.
(2) The 3-hour peak HF emissions period is the period of 3 consecutive hours over which the sum of the hourly HF mass emissions rates is greater than the sum of the hourly HF mass emissions rates for any other period of 3 consecutive hours during the same batch process cycle.
(1) For a corporation: a president, secretary, treasurer, or vice-president of the corporation in charge of a principal business function, or any other person who performs similar policy or decisionmaking functions for the corporation, or a duly authorized representative of such person if the representative is responsible for the overall operation of one or more manufacturing, production, or operating facilities applying for or subject to a permit and either:
(i) The facilities employ more than 250 persons or have gross annual sales or expenditures exceeding $25 million (in second quarter 1980 dollars); or
(ii) The delegation of authority to such representatives is approved in advance by the Administrator;
(2) For a partnership or sole proprietorship: a general partner or the proprietor, respectively;
(3) For a municipality, State, Federal, or other public agency: either a principal executive officer or ranking elected official. For the purposes of this part, a principal executive officer of a Federal agency includes the chief executive officer having responsibility for the overall operations of a principal geographic unit of the agency (
(4) For affected sources (as defined in this subpart) applying for or subject to a title V permit: “responsible official” shall have the same meaning as defined in part 70 or Federal title V regulations in this chapter (42 U.S.C. 7661), whichever is applicable.
As stated in § 63.9788, you must comply with the emission limits for affected sources in the following table:
As stated in § 63.9788, you must comply with the operating limits for affected sources in the following table:
As stated in § 63.9788, you must comply with the work practice standards for affected sources in the following table:
As stated in § 63.9800, you must comply with the requirements for performance tests for affected sources in the following table:
As stated in § 63.9806, you must show initial compliance with the emission limits for affected sources according to the following table:
As stated in § 63.9806, you must show initial compliance with the work practice standards for affected sources according to the following table:
As stated in § 63.9810, you must show continuous compliance with the emission limits for affected sources according to the following table:
As stated in § 63.9810, you must show continuous compliance with the operating limits for affected sources according to the following table:
As stated in § 63.9810, you must show continuous compliance with the work practice standards for affected sources according to the following table:
As stated in § 63.9814, you must comply with the requirements for reports in the following table:
As stated in § 63.9820, you must comply with the applicable General Provisions requirements according to the following table:
This subpart establishes national emission standards for hazardous air pollutants (NESHAP) for primary magnesium refineries. This subpart also establishes requirements to demonstrate initial and continuous compliance with all applicable emission limitations, work practice standards, and operation and maintenance requirements.
You are subject to this subpart if you own or operate a primary magnesium refinery that is (or is part of) a major source of hazardous air pollutant (HAP) emissions. Your primary magnesium refinery is a major source of HAP if it emits or has the potential to emit any single HAP at a rate of 10 tons or more per year or any combination of HAP at a rate of 25 tons or more per year.
(a) The affected sources are each new and existing primary magnesium refining facility.
(b) This subpart covers emissions from each spray dryer stack, magnesium chloride storage bins scrubber stack, melt/reactor system stack, and launder off-gas system stack at your primary magnesium refining facility. This subpart also covers fugitive dust emissions.
(c) Each primary magnesium refining facility is existing if you commenced construction or reconstruction of the affected source before January 22, 2003.
(d) Each primary magnesium refining facility is new if you commence construction or reconstruction of the affected source on or after January 22, 2003. An affected source is reconstructed if it meets the definition of reconstruction in § 63.2.
(a) If you have an existing source, you must comply with each emission limitation, work practice standard, and operation and maintenance requirement in this subpart that applies to you no later than October 11, 2004.
(b) If you have a new affected source and its initial startup date is on or before October 11, 2003, you must comply with each emission limitation, work practice standard, and operation and maintenance requirement in this subpart that applies to you by October 10, 2003.
(c) If you have a new affected source and its initial startup date is after October 10, 2003, you must comply with each emission limitation, work practice standard, and operation and maintenance requirement in this subpart that applies to you upon initial startup.
(d) If your primary magnesium refinery is an area source that becomes a major source of HAP, the compliance
(1) Any portion of the existing primary magnesium refinery that is a new affected source or a new reconstructed source must be in compliance with this subpart upon startup.
(2) All other parts of the primary magnesium refinery must be in compliance with this subpart no later than 2 years after it becomes a major source.
(e) You must meet the notification and schedule requirements in § 63.9930. Several of these notifications must be submitted before the compliance date for your affected source.
(a) You must meet each emission limit in Table 1 to this subpart that applies to you.
(b) For each wet scrubber applied to meet any particulate matter, particulate matter less than 10 microns (PM
(a) You must prepare and at all times operate according to a fugitive dust emissions control plan that describes in detail the measures that will be put in place to control fugitive dust emissions from all unpaved roads and other unpaved operational areas.
(b) You must submit a copy of your fugitive dust emissions control plan for approval to the Administrator on or before the applicable compliance date for the affected source as specified in § 63.9883. The requirement to operate according to the fugitive dust emissions control plan must be incorporated by reference in the source's operating permit issued by the permitting authority under 40 CFR part 70 or 40 CFR part 71.
(c) You can use an existing fugitive dust emissions control plan provided it meets the requirements in paragraphs (c)(1) through (3) of this section.
(1) The plan satisfies the requirements of paragraph (a) of this section.
(2) The plan describes the current measures to control fugitive dust emission sources.
(3) The plan has been approved as part of a State implementation plan or title V permit.
(d) You must maintain a current copy of the fugitive dust emissions control plan on-site and available for inspection upon request. You must keep the plan for the life of the affected source or until the affected source is no longer subject to the requirements of this subpart.
(a) As required by § 63.6(e)(1)(i), you must always operate and maintain your affected source, including air pollution control and monitoring equipment, in a manner consistent with good air pollution control practices for minimizing emissions at least to the levels required by this subpart.
(b) You must prepare and operate at all times according to a written operation and maintenance plan for each control device subject to an operating limit in § 63.9890(b). Each plan must address preventative maintenance for each control device, including a preventative maintenance schedule that is consistent with the manufacturer's instructions for routine and long-term maintenance.
(c) You must maintain a current copy of the operation and maintenance plan required in paragraph (b) of this section on-site and available for inspection upon request. You must keep the plan for the life of the affected source or until the affected source is no longer subject to the requirements of this subpart.
(a) You must be in compliance with the emission limitations, work practice standards, and operation and maintenance requirements in this subpart at all times, except during periods of startup, shutdown, and malfunction as defined in § 63.2.
(b) You must develop a written startup, shutdown, and malfunction plan according to the provisions in § 63.6(e)(3).
(a) As required in § 63.7(a)(2), you must conduct a performance test to demonstrate initial compliance with each emission limit in Table 1 to this subpart that applies to you as indicated in paragraphs (a)(1) through (3) of this section:
(1) Within 180 calendar days after the compliance date that is specified in § 63.9883 for your existing affected source;
(2) By April 7, 2004 for a new source that has an initial startup date before October 10, 2003; or
(3) Within 180 days after initial startup for a new source that has an initial startup date after October 10, 2003.
(b) For each operation and maintenance requirement that applies to you where initial compliance is not demonstrated using a performance test, you must demonstrate initial compliance within 30 calendar days after the compliance date that is specified for your affected source in § 63.9883.
(c) If you commenced construction or reconstruction between January 22, 2003 and October 10, 2003, you must demonstrate initial compliance with either the proposed emission limitation or the promulgated emission limitation no later than April 7, 2004 or no later than 180 calendar days after startup of the source, whichever is later, according to § 63.7(a)(2)(ix).
(d) If you commenced construction or reconstruction between January 22, 2003 and October 10, 2003, and you chose to comply with the proposed emission limit when demonstrating initial compliance, you must conduct a second performance test to demonstrate compliance with the promulgated emission limit by April 11, 2005, or after startup of the source, whichever is later, according to § 63.7(a)(2)(ix).
You must conduct subsequent performance tests to demonstrate continuous compliance with all applicable emission limits in Table 1 to this subpart no less frequently than twice (at mid-term and renewal) during each term of your title V operating permit.
(a) You must conduct each performance test that applies to your affected source according to the requirements in § 63.7(e)(1).
(b) To determine compliance with the applicable emission limits for particulate matter in Table 1 to this subpart, you must follow the test methods and procedures in paragraphs (b)(1) and (2) of this section.
(1) Determine the concentration of particulate matter according to the following test methods in appendix A to 40 CFR part 60:
(i) Method 1 to select sampling port locations and the number of traverse points. Sampling ports must be located at the outlet of the control device and prior to any releases to the atmosphere.
(ii) Method 2, 2F, or 2G to determine the volumetric flow rate of the stack gas.
(iii) Method 3, 3A, or 3B to determine the dry molecular weight of the stack gas.
(iv) Method 4 to determine the moisture content of the stack gas.
(v) Method 5 or 5D, as applicable, to determine the concentration of particulate matter.
(vi) Method 201 or 201A, as applicable, to determine the concentration of PM
(2) Collect a minimum sample volume of 60 dry standard cubic feet (dscf) during each particulate matter or PM
(c) Compute the mass emissions rate in pounds per hour (lbs/hr) for each test run using Equation 1 of this section:
(a) You must conduct each performance test that applies to your affected source according to the requirements in § 63.7(e)(1).
(b) To determine compliance with the applicable emission limits for chlorine and hydrochloric acid in Table 1 to this subpart, you must follow the test methods and procedures specified in paragraphs (b)(1) and (2) of this section.
(1) Determine the concentration of chlorine and hydrochloric acid according to the following test methods in appendix A to 40 CFR part 60:
(i) Method 1 to select sampling port locations and the number of traverse points. Sampling ports must be located at the outlet of the control device and prior to any releases to the atmosphere.
(ii) Method 2, 2F, or 2G to determine the volumetric flow of the stack gas.
(iii) Method 3, 3A, or 3B to determine the dry molecular weight of the stack gas.
(iv) Method 4 to determine the moisture content of the stack gas.
(v) Method 26 or 26A, as applicable, to determine the concentration of hydrochloric acid and chlorine.
(2) Collect a minimum sample of 60 dscf during each test run for chlorine and hydrochloric acid. Three valid test runs are needed to comprise a performance test.
(c) Compute the mass emissions rate (lbs/hr) for each test run using Equation 1 of this section:
(a) You must conduct each performance test that applies to your affected source according to the requirements in § 63.7(e)(1).
(b) To determine compliance with the applicable emission limit for dioxins/furans in Table 1 to this subpart, you must follow the test methods and procedures specified in paragraphs (b)(1) and (2) of this section.
(1) Determine the concentration of dioxin and furan according to the following test methods in appendix A to 40 CFR part 60:
(i) Method 1 to select sampling port locations and the number of traverse points. Sampling ports must be located at the outlet of the control device and prior to any releases to the atmosphere.
(ii) Method 2, 2F, or 2G to determine the volumetric flow of the stack gas.
(iii) Method 3, 3A, or 3B to determine the dry molecular weight of the stack gas.
(iv) Method 4 to determine the moisture content of the stack gas.
(v) Method 23 to determine the concentration of dioxins/furans. For each
(2) Collect a minimum sample of 100 dscf during each test run. Three valid test runs are needed to comprise a performance test.
For a wet scrubber subject to operating limits for pressure drop and scrubber water flow rate in § 63.9890(b), you must establish site-specific operating limits according to the procedures in paragraphs (a) and (b) of this section.
(a) Using the continuous parameter monitoring system (CPMS) required in § 63.9920, measure and record the pressure drop and scrubber water flow rate at least every 15 minutes during each run of the particulate matter performance test.
(b) Compute and record the average pressure drop and scrubber water flow rate for each individual test run. Your operating limits are the lowest average individual pressure drop and scrubber water flow rate values in any of the three runs that meet the applicable emission limit.
(a) For each affected source subject to an emission limit in Table 1 to this subpart, you have demonstrated initial compliance if:
(1) You have met the conditions in Table 3 to this subpart; and
(2) For each wet scrubber subject to the operating limits for pressure drop and scrubber water flow rate in § 63.9890(b), you have established appropriate site-specific operating limits and have a record of the pressure drop and scrubber water flow rate measured during the performance test in accordance with § 63.9916.
(b) You have demonstrated initial compliance with the work practice standards in § 63.9891 if you have certified in your notification of compliance status that:
(1) You have prepared a fugitive dust emissions control plan according to the requirements in § 63.9891 and submitted the plan for approval; and
(2) You will operate according to the requirements in the plan.
You must demonstrate initial compliance by certifying in your notification of compliance status that you have met the requirements in paragraphs (a) and (b) of this section.
(a) You have prepared the operation and maintenance plan according to the requirements in § 63.9910; and
(b) You will operate each control device according to the procedures in the plan.
For each wet scrubber subject to the operating limits for pressure drop and scrubber water flow rates in § 63.9890(b), you must at all times monitor the hourly average pressure drop and liquid flow rate using a CPMS according to the requirements in § 63.9921(a).
(a) For each wet scrubber subject to the operating limits in § 63.9890(b) for pressure drop and scrubber water flow rate, you must install, operate, and maintain each CPMS according to the requirements in paragraphs (a)(1) and (2) of this section.
(1) For the pressure drop CPMS, you must:
(i) Locate the pressure sensor(s) in or as close to a position that provides a representative measurement of the pressure and that minimizes or eliminates pulsating pressure, vibration, and internal and external corrosion.
(ii) Use a gauge with a minimum measurement sensitivity of 0.5 inch of water or a transducer with a minimum measurement sensitivity of 1 percent of the pressure range.
(iii) Check the pressure tap for pluggage daily.
(iv) Using a manometer, check gauge calibration quarterly and transducer calibration monthly.
(v) Conduct calibration checks any time the sensor exceeds the manufacturer's specified maximum operating pressure range, or install a new pressure sensor.
(vi) At least monthly, inspect all components for integrity, all electrical connections for continuity, and all mechanical connections for leakage.
(2) For the scrubber water flow rate CPMS, you must:
(i) Locate the flow sensor and other necessary equipment in a position that provides a representative flow and that reduces swirling flow or abnormal velocity distributions due to upstream and downstream disturbances.
(ii) Use a flow sensor with a minimum measurement sensitivity of 2 percent of the flow rate.
(iii) Conduct a flow sensor calibration check at least semiannually according to the manufacturer's instructions.
(iv) At least monthly, inspect all components for integrity, all electrical connections for continuity, and all mechanical connections for leakage.
(b) You must install, operate, and maintain each CPMS for a wet scrubber according to the requirements in paragraphs (b)(1) through (3) of this section.
(1) Each CPMS must complete a minimum of one cycle of operation for each successive 15-minute period.
(2) Each CPMS must have valid data for at least 95 percent of every averaging period.
(3) Each CPMS must determine and record the hourly average of all recorded readings.
(a) Except for monitoring malfunctions, associated repairs, and required quality assurance or control activities (including, as applicable, calibration checks and required zero and span adjustments), you must monitor continuously (or collect data at all required intervals) at all times an affected source is operating.
(b) You may not use data recorded during monitoring malfunctions, associated repairs, and required quality assurance or control activities in data averages and calculations used to report emission or operating levels or to fulfill a minimum data availability requirement, if applicable. You must use all the data collected during all other periods in assessing compliance.
(c) A monitoring malfunction is any sudden, infrequent, not reasonably preventable failure of the monitoring to provide valid data. Monitoring failures that are caused in part by poor maintenance or careless operation are not malfunctions.
(a) For each affected source subject to an emission limit in Table 1 to this subpart, you must demonstrate continuous compliance according to the requirements in Table 4 to this subpart.
(b) For each wet scrubber subject to the operating limits for pressure drop and scrubber water flow rate in § 63.9890(b), you must demonstrate continuous compliance according to the requirements in paragraphs (b)(1) and (2) of this section.
(1) Collecting and reducing the monitoring data according to § 63.9921(b); and
(2) Maintaining the hourly average pressure drop and scrubber water flow rate at or above the minimum level established during the initial or subsequent performance.
(c) You must demonstrate continuous compliance with the work practice standards in § 63.9891 by operating according to the requirements in your fugitive dust emissions control plan and recording information needed to document conformance with the requirements.
For each emission point subject to an emission limit in Table 1 to this subpart, you must demonstrate continuous compliance with the operation and maintenance requirements in § 63.9900 by performing preventive maintenance for each control device according to § 63.9900(b) and recording all information needed to document conformance with these requirements.
(a)
(b)
(2) The Administrator will determine whether deviations that occur during a period of startup, shutdown, or malfunction are violations, according to the provisions in § 63.6(e).
(a) You must submit all of the notifications in §§ 63.7(b) and (c), 63.8(f)(4), 63.9(b), and 63.9(h) that apply to you by the specified dates.
(b) As specified in § 63.9(b)(2), if you startup your affected source before October 10, 2003, you must submit your initial notification no later than February 9, 2004.
(c) As specified in § 63.9(b)(3), if you start your new affected source on or after October 10, 2003, you must submit your initial notification no later that 120 calendar days after you become subject to this subpart.
(d) If you are required to conduct a performance test, you must submit a notification of intent to conduct a performance test at least 60 calendar days before the performance test is scheduled to begin as required in § 63.7(b)(1).
(e) If you are required to conduct a performance test or other initial compliance demonstration, you must submit a notification of compliance status according to § 63.9(h)(2)(ii), and the requirements in paragraphs (e)(1) and (2) of this section:
(1) For each initial compliance demonstration that does not include a performance test, you must submit the notification of compliance status before the close of business on the 30th calendar day following completion of the initial compliance demonstration.
(2) For each initial compliance demonstration that does include a performance test, you must submit the notification of compliance status, including the performance test results, before the close of business on the 60th calendar day following the completion of the performance test according to § 63.10(d)(2).
(a)
(1) The first compliance report must cover the period beginning on the compliance date that is specified for your affected source in § 63.9883 and ending on June 30 or December 31, whichever date comes after the compliance date that is specified for your source in § 63.9883.
(2) The first compliance report must be postmarked or delivered no later than July 31 or January 31, whichever date comes first after your compliance report is due.
(3) Each subsequent compliance report must cover the semiannual reporting period from January 1 through June 30 or the semiannual reporting period from July 1 through December 31.
(4) Each subsequent compliance report must be postmarked or delivered no later than July 31 or January 31, whichever date comes first after the end of the semiannual reporting period.
(5) For each affected source that is subject to permitting regulations pursuant to 40 CFR part 70 or 40 CFR part 71, and if the permitting authority has established dates for submitting semiannual reports pursuant to 40 CFR 70.6(a)(3)(iii)(A) or 40 CFR 71.6(a)(3)(iii)(A), you may submit the first and subsequent compliance reports according to the dates the permitting authority has established instead of according to the dates in paragraphs (a)(1) through (4) of this section.
(b)
(1) Company name and address.
(2) Statement by a responsible official, with that official's name, title, and signature, certifying the truth, accuracy, and completeness of the content of the report.
(3) Date of report and beginning and ending dates of the reporting period.
(4) If you had a startup, shutdown, or malfunction during the reporting period and you took actions consistent with your startup, shutdown, and malfunction plan, the compliance report must include the information in § 63.10(d)(5)(i).
(5) If there were no deviations from the continuous compliance requirements in §§ 63.9923 and 63.9924 that apply to you, a statement that there were no deviations from the emission limitations, work practice standards, or operation and maintenance requirements during the reporting period.
(6) If there were no periods during which a CPMS was out-of-control as specified in § 63.8(c)(7), a statement that there were no periods during which the CPMS was out-of-control during the reporting period.
(7) For each deviation from an emission limitation in § 63.9890 that occurs at an affected source where you are not using a CPMS to comply with an emission limitation in this subpart, the compliance report must contain the information in paragraphs (b)(1) through (4) of this section and the information in paragraphs (b)(7)(i) and (ii) of this section. This includes periods of startup, shutdown, and malfunction.
(i) The total operating time of each affected source during the reporting period.
(ii) Information on the number, duration, and cause of deviations (including unknown cause, if applicable) as applicable and the corrective action taken.
(8) For each deviation from an emission limitation occurring at an affected source where you are using a CPMS to comply with the emission limitation in this subpart, you must include the information in paragraphs (b)(1) through (4) of this section and the information in paragraphs (b)(8)(i) through (xi) of this section. This includes periods of startup, shutdown, and malfunction.
(i) The date and time that each malfunction started and stopped.
(ii) The date and time that each continuous monitoring was inoperative, except for zero (low-level) and high-level checks.
(iii) The date, time, and duration that each continuous monitoring system was out-of-control, including the information in § 63.8(c)(8).
(iv) The date and time that each deviation started and stopped, and whether each deviation occurred during a period of startup, shutdown, or malfunction or during another period.
(v) A summary of the total duration of the deviation during the reporting period and the total duration as a percent of the total source operating time during that reporting period.
(vi) A breakdown of the total duration of the deviations during the reporting period including those that are due to startup, shutdown, control
(vii) A summary of the total duration of continuous monitoring system downtime during the reporting period and the total duration of continuous monitoring system downtime as a percent of the total source operating time during the reporting period.
(viii) A brief description of the process units.
(ix) A brief description of the continuous monitoring system.
(x) The date of the latest continuous monitoring system certification or audit.
(xi) A description of any changes in continuous monitoring systems, processes, or controls since the last reporting period.
(c)
(d)
(a) You must keep the records as indicated in paragraphs (a)(1) through (3) of this section:
(1) A copy of each notification and report that you submitted to comply with this subpart, including all documentation supporting any initial notification or notification of compliance status that you submitted, according to the requirements in § 63.10(b)(2)(xiv).
(2) The records in § 63.6(e)(3)(iii) through (v) related to startup, shutdown, and malfunction.
(3) Records of performance tests and performance evaluations as required in § 63.10(b)(2)(viii).
(b) You must keep the records required in §§ 63.9932 and 63.9933 to show continuous compliance with each emission limitation, work practice standard, and operating and maintenance requirement that applies to you.
(a) Your records must be in a form suitable and readily available for expeditious review, according to § 63.10(b)(1).
(b) As specified in § 63.10(b)(1), you must keep each record for 5 years following the date of each occurrence, measurement, maintenance, corrective action, report, or record.
(c) You must keep each record on site for at least 2 years after the date of each occurrence, measurement, maintenance, corrective action, report, or record according to § 63.10(b)(1). You can keep the records off site for the remaining 3 years.
(d) You must keep your fugitive dust emissions control plan and your operation and maintenance plan on-site according to the requirements in §§ 63.9891(d) and 63.9900(c).
Table 4 to this subpart shows which parts of the General Provisions in §§ 63.1 through 63.15 apply to you.
(a) This subpart can be implemented and enforced by us, the United States Environmental Protection Agency (U.S. EPA) or a delegated authority such as your State, local, or tribal agency. If the EPA Administrator has delegated authority to your State, local, or tribal agency, then that agency 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 under subpart E of this part, the authorities contained in paragraph (c) of this section are retained by the Administrator of the EPA and are not transferred to the State, local, or tribal agency.
(c) The authorities that will not be delegated to State, local, or tribal agencies are specified in paragraphs (c)(1) through (4) of this section.
(1) Approval of alternatives to the non-opacity emission limitations in § 63.9890 and work practice standards in § 63.9891 under § 63.6(g).
(2) Approval of major alternatives to test methods under § 63.7(e)(2)(ii) and (f) and as defined in § 63.90.
(3) Approval of major alternatives to monitoring under § 63.8(f) and as defined in § 63.90.
(4) Approval of major alternatives to recordkeeping and reporting under § 63.10(f) and as defined in § 63.90.
Terms used in this subpart are defined in the Clean Air Act, in § 63.2, and in this section as follows:
(1) Fails to meet any requirement or obligation established by this subpart, including but not limited to any emission limitation (including operating limits) or operation and maintenance requirement;
(2) Fails to meet any term or condition that is adopted to implement an applicable requirement in this subpart and that is included in the operating permit for any affected source required to obtain such a permit; or
(3) Fails to meet any emission limitation in this subpart during startup, shutdown, or malfunction, regardless of whether or not such failure is permitted by this subpart.
As required in § 63.9890(a), you must comply with each applicable emission limit in the following table:
As required in 63.9916, you must demonstrate initial compliance with the emission limits according to the following table:
As required in § 63.9923, you must demonstrate continuous compliance with the emission limits according to the following table:
As required in § 63.9950, you must comply with the requirements of the NESHAP General Provisions (40 CFR part 63, subpart A) shown in the following table:
1.1
1.1.1If 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. A list of validated methods may be obtained by contacting the Emission Measurement Technical Information Center (EMTIC), Mail Drop 19, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711, (919) 541-0200. Procedures for obtaining a waiver are in Section 12.0.
1.1.2This method includes optional procedures that may be used to expand the applicability of the proposed method. Section 7.0 involves ruggedness testing (Laboratory Evaluation), which demonstrates the sensitivity of the method to various parameters. Section 8.0 involves a procedure for including sample stability in bias and precision for assessing sample recovery and analysis times; Section 9.0 involves a procedure for the determination of the practical limit of quantitation for determining the lower limit of the method. These optional procedures are required for the waiver consideration outlined in Section 12.0.
1.2
1.2.1
1.2.2
2.1
2.2
2.3
2.4
2.5
2.6
The reference materials shall be obtained or prepared at the level of the standard. Additional runs with higher and lower reference material concentrations may be made to expand the applicable range of the method, in accordance with the ruggedness test procedures.
3.1
3.2
3.3
3.4
4.1To assess the method bias independently, the analyst shall use (in addition to the reference material) an EPA performance audit material, if it is available. The analyst may contact EMTIC (see section 1.1.1) to receive a list of currently available EPA audit materials. If the analyte is listed, the analyst should request the audit material at least 30 days before the validation test. If an EPA audit material is not available, request documentation from the validation report reviewing authority that the audit material is currently not available from EPA. Include this documentation with the field validation report.
4.2The analyst shall sample and analyze the performance audit sample three times according to the instructions provided with
The analyst shall select one of the sampling approaches below to determine the bias and precision of the data. After analyzing the samples, the analyst shall calculate the bias and precision according to the procedure described in section 6.0. When sampling a stationary source, follow the probe placement procedures in section 5.4.
5.1
5.1.1
5.1.2
5.1.2.1
5.1.2.1.1
5.1.2.1.2
5.1.2.1.3
5.1.2.1.4
5.1.2.2
5.2
5.2.1
5.2.2
5.3
5.3.1
5.3.2In each quadruplet set, spike half of the samples (two out of the four) with the reference material according to the applicable procedure in section 5.1.2.1 or 5.1.2.2.
5.4
Data resulting from the procedures specified in section 5.0 shall be treated as follows to determine bias, correction factors, relative standard deviations, precision, and data acceptance.
6.1
6.1.1Calculate 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:
6.1.2Calculate the standard deviation of the S
6.1.3.Calculate the standard deviation of the mean (SDM) as follows:
6.1.4 Test the bias for statistical significance by calculating the t-statistic,
6.1.5
6.1.6
6.2
6.2.1
6.2.1.1.
6.2.1.2Calculate the variance of the proposed method, S
6.2.1.3
Compare the experimental F value with the critical value of F. The critical value is 1.0 when the procedure specified in section 5.2.1 for paired trains is followed. If the calculated F is greater than the critical value, the difference in precision is significant and the data and proposed method are unacceptable.
6.2.1.4
Calculate the value of the t-statistic using the following equation:
6.2.1.5
Multiply all analytical results by CF to obtain the final values. The method results, and the method, are unacceptable if the correction factor is outside the range of 0.9 to 1.10.
6.2.2
6.2.2.1
6.2.2.2Calculate the variance of the proposed method, S
6.2.2.3
6.2.2.4
Calculate the t-statistic using Equation 301-9 where n is the total number of test sample differences (d
6.2.2.5
6.3
6.3.1
6.3.1.1
Calculate the relative standard deviation of the proposed spiked method using Equation 301-6 where S
6.3.1.2
6.3.2
6.3.2.1Calculate the standard deviation of the mean using the following equation where SD
6.3.2.2Test the bias for statistical significance by calculating the t-statistic using Equation 301-4 and comparing it with the critical value of the two-sided t-distribution at the 95-percent confidence level and n-1 degrees of freedom. This critical value is 2.201 for the eleven degrees of freedom.
6.3.3
7.1
7.1.1Ruggedness testing is a useful and cost-effective laboratory study to determine the sensitivity of a method to certain parameters such as sample collection rate, interferant concentration, collecting medium temperature, or sample recovery temperature. This Section generally discusses the principle of the ruggedness test. A more detailed description is presented in citation 10 of Section 13.0.
7.1.2In a ruggedness test, several variables are changed simultaneously rather than one variable at a time. This reduces the number of experiments required to evaluate the effect of a variable. For example, the effect of seven variables can be determined in eight experiments rather than 128 (W.J. Youden, Statistical Manual of the Association of Official Analytical Chemists, Association of Official Analytical Chemists, Washington, DC, 1975, pp. 33-36).
7.1.3Data from ruggedness tests are helpful in extending the applicability of a test method to different source concentrations or source categories.
8.1
8.1.1The test method being evaluated must include procedures for sample storage and the time within which the collected samples shall be analyzed.
8.1.2This section identifies the procedures for including the effect of storage time
8.2
8.2.1Stack Emission Testing.
8.2.1.1For sample container (bag or canister) and impinger sampling systems, sections 5.1 and 5.3, analyze six of the samples at the minimum storage time. Then analyze the same six samples at the maximum storage time.
8.2.1.2For sorbent and impinger sampling systems, sections 5.1 and 5.3, that require extraction or digestion, extract or digest six of the samples at the minimum storage time and extract or digest six other samples at the maximum storage time. Analyze an aliquot of the first six extracts (digestates) at both the minimum and maximum storage times. This will provide some freedom to analyze extract storage impacts.
8.2.1.3For sorbent sampling systems, sections 5.1 and 5.3, that require thermal desorption, analyze six samples at the minimum storage time. Analyze another set of six samples at the maximum storage time.
8.2.1.4For systems set up in accordance with section 5.2, the number of samples analyzed at the minimum and maximum storage times shall be half those collected (8 or 9). The procedures for samples requiring extraction or digestion should parallel those in section 8.2.1.
8.2.2
9.1
9.1.1The practical limit of quantitation (PLQ) is the lowest level above which quantitative results may be obtained with an acceptable degree of confidence. For this protocol, the PLQ is defined as 10 times the standard deviation, s
9.1.2The PLQ will be used to establish the lower limit of the test method.
9.2
9.2.1Estimate the PLQ and prepare a test standard at this level. The test standard could consist of a dilution of the reference material described in section 3.0.
9.2.2Using the normal sampling and analytical procedures for the method, sample and analyze this standard at least seven times in the laboratory.
9.2.3Calculate the standard deviation, s
9.2.4Calculate the PLQ as 10 times s
9.3
9.3.1Prepare two additional standards at concentration levels lower than the standard used in Procedure I.
9.3.2Sample and analyze each of these standards at least seven times.
9.3.3Calculate the standard deviation for each concentration level.
9.3.4Plot the standard deviations of the three test standards as a function of the standard concentrations.
9.3.5Draw a best-fit straight line through the data points and extrapolate to zero concentration. The standard deviation at zero concentration is S
9.3.6Calculate the PLQ as 10 times S
The field validation report shall include a discussion of the regulatory objectives for the testing which describe the reasons for the test, applicable emission limits, and a description of the source. In addition, validation results shall include:
10.1Summary of the results and calculations shown in section 6.0.
10.2Reference material certification and value(s).
10.3Performance audit results or letter from the reviewing authority stating the audit material is currently not available.
10.4Laboratory demonstration of the quality of the spiking system.
10.5Discussion of laboratory evaluations.
10.6Discussion of field sampling.
10.7Discussion of sample preparations and analysis.
10.8Storage times of samples (and extracts, if applicable).
10.9Reasons for eliminating any results.
The correction factor calculated in section 6.0 shall be used to adjust the sample concentrations in all followup tests conducted at the same source. These tests shall consist of at least three replicate samples, and the average shall be used to determine the pollutant concentration. The number of samples to be collected and analyzed shall be as follows, depending on the validated method precision level:
11.1Validated relative standard deviation (RSD) ≤ ±15 Percent. Three replicate samples.
11.2Validated RSD ≤ ±30 Percent. Six replicate samples.
11.3Validated RSD ≤ ±50 Percent. Nine replicate samples.
11.4Equivalent method. Three replicate samples.
12.1
12.1.1
12.1.2“
12.1.3“
12.2
12.2.1A clearly written test method, preferably in the format of 40 CFR part 60, appendix A Test Methods. The method must include an applicability statement, concentration range, precision, bias (accuracy), and time in which samples must be analyzed.
12.2.2.2Summaries (see section 10.0) of previous validation tests or other supporting documents. If a different procedure from that described in this method was used, the requester shall provide appropriate documents substantiating (to the satisfaction of the Administrator) the bias and precision values.
12.2.2.3Results of testing conducted with respect to sections 7.0, 8.0, and 9.0.
12.2.3Discussion of the applicability statement and arguments for approval of the waiver. This discussion should address as applicable the following: Applicable regulation, emission standards, effluent characteristics, and process operations.
12.3
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.
2. 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.
3. 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.
4. Maxwell, E.A. 1974. Estimating variances from one or two measurements on each sample. Amer. Statistician 28:96-97.
5. Midgett, M.R. 1977. How EPA Validates NSPS Methodology. Environ. Sci. & Technol. 11(7):655-659.
6. Mitchell, W.J., and M.R. Midgett. 1976. Means to evaluate performance of stationary source test methods. Environ. Sci. & Technol. 10:85-88.
7. Plackett, R.L., and J.P. Burman. 1946. The design of optimum multifactorial experiments. Biometrika, 33:305.
8. Taylor, J.K. 1987. Quality Assurance of Chemical Measurements. Lewis Publishers, Inc., pp. 79-81.
9. 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.
10. 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-
11. 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.
12. Youdon, W.J. Statistical techniques for collaborative tests. In: Statistical Manual of the Association of Official Analytical Chemists, Association of Official Analytical Chemists, Washington, DC, 1975, pp. 33-36.
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.
1.1Applicability. 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.
2.1A 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.
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12
3.13
3.14
3.15
3.16
3.17
3.18
3.19
3.20
3.21
3.22
5.1Disclaimer. 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.
5.2Safety 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.
Observer certification and training requirements are as follows:
10.1Certification 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.
10.1.1The 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.
10.1.2The 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.
10.1.3All 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 (
10.2Observer 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.
10.3The 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.
10.4An 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.
11.1Procedure for Determining VE from Charging Systems During Charging.
11.1.1Number 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).
11.1.2Data 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.
11.1.3Observer 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.
11.1.4Observation. 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.
11.1.4.1Using 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.
11.1.4.2When 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.
11.1.5Visual Interference. If fugitive VE from other sources at the coke oven battery site (
11.1.6VE Exemptions. Do not time the following VE:
11.1.6.1The VE from burning or smoldering coal spilled on top of the oven, topside port lid, or larry car surfaces;
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.
11.1.6.2The VE from the coke oven doors or from the leveler bar; or
11.1.6.3The VE that drift from the top of a larry car hopper if the emissions had already been timed as VE from the drop sleeve.
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.
11.1.7Total Time Record. Record the total time that VE were observed for each charging operation in the appropriate column on the charging system inspection sheet.
11.1.8Determination 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.
11.1.9Log 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.
11.2.1Number of Runs. Refer to § 63.309(c)(1) of this part for the appropriate number of runs.
11.2.2Battery 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.
11.2.2.1Include 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.
11.2.2.2Various 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.
11.2.2.3When 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.
11.2.3Observations. 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 (
11.2.3.1Begin 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.
11.2.3.2During 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 (
Multiple VE from the same door area (
11.2.3.3Do not record the following sources as door area VE:
11.2.3.3.1VE from ovens with doors removed. Record the oven number and make an appropriate notation under “Comments;”
11.2.3.3.2VE 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
11.2.3.3.3VE from hot coke that has been spilled on the bench as a result of pushing.
11.2.4Criteria 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.
11.2.5Percent 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.
11.3Procedure for Determining VE from Topside Port Lids and Offtake Systems.
11.3.1Number 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.
11.3.2Battery 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.
11.3.3Topside 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 (
11.3.3.1To 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.
Count the number of topside ports, not the number of points, exhibiting VE,
11.3.3.2Do not count the following as topside port lid VE:
11.3.3.2.1VE from between the brickwork and oven lid casing or VE from cracks in the oven brickwork. Note these VE under “Comments;”
11.3.3.2.2VE from topside ports involved in a charging operation. Record the oven number, and make an appropriate notation (
11.3.3.2.3Topside ports having maintenance work done. Record the oven number and make an appropriate notation under “Comments;” or
11.3.3.2.4Condensing water from wet-sealing material. Ports with only visible condensing water from wet-sealing material are counted as observed but not as having VE.
11.3.3.2.5Visible emissions from the flue inspection ports and caps.
11.3.4Offtake 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 (
11.3.4.1Do 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.
11.3.4.2If the centerline does not provide a clear view of the entire offtake system for each oven (
11.3.4.3Upon 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.
11.3.4.4If 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.
11.3.4.5Do 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 (
VE from open standpipes of an oven being charged count as charging emissions. All VE from closed standpipe caps count as offtake leaks.
11.3.5Criteria 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.
11.3.6In 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:
11.3.6.1Empty ovens, including ovens undergoing maintenance, which are properly dampered off from the main.
11.3.6.2Ovens being charged or being pushed.
11.3.6.3Up to 3 full ovens that have been dampered off from the main prior to pushing.
11.3.6.4Up 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.
11.3.7Percent 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.
11.4Procedure for Determining VE from Collecting Mains.
11.4.1Traverse. 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.
11.4.2Data 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.
11.4.3Collecting 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
12.1Nomenclature.
12.2Criteria 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:
12.3Criteria 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:
12.4Average 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.
12.5Percent Leaking Doors (PLD). Determine the total number of doors for which observations were made on the coke oven battery as follows:
12.5.1For 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.
12.5.2Calculate percent leaking doors by using Equation 303-5:
12.5.3When 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:
12.5.3.1Use Equation 303-7 to calculate PLD:
12.5.3.2Average 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.
12.6Topside Port Lids. Determine the percent leaking topside port lids for each run as follows:
12.6.1Round off this percentage to the nearest hundredth of 1 percent and record this percentage as the percent leaking topside port lids for the run.
12.6.2Average 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.
12.7Offtake Systems. Determine the percent leaking offtake systems for the run as follows:
12.7.1Round off this percentage to the nearest hundredth of 1 percent and record this percentage as the percent leaking offtake systems for the run.
12.7.2Average 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.
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.
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.
1.1Applicability. This method is applicable for the determination of visible emissions (VE) from leaking doors at nonrecovery coke oven batteries.
2.1A 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.
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
5.1Disclaimer. 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.
5.2Safety 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.
10.1Training. 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.
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.
11.1Number of Runs. Refer to § 63.309(c)(1) of this part for the appropriate number of runs.
11.2Battery 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.
11.2.1Various 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).
Extra time incurred for handling obstructions is not counted in the traverse time.
11.2.2When 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.
11.3Observations. 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,
11.3.1Begin the test run by traversing either the coke side or the push side of the battery. After completing one side, traverse the other side.
11.3.2During 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).
11.3.3Do not record the following sources as door area VE:
11.3.3.1VE from ovens with doors removed. Record the oven number and make an appropriate notation under “Comments”;
11.3.3.2VE from ovens where maintenance work is being conducted. Record the oven number and make an appropriate notation under “Comments”; or
11.3.3.3VE from hot coke that has been spilled on the bench as a result of pushing.
Same as Method 303, Section 12.1, 12.2, 12.3, 12.4, and 12.5.
Same as Method 303, Section 16.0.
1.1Applicability. 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.
2.1A 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
5.1If 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.
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.
6.1Benchtop 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).
6.2Aeration 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 (
6.3Wastewater Feed. Supply the wastewater feed to the benchtop bioreactor in a collapsible low-density polyethylene container or collapsible liner in a container (
6.3.1Refrigeration 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.
6.3.2Wastewater 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.
6.3.3Treated wastewater feed. The benchtop bioreactor effluent exits at the bottom of the reactor through a tube and proceeds to the clarifier.
6.4Clarifier. The effluent flows to a separate closed clarifier that allows separation of biomass and effluent (
6.5Temperature 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.
6.5.1Temperature Monitoring Device. A resistance type temperature probe or a thermocouple connected to a temperature readout with a resolution of 0.1 °C or better.
6.5.2Benchtop Bioreactor Heater. The heater is connected to the temperature control device.
6.6Oxygen 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.
6.6.1Dissolved Oxygen Monitor. Dissolved oxygen is monitored with a polarographic probe (gas permeable membrane) connected to a dissolved oxygen meter (
6.6.2Benchtop 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.
6.7Connecting 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.
Mention of trade names or products does not constitute endorsement by the U.S. Environmental Protection Agency.
7.1Wastewater. 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.
7.2Biomass. 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 (
8.1Benchtop 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
8.1.1Wastewater 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.
8.1.2Wastewater Flow Rate.
8.1.2.1The 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.
8.1.2.2The 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.
8.1.3Sludge 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.
8.1.4Benchtop 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 Methods
8.1.5Inspection 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.
8.2Test 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
8.2.1Frequency 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 (
8.2.2Sampling 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.
9.1Dissolved 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.
9.2Sludge Wasting.
9.2.1Determine 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:
9.2.2Remove 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.
9.3Sludge 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:
10.1Wastewater 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.
10.2Calibration 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.
11.1Analysis. 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.
11.1.1After 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.
12.1Nomenclature. The following symbols are used in the calculations.
12.2Residence 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):
12.3Rate of Biodegradation. Calculate the rate of biodegradation for each component with the following equation:
12.4First-Order Biorate Constant. Calculate the first-order biorate constant (K1) for each component with the following equation:
12.5Relative Standard Deviation (RSD). Determine the standard deviation of both the influent and effluent sample concentrations (S) using the following equation:
12.6Determination 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 (F
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.
1.1Applicability. 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
2.1A 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.
5.1If 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.
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.
6.1Benchtop 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).
6.2Aeration 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 (
6.3Wastewater Feed. Supply the wastewater feed to the benchtop bioreactor in a collapsible low-density polyethylene container or collapsible liner in a container (
6.3.1Refrigeration System. Keep the wastewater feed cool by ice or by refrigeration to 4 °C. If using a bleed stream from the
6.3.2Wastewater 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.
6.3.3Treated wastewater feed. The benchtop bioreactor effluent exits at the bottom of the reactor through a tube and proceeds to the clarifier.
6.4Clarifier. The effluent flows to a separate closed clarifier that allows separation of biomass and effluent (
6.5Temperature 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.
6.5.1Temperature Monitoring Device. A resistance type temperature probe or a thermocouple connected to a temperature readout with a resolution of 0.1 °C or better.
6.5.2Benchtop Bioreactor Heater. The heater is connected to the temperature control device.
6.6Oxygen 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.
6.6.1Dissolved Oxygen Monitor. Dissolved oxygen is monitored with a polarographic probe (gas permeable membrane) connected to a dissolved oxygen meter (
6.6.2Benchtop 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.
6.7Connecting 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.
Mention of trade names or products does not constitute endorsement by the U.S. Environmental Protection Agency.
7.1Wastewater. 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.
7.2Biomass. 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 (
8.1Benchtop 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.
8.1.1Wastewater 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.
8.1.2Wastewater Flow Rate.
8.1.2.1The 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.
8.1.2.2The 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 (
8.1.3Sludge 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.
8.1.4Benchtop 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 Methods
8.1.5Inspection 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.
8.2Test 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.
8.2.1Frequency 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 (
8.2.2Sampling 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.
9.1Dissolved 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 (
9.2Sludge Wasting.
9.2.1Determine 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:
9.2.2Remove 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
9.3Sludge 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:
10.1Wastewater 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.
10.2Calibration 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.
11.1Analysis. 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.
11.1.1After 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.
12.1Nomenclature. The following symbols are used in the calculations.
12.2Residence 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)
12.3Rate of Biodegradation. Calculate the rate of biodegradation for each component with the following equation:
12.4First-Order Biorate Constant. Calculate the first-order biorate constant (K1) for each component with the following equation:
12.5Relative Standard Deviation (RSD). Determine the standard deviation of both the influent and effluent sample concentrations (S) using the following equation:
12.6Determination 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 (F
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.
This method does not include all of the specifications (
1.1Analyte. Volatile Organics. No CAS No. assigned.
1.2Applicability. This procedure is used to determine the emission potential of individual volatile organics (VOs) in waste.
1.3Data Quality Objectives. Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.
2.1The 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 (
5.1Disclaimer. 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.
6.1Method 25D Purge Apparatus.
6.1.1Purge 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.
6.1.2Flow 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.
6.1.3Coalescing 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.
6.1.4Oven. A forced convection airflow oven capable of maintaining the purge chamber and coalescing filter at 75 ±2 °C (167 ±3.6 °F).
6.1.5Toggle 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.
6.1.6Flow Controller. High-quality stainless steel flow controller capable of restricting a flow of nitrogen to 6 ±0.06 L/min (0.2 ±0.002 ft
6.1.7Polyethylene Glycol Cleaning System.
6.1.7.1Round-Bottom Flask. One liter, three-neck glass round-bottom flask for cleaning PEG. Standard taper 24/40 joints are mounted on each neck.
6.1.7.2Heating Mantle. Capable of heating contents of the 1-L flask to 120 °C (248 °F).
6.1.7.3Nitrogen Bubbler. Teflon
6.1.7.4Temperature Sensor. Partial immersion glass thermometer.
6.1.7.5Hose Adapter. Glass with 24/40 standard tapered joint.
6.2Volatile Organic Recovery System.
6.2.1Splitter Valve (Optional). Stainless steel cross-pattern valve capable of splitting nominal flow rates from the purge flow of 6 L/min (0.2 ft
The splitter valve design is optional; it may be used in cases where the concentration of a pollutant would saturate the adsorbents.
6.2.2Injection Port. Stainless steel 1/4 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.
6.2.3Knockout 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.
6.2.4Insulated Ice Bath. A 350 mL dewar or other type of insulated bath is used to
6.2.5Sorbent 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.
6.2.6Volumetric Glassware. Type A glass 10 mL volumetric flasks for measuring a final volume from the water catch in the knockout trap.
6.2.7Thermal 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.
6.2.8Ultrasonic 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.
6.2.9Desorption Vials. Four-dram (15 mL) capacity borosilicate glass vials with Teflon-lined caps.
6.3Analytical 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.
6.3.1Gas 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.
6.3.2GC 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 (
6.3.3Data System. A programmable electronic integrator for recording, analyzing, and storing the signal generated by the detector.
7.1Method 25D Purge Apparatus.
7.1.1Polyethylene 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 ft
7.1.2Water. Organic-free deionized water is required.
7.1.3Nitrogen. 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.
7.2Volatile Organic Recovery System.
7.2.1Water. Organic-free deionized water is required.
7.2.2Desorption 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.
7.3Analytical System. The gases required for GC operation shall be of the highest obtainable purity (hydrocarbon free). Consult the operating manual for recommended settings.
8.1Assemble 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.
8.2Recovery 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
8.3Sample Collection and Recovery.
8.3.1The 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.
8.3.2Allow 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.
8.3.3Stop 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.
9.1Miscellaneous Quality Control Measures.
10.1The 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.
10.2The 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-
11.1Water 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.
11.2Sample 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.
11.2.1Recover 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).
11.2.2Analyze 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).
11.2.3Repeat 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).
12.1Nomenclature.
12.2Recovery efficiency for determining trapping/desorption efficiency of individual test compounds in the spike solution, decimal value.
12.3Weight of waste sample (g).
12.4Response factor for individual test compounds.
12.5Corrected weight of a test compound in the sample, in µg.
12.6Final concentration of a test compound in the sample in ppmw.
12.7Relative standard deviation (RSD) calculation.
This method does not include all of the specifications (
1.1Analytes.
1.2Applicability. 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.
1.3Data Quality Objectives. [Reserved]
2.1Sampling. 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 (NaHCO
2.2Analysis.
2.2.1Total chromium samples with high chromium concentrations (≥35 µg/L) may be analyzed using inductively coupled plasma emission spectrometry (ICP) at 267.72 nm.
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.
2.2.2Alternatively, 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.
2.2.3If it is desirable to determine hexavalent chromium (Cr
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12
3.13
3.14
4.1ICP Interferences.
4.1.1ICP 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.
4.1.2ICP 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 (
4.1.3ICP 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.
4.2GFAAS Interferences.
4.2.1GFAAS 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.
4.2.2GFAAS Cyanide Band Interferences. Nitrogen should not be used as the purge gas due to cyanide band interference.
4.2.3GFAAS Spectral Interferences. Background correction may be required because of possible significant levels of nonspecific absorption and scattering at the 357.9 nm analytical wavelength.
4.2.4GFAAS Background Interferences. Zeeman or Smith-Hieftje background correction is recommended for interferences resulting from high levels of dissolved solids in the alkaline impinger solutions.
4.3IC/PCR Interferences.
4.3.1IC/PCR Chemical Interferences. Components in the sample matrix may cause Cr
4.3.2IC/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.
5.1Disclaimer. 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.
5.2Hexavalent chromium compounds have been listed as carcinogens although chromium (III) compounds show little or no toxicity. Chromium can be a skin and respiratory irritant.
6.1Sampling Train.
6.1.1A 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.
6.1.2Probe 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.
6.1.3Use 0.1 N NaOH or 0.1 N NaHCO
6.1.4Operating 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.
6.1.5Similar collection systems which have been approved by the Administrator may be used.
6.2Sample Recovery. Same as Method 5, [40 CFR Part 60, Appendix A], with the following exceptions:
6.2.1Probe-Liner and Probe-Nozzle Brushes. Brushes are not necessary for sample recovery. If a probe brush is used, it must be non-metallic.
6.2.2Sample Recovery Solution. Use 0.1 N NaOH or 0.1 N NaHCO
6.2.3Sample Storage Containers. Polyethylene, with leak-free screw cap, 250 mL, 500 mL or 1,000 mL.
6.3Analysis.
6.3.1General. For analysis, the following equipment is needed.
6.3.1.1Phillips Beakers. (Phillips beakers are preferred, but regular beakers may also be used.)
6.3.1.2Hot Plate.
6.3.1.3Volumetric Flasks. Class A, various sizes as appropriate.
6.3.1.4Assorted Pipettes.
6.3.2Analysis by ICP.
6.3.2.1ICP Spectrometer. Computer-controlled emission spectrometer with background correction and radio frequency generator.
6.3.2.2Argon Gas Supply. Welding grade or better.
6.3.3Analysis by GFAAS.
6.3.3.1Chromium Hollow Cathode Lamp or Electrodeless Discharge Lamp.
6.3.3.2Graphite Furnace Atomic Absorption Spectrophotometer.
6.3.3.3Furnace Autosampler.
6.3.4Analysis by IC/PCR.
6.3.4.1IC/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.
6.3.4.2Analytical 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.
6.3.4.3Preconcentration 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.
6.3.4.4Filtration Apparatus for IC/PCR.
6.3.4.4.1Teflon, or equivalent, filter holder to accommodate 0.45-µm acetate, or equivalent, filter, if needed to remove insoluble particulate matter.
6.3.4.4.20.45-µm Filter Cartridge. For the removal of insoluble material. To be used just prior to sample injection/analysis.
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
7.1Sampling.
7.1.1Water. 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.
7.1.2Sodium 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.
7.1.3Sodium Bicarbonate (NaHCO
7.1.4Chromium Contamination.
7.1.4.1The absorbing solution shall not exceed the QC criteria noted in Section 7.1.1 (≤ 3 times the instrument detection limit).
7.1.4.2When the Cr
At sources with high concentrations of acids and/or SO
7.1.5Silica Gel. Same as in Method 5.
7.2Sample Recovery.
7.2.10.1 N NaOH or 0.1 N NaHCO
7.2.2pH 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.
7.3Sample Preparation and Analysis.
7.3.1Nitric Acid (HNO
7.3.2HNO
7.3.3Calcium Nitrate Ca(NO
7.3.4Matrix Modifier, for GFAAS. See instrument manufacturer's manual for suggested matrix modifier.
7.3.5Chromatographic Eluent, for IC/PCR. The eluent used in the analytical system is ammonium sulfate based.
7.3.5.1Prepare by adding 6.5 mL of 29 percent ammonium hydroxide (NH
7.3.5.2Other 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.
7.3.6Post-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.
7.3.7Chromium Standard Stock Solution (1000 mg/L). Procure a certified aqueous standard or dissolve 2.829 g of potassium dichromate (K
7.3.8Calibration 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
7.3.9Calibration Standards for GFAAS. Chromium solutions for GFAAS calibration shall contain 1.0 percent (v/v) HNO
7.4Glassware Cleaning Reagents.
7.4.1HNO
7.4.2Water. Reagent water that conforms to ASTM Specification D1193-77 or 91 Type II.
7.4.3HNO
7.5Quality Assurance Audit Samples.
7.5.1When making compliance determinations, and upon availability, audit samples shall be obtained from the appropriate EPA regional Office or from the responsible enforcement authority and analyzed in conjunction with the field samples.
7.5.2If EPA or National Institute of Standards and Technology (NIST) reference audit sample are not available, a mid-range standard, prepared from an independent commercial source, may be used.
To order audit samples, contact the responsible enforcement authority at least 30 days prior to the test date to allow sufficient time for the audit sample to be delivered.
Prior to sample collection, consideration should be given to the type of analysis (Cr
8.1Sample Collection. Same as Method 5 (40 CFR part 60, Appendix A), with the following exceptions.
8.1.1Omit 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 NaHCO
8.1.2Clean 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) HNO
8.1.3Train Operation. Follow the basic procedures outlined in Method 5 in conjunction with the following instructions. Train sampling rate shall not exceed 0.030 m
8.2Sample Recovery. Follow the basic procedures of Method 5, with the exceptions noted.
8.2.1A particulate filter is not recovered from this train.
8.2.2Tester shall select either the total Cr or Cr
8.2.3Samples to be analyzed for both total Cr and Cr
8.2.4A field reagent blank shall be collected for either of the Cr or the Cr
Since particulate matter is not usually present at chromium electroplating and/or chromium anodizing operations, it is not necessary to filter the Cr
8.2.5Total Cr Sample Option.
8.2.5.1Container No. 1. Measure the volume of the liquid in the first, second, and third impingers and quantitatively transfer into a labeled sample container.
8.2.5.2Use approximately 200 to 300 mL of the 0.1 N NaOH or 0.1 N NaHCO
8.2.6Cr
8.2.6.1Container No. 1. Measure and record the pH of the absorbing solution contained in the
8.2.6.2After 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.
8.2.7Field Reagent Blank.
8.2.7.1Container No. 2.
8.2.7.2Place approximately 500 mL of the 0.1 N NaOH or 0.1 N NaHCO
8.3Sample Preservation, Storage, and Transport.
8.3.1Total Cr Sample Option. Samples to be analyzed for total Cr need not be refrigerated.
8.3.2Cr
8.4Sample Holding Times.
8.4.1Total Cr Sample Option. Samples to be analyzed for total Cr shall be analyzed within 60 days of collection.
8.4.2Cr
9.1ICP Quality Control.
9.1.1ICP 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.
9.1.1.1This reference standard must be prepared from a different Cr stock solution source than that used for preparation of the calibration curve standards.
9.1.1.2Prior to sample analysis, analyze at least one reference standard.
9.1.1.3The calibration reference standard must be measured within 10 percent of it's true value for the curve to be considered valid.
9.1.1.4The curve must be validated before sample analyses are performed.
9.1.2ICP Continuing Check Standard.
9.1.2.1Perform 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).
9.1.2.2The 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.
9.1.3ICP Calibration Blank.
9.1.3.1Perform 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).
9.1.3.2The 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.
9.1.4ICP 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.
9.1.4.1Two 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 HNO
9.1.4.2Verify 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.
9.1.4.3Negative 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.
9.1.5ICP Duplicate Sample Analysis. Perform one duplicate sample analysis for each compliance sample batch (3 runs).
9.1.5.1As 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.
9.1.5.2Duplicate sample analyses shall agree within 10 percent of the original measurement value.
9.1.5.3Report 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.
9.1.6ICP 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.
9.1.6.1Spiked sample recovery analyses should indicate a recovery for the Cr spike of between 75 and 125 percent.
9.1.6.2Cr 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.
9.1.6.3If 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.
9.1.6.4If 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.
9.1.7ICP Field Reagent Blank.
9.1.7.1Analyze 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.
9.1.7.2If contamination or memory effects are observed, perform corrective action to identify and correct the problem before reanalyzing the samples.
9.1.8Audit Sample Analysis.
9.1.8.1When the method is used to analyze samples to demonstrate compliance with a source emission regulation, an audit sample must be analyzed, subject to availability.
9.1.8.2Concurrently analyze the audit sample and the compliance samples in the same manner to evaluate the technique of the analyst and the standards preparation.
9.1.8.3The same analyst, analytical reagents, and analytical system shall be used for the compliance samples and the audit sample. If this condition is met, duplicate auditing of subsequent compliance analyses for the same enforcement agency within a 30-day period is waived. An audit sample set may not be used to validate different sets of compliance samples under the jurisdiction of separate enforcement agencies, unless prior arrangements have been made with both enforcement agencies.
9.1.9Audit Sample Results.
9.1.9.1Calculate the audit sample concentrations and submit results using the instructions provided with the audit samples.
9.1.9.2Report the results of the audit samples and the compliance determination samples along with their identification numbers, and the analyst's name to the responsible enforcement authority. Include this information with reports of any subsequent compliance analyses for the same enforcement authority during the 30-day period.
9.1.9.3The concentrations of the audit samples obtained by the analyst shall agree within the values specified by the compliance auditor. If the specified range is not met, reanalyze the compliance and audit samples, and include initial and reanalysis values in the test report.
9.1.9.4Failure to meet the specified range may require retests unless the audit problems are resolved. However, if the audit results do not affect the compliance or noncompliance status of the affected facility, the Administrator may waive the reanalysis requirement, further audits, or retests and accept the results of the compliance test. While steps are being taken to resolve audit analysis problems, the Administrator may also choose to use the data to determine the compliance or noncompliance status of the affected facility.
9.2GFAAS Quality Control.
9.2.1GFAAS 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.
9.2.1.1The calibration curve must be validated before sample analyses are performed.
9.2.1.2The calibration reference standard must be measured within 10 percent of its true value for the curve to be considered valid.
9.2.2GFAAS Continuing Check Standard.
9.2.2.1Perform 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).
9.2.2.2These 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.
9.2.2.3The check standard may be either the mid-range calibration standard or the reference standard.
9.2.2.4The results of the check standard shall agree within 10 percent of the expected value.
9.2.2.5If not, terminate the analyses, correct the problem, recalibrate the instrument, and reanalyze all samples analyzed subsequent to the last acceptable check standard analysis.
9.2.3GFAAS Calibration Blank.
9.2.3.1Perform 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).
9.2.3.2The 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.
9.2.3.3The results of the calibration blank shall agree within three standard deviations of the mean blank value.
9.2.3.4If 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.
9.2.4GFAAS Duplicate Sample Analysis. Perform one duplicate sample analysis for each compliance sample batch (3 runs).
9.2.4.1A 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.
9.2.4.2Duplicate sample analyses results incorporating duplicate digestions shall agree within 20 percent for sample results exceeding ten (10) times the detection limit.
9.2.4.3Report the original analysis value for the sample and report the duplicate analysis value as the QC check value.
9.2.4.4If 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.
9.2.5GFAAS Matrix Spiking.
9.2.5.1Spiked 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.
9.2.5.2Cr spikes are added prior to any sample preparation.
9.2.5.3Cr 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.
9.2.5.4Spiked sample recovery analyses should indicate a recovery for the Cr spike of between 75 and 125 percent.
9.2.5.5If 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.
9.2.6GFAAS Method of Standard Additions.
9.2.6.1Method of Standard Additions. Perform procedures in Section 5.4 of Method 12 (40 CFR Part 60, Appendix A)
9.2.6.2Whenever 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.
9.2.7GFAAS Field Reagent Blank.
9.2.7.1Analyze 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.
9.2.8Audit Sample Analysis.
9.2.8.1When the method is used to analyze samples to demonstrate compliance with a source emission regulation, an audit sample must be analyzed, subject to availability.
9.2.8.2Concurrently analyze the audit sample and the compliance samples in the same manner to evaluate the technique of the analyst and the standards preparation.
9.2.8.3The same analyst, analytical reagents, and analytical system shall be used for the compliance samples and the audit sample. If this condition is met, duplicate auditing of subsequent compliance analyses for the same enforcement agency within a 30-day period is waived. An audit sample set may not be used to validate different sets of compliance samples under the jurisdiction of separate enforcement agencies, unless prior arrangements have been made with both enforcement agencies.
9.2.9Audit Sample Results.
9.2.9.1Calculate the audit sample concentrations and submit results using the instructions provided with the audit samples.
9.2.9.2Report the results of the audit samples and the compliance determination samples along with their identification numbers, and the analyst's name to the responsible enforcement authority. Include this information with reports of any subsequent compliance analyses for the same enforcement authority during the 30-day period.
9.2.9.3The concentrations of the audit samples obtained by the analyst shall agree within the values specified by the compliance auditor. If the specified range is not met, reanalyze the compliance and audit samples, and include initial and reanalysis values in the test report.
9.2.9.4Failure to meet the specified range may require retests unless the audit problems are resolved. However, if the audit results do not affect the compliance or noncompliance status of the affected facility, the Administrator may waive the reanalysis requirement, further audits, or retests and accept the results of the compliance test. While steps are being taken to resolve audit analysis problems, the Administrator may also choose to use the data to determine the compliance or noncompliance status of the affected facility.
9.3IC/PCR Quality Control.
9.3.1IC/PCR Calibration Reference Standards.
9.3.1.1Prepare 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
9.3.1.2The 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.
9.3.1.3The 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.
9.3.2IC/PCR Continuing Check Standard and Calibration Blank.
9.3.2.1Perform 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).
9.3.2.2The result from the check standard must be within 10 percent of the expected value.
9.3.2.3If 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.
9.3.2.4The results of the calibration blank analyses must agree within three standard deviations of the mean blank value.
9.3.2.5If not, analyze the calibration blank two more times and average the results.
9.3.2.6If 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.
9.3.3IC/PCR Duplicate Sample Analysis.
9.3.3.1Perform one duplicate sample analysis for each compliance sample batch (3 runs).
9.3.3.2An 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).
9.3.3.3Duplicate sample injection results shall agree within 10 percent for sample results exceeding ten (10) times the detection limit.
9.3.3.4Report the original analysis value for the sample and report the duplicate analysis value as the QC check value.
9.3.3.5If agreement is not achieved, perform the duplicate analysis again.
9.3.3.6If 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.
9.3.4ICP/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.
9.3.4.1Spiked sample recovery analysis should indicate a recovery of the Cr
9.3.4.2The 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.
9.3.4.3If the recoveries for the Cr
9.3.5IC/PCR Field Reagent Blank.
9.3.5.1Analyze 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.
9.3.5.2If contamination or memory effects are observed, perform corrective action to identify and correct the problem before reanalyzing the samples.
9.3.6Audit Sample Analysis.
9.3.6.1When the method is used to analyze samples to demonstrate compliance with source emission regulation, an audit sample must be analyzed, subject to availability.
9.3.6.2Concurrently analyze the audit sample and the compliance samples in the same manner to evaluate the technique of the analyst and the standards preparation.
9.3.6.3The same analyst, analytical reagents, and analytical system shall be used for the compliance samples and the audit sample. If this condition is met, duplicate auditing of subsequent compliance analyses for the same enforcement agency within a 30-day period is waived. An audit sample set may not be used to validate different sets of compliance samples under the jurisdiction of separate enforcement agencies, unless prior arrangements have been made with both enforcement agencies.
9.3.7Audit Sample Results.
9.3.7.1Calculate the audit sample concentrations and submit results using the instructions provided with the audit samples.
9.3.7.2Report the results of the audit samples and the compliance determination samples along with their identification numbers, and the analyst's name to the responsible enforcement authority. Include this information with reports of any subsequent compliance analyses for the same enforcement authority during the 30-day period.
9.3.7.3The concentrations of the audit samples obtained by the analyst shall agree within the values specified by the compliance auditor. If the specified range is not met, reanalyze the compliance and audit samples, and include initial and reanalysis values in the test report.
9.3.7.4Failure to meet the specified range may require retests unless the audit problems are resolved. However, if the audit results do not affect the compliance or noncompliance status of the affected facility, the Administrator may waive the reanalysis requirement, further audits, or retests and accept the results of the compliance test. While steps are being taken to resolve audit analysis problems, the Administrator may also choose to use the data to determine the compliance or noncompliance status of the affected facility.
10.1Sampling 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.
10.2ICP Calibration.
10.2.1Calibrate the instrument according to the instrument manufacturer's recommended procedures, using a calibration blank and three standards for the initial calibration.
10.2.2Calibration 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.
10.2.3Use the average intensity of multiple exposures (3 or more) for both standardization and sample analysis to reduce random error.
10.2.4Employing linear regression, calculate the correlation coefficient .
10.2.5The correlation coefficient must equal or exceed 0.995.
10.2.6If linearity is not acceptable, prepare and rerun another set of calibration standards or reduce the range of the calibration standards, as necessary.
10.3GFAAS Calibration.
10.3.1For instruments that measure directly in concentration, set the instrument software to display the correct concentration, if applicable.
10.3.2Curve 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.
10.3.3The 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.
10.3.4The calibration curve acceptance criteria must equal or exceed 0.995.
10.3.5If linearity is not acceptable, prepare and rerun another set of calibration standards or reduce the range of calibration standards, as necessary.
10.4IC/PCR Calibration.
10.4.1Prepare a calibration curve using the calibration blank and three calibration standards prepared fresh daily as described in Section 7.3.8.
10.4.2The calibration curve acceptance criteria must equal or exceed 0.995.
10.4.3If linearity is not acceptable, remake and/or rerun the calibration standards. If the calibration curve is still unacceptable, reduce the range of the curve.
10.4.4Analyze the standards with the field samples as described in Section 11.6.
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.
11.1ICP Sample Preparation.
11.1.1The ICP analysis is performed directly on the alkaline impinger solution; acid digestion is not necessary, provided the samples and standards are matrix matched.
11.1.2The 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.
11.2ICP Sample Analysis.
11.2.1The ICP analysis is applicable for the determination of total chromium only.
11.2.2ICP Blanks. Two types of blanks are required for the ICP analysis.
11.2.2.1Calibration 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 NaHCO
11.2.2.2Field 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.
11.2.3ICP Instrument Adjustment.
11.2.3.1Adjust the ICP instrument for proper operating parameters including wavelength, background correction settings (if necessary), and interfering element correction settings (if necessary).
11.2.3.2The instrument must be allowed to become thermally stable before beginning measurements (usually requiring at least 30
11.2.4ICP Instrument Calibration.
11.2.4.1Calibrate the instrument according to the instrument manufacturer's recommended procedures, and the procedures specified in Section 10.2.
11.2.4.2Prior to analyzing the field samples, reanalyze the highest calibration standard as if it were a sample.
11.2.4.3Concentration 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).
11.2.4.4If they do, follow the recommendations of the instrument manufacturer to correct the problem.
11.2.5ICP Operational Quality Control Procedures.
11.2.5.1Flush the system with the calibration blank solution for at least 1 min before the analysis of each sample or standard.
11.2.5.2Analyze the continuing check standard and the calibration blank after each batch of 10 samples.
11.2.5.3Use the average intensity of multiple exposures for both standardization and sample analysis to reduce random error.
11.2.6ICP Sample Dilution.
11.2.6.1Dilute 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.
11.2.6.2When dilutions are performed, the appropriate factors must be applied to sample measurement results.
11.2.7Reporting Analytical Results. All analytical results should be reported in µg Cr/mL using three significant figures. Field sample volumes (mL) must be reported also.
11.3GFAAS Sample Preparation.
11.3.1GFAAS Acid Digestion. An acid digestion of the alkaline impinger solution is required for the GFAAS analysis.
11.3.1.1In a beaker, add 10 mL of concentrated HNO
11.3.1.2The final concentration of HNO
11.3.1.3Transfer the digested sample to a 50-mL volumetric flask. Add 0.5 mL of concentrated HNO
11.3.2HNO
11.4GFAAS Sample Analysis.
11.4.1The GFAAS analysis is applicable for the determination of total chromium only.
11.4.2GFAAS Blanks. Two types of blanks are required for the GFAAS analysis.
11.4.2.1Calibration Blank. The 1.0 percent HNO
11.4.2.2Field Reagent Blank. An aliquot of the 0.1 N NaOH solution or the 0.1 N NaHCO
11.4.2.2.1The reagent blank must be subjected to the entire series of sample preparation and analytical procedures, including the acid digestion.
11.4.2.2.2The reagent blank's final solution must contain the same acid concentration as the sample solutions.
11.4.3GFAAS Instrument Adjustment.
11.4.3.1The 357.9 nm wavelength line shall be used.
11.4.3.2Follow the manufacturer's instructions for all other spectrophotometer operating parameters.
11.4.4Furnace Operational Parameters. Parameters suggested by the manufacturer should be employed as guidelines.
11.4.4.1Temperature-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.
11.4.4.2Similar 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.
11.4.5GFAAS Operational Quality Control Procedures.
11.4.5.1Introduce a measured aliquot of digested sample into the furnace and atomize.
11.4.5.2If the measured concentration exceeds the calibration range, the sample should be diluted with the calibration blank solution (1.0 percent HNO
11.4.5.3Consult the operator's manual for suggested injection volumes. The use of multiple injections can improve accuracy and assist in detecting furnace pipetting errors.
11.4.5.4Analyze a minimum of one matrix-matched reagent blank per sample batch
11.4.5.5Analyze a calibration blank and a continuing check standard after approximately every batch of 10 sample injections.
11.4.6GFAAS Sample Dilution.
11.4.6.1Dilute and reanalyze samples that are more concentrated than the instrument calibration range.
11.4.6.2If dilutions are performed, the appropriate factors must be applied to sample measurement results.
11.4.7Reporting Analytical Results.
11.4.7.1Calculate 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.
11.4.7.2Analytical results should be reported in µg Cr/mL using three significant figures. Field sample volumes (mL) must be reported also.
11.5IC/PCR Sample Preparation.
11.5.1Sample pH. Measure and record the sample pH prior to analysis.
11.5.2Sample 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.
11.5.2.1Use a portion of the sample to rinse the syringe filtration unit and acetate filter and then collect the required volume of filtrate.
11.5.2.2Retain the filter if total Cr is to be determined also.
11.5.3Sample Preconcentration (older instruments).
11.5.3.1For older instruments, a preconcentration system may be used in conjunction with the IC/PCR to increase sensitivity for trace levels of Cr
11.5.3.2The preconcentration is accomplished by selectively retaining the analyte on a solid absorbent, followed by removal of the analyte from the absorbent (consult instrument manual).
11.5.3.3For a manual system, position the injection valve so that the eluent displaces the concentrated Cr
11.6IC/PCR Sample Analyses.
11.6.1The IC/PCR analysis is applicable for hexavalent chromium measurements only.
11.6.2IC/PCR Blanks. Two types of blanks are required for the IC/PCR analysis.
11.6.2.1Calibration 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 NaHCO
11.6.2.2Field Reagent Blank. An aliquot of the 0.1 N NaOH solution or the 0.1 N NaHCO
11.6.3Stabilized 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.
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
11.6.4Sample Injection Loop. Size of injection loop is based on standard/sample concentrations and the selected attenuator setting.
11.6.4.1A 50-µL loop is normally sufficient for most higher concentrations.
11.6.4.2The 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.
11.6.5IC/PCR Instrument Calibration.
11.6.5.1First, 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.
11.6.5.2Check the performance of the instrument and verify the calibration using data gathered from analyses of laboratory blanks, calibration standards, and a quality control sample.
11.6.5.3Verify 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.
11.6.6IC/PCR Instrument Operation.
11.6.6.1Inject 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.
11.6.6.1.1Standards (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
11.6.6.1.2After separation from other sample components, the Cr
11.6.6.1.3The amount of absorbance measured is proportional to the concentration of the Cr
11.6.6.1.4The IC retention time and the absorbance of the Cr
11.6.6.1.5If a sample peak appears near the expected retention time of the Cr
11.6.7IC/PCR Operational Quality Control Procedures.
11.6.7.1Samples should be at a pH ≥8.5 for NaOH and ≥8.0 if using NaHCO
11.6.7.2Refrigerated samples should be allowed to equilibrate to ambient temperature prior to preparation and analysis.
11.6.7.3Repeat the injection of the calibration standards at the end of the analytical run to assess instrument drift. Measure areas or heights of the Cr
11.6.7.4To 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.
11.6.7.5If the 10 percent criteria duplicate injection cannot be achieved, identify the source of the problem and rerun the calibration standards.
11.6.7.6Use 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.
11.6.8IC/PCR Sample Dilution.
11.6.8.1Samples having concentrations higher than the established calibration range must be diluted into the calibration range and re-analyzed.
11.6.8.2If dilutions are performed, the appropriate factors must be applied to sample measurement results.
11.6.9Reporting Analytical Results. Results should be reported in µg Cr
12.1Pretest Calculations.
12.1.1Pretest Protocol (Site Test Plan).
12.1.1.1The 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.
12.1.1.1.1Estimated source concentration for total chromium and/or Cr
12.1.1.1.2Estimated 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
12.1.1.1.3Demonstrate 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.
12.1.1.2The pre-test protocol should include information on equipment, logistics, personnel, process operation, and other resources necessary for an efficient and coordinated test.
12.1.1.3At 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.
12.1.2Post Test Calculations.
12.1.2.1Perform the calculations, retaining one extra decimal figure beyond that of the acquired data. Round off figures after final calculations.
12.1.2.2Nomenclature.
12.1.2.3Dilution 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:
12.1.2.4Digestion 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.
12.1.2.5Total Cr in Sample. Calculate MCr, the total µg Cr in each sample, using the following equation:
12.1.2.6Average Dry Gas Meter Temperature and Average Orifice Pressure Drop. Same as Method 5.
12.1.2.7Dry Gas Volume, Volume of Water Vapor, Moisture Content. Same as Method 5.
12.1.2.8Cr Emission Concentration (C
12.1.2.9Isokinetic Variation, Acceptable Results. Same as Method 5.
13.1Range. 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.
13.2Sensitivity.
13.2.1Analytical 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.
13.2.1.2ICP 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.
13.2.1.3GFAAS 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.
13.2.1.4IC/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
1.3.2.1.5Determination of Detection Limits. The laboratory performing the Cr
13.2.2In-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 1/2 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
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
13.3Precision.
13.3.1The 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.
13.3.2Bias data is also reported for GFAAS.
13.4ICP Precision.
13.4.1As 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.
13.4.2In 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.
13.5GFAAS 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.
13.6IC/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
14.1The 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.
14.2Cleaning solutions containing acids should be prepared in volumes consistent with use to minimize the disposal of excessive volumes of acid.
14.3To the extent possible, the containers/vessels used to collect and prepare samples should be cleaned and reused to minimize the generation of solid waste.
15.1It 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.
15.2For 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.
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
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.
6. Walpole, R.E., and R.H. Myers. “Probability and Statistics for Scientists and Engineering.” 3rd Edition. MacMillan Publishing Co., NewYork, N.Y., 1985.
This method does not include all of the specifications (
1.1Analyte. Chromium. CAS Number (7440-47-3).
1.2Applicability.
1.2.1This 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.
1.2.2The method is also applicable to electroplating and anodizing sources controlled by wet scrubbers.
1.3Data Quality Objectives.
1.3.1Pretest Protocol.
1.3.1.1The 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.
1.3.1.1.1Estimated source concentration for total chromium and/or Cr
1.3.1.1.2Estimated 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
1.3.1.1.3Demonstrate 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.
1.3.1.2The pre-test protocol should include information on equipment, logistics, personnel, process operation, and other resources necessary for an efficient and coordinated performance test.
1.3.1.3At 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.
2.1Sampling.
2.1.1An 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.
2.1.2The 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).
2.1.2.1Total chromium samples with high chromium concentrations (≥35 µg/L) may be analyzed using inductively coupled plasma emission spectrometry (ICP) at 267.72 nm.
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.
2.1.2.2Alternatively, 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.
2.1.2.3If it is desirable to determine hexavalent chromium (Cr
3.1
3.2
3.3
3.4
3.5
3.6
4.1Same as in Method 306, Section 4.0.
5.1Disclaimer. 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.
5.2Chromium 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.
Mention of trade names or specific products does not constitute endorsement by the Environmental Protection Agency.
6.1Sampling 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.
6.1.1Probe Nozzle/Tubing and Sheath.
6.1.1.1Use approximately 6.4-mm (
6.1.1.2Use 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).
6.1.3Temperature Sensor.
6.1.3.1A 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.
6.1.3.2The 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.
6.1.4Sample Train Connectors.
6.1.4.1Use thick wall flexible plastic tubing (polyethylene, polypropylene, or polyvinyl chloride) ∼ 6.4-mm (
6.1.4.2A 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.
6.1.5Impingers. 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.
6.1.5.1One-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.
6.1.5.2Canning 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 (
6.1.5.2.1When assembling the first container, place the orifice tip end of the tube approximately 4.8 mm (
6.1.5.2.2For 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.
6.1.5.2.3The inlet tube of the third container should extend to approximately 12.7 mm (
6.1.5.2.4Extend the outlet tube for each container approximately 50 mm (2 in.) above the jar lid and downward through the lid, approximately 12.7 mm (
6.1.5.3Greenburg-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 (
6.1.5.4Greenburg-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.
6.1.6Manometer. Inclined/vertical type, or equivalent device, as described in Section 6.2 of Method 2 (40 CFR Part 60, Appendix A).
6.1.7Critical 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 (m
6.1.7.1The critical orifice can be constructed by sealing a 2.4-mm (
6.1.7.2Materials 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.
6.1.8Connecting Hardware. Standard pipe and fittings, 9.5-mm (
6.1.9Vacuum Gauge. Capable of measuring approximately 760 mm H
6.1.10Pump 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.
6.1.11Vacuum Pump. Gast Model 0522-V103-G18DX, or equivalent, capable of delivering at least 1.5 cfm at 15 in. H
6.1.12Oil 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.
6.1.13By-pass Fine Adjust Valve (Optional). Needle valve assembly 6.4-mm (
6.1.13.1A 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.
6.1.13.1.1The tester must conduct the post test leak check at a vacuum equal to or greater than the maximum vacuum encountered during the sampling run.
6.1.13.1.2The 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.
6.1.14Dry 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.
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
6.2Barometer. Mercury aneroid barometer, or other barometer equivalent, capable of measuring atmospheric pressure to within ±2.5 mm H
6.2.1A preliminary check of the barometer shall be made against a mercury-in-glass reference barometer or its equivalent.
6.2.2Tester may elect to obtain the absolute barometric pressure from a nearby National Weather Service station.
6.2.2.1The 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 H
6.2.2.2If the field barometer cannot be adjusted to agree within 0.1 in. H
6.3Sample Recovery. Same as Method 5, Section 6.2 (40 CFR Part 60, Appendix A), with the following exceptions:
6.3.1Probe-Liner and Probe-Nozzle Brushes. Brushes are not necessary for sample recovery. If a probe brush is used, it must be non-metallic.
6.3.2Wash Bottles. Polyethylene wash bottle, for sample recovery absorbing solution.
6.3.3Sample Recovery Solution. Use 0.1 N NaOH or 0.1 N NaHCO
6.3.4Sample Storage Containers.
6.3.4.1Glass 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.
6.3.4.2Polyethylene 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.
6.3.5pH Indicator Strip, for Cr
6.3.6Plastic Storage Containers. Air tight containers to store silica gel.
6.4Analysis. Same as Method 306, Section 6.3.
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
7.1Sampling.
7.1.1Water. 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.
7.1.2Sodium 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.
7.1.3Sodium Bicarbonate (NaHCO
7.1.4Chromium Contamination.
7.1.4.1The absorbing solution shall not exceed the QC criteria noted in Method 306, Section 7.1.1 (≤3 times the instrument detection limit).
7.1.4.2When the Cr
At sources with high concentrations of acids and/or SO
7.1.3Desiccant. Silica Gel, 6-16 mesh, indicating type. Alternatively, other types of desiccants may be used, subject to the approval of the Administrator.
7.2Sample Recovery. Same as Method 306, Section 7.2.
7.3Sample Preparation and Analysis. Same as Method 306, Section 7.3.
7.4Glassware Cleaning Reagents. Same as Method 306, Section 7.4.
7.5Quality Assurance Audit Samples.
7.5.1It is recommended, but not required, that a performance audit sample be analyzed in conjunction with the field samples. The audit sample should be in a suitable sample matrix at a concentration similar to the actual field samples.
7.5.2When making compliance determinations, and upon availability, audit samples may be obtained from the appropriate EPA regional Office or from the responsible enforcement authority and analyzed in conjunction with the field samples.
The responsible enforcement authority should be notified at least 30 days prior to the test date to allow sufficient time for the audit sample to be delivered.
Prior to sample collection, consideration should be given as to the type of analysis (Cr
8.1Sample Collection.
8.1.1Pretest Preparation.
8.1.1.1Selection of Measurement Site. Locate the sampling ports as specified in Section 11.0 of Method 1 (40 CFR Part 60, Appendix A).
8.1.1.2Location of Traverse Points.
8.1.1.2.1Locate 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.
8.1.1.2.2For round ducts less than 12 inches in diameter, use a total of 16 points.
8.1.1.3Velocity Pressure Traverse. Perform an initial velocity traverse before obtaining samples. The Figure 306A-2 data sheet may be used to record velocity traverse data.
8.1.1.3.1To 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.
8.1.1.3.2Perform 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.
8.1.1.4Verification 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).
8.1.1.4.1If 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.
8.1.1.4.2Alternative procedures, subject to approval of the Administrator,
8.1.1.5Stack Gas Moisture Measurements.
8.1.1.5.1The tester may elect to either measure the actual stack gas moisture during the sampling run or utilize a nominal moisture value of 2 percent.
8.1.1.5.2For additional information on determining sampling train moisture, please refer to Method 4 (40 CFR Part 60, Appendix A).
8.1.1.6Stack 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,
8.1.1.7Point 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.
8.1.1.7.1If the sampling period (3 runs) is to be completed in a single day, the point sampling times shall be calculated only once.
8.1.1.7.2If 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).
8.1.1.7.3If 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:
Convert the decimal fractions for minutes to seconds.
8.1.1.8Pretest 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.
8.1.1.8.1Sample 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.
8.1.1.8.2At 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 (NaHCO
8.1.1.8.3If separate sample shipping containers are to be used, these also should be precleaned using the specified cleaning procedures.
8.1.1.9Preparation 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.
8.1.1.9.1Place 250 mL of 0.1 N NaOH or 0.1 N NaHCO
8.1.1.9.2Place 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.
8.1.1.10Pretest 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.
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.
8.1.1.11Leak-Checks During Sample Run. If, during the sampling run, a component (e.g., jar container) exchange becomes necessary, a leak-check shall be conducted
8.1.1.12Post 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.
8.1.1.12.1If the leak rate does not exceed 0.02 cfm, the results are acceptable and no sample volume correction is necessary.
8.1.1.12.2If, 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.
8.1.2Sample Train Operation.
8.1.2.1Data 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.
8.1.2.2Starting 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.
8.1.2.3Critical 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.
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.
8.1.2.4Completion of Test.
8.1.2.4.1Circular 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.
8.1.2.4.2Rectangle Stacks. Complete each port traverse as per the instructions provided in 8.1.2.4.1.
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.
8.2Sample 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
Collect a reagent blank sample for each of the total Cr or the Cr
8.2.1Total Cr Sample Option.
8.2.1.1Shipping 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.
8.2.1.1.1Unscrew the lid from the first jar/impinger container.
8.2.1.1.2Lift 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.
8.2.1.2Recover the contents of the second jar/impinger container by removing the lid and pouring any contents into the first shipping container.
8.2.1.2.1Rinse twice, using fresh absorbing solution, the inner walls of the second container including the inside and outside of the inner tube.
8.2.1.2.2Rinse the connecting tubing between the first and second sample containers with absorbing solution and place the rinses into the first container.
8.2.1.3Position the nozzle, probe and connecting plastic tubing in a vertical position so that the tubing forms a “U”.
8.2.1.3.1Using 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
8.2.1.3.2Repeat 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.
8.2.1.4Use approximately 200 to 300 mL of the 0.1 N NaOH or 0.1 N NaHCO
8.2.1.5Place 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.
8.2.1.5.1Label the jar clearly to identify its contents, sample number and date.
8.2.1.5.2Mark the height of the liquid level on the container to identify any losses during shipping and handling.
8.2.1.5.3Prepare a chain-of-custody sheet to accompany the sample to the laboratory.
8.2.2Cr
8.2.2.1Shipping 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.
8.2.2.1.1Unscrew and remove the lid from the first jar container.
8.2.2.1.2Measure 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 NaHCO
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.
Since particulate matter is not usually present at chromium electroplating and/or chromium anodizing facilities, it is not necessary to filter the Cr
8.2.3Silica 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.
8.2.4Total Cr and/or Cr
8.2.4.1Shipping Container No. 2. Place approximately 500 mL of the 0.1 N NaOH or 0.1 N NaHCO
8.3Sample Preservation, Storage, and Transport.
8.3.1Total Cr Option. Samples that are to be analyzed for total Cr need not be refrigerated.
8.3.2Cr
Allow Cr
8.4Sample Holding Times.
8.4.1Total Cr Option. Samples that are to be analyzed for total chromium must be analyzed within 60 days of collection.
8.4.2Cr
9.1Same as Method 306, Section 9.0.
Tester shall maintain a performance log of all calibration results.
10.1Pitot Tube. The Type S pitot tube assembly shall be calibrated according to the procedures outlined in Section 10.1 of Method 2.
10.2Temperature Sensor. Use the procedure in Section 10.3 of Method 2 to calibrate the in-stack temperature sensor.
10.3Metering System.
10.3.1Sample 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.
10.3.2Dry Gas Meter Calibration Coefficient (Y
10.3.3Calibration 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 Y
10.3.4Y
10.3.4.1The Y
10.3.4.2If 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.
10.3.4.3Perform 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 V
10.3.5Y
10.3.6Y
10.3.6.1If this ratio is between 0.95 and 1.05, the designated Y
10.3.6.1.1If 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 Y
10.3.6.1.2If the post test dry gas meter Y
10.3.6.1.3The 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.
10.3.6.1.4The calibration of the dry gas meter must be verified after each field test program using the same procedures.
The tester may elect to use the Y
10.4Barometer. Calibrate against a mercury barometer that has been corrected for temperature and elevation.
10.5ICP Spectrometer Calibration. Same as Method 306, Section 10.2.
10.6GFAA Spectrometer Calibration. Same as Method 306, Section 10.3.
10.7IC/PCR Calibration. Same as Method 306, Section 10.4.
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.
11.1Analysis. Refer to Method 306 for sample preparation and analysis procedures.
12.1Calculations. 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.
12.2Nomenclature.
12.3Dilution 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:
12.4Digestion 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.
12.5Total Cr in Sample. Calculate M
12.6Dry 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:
12.7Cr Emission Concentration (C
To convert µg/dscm (µg/dscf) to mg/dscm (mg/dscf), divide by 1000.
12.8Stack Gas Velocity.
12.8.2Average Stack Gas Velocity.
12.9Cross sectional area of stack.
12.10Average Stack Gas Dry Volumetric Flow Rate.
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:
To convert Q
12.11Mass emission rate, mg/hr (lb/hr):
13.1Range. 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.
13.2Sensitivity.
13.2.1Analytical Sensitivity. The estimated instrumental detection limits listed are provided as a guide for an instrumental limit. The actual method detection limits
13.2.1.1ICP 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.
13.2.1.2GFAAS 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.
13.2.1.3IC/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
13.2.2In-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
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
13.3Precision.
13.3.1The 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.
13.3.2Bias data is also reported for GFAAS.
13.4ICP Precision.
13.4.1As 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.
13.4.2In 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.
13.5GFAAS 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.
13.6IC/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
14.1The 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.
14.2Cleaning solutions containing acids should be prepared in volumes consistent with use to minimize the disposal of excessive volumes of acid.
14.3To the extent possible, the containers/vessels used to collect and prepare samples should be cleaned and reused to minimize the generation of solid waste.
15.1It 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.
15.2For 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.
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.
This method does not include all of the specifications (
1.1Analyte. Not applicable.
1.2Applicability. This method is applicable to all decorative chromium plating 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.
2.1During 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.
2.2This method determines the surface tension of the bath using a stalagmometer or
5.1Disclaimer. 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.
6.1Stalagmometer. 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.
6.2Tensiometer. 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.
11.1Procedure. The surface tension of the tank bath may be measured by using a tensiometer, a stalagmometer or any other equivalent surface tension measuring device approved by the Administrator for measuring surface tension in dynes per centimeter. If the tensiometer is used, the procedures specified in ASTM Method D 1331-89 must be followed. If a stalagmometer or other device is used to measure surface tension, the instructions provided with the measuring device must be followed.
11.2Frequency of Measurements.
11.2.1Measurements 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.
11.2.1.1Initially, 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.
11.2.1.2Once there are no exceedances during a period of 40 hours of tank operation, measurements may be conducted once every 8 hours of tank operation.
11.2.1.3Once 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.
11.2.2If a measurement of the surface tension of the solution is above the 45 dynes per centimeter limit, 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.
12.1Log Book of Surface Tension Measurements and Fume Suppressant Additions.
12.1.1The surface tension of the plating or anodizing tank bath must be measured as specified in Section 11.2.
12.1.2The 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.
12.1.3The log book will be readily available for inspection by regulatory personnel.
12.2Instructions for Apparatus Used in Measuring Surface Tension.
12.2.1Included 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.
12.2.2If a tensiometer is used, a copy of ASTM Method D 1331-89 must be included with the log book.
1.1Applicability. This method is applicable to the determination of the halogenated solvent emissions from solvent vapor cleaners in the idling mode.
1.2Principle. 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.
Mention of trade names or specific products does not constitute endorsement by the Environmental Protection Agency.
2.1Inclined 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.
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.
2.2Horizontal Indicator. Device to check the inclined liquid level indicators orientation relative to horizontal.
2.3Velocity 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.
3.1Connection 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.
3.2Positioning of Velocity Meter. Position the velocity meter so that it measures the flow rate of the air passing directly across the solvent cleaning machine.
3.3Level the Inclined Liquid Level Indicators.
3.4Initial 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
3.5Final 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.
3.6Determination 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.
4.1Nomenclature.
4.2Area of Sump Interfaces. Calculate the areas of the boiling and immersion sump interfaces as follows:
4.3Area of Solvent/Air Interface. Calculate the area of the solvent vapor/air interface as follows:
4.4Emission Rate. Calculate the emission rate as follows:
1.1Analyte. Methanol. Chemical Abstract Service (CAS) No. 67-56-1.
1.2Applicability. This method applies to the measurement of methanol emissions from specified stationary sources.
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.
5.1Disclaimer. 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.
5.2Methanol Characteristics. Methanol is flammable and a dangerous fire and explosion risk. It is moderately toxic by ingestion and inhalation.
6.1Sample Collection. The following items are required for sample collection:
6.1.1Sampling Train. The sampling train is shown in Figure 308-1 and component parts are discussed below.
6.1.1.1Probe. Teflon
6.1.1.2Impinger. 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.
6.1.1.3Adsorbent Tube. Glass tubes packed with the required amount of the specified adsorbent.
6.1.1.4Valve. Needle valve, to regulate sample gas flow rate.
6.1.1.5Pump. 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.
6.1.1.6Rate 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.
6.1.1.7Volume 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).
6.1.1.8Barometer. 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.
6.1.1.9Vacuum 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.
6.2Sample Recovery. The following items are required for sample recovery:
6.2.1Wash Bottles. Polyethylene or glass, 500-ml, two.
6.2.2Sample Vials. Glass, 40-ml, with Teflon
6.2.3Graduated Cylinder. 100-ml size.
6.3Analysis. The following are required for analysis:
6.3.1Gas Chromatograph. GC with an FID, programmable temperature control, and heated liquid injection port.
6.3.2Pump. Capable of pumping 100 ml/min. For flushing sample loop.
6.3.3Flow Meter. To monitor accurately sample loop flow rate of 100 ml/min.
6.3.4Regulators. Two-stage regulators used on gas cylinders for GC and for cylinder standards.
6.3.5Recorder. To record, integrate, and store chromatograms.
6.3.6Syringes. 1.0- and 10-microliter (l) size, calibrated, for injecting samples.
6.3.7Tubing Fittings. Stainless steel, to plumb GC and gas cylinders.
6.3.8Vials. Two 5.0-ml glass vials with screw caps fitted with Teflon
6.3.9Pipettes. Volumetric type, assorted sizes for preparing calibration standards.
6.3.10Volumetric Flasks. Assorted sizes for preparing calibration standards.
6.3.11Vials. Glass 40-ml with Teflon
Unless otherwise indicated, all reagents must conform to the specifications
7.1Sampling. The following are required for sampling:
7.1.1Water. 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 (KMnO
7.1.2Silica 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.
7.2Analysis. The following are required for analysis:
7.2.1Water. Same as specified in section 7.1.1.
7.2.2n-Propanol, 3 Percent. Mix 3 ml of n-propanol with 97 ml of water.
7.2.3Methanol 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.
7.2.3.1Methanol 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.
7.2.3.2Methanol 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
7.2.3.3Methanol 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
7.2.4GC 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.
7.2.5Helium. Ultra high purity.
7.2.6Hydrogen. Zero grade.
7.2.7Oxygen. Zero grade.
8.1Sampling. The following items are required for sampling:
8.1.1Preparation 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.
8.1.2Leak 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.
Carefully release the probe inlet plug before turning off the pump.
8.1.3Sample Collection. Record the initial DGM reading and barometric pressure. To begin sampling, position the tip of the Teflon
8.2Sample Recovery. The following items are required for sample recovery:
8.2.1Impinger. 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
8.2.2.Adsorbent Tubes. Seal the silica gel adsorbent tubes and place them in an ice chest for shipment to the laboratory.
9.1Miscellaneous Quality Control Measures. The following quality control measures are required:
9.2Applicability. When the method is used to analyze samples to demonstrate compliance with a source emission regulation, an audit sample must be analyzed, subject to availability.
9.3Audit Procedure. Analyze an audit sample with each set of compliance samples. Concurrently analyze the audit sample and a set of compliance samples in the same manner to evaluate the technique of the analyst and the standards preparation. The same analyst, analytical reagents, and analytical system shall be used both for the compliance samples and the EPA audit sample.
9.4Audit Sample Availability. Audit samples will be supplied only to enforcement agencies for compliance tests. Audit samples may be obtained by writing: Source Test Audit Coordinator (MD-77B), Air Measurement Research Division, National Exposure Research Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, NC 27711; or by calling the Source Test Audit Coordinator (STAC) at (919) 541-7834. The audit sample request must be made at least 30 days prior to the scheduled compliance sample analysis.
9.5Audit Results. Calculate the audit sample concentration according to the calculation procedure provided in the audit instructions included with the audit sample. Fill in the audit sample concentration and the analyst's name on the audit response form included with the audit instructions. Send one copy to the EPA Regional Office or the appropriate enforcement agency and a second copy to the STAC. The EPA Regional office or the appropriate enforcement agency will report the results of the audit to the laboratory being audited. Include this response with the results of the compliance samples in relevant reports to the EPA Regional Office or the appropriate enforcement agency.
10.1Metering System. The following items are required for the metering system:
10.1.1Initial Calibration.
10.1.1.1Before 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.
10.1.1.2Next, 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.
10.1.2Posttest 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.
10.1.3Temperature Sensors. Calibrate against mercury-in-glass thermometers.
10.1.4Rotameter. The rotameter need not be calibrated, but should be cleaned and maintained according to the manufacturer's instruction.
10.1.5Barometer. Calibrate against a mercury barometer.
10.2Gas Chromatograph. The following procedures are required for the gas chromatograph:
10.2.1Initial 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.
10.2.2Continuing 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.
11.1Gas Chromatograph Operating Conditions. The following operating conditions are required for the GC:
11.1.1Injector. Configured for capillary column, splitless, 200 °C (392 °F).
11.1.2Carrier. Helium at 10 ml/min.
11.1.3Oven. Initially at 45 °C for 3 minutes; then raise by 10 °C to 70 °C; then raise by 70 °C/min to 200 °C.
11.2Impinger 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.
11.3Silica Gel Adsorbent Sample. The following items are required for the silica gel adsorbent samples:
11.3.1Preparation 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.
11.3.2Desorption 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.
11.3.3Inject 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.
12.1Nomenclature.
12.2Mass of Methanol. Calculate the total mass of methanol collected in the sampling train using Equation 308-1.
12.3Dry Sample Gas Volume, Corrected to Standard Conditions. Calculate the volume of gas sampled at standard conditions using Equation 308-2.
12.4Mass Emission Rate of Methanol. Calculate the mass emission rate of methanol using Equation 308-3.
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.
4. Yu, K.K. “Evaluation of Moisture Effect on Dry Gas Meter Calibration.” Source Evaluation Society Newsletter.
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.
1.1This method is used to analyze any crumb rubber or water samples for residual hexane content.
1.2The sample is heated in a sealed bottle with an internal standard and the vapor is analyzed by gas chromatography.
2.1This method, utilizing a capillary column gas chromatograph with a flame ionization detector, determines the concentration of residual hexane in rubber crumb samples.
3.1The definitions are included in the text as needed.
4.1There are no known interferences.
5.1It is the responsibility of the user of this procedure to establish safety and health practices applicable to their specific operation.
6.1Gas Chromatograph with a flame ionization detector and data handling station equipped with a capillary column 30 meters long.
6.2Chromatograph conditions for Sigma 1:
6.2.1Helium pressure: 50# inlet A, 14# aux
6.2.2Carrier flow: 25 cc/min
6.2.3Range switch: 100x
6.2.4DB: 1 capillary column
6.3Chromatograph conditions for Hewlett-Packard GC:
6.3.1Initial temperature: 40 °C
6.3.2Initial time: 8 min
6.3.3Rate: 0
6.3.4Range: 2
6.3.5DB: 1705 capillary column
6.4Septum bottles and stoppers
6.5Gas Syringe—0.5 cc
7.1Chloroform, 99.9+%, A.S.C. HPLC grade
8.1A representative sample should be caught in a clean 8 oz. container with a secure lid.
8.2The container should be labeled with sample identification, date and time.
9.1The instrument is calibrated by injecting calibration solution (Section 10.2 of this method) five times.
9.2The retention time for components of interest and relative response of monomer to the internal standard is determined.
9.3Recovery efficiency must be determined once for each sample type and whenever modifications are made to the method.
9.3.1Determine the percent hexane in three separate dried rubber crumb samples.
9.3.2Weigh 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.
9.3.3Repeat the previous step using twice the hexane level (20 microliters), analyze and calculate the percent recovery of the known added hexane.
9.3.4Set 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.
9.3.5A value of R between 0.70 and 1.30 is acceptable.
9.3.6R 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.
10.1Calibrate 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.%
10.2Analyze 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.
10.3Heat the standard bottle for 30 minutes in a 105 °C oven.
10.4Inject 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.
11.1Using a cold mill set at a wide roller gap (125-150 mm), mill about 250 grams of crumb two times to homogenize the sample.
11.2Weigh 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.
11.3Run the moisture content on a separate portion of the sample and calculate the grams of dry rubber put into the septum bottle.
11.4Set up the data station on the required method and enter the dry rubber weight in the sample weight field.
11.5Inject a 0.25 cc vapor sample into the chromatograph and push the start button.
11.6At the end of the analysis, the data station will print a report listing the concentration of each identified component.
11.7To 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.
11.8Enter 5 grams into the sample weight field.
11.9Inject a 0.25 cc vapor sample into the chromatograph and push the start button.
11.10At the end of the analysis, the data station will print a report listing the concentration of each identified component.
12.1For samples that are prepared as in section 11 of this method, ppm n-hexane is read directly from the computer.
12.2The formulas for calculation of the results are as follows:
12.3Correct the results by the value of R (as determined in sections 9.3.4, 9.3.5, and 9.3.6 of this method).
13.1The 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.
14.1Waste generation should be minimized where possible. Sample size should be an amount necessary to adequately run the analysis.
15.1All waste shall be handled in accordance with federal and state environmental regulations.
16.1DSM Copolymer Test Method T-3380.
1.1Data 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.
2.1The 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).
3.1Included in text as needed.
4.1None known.
4.2Benzene, introduced as a contaminant in the toluene solvent, elutes between methyl cyclopentane and cyclohexane. However, the benzene peak is completely resolved.
4.32,2-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.
5.1This 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.
5.2Chemicals 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.
5.3Hexane 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.
5.4Termonomer 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.
5.5Toluene 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.
5.6Acetone, 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.
5.7Heptane 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.
5.8The steam oven used to dry the polymer in this procedure is set at 110 °C. Wear leather gloves when removing bottles from the oven.
6.14000-ml volumetric flask
6.2100-ml volumetric pipette
6.31000-ml volumetric flask
6.48-oz. French Square sample bottles with plastic-lined caps
6.5Top-loading balance
6.6Laboratory shaker
6.7Laboratory oven set at 110 °C (steam oven)
6.8Gas 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.
6.9GC column, capillary type, 50m × 0.53mm, methyl silicone, 5 micron film thickness, Quadrex, or equivalent.
6.10Computerized data acquisition system, such as CIS/CALS
6.11Crimp-top sample vials and HP p/n 5181-1211 crimp caps, or screw-top autosampler vials and screw tops.
6.12Glass syringes, 5-ml, with “Luer-lock” fitting
6.13Filters, PTFE, .45 µm pore size, Gelman Acrodisc or equivalent, to fit on Luer-lock syringes (in 6.12, above).
7.1Reagent 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).
7.2Reagent acetone, EM Science Omnisolv HR-GC (or equivalent)
7.3Reagent heptane, Aldrich Chemical Gold Label, Cat #15,487-3 (or equivalent)
7.4Internal 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.
7.5Polymer Dissolving Solution (“PDS”)—Heptane (as internal standard) in toluene. This solution contains 0.3g of heptane internal standard per 100 ml of solution.
7.5.1Preparation of Polymer Dissolving Solution. Fill a 4,000-ml volumetric flask about
7.5.2Add 100 ml of the internal standard solution (section 7.4 of this method) to the flask using the 100ml pipette.
7.5.3Fill the flask to the mark with toluene. Discard any excess.
7.5.4Add a large magnetic stirring bar to the flask and mix by stirring.
7.5.5Transfer the polymer solvent solution to the one-gallon labeled container with 50ml volumetric dispenser attached.
7.5.6Purity Check: Analyze according to section 11.2.
7.5.7Tag the bottle with the following information:
7.6Quality 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.
7.6.1In 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.
7.6.2In 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.
8.1Line up facility to catch crumb samples. The facility is a special facility where the sample is drawn.
8.1.1Ensure that the cock valve beneath facility is closed.
8.1.2Line up the system from the slurry line cock valve to the cock valve at the nozzle on the stripper.
8.1.3Allow the system to flush through facility for a period of 30 seconds.
8.2Catch a slurry crumb sample.
8.2.1Simultaneously close the cock valves upstream and downstream of facility.
8.2.2Close the cock valve beneath the slurry line in service.
8.2.3Line up the cooling tower water through the sample bomb water jacket to the sewer for a minimum of 30 minutes.
8.2.4Place the sample catching basket beneath facility and open the cock valve underneath the bomb to retrieve the rubber crumb.
8.2.5If 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.
8.2.6Close the cock valve underneath the sample bomb.
8.3Fill a plastic “Whirl-pak” sample bag with slurry crumb and send it to the lab immediately.
8.4Once 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.
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.
9.1Fill 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).
9.2Add 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.
Also, verify that the instrument has detected both isomers of termonomer (quantification not necessary—see section 7.0 of this method).
9.3Recovery 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).
9.3.1Approximately 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.
9.3.2The 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.
9.3.3The 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.
9.3.4The 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.
9.3.5The 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).
The procedure for preparing a Quality Control sample with the internal standard in it is outlined in section 7.6 of this method.
10.1The 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.
10.2If 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.
10.2.1Weigh 5 g heptane into a tared scintillation vial to five places.
10.2.2Add 0.2 ml termonomer to the vial and reweigh.
10.2.3Add 0.5 ml hexane to the vial and reweigh.
10.2.4Cap, and shake vigorously to mix.
10.2.5Calculate 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.
10.2.6Add 0.4 ml of this mixture to a mixture of 100 ml toluene and 100 ml of acetone. Cap and shake vigorously to mix.
10.2.7Analyze the sample.
10.2.8Divide 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.
10.2.9Divide 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.
11.1SAMPLE PREPARATION
11.1.1Tare an 8oz sample bottle—Tag attached, cap off; record weight and sample ID on tag in pencil.
11.1.2Place crumb sample in bottle: RLA-3: 10 g (gives a dry wt. of ∼5.5 g).
11.1.3Dispense 100ml of PDS into each bottle. SAMPLE SHOULD BE PLACED INTO SOLUTION ASAP TO AVOID HEXANE LOSS—Using “Dispensette” pipettor.
11.1.4Tightly cap bottles and load samples into shaker.
11.1.5Insure that “ON-OFF” switch on the shaker itself is “ON.”
11.1.6Locate shaker timer. Insure that toggle switch atop timer control box is in
11.1.7After 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.
11.1.8Using 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.
11.1.9Decant 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).
11.1.10Cool, weigh and record final weight of bottle.
11.2GC ANALYSIS
11.2.1Initiate the CALS computer channel.
11.2.2Enter the correct instrument method into the GC's integrator.
11.2.3Load sample vial(s) into autosampler.
11.2.4Start the integrator.
11.2.5When analysis is complete, plot CALS run to check baseline skim.
12.1Add the concentrations of the hexane peaks as they appear on the CALS printout. Do not include the benzene peak in the sum.
12.2Subtract any hexane interferences found in the PDS (see section 7.5.6 of this method); record the result.
12.3Note 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.
12.4Record 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.
12.5After 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).
12.6Divide 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.
12.7Correct all results by the recovery efficiency value (R).
13.1The 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.
14.1Dispose of all hydrocarbon liquids in the appropriate disposal sink system; never pour hydrocarbons down a water sink.
14.2As 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.
15.1The Technician conducting the analysis should follow the proper waste management practices for their laboratory location.
16.1Baton Rouge Chemical Plant Analytical Procedure no. BRCP 1302
16.2Material Safety Data Sheets (from chemical vendors) for hexane, ENB, toluene, acetone, and heptane
1.1This 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.
1.2This 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.
2.1Residual 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.
3.1Hexane—refers to n-hexane
3.2Heptane—refers to n-heptane
3.3MIBK—methyl isobutyl ketone (4 methyl 2—Pentanone)
4.1Material 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.
5.1Review Material Safety Data Sheets of the chemicals used in this method.
6.14 oz round glass jar with a wide mouth screw cap lid.
6.2Vacuum oven.
6.350 ml pipettes.
6.4A gas chromatograph with an auto sampler and a 50 meter, 0.53 ID, methyl silicone column with 5 micron phase thickness.
6.5Shaker, large enough to hold 10, 4 oz. jars.
6.61000 and 4000 ml volumetric flasks.
6.7Electronic integrator or equivalent data system.
6.8GC autosampler vials.
6.950 uL syringe.
7.1Reagent grade Methyl-Iso-Butyl-Ketone (MIBK)
7.2n-heptane, 99% + purity
7.3n-hexane, 99% + purity
8.1Trap 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.
9.1The 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.
9.2Follow 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.
9.3After 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.
9.4Add the percent hexane obtained from the three extractions for a total percent hexane in the sample.
9.5Use 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
10.1Preparation 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.
10.2Preparation 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.
10.3Conditions 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.
10.4Fill an autosampler vial with the HS, analyze it three times and calculate a Hexane Relative Response Factor (RF) as follows:
11.1Weight 10 grams of wet crumb into a tared (W1), wide mouth 4 oz. jar.
11.2Pipette 50 ml of Solution B into the jar with the wet crumb rubber.
11.3Screw the cap on tightly and place it on a shaker for 4 hours.
11.4Remove the sample from the shaker and fill an autosampler vial with the MIBK extract.
11.5Analyze the sample two times.
11.6Analyze 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.
12.1Drain 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)
12.2Should 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)
13.1Performance must be determined for each sample type by following the procedures in section 9 of this method.
14.1Waste generation should be minimized where possible.
15.1All waste shall be handled in accordance with Federal and State environmental regulations.
1.1Applicability. 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.
1.2Principle. 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
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.
4.1Coating 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.
4.2The 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.
4.3Cross-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.
4.4Cross-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.
5.1Many 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.
5.2Dimethylformamide 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.
5.3User's manuals for the gas chromatograph and other related equipment should be consulted for specific precautions to be taken related to their use.
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.
6.1Sample Collection.
6.1.1Sampling 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 (
6.1.1.1Other routine sampling supplies needed include waterproof marking pens, tubing, scrappers/spatulas, clean rags, paper towels, cooler/ice, long handle tongs, and mixing/stirring paddles.
6.1.2Personal safety equipment needed includes eye protection, respiratory protection, a hard hat, gloves, steel toe shoes, etc.
6.1.3Shipping supplies needed include shipping boxes, packing material, shipping labels, strapping tape, etc.
6.1.4Data recording forms and labels needed include coating data sheets and sample can labels.
The actual requirements will depend upon the conditions existing at the source sampled.
6.2Laboratory Equipment and Supplies.
6.2.1Gas 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
6.2.2Recorder. 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.
6.2.3Column. The column must be constructed of materials that do not react with components of the sample (
6.2.4Tube and Tube Fittings. Supplies to connect the GC and gas cylinders.
6.2.5Pressure Regulators. Devices used to regulate the pressure between gas cylinders and the GC.
6.2.6Flow 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.
6.2.7Septa. Seals on the GC injection port through which liquid or gas samples can be injected using a syringe.
6.2.8Liquid Charging Devices. Devices used to inject samples into the GC such as clean and graduated 1, 5, and 10 microliter (µl) capacity syringes.
6.2.9Vials. Containers that can be sealed with a septum in which samples may be prepared or stored. The recommended size is 25 ml capacity. Mininert
6.2.10Balance. Device used to determine the weights of standards and samples. An analytical balance capable of accurately weighing to 0.0001 g is required.
7.1Purity 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.
7.2Carrier 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.
7.3Dimethylformamide (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.
DMF may coelute with ethylbenzene or p-xylene under the conditions described in the note under Section 6.2.3.
7.4Internal 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.
7.5Reference 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.
7.6Stock 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.
7.6.1Stock 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
Although a glass-stoppered volumetric flask is convenient, any suitable glass container may be used because stock reference standards are prepared by weight.
7.6.2Transfer 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.
7.6.3Prepare 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.
7.7Calibration 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.
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.
7.7.1Preparation 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
7.7.2Preparation 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
8.1Copies 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.
8.2A 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.
8.3Prior 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.
8.3.1Water-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.
8.3.2Each 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.
8.4Sample 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.
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.
8.5Once 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.
8.5.1Affix a sample label (see Section 18) clearly identifying the sample, date collected, and person collecting the sample.
8.5.2Prepare 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.
8.9The 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.
9.1Laboratories 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.
9.2Before 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.
9.3Required instrument quality control parameters are found in the following sections:
9.3.1Baseline stability must be demonstrated to be ≤5 percent of full scale using the procedures given in Section 10.1.
9.3.2The 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.
9.3.3The 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.
9.3.4The GC system must be calibrated as specified in Section 10.2.
9.3.5A one-point daily calibration check must be performed as specified in Section 10.3.
9.4To establish the ability to generate results having acceptable accuracy and precision, the analyst must perform the following operations.
9.4.1Prepare 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.
9.4.2Analyze 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.
9.4.3Calculate the mean weight percent (X
9.4.4Calculate the percent accuracy for each analyte using the known concentrations (Ti) in the QCCS using Equation 3, Section 12.
9.4.5Calculate 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.
9.4.6If 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.
9.5Great 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.
9.6Unless otherwise specified, all weights are to be recorded within 0.1 mg.
10.1Column 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.
10.2Calibration of GC. Bring all stock standards and calibration standards to room temperature while establishing the GC at the determined operating conditions.
10.2.1Retention Times (RT's) for Individual Compounds.
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
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.
10.2.2Calibration. 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.
10.2.2.1Calculate 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.
10.2.2.2Compare 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.
10.2.2.3Tabulate 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 (RF
10.2.2.4Using 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
10.3Daily 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.
10.3.1For 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.
10.3.2If the RF
10.3.3The 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.
11.1All 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.
11.2Bring the GC system to the determined operating conditions and condition the column as described in Section 10.1.
The temperature of the injection port may be an especially critical parameter.Information about the proper temperature may be found on the CPDS.
11.3Perform 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.
11.4Place 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
11.5.1Add 16 g of dimethylformamide to each of two tared vials (A and B) capable of being septum sealed.
11.5.2To 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.
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
11.5.3Add 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.
11.5.4Seal the vials with crimp-on or Mininert
11.6Shake 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.
11.7Analyses should be conducted in the following order: daily calibration check sample, method blank, up to 10 injections from sample vials (
11.8Inject 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.
The analyst has the option of injecting the unseparated sample.
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:
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:
12.4 Calculate the percent accuracy for analytes in the QCCS (See Section 9.4) as follows:
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:
12.6 Calculate the response factor for the internal standard (See Section 10.2.2.3) as follows:
A
C
12.7 Calculate the relative response factors for analytes in the calibration standards (See Section 10.2.2.3) as follows:
RRF
A
C
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:
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:
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.
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.”
1.1This 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.
1.2The sample is separated in a gas chromatograph equipped with a packed column and a flame ionization detector.
2.1This 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.
3.1The definitions are included in the text as needed.
4.1In order to reduce matrix effects and emulsify the styrene, similar styrene free latex is added to the internal standard. There are no known interferences.
4.2The operating parameters are selected to obtain resolution necessary to determine styrene monomer concentrations in latex.
5.1It is the responsibility of the user of this procedure to establish appropriate safety and health practices.
6.1Adjustable bottle-top dispenser, set to deliver 3 ml. (for internal standard), Brinkmann Dispensette, or equivalent.
6.2Pipettor, set to 10 ml., Oxford Macro-set, or equivalent.
6.3Volumetric flask, 100-ml, with stopper.
6.4Hewlett Packard Model 5710A dual channel gas chromatograph equipped with flame ionization detector.
6.4.111 ft. ×
6.4.2Perkin Elmer Model 023 strip chart recorder, or equivalent.
6.5Helium carrier gas, zero grade.
6.6Liquid syringe, 25-µl.
6.7Digital MicroVAX 3100 computer with VG Multichrom software, or equivalent data handling system.
6.6Wire Screens, circular, 70-mm, 80-mesh diamond weave.
6.7DEHA—(N,N-Diethyl hydroxylamine), 97+% purity, CAS No. 3710-84-7
6.8p-Dioxane, CAS No. 123-91-1
7.1Internal standard preparation.
7.1.1Pipette 5 ml p-dioxane into a 1000-ml volumetric flask and fill to the mark with distilled water and mix thoroughly.
7.2Calibration solution preparation.
7.2.1Pipette 10 ml styrene-free latex (eg: NBR latex) into a 100-ml volumetric flask.
7.2.2Add 3 ml internal standard (section 7.1.1 of this method).
7.2.3Weigh exactly 10 µl fresh styrene and record the weight.
7.2.4Inject the styrene into the flask and mix well.
7.2.5Add 2 drops of DEHA, fill to the mark with water and mix well again.
7.2.6Calculate concentration of the calibration solution as follows:
mg/l styrene=(mg styrene added)/0.1 L
8.1A 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.
8.2The container should be labeled with sample identification, date and time.
9.1The instrument is calibrated by injecting calibration solution (Section 7.2 of this method) five times.
9.2The retention time for components of interest and relative response of monomer to the internal standard is determined.
9.3Recovery efficiency must be determined once for each sample type and whenever modifications are made to the method.
9.3.1A 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.
9.3.2The 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.
9.3.3For each hydrocarbon, calculate the average recovery efficiency (R) using the following equations:
9.3.4A value of R between 0.70 and 1.30 is acceptable.
9.3.5R 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.
10.1Injection port temperature, 250 °C.
10.2Oven temperature, 110 °C, isothermal.
10.3Carrier gas flow, 25 cc/min.
10.4Detector temperature, 250 °C.
10.5Range, 1X.
11.1Turn on recorder and adjust baseline to zero.
11.2Prepare sample.
11.2.1For 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.
11.2.2For 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.
11.3Flush syringe with sample.
11.4Carefully inject 2 µl of sample into the gas chromatograph column injection port and press the start button.
11.5When the run is complete the computer will print a report of the analysis.
12.1For samples that are prepared as in section 11.2.1 of this method:
12.2For samples that are prepared as in section 11.2.2 of this method, ppm styrene is read directly from the computer.
13.1This 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.
14.1Waste generation should be minimized where possible. Sample size should be an amount necessary to adequately run the analysis.
15.1All waste shall be handled in accordance with Federal and State environmental regulations.
16.140 CFR 63 Appendix A—Method 301 Test Methods Field Validation of Pollutant Measurement
16.2DSM Copolymer Test Method T-3060, dated October 19, 1995, entitled:
1.1This method is applicable to SBR latex solutions.
1.2This method quantitatively determines residual styrene concentrations in SBR latex solutions at levels from 80 to 1200 ppm.
2.1A 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.
3.1The definitions are included in the text as needed.
5.1This 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.
6.1Analytical balance, 160 g capacity, and 0.1 mg resolution
6.2Bottles, 2-oz capacity, with poly-cap screw lids
6.3Mechanical shaker
6.4Syringe, 10-ul capacity
6.5Gas chromatograph, Hewlett Packard model 5890A, or equivalent, configured with FID with a megabore jet, splitless injector packed with silanized glass wool.
6.5.1Establish 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.
6.6Gas chromatographic column, DB-1, 30 M X 0.53 ID, or equivalent, with a 1.5 micron film thickness.
6.7Data collection system, Perkin-Elmer/Nelson Series Turbochrom 4 Series 900 Interface, or equivalent.
6.8Pipet, automatic dispensing, 50-ml capacity, and 2-liter reservoir.
6.9Flasks, volumetric, class A, 100-ml and 1000-ml capacity.
6.10Pipet, volumetric delivery, 10-ml capacity, class A.
CHEMICALS:
REAGENTS:
7.4Internal Standard Stock Solution: 5.0 mg/ml AMS in ethyl alcohol.
7.4.1Into a 100-ml volumetric flask, weigh 0.50 g of AMS to the nearest 0.1 mg.
7.4.2Dilute 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.
7.5Internal Standard Working Solution: 2500 ug/50 ml of AMS in ethyl alcohol.
7.5.1Using a 10 ml volumetric pipet, quantitatively transfer 10.0 ml of the AMS STOCK SOLUTION into a 1000-ml volumetric flask.
7.5.2Dilute 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.
7.5.3Transfer the AMS WORKING SOLUTION to the automatic dispensing pipet reservoir.
7.6Styrene Stock Solution: 5.0 mg/ml styrene in ethyl alcohol.
7.6.1Into a 100-ml volumetric flask, weigh 0.50 g of styrene to the nearest 0.1 mg.
7.6.2Dilute 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.
7.7Styrene Working Solution: 5000 ug/10 ml of styrene in ethyl alcohol.
7.7.1Using a 10-ml volumetric pipet, quantitatively transfer 10.0 ml of the STYRENE STOCK SOLUTION into a 100-ml volumetric flask.
7.7.2Dilute 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.
8.1Label a 2-oz sample poly-cap lid with the identity, date and time of the sample to be obtained.
8.2At the sample location, open sample valve for at least 15 seconds to ensure that the sampling pipe has been properly flushed with fresh sample.
8.3Fill the sample jar to the top (no headspace) with sample, then cap it tightly.
8.4Deliver sample to the Laboratory for testing within one hour of sampling.
8.5Laboratory testing will be done within two hours of the sampling time.
8.6No special storage conditions are required unless the storage time exceeds 2
9.1For 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.
9.2The six vials labeled “spiked” shall be spiked with an amount of styrene to approximate 50% of the solution's expected residual styrene level.
9.3The spiked samples shall be shaken for several hours and allowed to cool to room temperature before analysis.
9.4The 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.
9.5The six samples of the spiked solution shall be coagulated and the results of the analyses shall be determined using the following equations:
9.6A value of R between 0.70 and 1.30 is acceptable.
9.7R 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.
10.1Using 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.
10.2Using 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.
10.3Cap the 2-oz bottle and swirl. This is the calibration standard, which contains 5000 µg of styrene and 2500 µg of AMS.
10.4Using the conditions prescribed (section 6.5 of this method), chromatograph 1 µl of the calibration standard.
10.5Obtain the peak areas and calculate the relative response factor as described in the calculations section (section 12.1 of this method).
11.1Into a tared 2-oz bottle, weigh 10.0 g of latex to the nearest 0.1 g.
11.2Using 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.
11.3Cap 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.
11.4Using the conditions prescribed (section 6.5 of this method), chromatograph 1 ul of the liquor.
11.5Obtain the peak areas and calculate the concentration of styrene in the latex as described in the calculations section (Section 12.2 of this method).
12.1Calibration:
13.1Precision 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.
14.1Waste generation should be minimized where possible. Sample size should be an amount necessary to adequately run the analysis.
15.1Discard liquid chemical waste into the chemical waste drum.
15.2Discard latex sample waste into the latex waste drum.
15.3Discard polymer waste into the polymer waste container.
16.1This method is based on Goodyear Chemical Division Test Method E-889.
1.1This method is applicable for determining the amount of residual styrene in SBR latex as produced in the emulsion polymerization process.
2.1A 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.
3.1The definitions are included in the text as needed.
5.1When using solvents, avoid contact with skin and eyes. Wear hand and eye protection. Wash thoroughly after use.
5.2Avoid overexposure to solvent vapors. Handle only in well ventilated areas.
6.1
6.2Wrist action shaker
6.3Automatic dispenser
6.4Automatic pipet, calibrated to deliver 5.0 ±0.01 grams of latex
6.5Four-ounce wide-mouth bottles with foil lined lids
6.6Crimp cap vials, 2ml, teflon lined septa
6.7Disposable pipets
6.8Qualitative filter paper
6.9Cap crimper
6.10Analytical balance
6.1110ml pipette
6.12Two-inch funnel
7.12-Propanol (HP2C grade)
7.2Alpha methyl styrene (99+% purity)
7.3Styrene (99+% purity)
7.4Zero air
7.5Hydrogen (chromatographic grade)
7.6Helium
7.7Internal Standard preparation
7.7.1Weigh 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.
Shelf life—6 months.
7.7.2Pipette 10ml of Stock “A” Solution into a 100ml volumetric flask and bring to mark with 2-propanol to prepare Stock “B” Solution.
7.7.3Pipette 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).
7.8Certification of Internal Standard—Each batch of Stock “B” Solution will be certified to confirm concentration.
7.8.1Prepare a Standard Styrene Control Solution in 2-propanol by the following method:
7.8.1.1Weigh 5.000 ±.005g of styrene to a 100ml volumetric flask and fill to mark with 2-propanol to make Styrene Stock “A” Solution.
7.8.1.2Pipette 10ml of Styrene Stock “A” Solution to a 100ml volumetric flask and fill to mark with 2-propanol to make Styrene Stock “B” Solution.
7.8.1.3Pipette 10ml of Styrene Stock “B” soluion to a 250ml volumtric flask and fill to mark wtih 2-propanol to make the Certification Solution.
7.8.2Certify Alpha-Methyl Styrene Stock “B” Solution.
7.8.2.1Pipette 5ml of the Certification Solution and 25ml of the Alpha Methyl Styrene Internal Standard Solution to a 4-oz. bottle, cap and shake well.
7.8.2.2Analyze the resulting mixture by GC using the residual styrene method. (11.4-11.6 of this method)
7.8.2.3Calculate the weight of alpha methyl styrene present in the 25ml aliquat of the new Alpha Methyl Styrene Standard by the following equation:
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.
8.1Collect a latex sample in a capped container. Cap the bottle and identify the sample as to location and time.
8.2Deliver sample to Laboratory for testing within one hour.
8.3Laboratory will test within two hours.
8.4No special storage conditions are required.
9.1The 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.
9.1.1When the method is first set up, a calibration is run and the recovery efficiency for each type of sample must be determined.
9.1.2If 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.
9.2Recovery 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:
9.2.5A 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 Ris 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.
A styrene control sample will be tested weekly to confirm the FID response and calibration.
10.1Using 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.
10.2Calculate the weight of styrene in the styrene control sample using the following equation:
The instrument can be considered calibrated if the weight of the styrene analyzed is within range of 0.00097-0.00103gms.
11.1Using an auto pipet, add 25ml of Internal Standard Solution to a 4 oz. wide-mouth bottle.
11.2Using a calibrated auto pipet, add 5.0 ±0.01g latex to the bottle containing the 25ml of Internal Standard Solution.
11.3Cap 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.
11.4Using 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.
11.5Place 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
12.1The integrator is programmed to do the following calculation at the end of the analysis:
12.2The 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:
13.1Performance must be determined for each sample type by following the procedures in section 9 of this method.
14.1Waste generation should be minimized where possible.
15.1All waste shall be handled in accordance with Federal and State environmental regulations.
1.1This 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.
1.2The 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.
1.3The 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.
2.1The 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.
2.2Identification of each component is performed by comparing the retention times to those of known standards.
2.3Results 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.
2.4Measured results of each compound are corrected by dividing each by the average recovery efficiency determined for the same compound in the same sample type.
3.1Stripper 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.
4.1Contamination is not normally a problem since samples are sealed into vials immediately on sampling.
4.2Cross 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.
4.3Interferences 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.
5.1The 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.
5.2Sampling 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
6.1Hewlett Packard (HP) 7694 Headspace sampler, or equivalent, with the following conditions:
6.2HP 5890 Series II capillary gas chromatograph, or equivalent, with the following conditions:
6.3HP Chemstation consisting of computer, printer and Chemstation software, or an equivalent chromatographic data system.
6.420 ml headspace vials with caps and septa.
6.5Headspace vial crimper.
6.6Microliter pipetting syringes.
6.7Drying oven at 100 deg C vented into cold trap or other means of trapping hydrocarbons released.
6.8Laboratory shaker or tumbler suitable for the headspace vials.
6.9Personal protective equipment required for sampling the process such as rubber gloves and face and eye protection.
7.1Toluene, 99.9+% purity, HPLC grade.
7.2Styrene, 99.9+% purity, HPLC grade.
7.3Dry rubber of same type as the stripper crumb samples.
8.1Collect a sample of crumb in a manner appropriate for the process equipment being sampled.
8.1.1If 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
8.1.2Alternatively 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.
8.2The 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.
9.1The 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.
9.1.1When 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).
9.1.2It 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).
9.1.3Ongoing 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.
9.1.4If 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
9.2Initial 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.
9.2.1Prepare 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).
9.2.2Determine 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.
9.2.3Prepare 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.
9.3A 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).
9.3.1Each 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.
9.3.2Run 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.
9.3.3If 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.
9.4Recovery efficiency must be determined once for each sample type and whenever modifications are made to the method.
9.4.1For 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.
9.4.2The 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.
9.4.3To 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.
9.4.4Place 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.
9.4.5Remove 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.
9.4.6Run 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.
9.4.7Open each of the vials labeled “spiked”, remove all the rubber crumb and
9.4.8For each hydrocarbon calculate the average recovery efficiency (R) using the following equations:
9.4.9A different R value should be obtained for each compound (styrene and toluene) and for each sample type.
9.4.10A value of R between 0.70 and 1.30 is acceptable.
9.4.11R 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.)
10.1Calibration standards are prepared by dosing known amounts of the hydrocarbons of interest into vials containing known amounts of rubber and water.
10.1.1Cut 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.
10.1.2Into each of a series of vials add 3.0 g of the dry rubber.
10.1.3Into 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).
10.1.4Into 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.
10.1.5Place 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.
10.1.6Remove 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.
10.2Run 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.
10.3Verify that the blanks are sufficiently free from toluene and styrene or any interfering hydrocarbons.
10.3.1It 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.
10.3.2It 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.
10.4Enter 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.
10.5At 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.
11.1Place 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.
11.2Make sure the correct method is loaded on the Chemstation. Turn on the gas flows and light the FID flame.
11.3Start 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.
12.1For 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.
12.2For each sample correct the measured amounts of toluene and styrene using the following equation:
12.3Report the recovery efficiency (R) and the corrected results of toluene and styrene for each sample.
13.1This 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.
13.2The 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.
14.1Samples should be kept sealed when possible in order to prevent evaporation of hydrocarbons.
14.2When drying of samples is required it should be done in an oven which vents into a suitable device that can trap the hydrocarbons released.
14.3Dispose of samples as described in section 15.
15.1Excess 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.
15.2Preferably this will be accomplished by having a system of returning unused and spent samples to the process.
16.1“HP 7694 Headspace Sampler—Operating and Service Manual”, Hewlett-Packard Company, publication number G1290-90310, June 1993.
1.1This method is applicable to solution polymerized polybutadiene (PBD).
1.2This method quantitatively determines n-hexane in wet crumb polymer at levels from 0.08 to 0.15% by weight.
1.3This method may be extended to the determination of other hydrocarbons in solution produced polymers with proper experimentation and documentation.
2.1A 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.
3.1The definitions are included in the text as needed.
5.1This 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.
6.1Analytical balance, 160 g capacity, 0.1 mg resolution
6.2Bottles, 2-oz capacity with poly-cap screw lids
6.3Mechanical shaker
6.4Syringe, 10-ul capacity
6.5Syringe, 2.5-ml capacity, with 22 gauge 1.25 inch needle, PP/PE material, disposable
6.6Gas chromatograph, Hewlett-Packard model 5890, or equivalent, configured with FID, split injector packed with silanized glass wool.
6.6.1Establish the following gas chromatographic conditions, and allow the system to thoroughly equilibrate before use.
6.6.2Injector parameters:
6.6.3Oven temperature program:
6.6.4Detector parameters:
6.7Gas 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.
6.7.1Column 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.
6.7.2Column parameters:
6.8Centrifuge
6.9Data collection system, Hewlett-Packard Model 3396, or equivalent
6.10Pipet, 25-ml capacity, automatic dispensing, and 2 liter reservoir
6.11Pipet, 2-ml capacity, volumetric delivery, class A
6.12Flasks, 100 and 1000-ml capacity, volumetric, class A
6.13Vial, serum, 50-ml capacity, red rubber septa and crimp ring seals
6.14Sample collection basket fabricated out of wire mesh to allow for drainage
CHEMICALS:
7.1alpha-Methyl Styrene, C9H10, 99+% purity, CAS 98-83-9
7.2n-Hexane, C6H14, 99+% purity, CAS 110-54-3
7.3Isopropyl alcohol, C3H8O 99.5+% purity, reagent grade, CAS 67-63-0
7.4Chloroform, CHCl3, 99% min., CAS 67-66-3
REAGENTS:
7.5Internal Standard Stock Solution: 10 mg/25 ml AMS in isopropyl alcohol.
7.5.1Into a 25-ml beaker, weigh 0.4 g of AMS to the nearest 0.1 mg.
7.5.2Quantitatively transfer this AMS into a 1-L volumetric flask. Dilute to the mark with isopropyl alcohol.
7.5.3Transfer this solution to the automatic dispensing pipet reservoir. This will be labeled the AMS STOCK SOLUTION.
7.6n-Hexane Stock Solution: 13mg/2ml hexane in isopropyl alcohol.
7.6.1Into a 100-ml volumetric flask, weigh 0.65 g of n-hexane to the nearest 0.1 mg.
7.6.2Dilute to the mark with isopropyl alcohol. This solution will be labeled the n-HEXANE STOCK SOLUTION.
8.1A 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.
8.2The crumb rubber is allowed to cool before opening the sampling device and removing the sample.
8.3The sampling device is opened and the crumb rubber sample is collected in the sampling basket.
8.4One pound of crumb rubber sample is placed into a polyethylene bag. The bag is labeled with the time, date and sample location.
8.5The sample should be delivered to the laboratory for testing within one hour of sampling.
8.6Laboratory testing will be done within 3 hours of the sampling time.
8.7No special storage conditions are required unless the storage time exceeds 3 hours in which case refrigeration of the samples is recommended.
9.1For 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.
9.2Determine 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.
9.3Run 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.
9.4For the recovery study, each sample of crumb shall be dissolved in chloroform containing a known amount of mixed hexane solvent.
9.5For each hydrocarbon, calculate the recovery efficiency (R) using the following equations:
9.6Normally a value of R between 0.70 and 1.30 is acceptable.
9.7R 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.
10.1Using 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.
10.2Using 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.
10.3Using the conditions prescribed (6.6 of this method), inject 1 µl of the supernate.
10.4Obtain the peak areas and calculate the response factor as described in the calculations section (12.1 of this method).
11.1Determination of Dry Polymer Weight
11.1.1Remove wet crumb from the polyethylene bag and place on paper towels to absorb excess surface moisture.
11.1.2Cut small slices or cubes from the center of the crumb sample to improve sample uniformity and further eliminate surface moisture.
11.1.3A 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.
11.2Determination of n-Hexane in Wet Crumb
11.2.1Remove wet crumb from the polyethylene bag and place on paper towels to absorb excess surface moisture.
11.2.2Cut small slices or cubes from the center of the crumb sample to improve sample uniformity and further eliminate surface moisture.
11.2.3Into a tared 2 oz bottle, weigh 1.5 g of wet polymer to the nearest 0.1 mg.
11.2.4Add 25 ml of chloroform to the 2 oz bottle and cap.
11.2.5Using a mechanical shaker, shake the bottle until the polymer dissolves.
11.2.6Using 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.
11.2.7Using a mechanical shaker, shake the bottle for 10 minutes to coagulate the dissolved polymer.
11.2.8Centrifuge the sample for 3 minutes at 2000 rpm.
11.2.9Using the conditions prescribed (6.6 of this method), chromatograph 1 µl of the supernate.
11.2.10Obtain the peak areas and calculate the concentration of the component of interest as described in the calculations (12.2 of this method).
12.1Calibration:
12.2Procedure:
12.2.1Correction Factor for calculating dry crumb weight.
12.2.2Moisture adjustment for chromatographic determination.
12.2.3Concentration (ppm) of hexane in the wet crumb.
13.1Precision 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.
14.1Waste generation should be minimized where possible.
15.1Discard liquid chemical waste into the chemical waste drum.
15.2Discard polymer waste into the polymer waste container.
16.1This method is based on Goodyear Chemical Division Test Method E-964.
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.
1.1Analytes. Particulate matter (PM). No CAS number assigned. Methylene chloride extractable matter (MCEM). No CAS number assigned.
1.2Applicability. 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.
1.3Data quality objectives. Adherence to the requirements of this method will enhance the quality of the data obtained from air pollutant sampling methods.
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.
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.
Mention of trade names or specific products does not constitute endorsement by the EPA.
6.1Sample collection. The following items are required for sample collection:
6.1.1Sampling 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. 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, see the following subsections.
The operating and maintenance procedures for the sampling train are described in APTD-0576 (Reference 3 in section 17.0 of
6.1.1.1Probe 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 (
6.1.1.2Probe 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).
6.1.1.3Pitot 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.
6.1.1.4Differential 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.
6.1.1.5Filter 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).
6.1.1.6Filter 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.
6.1.1.7Temperature 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.
6.1.1.8Condenser. 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.
6.1.1.9Metering 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
6.1.1.10Sampling 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.
6.1.2Barometer. Mercury, aneroid, or other barometer capable of measuring atmospheric pressure to within 2.5 mm (0.1 in.) Hg.
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.
6.1.3Gas 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.)
6.2Sample recovery. The following items are required for sample recovery:
6.2.1Probe-liner and probe-nozzle brushes. Nylon or Teflon
6.2.2Wash 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.
6.2.3Glass 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
6.2.4Petri dishes. For filter samples, glass, unless otherwise specified by the Administrator.
6.2.5Graduated 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.
6.2.6Plastic storage containers. Air-tight containers to store silica gel.
6.2.7Funnel and rubber policeman. To aid in transfer of silica gel to container; not necessary if silica gel is weighed in the field.
6.2.8Funnel. Glass or polyethylene, to aid in sample recovery.
6.3Sample analysis. The following equipment is required for sample analysis:
6.3.1Glass or Teflon
6.3.2Desiccator. It is recommended that fresh desiccant be used to minimize the chance for positive bias due to absorption of organic material during drying.
6.3.3Analytical balance. To measure to within 0.l mg.
6.3.4Balance. To measure to within 0.5 g.
6.3.5Beakers. 250 ml.
6.3.6Hygrometer. To measure the relative humidity of the laboratory environment.
6.3.7Temperature sensor. To measure the temperature of the laboratory environment.
6.3.8Buchner fritted funnel. 30 ml size, fine (<50 micron)-porosity fritted glass.
6.3.9Pressure filtration apparatus.
6.3.10Aluminum dish. Flat bottom, smooth sides, and flanged top, 18 mm deep and with an inside diameter of approximately 60 mm.
7.lSample collection. The following reagents are required for sample collection:
7.1.1Filters. 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
7.1.2Silica 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.
7.1.3Water. 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.
7.1.4Crushed ice.
7.1.5Stopcock 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.]
7.2Sample recovery. The following reagents are required for sample recovery:
7.2.1Acetone. 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.
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.
7.2.2Methylene 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.
A least one vendor quotes <1 mg/l for Environmental Analysis Solvents-grade methylene chloride.
7.3Sample analysis. The following reagents are required for sample analysis:
7.3.lAcetone. Same as in section 7.2.1 of this method.
7.3.2Desiccant. Anhydrous calcium sulfate, indicating type. Alternatively, other types of desiccants may be used, subject to the approval of the Administrator.
7.3.3Methylene chloride. Same as in section 7.2.2 of this method.
The complexity of this method is such that, in order to obtain reliable results, testers should be trained and experienced with the test procedures.
8.11Pretest preparation. It is suggested that sampling equipment be maintained according to the procedures described in APTD-0576.
8.1.1Weigh 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.
8.1.2A 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.
8.1.3Desiccate 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.
8.2Preliminary determinations.
8.2.1Select 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
8.2.2Select 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).
8.2.3Select 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.
8.2.4Select 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.
8.2.5The 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.
8.2.6In 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.
8.3Preparation of sampling train.
8.3.1During 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.
8.3.2Using 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.
8.3.3When 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.
8.3.4Set 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.
8.3.5Place crushed ice around the impingers.
8.4Leak-check procedures.
8.4.1Leak 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.
8.4.2Pretest leak check. A pretest leak-check is recommended but not required. If the pretest leak-check is conducted, the following procedure should be used.
8.4.2.1After 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.
A lower vacuum may be used, provided that it is not exceeded during the test.
8.4.2.2If 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
8.4.2.3The 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.
8.4.2.4When 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.
8.4.3Leak 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 m
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.
8.4.4Post-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 m
8.5Sampling 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.
8.5.1For 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.
8.5.2Clean 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 (C
8.5.3When 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.
8.5.4When the probe is in position, block off the openings around the probe and porthole to prevent unrepresentative dilution of the gas stream.
8.5.5Traverse 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.
8.5.6During 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.
8.5.7If 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.
8.5.8A 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.
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.
8.5.9At 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.
8.6Calculation 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.
8.7.1Proper 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.
8.7.2When 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.
8.7.3Before 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.
8.7.4Transfer 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.
8.7.5Save 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.
8.7.6Inspect the train prior to and during disassembly and note any abnormal conditions. Treat the samples as follows:
8.7.6.1Container 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.
8.7.6.2Container 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
8.7.6.2.1Carefully 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.
8.7.6.2.2Brush and rinse the inside parts of the Swagelok fitting with acetone in a similar way until no visible particles remain.
8.7.6.2.3Rinse 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.
8.7.6.2.4It is recommended that two people clean the probe to minimize sample losses. Between sampling runs, keep brushes clean and protected from contamination.
8.7.6.2.5After 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).
8.7.6.2.6After 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.
8.7.6.2.7After 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.
8.7.6.3Container 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.
8.7.6.4Impinger water. Treat the impingers as follows:
8.7.6.4.1Make 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.
8.7.6.4.2Following 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).
8.7.6.4.3Following 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.
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.
8.8Sample transport. Whenever possible, containers should be shipped in such a way that they remain upright at all times.
9.1Miscellaneous quality control measures.
9.2Volume 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.
9.2.1Meter orifice check. Using the calibration data obtained during the calibration procedure described in section 10.3 of this method, determine the ΔH
9.2.1.1Before 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 ΔH
9.2.1.2Compare the Y
9.2.2Calibrated 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.
Maintain a laboratory log of all calibrations.
10.1Probe 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.
10.2Pitot 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.
10.3Metering system.
10.3.1Calibration 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 ft
10.3.1.1Before 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 m
10.3.2Calibration 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 wet test meter and the inlet of the metering system. Calculate the average value of the DGM calibration factor. If the value has changed by more than 5 percent, recalibrate the meter over the full range of orifice settings, as previously detailed.
Alternative procedures, e.g., rechecking the orifice meter coefficient, may be used, subject to the approval of the Administrator.
10.3.3Acceptable variation in calibration. If the DGM coefficient values obtained before and after a test series differ by more than 5 percent, either the test series shall be voided or calculations for the test series shall be performed using whichever meter coefficient value (i.e., before or after) gives the lower value of total sample volume.
10.4Probe heater calibration. Use a heat source to generate air heated to selected temperatures that approximate those expected to occur in the sources to be sampled. Pass this air through the probe at a typical sample flow rate while measuring the probe inlet and outlet temperatures at various probe heater settings. For each air temperature generated, construct a graph of probe heating system setting versus probe outlet temperature. The procedure outlined in APTD-0576 can also be used. Probes constructed according to APTD-0581 need not be calibrated if the calibration curves in APTD-0576 are used. Also, probes with outlet temperature monitoring capabilities do not require calibration.
The probe heating system shall be calibrated before its initial use in the field.
10.5Temperature sensors. Use the procedure in section 10.3 of Method 2, 40 CFR part 60, appendix A to calibrate in-stack temperature sensors. Dial thermometers, such as are used for the DGM and condenser outlet, shall be calibrated against mercury-in-glass thermometers.
10.6Barometer. Calibrate against a mercury barometer.
11.1Record the data required on a sheet such as the one shown in Figure 315-1 of this method.
11.2Handle each sample container as follows:
11.2.1Container No. 1.
11.2.1.1PM analysis. Leave the contents in the shipping container or transfer the filter and any loose PM from the sample container to a tared glass weighing dish. Desiccate for 24 hours in a desiccator containing anhydrous calcium sulfate. Weigh to a constant weight and report the results to the nearest 0.1 mg. For purposes of this section, the term “constant weight” means a difference of no more than 0.5 mg or 1 percent of total weight less tare weight, whichever is greater, between two consecutive weighings, with no less than 6 hours of desiccation time between weighings (overnight desiccation is a common practice). If a third weighing is required and it agrees within ±0.5 mg, then the results of the second weighing should be used. For quality assurance purposes, record and report each individual weighing; if more than three weighings are required, note this in the results for the subsequent MCEM results.
11.2.1.2MCEM analysis. Transfer the filter and contents quantitatively into a beaker. Add 100 ml of methylene chloride and cover with aluminum foil. Sonicate for 3 minutes then allow to stand for 20 minutes. Set up the filtration apparatus. Decant the solution into a clean Buchner fritted funnel. Immediately pressure filter the solution through the tube into another clean, dry beaker. Continue decanting and pressure filtration until all the solvent is transferred. Rinse the beaker and filter with 10 to 20 ml methylene chloride, decant into the Buchner fritted funnel and pressure filter. Place the beaker on a low-temperature hot plate (maximum 40 °C) and slowly evaporate almost to
11.2.2Container No. 2.
11.2.2.1PM analysis. Note the level of liquid in the container, and confirm on the analysis sheet whether leakage occurred during transport. If a noticeable amount of leakage has occurred, either void the sample or use methods, subject to the approval of the Administrator, to correct the final results. Measure the liquid in this container either volumetrically to ±1 ml or gravimetrically to 1 ±0.5 g. Transfer the contents to a tared 250 ml beaker and evaporate to dryness at ambient temperature and pressure. Desiccate for 24 hours, and weigh to a constant weight. Report the results to the nearest 0.1 mg.
11.2.2.2MCEM analysis. Add 25 ml methylene chloride to the beaker and cover with aluminum foil. Sonicate for 3 minutes then allow to stand for 20 minutes; combine with contents of Container No. 2M and pressure filter and evaporate as described for Container 1 in section 11.2.1.2 of this method.
1. Light finger pressure only is necessary on 24/40 adaptor. A Chemplast adapter #15055-240 has been found satisfactory.
2. Avoid aluminum dishes made with fluted sides, as these may promote solvent “creep,” resulting in possible sample loss.
3. If multiple samples are being run, rinse the Buchner fritted funnel twice between samples with 5 ml solvent using pressure filtration. After the second rinse, continue the flow of air until the glass frit is completely dry. Clean the Buchner fritted funnels thoroughly after filtering five or six samples.
11.2.3Container No. 3. Weigh the spent silica gel (or silica gel plus impinger) to the nearest 0.5 g using a balance. This step may be conducted in the field.
11.2.4Container 3W (impinger water).
11.2.4.1MCEM analysis. Transfer the solution into a 1,000 ml separatory funnel quantitatively with methylene chloride washes. Add enough solvent to total approximately 50 ml, if necessary. Shake the funnel for 1 minute, allow the phases to separate, and drain the solvent layer into a 250 ml beaker. Repeat the extraction twice. Evaporate with low heat (less than 40 °C) until near dryness. Transfer the remaining few milliliters of solvent quantitatively with small solvent washes into a clean, dry, tared aluminum dish and evaporate to dryness. Remove from heat once solvent is evaporated. Reweigh the dish after a 30-minute equilibration in the balance room and determine the weight to the nearest 0.1 mg.
11.2.5Container 3S (solvent).
11.2.5.1MCEM analysis. Transfer the mixed solvent to 250 ml beaker(s). Evaporate and weigh following the procedures detailed for container 3W in section 11.2.4 of this method.
11.2.6Blank containers. Measure the distilled water, acetone, or methylene chloride in each container either volumetrically or gravimetrically. Transfer the “solvent” to a tared 250 ml beaker, and evaporate to dryness at ambient temperature and pressure. (Conduct a solvent blank on the distilled deionized water blank in an identical fashion to that described in section 11.2.4.1 of this method.) Desiccate for 24 hours, and weigh to a constant weight. Report the results to the nearest 0.l mg.
The contents of Containers No. 2, 3W, and 3M as well as the blank containers may be evaporated at temperatures higher than ambient. If evaporation is done at an elevated temperature, the temperature must be below the boiling point of the solvent; also, to prevent “bumping,” the evaporation process must be closely supervised, and the contents of the beaker must be swirled occasionally to maintain an even temperature. Use extreme care, as acetone and methylene chloride are highly flammable and have a low flash point.
12.1Carry out calculations, retaining at least one extra decimal figure beyond that of the acquired data. Round off figures after the final calculation. Other forms of the equations may be used as long as they give equivalent results.
12.2Nomenclature.
12.3 Average dry gas meter temperature and average orifice pressure drop. See data sheet (Figure 5-2 of Method 5, 40 CFR part 60, appendix A).
12.4 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) by using Equation 315-1.
Equation 315-1 can be used as written unless the leakage rate observed during any of the mandatory leak checks (i.e., the post-test leak check or leak checks conducted prior to component changes) exceeds L
(a) Case I. No component changes made during sampling run. In this case, replace V
(b) Case II. One or more component changes made during the sampling run. In this case, replace V
12.5Volume of water vapor condensed.
In saturated or water droplet-laden gas streams, two calculations of the moisture content of the stack gas shall be made, one from the impinger analysis (Equation 315-3), and a second from the assumption of saturated conditions. The lower of the two values of B
12.7Acetone blank concentration.
12.8Acetone wash blank.
12.9Total particulate weight. Determine the total PM catch from the sum of the weights obtained from Containers l and 2 less the acetone blank associated with these two containers (see Figure 315-1).
Refer to section 8.5.8 of this method to assist in calculation of results involving two or more filter assemblies or two or more sampling trains.
12.10Particulate concentration.
12.11Conversion factors.
12.12Isokinetic variation.
12.12.1Calculation from raw data.
12.12.2Calculation from intermediate values.
12.12.3Acceptable results. If 90 percent ≤ I ≤ 110 percent, the results are acceptable. If the PM or MCEM results are low in comparison to the standard, and “I” is over 110 percent or less than 90 percent, the Administrator may opt to accept the results. Reference 4 in the Bibliography may be used to make acceptability judgments. If “I” is judged to be unacceptable, reject the results, and repeat the test.
12.13Stack gas velocity and volumetric flow rate. Calculate the average stack gas velocity and volumetric flow rate, if needed, using data obtained in this method and the equations in sections 5.2 and 5.3 of Method 2, 40 CFR part 60, appendix A.
12.14MCEM results. Determine the MCEM concentration from the results from Containers 1, 2, 2M, 3W, and 3S less the acetone, methylene chloride, and filter blanks value as determined in the following equation:
16.1Dry gas meter as a calibration standard. A DGM may be used as a calibration standard for volume measurements in place of the wet test meter specified in section 16.1 of this method, provided that it is calibrated initially and recalibrated periodically as follows:
16.1.1 Standard dry gas meter calibration.
16.1.1.1. The DGM to be calibrated and used as a secondary reference meter should be of high quality and have an appropriately sized capacity, e.g., 3 liters/rev (0.1 ft
16.1.1.2Set up the components as shown in Figure 5-7 of Method 5, 40 CFR part 60, appendix A. A spirometer, or equivalent, may be used in place of the wet test meter in the system. Run the pump for at least 5 minutes at a flow rate of about 10 liters/min (0.35 cfm) to condition the interior surface of the wet test meter. The pressure drop indicated by the manometer at the inlet side of the DGM should be minimized (no greater than 100 mm H
16.1.1.3Collect the data as shown in the example data sheet (see Figure 5-8 of Method 5, 40 CFR part 60, appendix A). Make triplicate runs at each of the flow rates and at no less than five different flow rates. The range of flow rates should be between 10 and 34 liters/min (0.35 and 1.2 cfm) or over the expected operating range.
16.1.1.4Calculate flow rate, Q, for each run using the wet test meter volume, V
16.1.1.5Compare the three Y
16.1.1.6Prepare a curve of meter coefficient, Y
16.1.2Standard dry gas meter recalibration.
16.1.2.1Recalibrate the standard DGM against a wet test meter or spirometer annually or after every 200 hours of operation, whichever comes first. This requirement is valid provided the standard DGM is kept in a laboratory and, if transported, cared for as any other laboratory instrument. Abuse to the standard meter may cause a change in the calibration and will require more frequent recalibrations.
16.1.2.2As an alternative to full recalibration, a two-point calibration check may be made. Follow the same procedure and equipment arrangement as for a full recalibration, but run the meter at only two flow rates (suggested rates are 14 and 28 liters/min [0.5 and 1.0 cfm]). Calculate the meter coefficients for these two points, and compare the values with the meter calibration curve. If the two coefficients are within 1.5 percent of the calibration curve values at the same flow rates, the meter need not be recalibrated until the next date for a recalibration check.
6.2Critical orifices as calibration standards. Critical orifices may be used as calibration standards in place of the wet test meter specified in section 10.3 of this method, provided that they are selected, calibrated, and used as follows:
16.2.1Selection of critical orifices.
16.2.1.1The procedure that follows describes the use of hypodermic needles or stainless steel needle tubing that has been found suitable for use as critical orifices. Other materials and critical orifice designs may be used provided the orifices act as true critical orifices; i.e., a critical vacuum can be obtained, as described in section 7.2.2.2.3 of Method 5, 40 CFR part 60, appendix A. Select five critical orifices that are appropriately sized to cover the range of flow rates between 10 and 34 liters/min or the expected operating range. Two of the critical orifices should bracket the expected operating range. A minimum of three critical orifices will be needed to calibrate a Method 5 DGM; the other two critical orifices can serve as spares and provide better selection for bracketing the range of operating flow rates. The needle sizes and tubing lengths shown in Table 315-1 give the approximate flow rates indicated in the table.
16.2.1.2These needles can be adapted to a Method 5 type sampling train as follows: Insert a serum bottle stopper, 13×20 mm sleeve type, into a 0.5 in Swagelok quick connect. Insert the needle into the stopper as shown in Figure 5-9 of Method 5, 40 CFR part 60, appendix A.
16.2.2Critical orifice calibration. The procedure described in this section uses the Method 5 meter box configuration with a DGM as described in section 6.1.1.9 of this method to calibrate the critical orifices. Other schemes may be used, subject to the approval of the Administrator.
16.2.2.1Calibration of meter box. The critical orifices must be calibrated in the same configuration as they will be used; i.e., there should be no connections to the inlet of the orifice.
16.2.2.1.1Before calibrating the meter box, leak-check the system as follows: Fully open the coarse adjust valve and completely close the bypass valve. Plug the inlet. Then turn on the pump and determine whether there is any leakage. The leakage rate shall be zero; i.e., no detectable movement of the DGM dial shall be seen for 1 minute.
16.2.2.1.2Check also for leakages in that portion of the sampling train between the pump and the orifice meter. See section 5.6 of Method 5, 40 CFR part 60, appendix A for the procedure; make any corrections, if necessary. If leakage is detected, check for cracked gaskets, loose fittings, worn 0-rings, etc. and make the necessary repairs.
16.2.2.1.3After determining that the meter box is leakless, calibrate the meter box according to the procedure given in section 5.3 of Method 5, 40 CFR part 60, appendix A. Make sure that the wet test meter meets the requirements stated in section 7.1.1.1 of Method 5, 40 CFR part 60, appendix A. Check the water level in the wet test meter. Record the DGM calibration factor, Y.
16.2.2.2Calibration of critical orifices. Set up the apparatus as shown in Figure 5-10 of Method 5, 40 CFR part 60, appendix A.
16.2.2.2.1Allow a warm-up time of 15 minutes. This step is important to equilibrate the temperature conditions through the DGM.
16.2.2.2.2Leak-check the system as in section 7.2.2.1.1 of Method 5, 40 CFR part 60, appendix A. The leakage rate shall be zero.
16.2.2.2.3Before calibrating the critical orifice, determine its suitability and the appropriate operating vacuum as follows: turn on the pump, fully open the coarse adjust valve, and adjust the bypass valve to give a vacuum reading corresponding to about half of atmospheric pressure. Observe the meter box orifice manometer reading, DH. Slowly increase the vacuum reading until a stable reading is obtained on the meter box orifice manometer. Record the critical vacuum for each orifice. Orifices that do not reach a critical value shall not be used.
16.2.2.2.4Obtain the barometric pressure using a barometer as described in section 6.1.2 of this method. Record the barometric pressure, P
16.2.2.2.5Conduct duplicate runs at a vacuum of 25 to 50 mm Hg (1 to 2 in. Hg) above the critical vacuum. The runs shall be at least 5 minutes each. The DGM volume readings shall be in increments of complete revolutions of the DGM. As a guideline, the times should not differ by more than 3.0 seconds (this includes allowance for changes in the DGM temperatures) to achieve ±0.5 percent in K′. Record the information listed in Figure 5-11 of Method 5, 40 CFR part 60, appendix A.
16.2.2.2.6 Calculate K′ using Equation 315-11.
16.2.2.2.7Average the K′ values. The individual K′ values should not differ by more than ±0.5 percent from the average.
16.2.3Using the critical orifices as calibration standards.
16.2.3.1Record the barometric pressure.
16.2.3.2Calibrate the metering system according to the procedure outlined in sections 7.2.2.2.1 to 7.2.2.2.5 of Method 5, 40 CFR part 60, appendix A. Record the information listed in Figure 5-12 of Method 5, 40 CFR part 60, appendix A.
16.2.3.3Calculate the standard volumes of air passed through the DGM and the critical orifices, and calculate the DGM calibration factor, Y, using the equations below:
16.2.3.4Average the DGM calibration values for each of the flow rates. The calibration factor, Y, at each of the flow rates should not differ by more than ±2 percent from the average.
16.2.3.5To determine the need for recalibrating the critical orifices, compare the DGM Y factors obtained from two adjacent orifices each time a DGM is calibrated; for example, when checking orifice 13/2.5, use orifices 12/10.2 and 13/5.1. If any critical orifice yields a DGM Y factor differing by more than 2 percent from the others, recalibrate the critical orifice according to section 7.2.2.2 of Method 5, 40 CFR part 60, appendix A.
1. Addendum to Specifications for Incinerator Testing at Federal Facilities. PHS, NCAPC. December 6, 1967.
2. Martin, Robert M. Construction Details of Isokinetic Source-Sampling Equipment. Environmental Protection Agency. Research Triangle Park, NC. APTD-0581. April 1971.
3. Rom, Jerome J. Maintenance, Calibration, and Operation of Isokinetic Source Sampling Equipment. Environmental Protection Agency. Research Triangle Park, NC. APTD-0576. March 1972.
4. Smith, W.S., R.T. Shigehara, and W.F. Todd. A Method of Interpreting Stack Sampling Data. Paper Presented at the 63rd Annual Meeting of the Air Pollution Control Association, St. Louis, MO. June 14-19, 1970.
5. Smith, W.S., et al. Stack Gas Sampling Improved and Simplified With New Equipment. APCA Paper No. 67-119. 1967.
6. Specifications for Incinerator Testing at Federal Facilities. PHS, NCAPC. 1967.
7. Shigehara, R.T. Adjustment in the EPA Nomograph for Different Pitot Tube Coefficients and Dry Molecular Weights. Stack Sampling News
8. Vollaro, R.F. A Survey of Commercially Available Instrumentation for the Measurement of Low-Range Gas Velocities. U.S. Environmental Protection Agency, Emission Measurement Branch. Research Triangle Park, NC. November 1976 (unpublished paper).
9. Annual Book of ASTM Standards. Part 26. Gaseous Fuels; Coal and Coke; Atmospheric Analysis. American Society for Testing and Materials. Philadelphia, PA. 1974. pp. 617-622.
10. Felix, L.G., G.I. Clinard, G.E. Lacy, and J.D. McCain. Inertial Cascade Impactor Substrate Media for Flue Gas Sampling. U.S. Environmental Protection Agency. Research Triangle Park, NC 27711. Publication No. EPA-600/7-77-060. June 1977. 83 p.
11. Westlin, P.R., and R.T. Shigehara. Procedure for Calibrating and Using Dry Gas Volume Meters as Calibration Standards. Source Evaluation Society Newsletter.
12. Lodge, J.P., Jr., J.B. Pate, B.E. Ammons, and G.A. Swanson. The Use of Hypodermic Needles as Critical Orifices in Air Sampling. J. Air Pollution Control Association.
18.0Tables, Diagrams, Flowcharts, and Validation Data
This method is applicable to the determination of formaldehyde, CAS Registry number 50-00-0, from stationary sources in the mineral wool and wool fiber glass industries. High purity water is used to collect the formaldehyde. The formaldehyde concentrations in the stack samples are determined using the modified pararosaniline method. Formaldehyde can be detected as low as 8.8 × 10
Gaseous and particulate pollutants are withdrawn isokinetically from an emission source and are collected in high purity water. Formaldehyde present in the emissions is highly soluble in high purity water. The high purity water containing formaldehyde is then analyzed using the modified pararosaniline method. Formaldehyde in the sample reacts with acidic pararosaniline, and the sodium sulfite, forming a purple chromophore. The intensity of the purple color, measured spectrophotometrically, provides an accurate and precise measure of the formaldehyde concentration in the sample.
See the definitions in the General Provisions of this Subpart.
Sulfite and cyanide in solution interfere with the pararosaniline method. A procedure to overcome the interference by each compound has been described by Miksch, et al.
6.1A schematic of the sampling train is shown in Figure 1. This sampling train configuration is adapted from EPA Method 5, 40 CFR part 60, appendix A, procedures.
The sampling train consists of the following components: probe nozzle, probe liner, pitot tube, differential pressure gauge, impingers, metering system, barometer, and gas density determination equipment.
6.1.1Probe Nozzle:Quartz, glass, or stainless steel with sharp, tapered (30 ° angle) leading edge. The taper shall be on the outside to preserve a constant inner diameter. The nozzle shall be buttonhook or elbow design. A range of nozzle sizes suitable for isokinetic sampling should be available in increments of 0.15 cm (
6.1.2Probe Liner: Borosilicate glass or quartz shall be used for the probe liner. The probe shall be maintained at a temperature of 120 °C ±14 °C (248 °F ±25 °F).
6.1.3Pitot Tube: The pitot tube shall be Type S, as described in Section 2.1 of EPA Method 2, 40 CFR part 60, appendix A, or any other appropriate device. The pitot tube shall be attached to the probe 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 Figure 2-6b, EPA Method 2, 40 CFR part 60, appendix A) during sampling. The Type S pitot tube assembly shall have a known coefficient, determined as outlined in Section 4 of EPA Method 2, 40 CFR part 60, appendix A.
6.1.4Differential Pressure Gauge: The differential pressure gauge shall be an inclined manometer or equivalent device as described in Section 2.2 of EPA Method 2, 40 CFR part 60, appendix A. One manometer shall be used for velocity-head reading and the other for orifice differential pressure readings.
6.1.5Impingers: The sampling train requires a minimum of four impingers, connected as shown in Figure 1, with ground glass (or equivalent) vacuum-tight fittings. For the first, third, and fourth impingers, use the Greenburg-Smith design, modified by replacing the tip with a 1.3 cm inside diameters (
6.1.6Metering System: The necessary components are a vacuum gauge, leak-free pump, thermometers capable of measuring temperatures within 3 °C (5.4 °F), dry-gas meter capable of measuring volume to within 1 percent, and related equipment as shown in Figure 1. At a minimum, the pump should be capable of 4 cfm free flow, and the dry gas meter should have a recording capacity of 0-999.9 cu ft with a resolution of 0.005 cu ft. Other metering systems may be used which are capable of maintaining sample volumes to within 2 percent. The metering system may be used in conjunction with a pitot tube to enable checks of isokinetic sampling rates.
6.1.7Barometer: The barometer may be mercury, aneroid, or other barometer capable of measuring atmospheric pressure to within 2.5 mm Hg (0.1 in Hg). In many cases, the barometric reading may be obtained from a nearby National Weather Service Station, in which case the station value (which is the absolute barometric pressure) is requested and an adjustment for elevation differences between the weather station and sampling point is applied at a rate of minus 2.5 mm Hg (0.1 in Hg) per 30 m (100 ft) elevation increase (rate is plus 2.5 mm Hg per 30 m (100 ft) of elevation decrease).
6.1.8Gas Density Determination Equipment: Temperature sensor and pressure gauge (as described in Sections 2.3 and 2.3 of EPA Method 2, 40 CFR part 60, appendix A), and gas analyzer, if necessary (as described in EPA Method 3, 40 CFR part 60, appendix A). The temperature sensor ideally should be permanently attached to the pitot tube or sampling probe in a fixed configuration such that the top 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 openings (see Figure 2-7, EPA Method 2, 40 CFR part 60, appendix A). As a second alternative, if a difference of no more than 1 percent in the average velocity measurement is to be introduced, the temperature gauge need not be attached to the probe or pitot tube.
6.2Sample Recovery
6.2.1Probe Liner: Probe nozzle and brushes; bristle brushes with stainless steel wire handles are required. The probe brush shall have extensions of stainless steel, Teflon
6.2.2Wash Bottles: One wash bottle is required. Polyethylene, Teflon
6.2.3Graduated Cylinder and/or Balance: A graduated cylinder or balance is required to measure condensed water to the nearest 1 ml or 1 g. Graduated cylinders shall have division not >2 ml. Laboratory balances capable of weighing to ±0.5 g are required.
6.2.4Polyethylene Storage Containers: 500 ml wide-mouth polyethylene bottles are required to store impinger water samples.
6.2.5Rubber Policeman and Funnel: A rubber policeman and funnel are required to aid the transfer of material into and out of containers in the field.
6.3Sample Analysis
6.3.1Spectrophotometer—B&L 70, 710, 2000, etc., or equivalent; 1 cm pathlength cuvette holder.
6.3.2Disposable polystyrene cuvettes, pathlengh 1 cm, volume of about 4.5 ml.
6.3.3Pipettors—Fixed-volume Oxford pipet (250 µl; 500 µl; 1000 µl); adjustable volume Oxford or equivalent pipettor 1-5 ml model, set to 2.50 ml.
6.3.4Pipet tips for pipettors above.
6.3.5Parafilm, 2 ° wide; cut into about 1” squares.
7.1High purity water: All references to water in this method refer to high purity water (ASTM Type I water or equivalent). The water purity will dictate the lower limits of formaldehyde quantification.
7.2Silica Gel: Silica gel shall be indicting type, 6-16 mesh. If the silica gel has been used previously, dry at 175 °C (350 °F) for 2 hours before using. New silica gel may be used as received. Alternatively, other types of desiccants (equivalent or better) may be used.
7.3Crushed Ice: Quantities ranging from 10-50 lbs may be necessary during a sampling run, depending upon ambient temperature. Samples which have been taken must be stored and shipped cold; sufficient ice for this purpose must be allowed.
7.4Quaternary ammonium compound stock solution: Prepare a stock solution of dodecyltrimethylammonium chloride (98 percent minimum assay, reagent grade) by dissolving 1.0 gram in 1000 ml water. This solution contains nominally 1000 µg/ml quaternary ammonium compound, and is used as a biocide for some sources which are prone to microbial contamination.
7.5Pararosaniline: Weigh 0.16 grams pararosaniline (free base; assay of 95 percent or greater, C.I. 42500; Sigma P7632 has been found to be acceptable) into a 100 ml flask. Exercise care, since pararosaniline is a dye and will stain. Using a wash bottle with high-purity water, rinse the walls of the flask. Add no more than 25 ml water. Then,
7.6Sodium sulfite: Weigh 0.10 grams anhydrous sodium sulfite into a 100 ml flask. Dilute to the mark with high purity water. Invert 15-20 times to mix and dissolve the sodium sulfite. This solution must be prepared fresh every day.
7.7Formaldehyde standard solution: Pipet exactly 2.70 ml of 37 percent formaldehyde solution into a 1000 ml volumetric flask which contains about 500 ml of high-purity water. Dilute to the mark with high-purity water. This solution contains nominally 1000 µg/ml of formaldehyde, and is used to prepare the working formaldehyde standards. The exact formaldehyde concentration may be determined if needed by suitable modification of the sodium sulfite method (Reference: J.F. Walker, Formaldehyde (Third Edition), 1964.). The 1000 µg/ml formaldehyde stock solution is stable for at least a year if kept tightly closed, with the neck of the flask sealed with Parafilm. Store at room temperature.
7.8Working formaldehyde standards: Pipet exactly 10.0 ml of the 1000 µg/ml formaldehyde stock solution into a 100 ml volumetric flask which is about half full of high-purity water. Dilute to the mark with high-purity water, and invert 15-20 times to mix thoroughly. This solution contains nominally 100 µg/ml formaldehyde. Prepare the working standards from this 100 µg/ml standard solution and using the Oxford pipets:
8.1Because of the complexity of this method, field personnel should be trained in and experienced with the test procedures in order to obtain reliable results.
8.2.1All the components shall be maintained and calibrated according to the procedure described in APTD-0576, unless otherwise specified.
8.2.2Weigh several 200 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 containers. As an alternative to preweighing the silica gel, it may instead be weighed directly in the impinger or sampling holder just prior to train assembly.
8.3Preliminary Field Determinations
8.3.1Select the sampling site and the minimum number of sampling points according to EPA Method 1, 40 CFR part 60, appendix A, or other relevant criteria. Determine the stack pressure, temperature, and range of velocity heads using EPA Method 2, 40 CFR part 60, appendix A. A leak-check of the pitot lines according to Section 3.1 of EPA Method 2, 40 CFR part 60, appendix A, must be performed. Determine the stack gas moisture content using EPA Approximation Method 4,40 CFR part 60, appendix A, or its alternatives to establish estimates of isokinetic sampling rate settings. Determine the stack gas dry molecular weight, as described in EPA Method 2, 40 CFR part 60, appendix A, Section 3.6. If integrated EPA Method 3, 40 CFR part 60, appendix A, 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 sample run.
8.3.2Select a nozzle size based on the range of velocity heads so that it is not necessary to change the nozzle size in order to maintain isokinetic sampling rates below 28 l/min (1.0 cfm). During the run do not change the nozzle. Ensure that the proper differential pressure gauge is chosen for the range of velocity heads encountered (see Section 2.2 of EPA Method 2, 40 CFR part 60, appendix A).
8.3.3Select a suitable probe liner and probe length so that all traverse points can be sampled. For large stacks, to reduce the length of the probe, consider sampling from opposite sides of the stack.
8.3.4A minimum of 30 cu ft of sample volume is suggested for emission sources with stack concentrations not greater than 23,000,000 ppbv. Additional sample volume shall be collected as necessitated by the capacity of the water reagent and analytical detection limit constraint. Reduced sample volume may be collected as long as the final concentration of formaldehyde in the stack
8.3.5Determine the total length of sampling time needed to obtain the identified minimum volume by comparing the anticipated average sampling rate with the volume requirement. Allocate the same time to all traverse points defined by EPA Method 1, 40 CFR part 60, appendix A. To avoid timekeeping errors, the length of time sampled at each traverse point should be an integer or an integer plus 0.5 min.
8.3.6In some circumstances (e.g., batch cycles) it may be necessary to sample for shorter times at the traverse points and to obtain smaller gas-volume samples. In these cases, careful documentation must be maintained in order to allow accurate calculations of concentrations.
8.4Preparation of Collection Train
8.4.1During preparation and assembly of the sampling train, keep all openings where contamination can occur covered with Teflon
8.4.2Place 100 ml of water in each of the first two impingers, and leave the third impinger empty. If additional capacity is required for high expected concentrations of formaldehyde in the stack gas, 200 ml of water per impinger may be used or additional impingers may be used for sampling. Transfer approximately 200 to 300 g of pre-weighed silica gel from its container to the fourth impinger. Care should be taken to ensure that the silica gel is not entrained and carried out from the impinger during sampling. Place the silica gel 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.
8.4.3With a glass or quartz liner, install the selected nozzle using a Viton-A O-ring when stack temperatures are <260 °C (500 °F) and a woven glass-fiber gasket when temperatures are higher. See APTD-0576 for details. Other connection systems utilizing either 316 stainless steel or Teflon
8.4.4Assemble the train as shown in Figure 1. During assembly, a very light coating of silicone grease may be used on ground-glass joints of the impingers, but the silicone grease should be limited to the outer portion (see APTD-0576) of the ground-glass joints to minimize silicone grease contamination. If necessary, Teflon
8.4.5Place crushed ice all around the impingers.
8.4.6Turn on and set the probe heating system at the desired operating temperature. Allow time for the temperature to stabilize.
8.5Leak-Check Procedures
8.5.1Pre-test Leak-check: Recommended, but not required. If the tester elects to conduct the pre-test leak-check, the following procedure shall be used.
8.5.1.1After the sampling train has been assembled, turn on and set probe heating system at the desired operating temperature. Allow time for the temperature to stabilize. If a Viton-a O-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 381 mm Hg (15 in Hg) vacuum.
A lower vacuum may be used, provided that the lower vacuum is not exceeded during the test.
If a woven glass fiber gasket is used, do not connect the probe to the train during the leak-check. Instead, leak-check the train by first attaching a carbon-filled leak-check impinger to the inlet and then plugging the inlet and pulling a 381 mm Hg (15 in Hg) vacuum. (A lower vacuum may be used if this lower vacuum is not exceeded during the test.) Next connect the probe to the train and leak-check at about 25 mm Hg (1 in Hg) vacuum. Alternatively, leak-check the probe with the rest of the sampling train in one step at 381 mm Hg (15 in Hg) vacuum. Leakage rates in excess of (a) 4 percent of the average sampling rate or (b) 0.00057 m
8.5.1.2The following leak-check instructions for the sampling train described in APTD-0576 and APTD-0581 may be helpful. Start the pump with the fine-adjust valve fully open and coarse-valve completely closed. Partially open the coarse-adjust valve and slowly close the fine-adjust valve until the desired vacuum is reached. Do not reverse direction of the fine-adjust valve, as liquid will back up into the train. If the desired vacuum is exceeded, either perform the leak-check at this higher vacuum or end the leak-check, as described below, and start over.
8.5.1.3When the leak-check is completed, first slowly remove the plug from the inlet to the probe. When the vacuum drops to 127 mm (5 in) Hg or less, immediately close the coarse-adjust valve. Switch off the pumping system and reopen the fine-adjust valve. Do not reopen the fine-adjust valve until the coarse-adjust valve has been closed to prevent the liquid in the impingers from being forced backward in the sampling line and silica gel from being entrained backward into the third impinger.
8.5.2Leak-checks During Sampling Run:
8.5.2.1If, during the sampling run, a component change (e.g., impinger) becomes necessary, a leak-check shall be conducted immediately after the interruption of sampling and before the change is made. The leak-check shall be done according to the procedure described in Section 10.3.3, except that it shall be done at a vacuum greater than or equal to the maximum value recorded up to that point in the test. If the leakage rate is found to be no greater than 0.0057 m
Any correction of the sample volume by calculation reduces the integrity of the pollutant concentration data generated and must be avoided.
8.5.2.2Immediately after component changes, leak-checks are optional. If performed, the procedure described in section 8.5.1.1 shall be used.
8.5.3Post-test Leak-check:
8.5.3.1A leak-check is mandatory at the conclusion of each sampling run. The leak-check shall be done with the same procedures as the pre-test leak-check, except that the post-test leak-check shall be conducted at a vacuum greater than or equal to the maximum value reached during the sampling run. If the leakage rate is found to be no greater than 0.00057 m
8.6Sampling Train Operation
8.6.1During the sampling run, maintain an isokinetic sampling rate to within 10 percent of true isokinetic, below 28 l/min (1.0 cfm). Maintain a temperature around the probe of 120 °C ±14 °C (248 ° ±25 °F).
8.6.2For each run, record the data on a data sheet such as the one shown in Figure 2. Be sure to record the initial dry-gas meter reading. Record the dry-gas meter 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 required by Figure 2 at least once at each sample point during each time increment and additional readings when significant adjustments (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.
8.6.3Clean the stack access ports prior to the test run to eliminate the chance of sampling deposited material. To begin sampling, remove the nozzle cap, verify that the probe heating system are at the specified temperature, and verify 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, which aid in the rapid adjustment of the isokinetic sampling rate without excessive computations, are available. These nomographs are designed for use when the Type S pitot tube coefficient is 0.84 ±0.02 and the stack gas equivalent density (dry molecular weight) is equal to 29 ±4. APTD-0576 details the procedure for using the nomographs. If the stack gas molecular weight and the pitot tube coefficient are outside the above ranges, do not use the nomographs unless appropriate steps are taken to compensate for the deviations.
8.6.4When the stack is under significant negative pressure (equivalent to the height of the impinger stem), take care to close the coarse-adjust valve before inserting the probe into the stack in order to prevent liquid from backing up through the train. If necessary, a low vacuum on the train may have to be started prior to entering the stack.
8.6.5When the probe is in position, block off the openings around the probe and stack access port to prevent unrepresentative dilution of the gas stream.
8.6.6Traverse the stack cross section, as required by EPA Method 1, 40 CFR part 60, appendix A, 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 access port, in order to minimize the chance of extracting deposited material.
8.6.7During the test run, make periodic adjustments to keep the temperature around the probe at the proper levels. Add more ice and, if necessary, salt, to maintain a temperature of <20 °C (68 °F) at the silica gel outlet.
8.6.8A single train shall be used for the entire sampling 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. An additional train or trains may also be used for sampling when the capacity of a single train is exceeded.
8.6.9When two or more trains are used, separate analyses of components from each train shall be performed. If multiple trains have been used because the capacity of a single train would be exceeded, first impingers from each train may be combined, and second impingers from each train may be combined.
8.6.10At the end of the sampling run, turn off the coarse-adjust valve, remove the probe and nozzle from the stack, turn off the pump, record the final dry gas meter reading, and conduct a post-test leak-check. Also, check the pitot lines as described in EPA Method 2, 40 CFR part 60, appendix A. The lines must pass this leak-check in order to validate the velocity-head data.
8.6.11Calculate percent isokineticity (see Method 2) to determine whether the run was valid or another test should be made.
8.7Sample Preservation and Handling
8.7.1Samples from most sources applicable to this method have acceptable holding times using normal handling practices (shipping samples iced, storing in refrigerator at 2 °C until analysis). However, forming section stacks and other sources using waste water sprays may be subject to microbial contamination. For these sources, a biocide (quaternary ammonium compound solution) may be added to collected samples to improve sample stability and method ruggedness.
8.7.2Sample holding time: Samples should be analyzed within 14 days of collection. Samples must be refrigerated/kept cold for the entire period preceding analysis. After the samples have been brought to room
8.7.3Additional studies will be performed to evaluate whether longer sample holding times are feasible for this method.
8.8Sample Recovery
8.8.1Preparation:
8.8.1.1Proper 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. When the probe can be handled safely, wipe off all external particulate matter near the tip of the probe nozzle and place a cap over the tip to prevent losing or gaining particulate matter. Do not cap the probe tightly while the sampling train is cooling because a vacuum will be created, drawing liquid from the impingers back through the sampling train.
8.8.1.2Before moving the sampling train to the cleanup site, remove the probe from the sampling train and cap the open outlet, being careful not to lose any condensate that might be present. Remove the umbilical cord from the last impinger and cap the impinger. If a flexible line is used, let any condensed water or liquid drain into the impingers. Cap off any open impinger inlets and outlets. Ground glass stoppers, Teflon
8.8.1.3Transfer the probe and impinger assembly to an area that is clean and protected from wind so that the chances of contaminating or losing the sample are minimized.
8.8.1.4Inspect the train before and during disassembly, and note any abnormal conditions.
8.8.1.5Save a portion of the washing solution (high purity water) used for cleanup as a blank.
8.8.2Sample Containers:
8.8.2.1Container 1: Probe and Impinger Catches. Using a graduated cylinder, measure to the nearest ml, and record the volume of the solution in the first three impingers. Alternatively, the solution may be weighed to the nearest 0.5 g. Include any condensate in the probe in this determination. Transfer the combined impinger solution from the graduated cylinder into the polyethylene bottle. Taking care that dust on the outside of the probe or other exterior surfaces does not get into the sample, clean all surfaces to which the sample is exposed (including the probe nozzle, probe fitting, probe liner, first three impingers, and impinger connectors) with water. Use less than 400 ml for the entire waste (250 ml would be better, if possible). Add the rinse water to the sample container.
8.8.2.1.1Carefully remove the probe nozzle and rinse the inside surface with water from a wash bottle. Brush with a bristle brush and rinse until the rinse shows no visible particles, after which make a final rinse of the inside surface. Brush and rinse the inside parts of the Swagelok (or equivalent) fitting with water in a similar way.
8.8.2.1.2Rinse the probe liner with water. While squirting the water into the upper end of the probe, tilt and rotate the probe so that all inside surfaces will be wetted with water. Let the water drain from the lower end into the sample container. The tester may use a funnel (glass or polyethylene) to aid in transferring the liquid washes to the container. Follow the rinse with a bristle brush. Hold the probe in an inclined position, and squirt water into the upper end as the probe brush is being pushed with a twisting action through the probe. Hold the sample container underneath the lower end of the probe, and catch any water and particulate matter that is brushed from the probe. Run the brush through the probe three times or more. Rinse the brush with water and quantitatively collect these washings in the sample container. After the brushing, make a final rinse of the probe as describe above.
Two people should clean the probe in order to minimize sample losses. Between sampling runs, brushes must be kept clean and free from contamination.
8.8.2.1.3Rinse the inside surface of each of the first three impingers (and connecting tubing) three separate times. Use a small portion of water for each rinse, and brush each surface to which the sample is exposed with a bristle brush to ensure recovery of fine particulate matter. Make a final rinse of each surface and of the brush, using water.
8.8.2.1.4After all water washing and particulate matter have been collected in the sample container, tighten the lid so the sample will not leak out when the container is shipped to the laboratory. Mark the height of the fluid level to determine whether leakage occurs during transport. Label the container clearly to identify its contents.
8.8.2.1.5If the first two impingers are to be analyzed separately to check for breakthrough, separate the contents and rinses of the two impingers into individual containers. Care must be taken to avoid physical carryover from the first impinger to the second. Any physical carryover of collected moisture into the second impinger will invalidate a breakthrough assessment.
8.8.2.2Container 2: Sample Blank. Prepare a blank by using a polyethylene container and adding a volume of water equal to the total volume in Container 1. Process the blank in the same manner as Container 1.
8.8.2.3Container 3: Silica Gel. Note the color of the indicating silica gel to determine whether it has been completely spent
8.8.2.4Sample containers should be placed in a cooler, cooled by (although not in contact with) ice. Putting sample bottles in Zip-Lock
8.8.2.5A quaternary ammonium compound can be used as a biocide to stabilize samples against microbial degradation following collection. Using the stock quaternary ammonium compound (QAC) solution; add 2.5 ml QAC solution for every 100 ml of recovered sample volume (estimate of volume is satisfactory) immediately after collection. The total volume of QAC solution must be accurately known and recorded, to correct for any dilution caused by the QAC solution addition.
8.8.3Sample Preparation for Analysis 8.8.3.1 The sample should be refrigerated if the analysis will not be performed on the day of sampling. Allow the sample to warm at room temperature for about two hours (if it has been refrigerated) prior to analyzing.
8.8.3.2Analyze the sample by the pararosaniline method, as described in Section 11. If the color-developed sample has an absorbance above the highest standard, a suitable dilution in high purity water should be prepared and analyzed.
9.1Sampling: See EPA Manual 600/4-77-02b for Method 5 quality control.
9.2Analysis: The quality assurance program required for this method includes the analysis of the field and method blanks, and procedure validations. The positive identification and quantitation of formaldehyde are dependent on the integrity of the samples received and the precision and accuracy of the analytical methodology. Quality assurance procedures for this method are designed to monitor the performance of the analytical methodology and to provide the required information to take corrective action if problems are observed in laboratory operations or in field sampling activities.
9.2.1Field Blanks: Field blanks must be submitted with the samples collected at each sampling site. The field blanks include the sample bottles containing aliquots of sample recover water, and water reagent. At a minimum, one complete sampling train will be assembled in the field staging area, taken to the sampling area, and leak-checked at the beginning and end of the testing (or for the same total number of times as the actual sampling train). The probe of the blank train must be heated during the sample test. The train will be recovered as if it were an actual test sample. No gaseous sample will be passed through the blank sampling train.
9.2.2Blank Correction: The field blank formaldehyde concentrations will be subtracted from the appropriate sample formaldehyde concentrations. Blank formaldehyde concentrations above 0.25 µg/ml should be considered suspect, and subtraction from the sample formaldehyde concentrations should be performed in a manner acceptable to the Administrator.
9.2.3Method Blanks: A method blank must be prepared for each set of analytical operations, to evaluate contamination and artifacts that can be derived from glassware, reagents, and sample handling in the laboratory.
10.1Probe Nozzle: Probe nozzles shall be calibrated before their initial use in the field. Using a micrometer, measure the inside diameter of the nozzle to the nearest 0.025 mm (0.001 in). Make measurements at three separate places across the diameter 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 the nozzle becomes nicked or corroded, it shall be repaired and calibrated, or replaced with a calibrated nozzle before use. Each nozzle must be permanently and uniquely identified.
10.2Pitot Tube: The Type S pitot tube assembly shall be calibrated according to the procedure outlined in Section 4 of EPA Method 2, or assigned a nominal coefficient of 0.84 if it is not visibly nicked or corroded and if it meets design and intercomponent spacing specifications.
10.3Metering System
10.3.1Before its initial use in the field, the metering system shall be calibrated according to the procedure outlined in APTD-
10.3.2After each field use, check the calibration of the metering system by performing three calibration runs at a single intermediate orifice setting (based on the previous field test). Set the vacuum at the maximum value reached during the test series. To adjust the vacuum, insert a valve between the wet-test meter and the inlet of the metering system. Calculate the average value of the calibration factor. If the calibration has changed by more than 5 percent, recalibrate the meter over the full range of orifice settings, as outlined in APTD-0576.
10.3.3Leak-check of metering system: The portion of the sampling train from the pump to the orifice meter (see Figure 1) 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. Use the following procedure: 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 13-18 cm (5-7 in) water column by blowing into the rubber tubing. Pinch off the tubing and observe the manometer for 1 min. A loss of pressure on the manometer indicates a leak in the meter box. Leaks must be corrected.
If the dry-gas meter coefficient values obtained before and after a test series differ by >5 percent, either the test series must be voided or calculations for test series must be performed using whichever meter coefficient value (i.e., before or after) gives the lower value of total sample volume.
10.4Probe Heater: The probe heating system must be calibrated before its initial use in the field according to the procedure outlined in APTD-0576. Probes constructed according to APTD-0581 need not be calibrated if the calibration curves in APTD-0576 are used.
10.5Temperature gauges: Use the procedure in section 4.3 of USEPA Method 2 to calibrate in-stack temperature gauges. Dial thermometers such as are used for the dry gas meter and condenser outlet, shall be calibrated against mercury-in-glass thermometers.
10.6Barometer: Adjust the barometer initially and before each test series to agree to within ±2.5 mm Hg (0.1 in Hg) of the mercury barometer. Alternately, if a National Weather Service Station (NWSS) is located at the same altitude above sea level as the test site, the barometric pressure reported by the NWSS may be used.
10.7Balance: Calibrate the balance before each test series, using Class S standard weights. The weights must be within ±0.5 percent of the standards, or the balance must be adjusted to meet these limits.
The working formaldehyde standards (0.25, 0.50, 1.0, 2.0, and 3.0 µg/ml) are analyzed and a calibration curve is calculated for each day's analysis. The standards should be analyzed first to ensure that the method is working properly prior to analyzing the samples. In addition, a sample of the high-purity water should also be analyzed and used as a “0” formaldehyde standard.
The procedure for analysis of samples and standards is identical: Using the pipet set to 2.50 ml, pipet 2.50 ml of the solution to be analyzed into a polystyrene cuvette. Using the 250 µl pipet, pipet 250 µl of the pararosaniline reagent solution into the cuvette. Seal the top of the cuvette with a Parafilm square and shake at least 30 seconds to ensure the solution in the cuvette is well-mixed. Peel back a corner of the Parafilm so the next reagent can be added. Using the 250 µl pipet, pipet 250 µl of the sodium sulfite reagent solution into the cuvette. Reseal the cuvette with the Parafilm, and again shake for about 30 seconds to mix the solution in the cuvette. Record the time of addition of the sodium sulfite and let the color develop at room temperature for 60 minutes. Set the spectrophotometer to 570 nm and set to read in Absorbance Units. The spectrophotometer should be equipped with a holder for the 1-cm pathlength cuvettes. Place cuvette(s) containing high-purity water in the spectrophotometer and adjust to read 0.000 AU.
After the 60 minutes color development period, read the standard and samples in the spectrophotometer. Record the absorbance reading for each cuvette. The calibration curve is calculated by linear regression, with the formaldehyde concentration as the “x” coordinate of the pair, and the absorbance reading as the “y” coordinate. The procedure is very reproducible, and typically will yield values similar to these for the calibration curve:
11.1Notes on the Pararosaniline Procedure
11.1.1The pararosaniline method is temperature-sensitive. However, the small fluctuations typical of a laboratory will not significantly affect the results.
11.1.2The calibration curve is linear to beyond 4 “µg/ml” formaldehyde, however, a research-grade spectrophotometer is required to reproducibly read the high absorbance values. Consult your instrument manual to evaluate the capability of the spectrophotometer.
11.1.3The quality of the laboratory water used to prepare standards and make dilutions is critical. It is important that the cautions given in the Reagents section be observed. This procedure allows quantitation of formaldehyde at very low levels, and thus it is imperative to avoid contamination from other sources of formaldehyde and to exercise the degree of care required for trace analyses.
11.1.4The analyst should become familiar with the operation of the Oxford or equivalent pipettors before using them for an analysis. Follow the instructions of the manufacturer; one can pipet water into a tared container on any analytical balance to check pipet accuracy and precision. This will also establish if the proper technique is being used. Always use a new tip for each pipetting operation.
11.1.5This procedure follows the recommendations of ASTM Standard Guide D 3614, reading all solutions versus water in the reference cell. This allows the absorbance of the blank to be tracked on a daily basis. Refer to ASTM D 3614 for more information.
Carry out calculations, retaining at least one extra decimal figure beyond that of the acquired data. Round off figures after final calculations.
12.1Calculations of Total Formaldehyde
12.1.1To determine the total formaldehyde in mg, use the following equation if biocide was not used:
Total mg formaldehyde=
12.1.2To determine the total formaldehyde in mg, use the following equation if biocide was used:
Total mg formaldehyde=
12.2Formaldehyde concentration (mg/m
12.3Average dry gas meter temperature and average orifice pressure drop are obtained from the data sheet.
12.4Dry Gas Volume: Calculate V
12.5Volume of Water Vapor and Moisture Content: Calculated the volume of water vapor and moisture content from equations 5-2 and 5-3 of EPA Method 5.
The precision of this method is estimated to be better than ±5 percent, expressed as ± the percent relative standard deviation.
This method has been validated and approved for mineral wool and wool fiberglass sources. This method may not be applied to other source categories without validation and approval by the Administrator according to the procedures in Test Method 301, 40 CFR part 63, appendix A. For sources seeking to apply FTIR to other source categories, Test Method 320 (40 CFR part 63, appendix A) may be utilized.
1.1Scope. The analytes measured by this method and their CAS numbers are:
1.2Applicability
1.2.1This method is applicable for the determination of formaldehyde, phenol, methanol, carbonyl sulfide (COS) and carbon monoxide (CO) concentrations in controlled and uncontrolled emissions from manufacturing processes using phenolic resins. The compounds are analyzed in the mid-infrared spectral region (about 400 to 4000 cm−1 or 25 to 2.5 µm). Suggested analytical regions are given below (Table 1). Slight deviations from these recommended regions may be necessary due to variations in moisture content and ammonia concentration from source to source.
1.3Method Range and Sensitivity
1.3.1The analytical range is a function of instrumental design and composition of the gas stream. Theoretical detection limits depend, in part, on (a) the absorption coefficient of the compound in the analytical frequency region, (b) the spectral resolution, (c) interferometer sampling time, (d) detector sensitivity and response, and (e) absorption pathlength.
1.3.2Practically, there is no upper limit to the range. The practical lower detection limit is usually higher than the theoretical value, and depends on (a) moisture content of the flue gas, (b) presence of interferants, and (c) losses in the sampling system. In general, a 22 meter pathlength cell in a suitable sampling system can achieve practical detection limits of 1.5 ppm for three compounds (formaldehyde, phenol, and methanol) at moisture levels up to 15 percent by volume. Sources with uncontrolled emissions of CO and COS may require a 4 meter pathlength cell due to high concentration levels. For these two compounds, make sure absorbance of highest concentration component is <1.0.
1.4Data Quality Objectives
2.1Principle
2.1.1Molecules are composed of chemically bonded atoms, which are in constant motion. The atomic motions result in bond deformations (bond stretching and bond-angle bending). The number of fundamental (or independent) vibrational motions depends on the number of atoms (N) in the molecule. At typical testing temperatures, most molecules are in the ground-state vibrational state for most of their fundamental vibrational motions. A molecule can undergo a transition from its ground state (for a particular vibration) to the first excited state by absorbing a quantum of light at a frequency characteristic of the molecule and the molecular motion. Molecules also undergo rotational transitions by absorbing energies in the far-infrared or microwave spectral regions. Rotational transition absorbencies are superimposed on the vibrational absorbencies to give a characteristic shape to each rotational-vibrational absorbance “band.”
2.1.2Most molecules exhibit more than one absorbance band in several frequency regions to produce an infrared spectrum (a characteristic pattern of bands or a “fingerprint”) that is unique to each molecule. The infrared spectrum of a molecule depends on its structure (bond lengths, bond angles, bond strengths, and atomic masses). Even small differences in structure can produce significantly different spectra.
2.1.3Spectral band intensities vary with the concentration of the absorbing compound. Within constraints, the relationship between absorbance and sample concentration is linear. Sample spectra are compared to reference spectra to determine the species and their concentrations.
2.2Sampling and Analysis
2.2.1Flue gas is continuously extracted from the source, and the gas or a portion of the gas is conveyed to the FTIR gas cell, where a spectrum of the flue gas is recorded. Absorbance band intensities are related to sample concentrations by Beer's Law.
2.2.2After identifying a compound from the infrared spectrum, its concentration is determined by comparing band intensities in the sample spectrum to band intensities in “reference spectra” of the formaldehyde, phenol, methanol, COS and CO. These reference spectra are available in a permanent soft copy from the EPA spectral library on the EMTIC bulletin board. The source may also prepare reference spectra according to Section 4.5 of the FTIR Protocol.
Reference spectra not prepared according to the FTIR Protocol are not acceptable for use in this test method. Documentation detailing the FTIR Protocol steps used in preparing any non-EPA reference spectra shall be included in each test report submitted by the source.
2.3Operator Requirements. The analyst must have some knowledge of source sampling and of infrared spectral patterns to operate the sampling system and to choose a suitable instrument configuration. The analyst should also understand FTIR instrument operation well enough to choose an instrument configuration consistent with the data quality objectives.
See Appendix A of the
4.1Analytical (or Spectral) Interferences. Water vapor. High concentrations of ammonia (hundreds of ppm) may interfere with the analysis of low concentrations of methanol (1 to 5 ppm). For CO, carbon dioxide and water may be interferants. In cases where COS levels are low relative to CO levels, CO and water may be interferants.
4.2Sampling System Interferences. Water, if it condenses, and ammonia, which reacts with formaldehyde.
5.1Formaldehyde is a suspected carcinogen; therefore, exposure to this compound must be limited. Proper monitoring and safety precautions must be practiced in any atmosphere with potentially high concentrations of CO.
5.2This method may involve sampling at locations having high positive or negative pressures, high temperatures, elevated heights, high concentrations of hazardous or toxic pollutants, or other diverse sampling conditions. It is the responsibility of the tester(s) to ensure proper safety and health practices, and to determine the applicability of regulatory limitations before performing this test method.
The equipment and supplies are based on the schematic of a sampling train shown in Figure 1. Either the evacuated or purged sampling technique may be used with this sampling train. Alternatives may be used, provided that the data quality objectives of this method are met.
6.1Sampling Probe. Glass, stainless steel, or other appropriate material of sufficient length and physical integrity to sustain heating, prevent adsorption of analytes, and to reach gas sampling point.
6.2Particulate Filters. A glass wool plug (optional) inserted at the probe tip (for large particulate removal) and a filter rated at 1-micron (e.g., Balston
6.3Sampling Line/Heating System. Heated (maintained at 250 ±25 degrees F) stainless steel, Teflon
6.4Stainless Steel Tubing. Type 316, e.g.,
6.5Gas Regulators. Appropriate for individual gas cylinders.
6.6Teflon
6.7Sample Pump. A leak-free pump (e.g., KNF
6.8Gas Sample Manifold. A heated manifold that diverts part of the sample stream to the analyzer, and the rest to the by-pass discharge vent or other analytical instrumentation.
6.9Rotameter. A calibrated 0 to 20 L/min range rotameter.
6.10FTIR Analytical System. Spectrometer and detector, capable of measuring formaldehyde, phenol, methanol, COS and CO to the predetermined minimum detectable level. The system shall include a personal computer with compatible software that provides real-time updates of the spectral profile during sample collection and spectral collection.
6.11FTIR Cell Pump. Required for the evacuated sampling technique, capable of evacuating the FTIR cell volume within 2 minutes. The FTIR cell pump should allow the operator to obtain at least 8 sample spectra in 1 hour.
6.12Absolute Pressure Gauge. Heatable and capable of measuring pressure from 0 to 1000 mmHg to within ±2.5 mmHg (e.g., Baratron
6.13Temperature Gauge. Capable of measuring the cell temperature to within ±2 °C.
7.1Ethylene (Calibration Transfer Standard). Obtain NIST traceable (or Protocol) cylinder gas.
7.2Nitrogen. Ultra high purity (UHP) grade.
7.3Reference Spectra. Obtain reference spectra for the target pollutants at concentrations that bracket (in ppm-meter/K) the emission source levels. Also, obtain reference spectra for SF
Sampling should be performed in the following sequence: Collect background, collect CTS spectrum, collect samples, collect post-test CTS spectrum, verify that two copies of all data were stored on separate computer media.
8.1Pretest Preparations and Evaluations. Using the procedure in Section 4.0 of the
a. Test requirements: AU
b. Interferants: See Table 1.
c. Sampling system: L
d. Analytical regions: 1 through N
8.1.1If necessary, sample and acquire an initial spectrum. Then determine the proper operational pathlength of the instrument to obtain non-saturated absorbances of the target analytes.
8.1.2Set up the sampling train as shown in Figure 1.
8.2Sampling System Leak-check. Leak-check from the probe tip to pump outlet as follows: Connect a 0- to 250-mL/min rate meter (rotameter or bubble meter) to the outlet of the pump. Close off the inlet to the probe, and note the leakage rate. The leakage rate shall be ≤200 mL/min.
8.3Analytical System Leak-check.
8.3.1For the evacuated sample technique, close the valve to the FTIR cell, and evacuate the absorption cell to the minimum absolute pressure P
8.3.2For both the evacuated sample and purging techniques, pressurize the system to about 100 mmHg above atmospheric pressure. Isolate the pump and determine the change in pressure ΔP
8.3.3Measure the barometric pressure, P
8.3.4Determine the percent leak volume %V
8.3.5Leak volumes in excess of 4 percent of the sample system volume V
8.4Background Spectrum. Evacuate the gas cell to ≤5 mmHg, and fill with dry nitrogen gas to ambient pressure. Verify that no significant amounts of absorbing species (for example water vapor and CO
8.5Pre-Test Calibration Transfer Standard. Evacuate the gas cell to ≤5 mmHg absolute pressure, and fill the FTIR cell to atmospheric pressure with the CTS gas. Or, purge the cell with 10 cell volumes of CTS gas. Record the spectrum. If continuous sampling will be used during sample collection, collect the CTS spectrum with CTS gas flowing through the cell at the same pressure and temperature as will be used during sampling.
8.6Samples
8.6.1Evacuated Samples. Evacuate the absorbance cell to ≤5 mmHg absolute pressure. Fill the cell with flue gas to ambient pressure and record the spectrum. Before taking the next sample, evacuate the cell until no further evidence of absorption exists. Repeat this procedure to collect at least 8 separate spectra (samples) in 1 hour.
8.6.2Purge Sampling. Purge the FTIR cell with 10 cell volumes of flue gas and at least for about 10 minutes. Discontinue the gas cell purge, isolate the cell, and record the
8.6.3Continuous Sampling. Spectra can be collected continuously while the FTIR cell is being purged. The sample integration time, t
8.7Sampling QA, Data Storage and Reporting
8.7.1Sample integration times should be sufficient to achieve the required signal-to-noise ratios. Obtain an absorbance spectrum by filling the cell with nitrogen. Measure the RMSD in each analytical region in this absorbance spectrum. Verify that the number of scans is sufficient to achieve the target MAU (Table 2).
8.7.2Identify all sample spectra with unique file names.
8.7.3Store on two separate computer media a copy of sample interferograms and processed spectra. The data shall be available to the Administrator on request for the length of time specified in the applicable regulation.
8.7.4For each sample spectrum, document the sampling conditions, the sampling time (while the cell was being filled), the time the spectrum was recorded, the instrumental conditions (path length, temperature, pressure, resolution, integration time), and the spectral file name. Keep a hard copy of these data sheets.
8.8Signal Transmittance. While sampling, monitor the signal transmittance through the instrumental system. If signal transmittance (relative to the background) drops below 95 percent in any spectral region where the sample does not absorb infrared energy, obtain a new background spectrum.
8.9Post-run CTS. After each sampling run, record another CTS spectrum.
8.10Post-test QA
8.10.1Inspect the sample spectra immediately after the run to verify that the gas matrix composition was close to the expected (assumed) gas matrix.
8.10.2Verify that the sampling and instrumental parameters were appropriate for the conditions encountered. For example, if the moisture is much greater than anticipated, it will be necessary to use a shorter path length or dilute the sample.
8.10.3Compare the pre and post-run CTS spectra. They shall agree to within −5 percent. See FTIR Protocol, Appendix E.
Follow the quality assurance procedures in the method, including the analysis of pre and post-run calibration transfer standards (Sections 8.5 and 8.9) and the post-test quality assurance procedures in Section 8.10.
10.1Signal-to-Noise Ratio (S/N). The S/N shall be sufficient to meet the MAU in each analytical region.
10.2Absorbance Pathlength. Verify the absorbance path length by comparing CTS spectra to reference spectra of the calibration gas(es). See FTIR Protocol, Appendix E.
10.3Instrument Resolution. Measure the line width of appropriate CTS band(s) and compare to reference CTS spectra to verify instrumental resolution.
10.4Apodization Function. Choose appropriate apodization function. Determine any appropriate mathematical transformations that are required to correct instrumental errors by measuring the CTS. Any mathematical transformations must be documented and reproducible.
10.5FTIR Cell Volume. Evacuate the cell to ≤5 mmHg. Measure the initial absolute temperature (T
Refer to Sections 4.6-4.11, Sections 5, 6, and 7, and the appendices of the FTIR Protocol.
a. Data analysis is performed using appropriate reference spectra whose concentrations can be verified using CTS spectra. Various analytical programs are available to relate sample absorbance to a concentration standard. Calculated concentrations should be verified by analyzing spectral baselines after mathematically subtracting scaled reference spectra from the sample spectra. A full description of the data analysis and calculations may be found in the FTIR Protocol (Sections 4.0, 5.0, 6.0 and appendices).
b. Correct the calculated concentrations in sample spectra for differences in absorption pathlength between the reference and sample spectra by:
All interferograms used in determining source concentration shall be stored for the period of time required in the applicable regulation. The Administrator has the option of requesting the interferograms recorded during the test in electronic form as part of the test report.
Refer to the FTIR Protocol.
Laboratory standards prepared from the formaldehyde and phenol are handled according to the instructions in the materials safety data sheets (MSDS).
(1) “Field Validation Test Using Fourier Transform Infrared (FTIR) Spectrometry To Measure Formaldehyde, Phenol and Methanol at a Wool Fiberglass Production Facility.” Draft. U.S. Environmental Protection Agency Report, Entropy, Inc., EPA Contract No. 68D20163, Work Assignment I-32, December 1994 (docket item II-A-13).
(2) “Method 301—Field Validation of Pollutant Measurement Methods from Various Waste Media,” 40 CFR part 63, appendix A.
1.1This method applies to the determination of the initial, particle size dependent, filtration efficiency for paint arrestors over the particle diameter range from 0.3 to 10 µm. The method applies to single and multiple stage paint arrestors or paint arrestor media. The method is applicable to efficiency determinations from 0 to 99 percent. Two test aerosols are used—one liquid phase and one solid phase. Oleic acid, a low-volatility liquid (CAS Number 112-80-1), is used to simulate the behavior of wet paint overspray. The solid-phase aerosol is potassium chloride salt (KCl, CAS Number 7447-40-7) and is used to simulate the behavior of a dry overspray. The method is limited to determination of the initial, clean filtration efficiency of the arrestor. Changes in efficiency (either increase or decrease) due to the accumulation of paint overspray on and within the arrestor are not evaluated.
1.2Efficiency is defined as 1—Penetration (e.g., 70 percent efficiency is equal to 0.30 penetration). Penetration is based on the ratio of the downstream particle concentration to the upstream concentration. It is often more useful, from a mathematical or statistical point of view, to discuss the upstream and downstream counts in terms of penetration rather than the derived efficiency value. Thus, this document uses both penetration and efficiency as appropriate.
1.3For a paint arrestor system or subsystem which has been tested by this method, adding additional filtration devices to the system or subsystem shall be assumed to result in an efficiency of at least that of the original system without the requirement for additional testing. (For example, if the final stage of a three-stage paint arrestor system has been tested by itself, then the addition of the other two stages shall be assumed to maintain, as a minimum, the filtration efficiency provided by the final stage alone. Thus, in this example, if the final stage has been shown to meet the filtration requirements of Table 1 of § 63.745 of subpart GG, then the final stage in combination with any additional paint arrestor stages also passes the filtration requirements.)
2.1This method applies to the determination of the fractional (i.e., particle-size dependent) aerosol penetration of several types of paint arrestors. Fractional penetration is computed from aerosol concentrations measured upstream and downstream of an arrestor installed in a laboratory test rig. The aerosol concentrations upstream and downstream of the arrestors are measured with an aerosol analyzer that simultaneously counts and sizes the particles in the aerosol stream. The aerosol analyzer covers the particle diameter size range from 0.3 to 10 µm in a minimum of 12 contiguous sizing channels. Each sizing channel covers a narrow range of particle diameters. For example, Channel 1 may cover from 0.3 to 0.4 µm, Channel 2 from 0.4 to 0.5 µm, * * * By taking the ratio of the
2.2The upstream and downstream aerosol measurements are made while injecting the test aerosol into the air stream upstream of the arrestor (ambient aerosol is removed with HEPA filters on the inlet of the test rig). This test aerosol spans the particle size range from 0.3 to 10 µm and provides sufficient upstream concentration in each of the optical particle counter (OPC) sizing channels to allow accurate calculation of penetration, down to penetrations of approximately 0.01 (i.e., 1 percent penetration; 99 percent efficiency). Results are presented as a graph and a data table showing the aerodynamic particle diameter and the corresponding fractional efficiency.
Aerodynamic Diameter—diameter of a unit density sphere having the same aerodynamic properties as the particle in question.
Efficiency is defined as equal to 1—Penetration.
Optical Particle Counter (OPC)—an instrument that counts particles by size using light scattering. An OPC gives particle diameters based on size, index of refraction, and shape.
Penetration—the fraction of the aerosol that penetrates the filter at a given particle diameter. Penetration equals the downstream concentration divided by the upstream concentration.
4.1The influence of the known interferences (particle losses) are negated by correction of the data using blanks.
5.1There are no specific safety precautions for this method above those of good laboratory practice. This standard does not purport to address all of the safety problems, if any, 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.
6.1Test Facility. A schematic diagram of a test duct used in the development of the method is shown in Figure 319-1.
6.1.1The test section, paint spray section, and attached transitions are constructed of stainless and galvanized steel. The upstream and downstream ducting is 20 cm diameter polyvinyl chloride (PVC). The upstream transition provides a 7 ° angle of expansion to provide a uniform air flow distribution to the paint arrestors. Aerosol concentration is
6.1.2The configuration and dimensions of the test duct can deviate from those of Figure 319-1 provided that the following key elements are maintained: the test duct must meet the criteria specified in Table 319-1; the inlet air is HEPA filtered; the blower is on the upstream side of the duct thereby creating a positive pressure in the duct relative to the surrounding room; the challenge air has a temperature between 50 ° and 100 °F and a relative humidity of less than 65 percent; the angle of the upstream transition (if used) to the paint arrestor must not exceed 7 °; the angle of the downstream transition (if used) from the paint arrestor must not exceed 30 °; the test duct must provide a means for mixing the challenge aerosol with the upstream flow (in lieu of any mixing device, a duct length of 15 duct diameters fulfills this requirement); the test duct must provide a means for mixing any penetrating aerosol with the downstream flow (in lieu of any mixing device, a duct length of 15 duct diameters fulfills this requirement); the test section must provide a secure and leak-free mounting for single and multiple stage arrestors; and the test duct may utilize a 180 ° bend in the downstream duct.
6.2Aerosol Generator. The aerosol generator is used to produce a stable aerosol covering the particle size range from 0.3 to 10 µm diameter. The generator used in the development of this method consists of an air atomizing nozzle positioned at the top of a 0.30-m (12-in.) diameter, 1.3-m (51-in.) tall, acrylic, transparent, spray tower. This tower allows larger sized particles, which would otherwise foul the test duct and sample lines, to fall out of the aerosol. It also adds drying air to ensure that the KCl droplets dry to solid salt particles. After generation, the aerosol passes through an aerosol neutralizer (Kr85 radioactive source) to neutralize any electrostatic charge on the aerosol (electrostatic charge is an unavoidable consequence of most aerosol generation methods). To improve the mixing of the aerosol with the air stream, the aerosol is injected counter to the airflow. Generators of other designs may be used, but they must produce a stable aerosol concentration over the 0.3 to 10 µm diameter size range; provide a means of ensuring the complete drying of the KCl aerosol; and utilize a charge neutralizer to neutralize any electrostatic charge on the aerosol. The resultant challenge aerosol must meet the minimum count per channel and maximum concentration criteria of Table 319-1.
6.3Installation of Paint Arrestor. The paint arrestor is to be installed in the test duct in a manner that precludes air bypassing the arrestor. Since arrestor media are often sold unmounted, a mounting frame may be used to provide back support for the media in addition to sealing it into the duct. The mounting frame for 20 in.×20 in. arrestors will have minimum open internal dimensions of 18 in. square. Mounting frames for 24 in.×24 in. arrestors will have minimum open internal dimensions of 22 in. square. The open internal dimensions of the mounting frame shall not be less than 75 percent of the approach duct dimensions.
6.4Optical Particle Counter. The upstream and downstream aerosol concentrations are measured with a high-resolution optical particle counter (OPC). To ensure comparability of test results, the OPC shall utilize an optical design based on wide-angle light scattering and provided a minimum of 12 contiguous particle sizing channels from 0.3 to 10 µm diameter (based on response to PSL) where, for each channel, the ratio of the diameter corresponding to the upper channel bound to the lower channel bound must not exceed 1.5.
6.5Aerosol Sampling System. The upstream and downstream sample lines must be made of rigid electrically-grounded metallic tubing having a smooth inside surface, and they must be rigidly secured to prevent movement during testing. The upstream and downstream sample lines are to be nominally identical in geometry. The use of a short length (100 mm maximum) of straight flexible tubing to make the final connection to the OPC is acceptable. The inlet nozzles of the upstream and downstream probes must be sharp-edged and of appropriate entrance diameter to maintain isokinetic sampling within 20 percent of the air velocity.
6.5.1The sampling system may be designed to acquire the upstream and downstream samples using (a) sequential upstream-downstream sampling with a single OPC, (b) simultaneous upstream and downstream sampling with two OPC's, or (c) sequential upstream-downstream sampling with two OPC's.
6.5.2When two particle counters are used to acquire the upstream and downstream counts, they must be closely matched in flowrate and optical design.
6.6Airflow Monitor. The volumetric airflow through the system shall be measured with a calibrated orifice plate, flow nozzle, or laminar flow element. The measurement device must have an accuracy of 5 percent or better.
7.1The liquid test aerosol is reagent grade, 98 percent pure, oleic acid (Table 319-2). The solid test aerosol is KCl aerosolized from a solution of KCl in water. In addition to the test aerosol, a calibration aerosol of monodisperse polystyrene latex (PSL) spheres is used to verify the calibration of the OPC.
8.1In this test, all sampling occurs in real-time, thus no samples are collected that require preservation or storage during the test. The paint arrestors are shipped and stored to avoid structural damage or soiling. Each arrestor may be shipped in its original box from the manufacturer or similar cardboard box. Arrestors are stored at the test site in a location that keeps them clean and dry. Each arrestor is clearly labeled for tracking purposes.
9.1Table 319-1 lists the QC control limits.
9.2The standard deviation (σ) of the penetration (P) for a given test at each of the 15 OPC sizing channels is computed from the coefficient of variation (CV, the standard deviation divided by the mean) of the upstream and downstream measurements as:
9.3Data Quality Objectives (DQO).
9.3.1Fractional Penetration. From the triplicate tests of each paint arrestor model, the standard deviation for the penetration measurements at each particle size (i.e., for each sizing channel of the OPC) is computed as:
9.3.2Bias of the fractional penetration values is determined from triplicate no-filter and HEPA filter tests. These tests determine the measurement bias at 100 percent penetration and 0 percent penetration, respectively.
9.3.3PSL-Equivalent Light Scattering Diameter. The precision and bias of the OPC sizing determination are based on sampling a known diameter of PSL and noting whether the particle counts peak in the correct channel of the OPC. This is a pass/fail measurement with no calculations involved.
9.3.4Airflow. The precision of the measurement must be within 5 percent of the set point.
10.1Optical Particle Counter. The OPC must have an up-to-date factory calibration. Check the OPC zero at the beginning and end of each test by sampling HEPA-filtered air. Verify the sizing accuracy on a daily basis (for days when tests are performed) with 1-size PSL spheres.
10.2Airflow Measurement. Airflow measurement devices must have an accuracy of 5 percent or better. Manometers used in conjunction with the orifice plate must be inspected prior to use for proper level, zero, and mechanical integrity. Tubing connections to the manometer must be free from kinks and have secure connections.
10.3Pressure Drop. Measure pressure drop across the paint arrestor with an inclined manometer readable to within 0.01 in. H
11.1Filtration Efficiency. For both the oleic acid and KCl challenges, this procedure is performed in triplicate using a new arrestor for each test.
11.1.1General Information and Test Duct Preparation
11.1.1.1Use the “Test Run Sheet” form (Figure 319-2) to record the test information.
Condition of arrestor (i.e., is there any damage? Must be new condition to proceed):
Manometer zero and level confirmed?
Condition of arrestor at end of test (note any physical deterioration):
Other report formats which contain the same information are acceptable.
11.1.1.2Record the date, time, test operator, Test #, paint arrestor brand/model and its assigned ID number. For tests with no arrestor, record none.
11.1.1.3Ensure that the arrestor is undamaged and is in “new” condition.
11.1.1.4Mount the arrestor in the appropriate frame. Inspect for any airflow leak paths.
11.1.1.5Install frame-mounted arrestor in the test duct. Examine the installed arrestor to verify that it is sealed in the duct. For tests with no arrestor, install the empty frame.
11.1.1.6Visually confirm the manometer zero and level. Adjust as needed.
11.1.2Clean Efficiency Test.
11.1.2.1Record the date and time upon beginning this section.
11.1.2.2Optical Particle Counter.
11.1.2.2.1General: Operate the OPC per the manufacturer's instructions allowing a minimum of 20 minutes warm up before making any measurements.
11.1.2.2.2Overload: The OPC will yield inaccurate data if the aerosol concentration it is attempting to measure exceeds its operating limit. To ensure reliable measurements, the maximum aerosol concentration will not exceed 10 percent of the manufacturer's claimed upper concentration limit corresponding to a 10 percent count error. If this value is exceeded, reduce the aerosol concentration until the acceptable conditions are met.
11.1.2.2.3Zero Count: Connect a HEPA capsule to the inlet of the OPC and obtain printouts for three samples (each a minimum of 1-minute each). Record maximum cumulative zero count. If the count rate exceeds 50 counts per minute, the OPC requires servicing before continuing.
11.1.2.2.4PSL Check of OPC Calibration: Confirm the calibration of the OPC by sampling a known size PSL aerosol. Aerosolize the PSL using an appropriate nebulizer. Record whether the peak count is observed in the proper channel. If the peak is not seen in the appropriate channel, have the OPC recalibrated.
11.1.2.3Test Conditions:
11.1.2.3.1Airflow: The test airflow corresponds to a nominal face velocity of 120 FPM through the arrestor. For arrestors having nominal 20 in.×20 in. face dimensions, this measurement corresponds to an airflow of 333 cfm. For arrestors having nominal face dimensions of 24 in.×24 in., this measurement corresponds to an airflow of 480 cfm.
11.1.2.3.2Temperature and Relative Humidity: The temperature and relative humidity of the challenge air stream will be measured to within an accuracy of ±2 °F and ±10 percent RH. To protect the probe from fouling, it may be removed during periods of aerosol generation.
11.1.2.3.3Barometric Pressure: Use a mercury barometer. Record the atmospheric pressure.
11.1.2.4Upstream and Downstream Background Counts.
11.1.2.4.1With the arrestor installed in the test duct and the airflow set at the proper value, turn on the data acquisition computer and bring up the data acquisition program.
11.1.2.4.2Set the OPC settings for the appropriate test sample duration with output for both printer and computer data collection.
11.1.2.4.3Obtain one set of upstream-downstream background measurements.
11.1.2.4.4After obtaining the upstream-downstream measurements, stop data acquisition.
11.1.2.5Efficiency Measurements:
11.1.2.5.1Record the arrestor pressure drop.
11.1.2.5.2Turn on the Aerosol Generator. Begin aerosol generation and record the operating parameters.
11.1.2.5.3Monitor the particle counts. Allow a minimum of 5 minutes for the generator to stabilize.
11.1.2.5.4Confirm that the total particle count does not exceed the predetermined upper limit. Adjust generator as needed.
11.1.2.5.5Confirm that a minimum of 50 particle counts are measured in the upstream sample in each of the OPC channels per sample. (A minimum of 50 counts per channel per sample will yield the required minimum 500 counts per channel total for the 10 upstream samples as specified in Table 319-1.) Adjust generator or sample time as needed.
11.1.2.5.6If you are unable to obtain a stable concentration within the concentration limit and with the 50 count minimum per channel, adjust the aerosol generator.
11.1.2.5.7When the counts are stable, perform repeated upstream-downstream sampling until 10 upstream-downstream measurements are obtained.
11.1.2.5.8After collection of the 10 upstream-downstream samples, stop data acquisition and allow 2 more minutes for final purging of generator.
11.1.2.5.9Obtain one additional set of upstream-downstream background samples.
11.1.2.5.10After obtaining the upstream-downstream background samples, stop data acquisition.
11.1.2.5.11Record the arrestor pressure drop.
11.1.2.5.12Turn off blower.
11.1.2.5.13Remove the paint arrestor assembly from the test duct. Note any signs of physical deterioration.
11.1.2.5.14Remove the arrestor from the frame and place the arrestor in an appropriate storage bag.
11.2Control Test: 100 Percent Penetration Test. A 100 percent penetration test must be performed immediately before each individual paint arrestor test using the same challenge aerosol substance (i.e., oleic acid or KCl) as to be used in the arrestor test. These tests are performed with no arrestor installed in the test housing. This test is a relatively stringent test of the adequacy of the overall duct, sampling, measurement, and aerosol generation system. The test is performed as a normal penetration test except the paint arrestor is not used. A perfect system would yield a measured penetration of 1 at all particle sizes. Deviations from 1
11.3Control Test: 0 Percent Penetration. One 0 percent penetration test must be performed at least monthly during testing. The test is performed by using a HEPA filter rather than a paint arrestor. This test assesses the adequacy of the instrument response time and sample line lag.
12.1Analysis. The analytical procedures for the fractional penetration and flow velocity measurements are described in Section 11. Note that the primary measurements, those of the upstream and downstream aerosol concentrations, are performed with the OPC which acquires the sample and analyzes it in real time. Because all the test data are collected in real time, there are no analytical procedures performed subsequent to the actual test, only data analysis.
12.2Calculations.
12.2.1Penetration.
Overbar denotes arithmetic mean of quantity.
Analysis of each test involves the following quantities:
• P
• 2 upstream background values,
• 2 downstream background values,
• 10 upstream values with aerosol generator on, and
• 10 downstream values with aerosol generator on.
Using the values associated with each sizing channel, the penetration associated with each particle-sizing channel is calculated as:
Most often, the background levels are small compared to the values when the aerosol generator is on.
12.3The relationship between the physical diameter (D
12.4Presentation of Results. For a given arrestor, results will be presented for:
• Triplicate arrestor tests with the liquid-phase challenge aerosol,
sbull; Triplicate arrestor tests with the solid-phase challenge aerosol,
sbull; Triplicate 100 percent penetration tests with the liquid-phase challenge aerosol,
sbull; Triplicate 100 percent penetration tests with the solid-phase challenge aerosol, and
sbull; One 0 percent filter test (using either the liquid-phase or solid-phase aerosol and performed at least monthly).
12.4.1Results for the paint arrestor test must be presented in both graphical and tabular form. The X-axis of the graph will be a logarithmic scale of aerodynamic diameter from 0.1 to 100 µm. The Y-axis will be efficiency (%) on a linear scale from 0 to 100. Plots for each individual run and a plot of
12.4.2Tabulated data from each test must be provided. The data must include the upper and lower diameter bound and geometric mean diameter of each of the OPC sizing channels, the background particle counts for each channel for each sample, the upstream particle counts for each channel for each sample, the downstream particle counts for each channel for each sample, the 100 percent penetration values computed for each channel, and the 0 percent penetration values computed for each channel.
13.1The quantities of materials to be aerosolized should be prepared in accord with the amount needed for the current tests so as to prevent wasteful excess.
14.1Paint arrestors may be returned to originator, if requested, or disposed of with regular laboratory waste.
1. Hanley, J.T., D.D. Smith and L. Cox. “Fractional Penetration of Paint Overspray Arrestors, Draft Final Report,” EPA Cooperative Agreement CR-817083-01-0, January 1994.
2. Hanley, J.T., D.D. Smith, and D.S. Ensor. “Define a Fractional Efficiency Test Method that is Compatible with Particulate Removal Air Cleaners Used in General Ventilation,” Final Report, 671-RP, American Society of Heating, Refrigerating, and Air-Conditioning Engineers, Inc., December 1993.
3. “Project Work and Quality Assurance Plan: Fractional Penetration of Paint Overspray Arrestors, Category II,” EPA Cooperative Agreement No. CR-817083, July 1994.
Persons unfamiliar with basic elements of FTIR spectroscopy should not attempt to use this method. This method describes sampling and analytical procedures for extractive emission measurements using Fourier transform infrared (FTIR) spectroscopy. Detailed analytical procedures for interpreting infrared spectra are described in the “Protocol for the Use of Extractive Fourier Transform Infrared (FTIR) Spectrometry in Analyses of Gaseous Emissions from Stationary Sources,” hereafter referred to as the “Protocol.” Definitions not given in this method are given in appendix A of the Protocol. References to specific sections in the Protocol are made throughout this Method. For additional information refer to references 1 and 2, and other EPA reports, which describe the use of FTIR spectrometry in specific field measurement applications and validation tests. The sampling procedure described here is extractive. Flue gas is extracted through a heated gas transport and handling system. For some sources, sample conditioning systems may be applicable. Some examples are given in this method.
sample conditioning systems may be used providing the method validation requirements in Sections 9.2 and 13.0 of this method are met.
1.1Scope and Applicability.
1.1.1
1.1.2
1.2
1.2.1For any optical configuration the analytical range is between the absorbance values of about .01 (infrared transmittance relative to the background = 0.98) and 1.0
1.2.2The concentrations associated with this absorbance range depend primarily on the cell path length and the sample temperature. An analyte absorbance greater than 1.0, can be lowered by decreasing the optical path length. Analyte absorbance increases with a longer path length. Analyte detection also depends on the presence of other species exhibiting absorbance in the same analytical region. Additionally, the estimated lower absorbance (A) limit
1.2.3The concentration range of this method is determined by the choice of optical configuration.
1.2.3.1The absorbance for a given concentration can be decreased by decreasing the path length or by diluting the sample. There is no practical upper limit to the measurement range.
1.2.3.2The analyte absorbance for a given concentration may be increased by increasing the cell path length or (to some extent) using a higher resolution. Both modifications also cause a corresponding increased absorbance for all compounds in the sample, and a decrease in the signal throughput. For this reason the practical lower detection range (quantitation limit) usually depends on sample characteristics such as moisture content of the gas, the presence of other interferants, and losses in the sampling system.
1.3
1.4
1.4.1Measurement objectives shall be established by the choice of detection limit (DL
1.4.2An instrumental configuration shall be selected. An estimate of gas composition shall be made based on previous test data, data from a similar source or information gathered in a pre-test site survey. Spectral interferants shall be identified using the selected DL
1.4.3Data quality for the application shall be determined, in part, by measuring the RMS (root mean square) noise level in each analytical spectral region (appendix C of the Protocol). The RMS noise is defined as the RMSD of the absorbance values in an analytical region from the mean absorbance value in the region.
1.4.4The MAU is the minimum analyte concentration for which the AU
2.1
2.1.1Infrared absorption spectroscopy is performed by directing an infrared beam through a sample to a detector. The frequency-dependent infrared absorbance of the sample is measured by comparing this detector signal (single beam spectrum) to a signal obtained without a sample in the beam path (background).
2.1.2Most molecules absorb infrared radiation and the absorbance occurs in a characteristic and reproducible pattern. The infrared spectrum measures fundamental molecular properties and a compound can be identified from its infrared spectrum alone.
2.1.3Within constraints, there is a linear relationship between infrared absorption and compound concentration. If this frequency dependent relationship (absorptivity) is known (measured), it can be used to determine compound concentration in a sample mixture.
2.1.4Absorptivity is measured by preparing, in the laboratory, standard samples of compounds at known concentrations and measuring the FTIR “reference spectra” of these standard samples. These “reference spectra” are then used in sample analysis: (1) Compounds are detected by matching sample absorbance bands with bands in reference spectra, and (2) concentrations are measured by comparing sample band intensities with reference band intensities.
2.1.5This method is self-validating provided that the results meet the performance requirement of the QA spike in sections 8.6.2 and 9.0 of this method, and results from a previous method validation study support the use of this method in the application.
2.2
2.2.1The digitized infrared spectrum of the sample in the FTIR gas cell is measured and stored on a computer. Absorbance band intensities in the spectrum are related to sample concentrations by what is commonly referred to as Beer's Law.
2.2.2Analyte spiking is used for quality assurance (QA). In this procedure (section 8.6.2 of this method) an analyte is spiked into the gas stream at the back end of the sample probe. Analyte concentrations in the spiked samples are compared to analyte concentrations in unspiked samples. Since the concentration of the spike is known, this procedure can be used to determine if the sampling system is removing the spiked analyte(s) from the sample stream.
2.3
2.4
2.4.1The spectral analysis shall be supervised by someone familiar with EPA FTIR Protocol procedures.
2.4.2A technician trained in instrumental test methods is qualified to install and operate the sampling system. This includes installing the probe and heated line assembly, operating the analyte spike system, and performing moisture and flow measurements.
See appendix A of the Protocol for definitions relating to infrared spectroscopy. Additional definitions are given in sections 3.1 through 3.29.
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12
3.13
3.14
3.15
3.16
3.17
3.18
3.19
3.20
3.21
3.22
3.23
3.24
3.25
3.26
3.27
3.28
3.29
Interferences are divided into two classifications: analytical and sampling.
4.1
4.1.1
4.1.2
4.2
4.2.1
4.2.2
4.2.3
4.2.4
The hazards of performing this method are those associated with any stack sampling method and the same precautions shall be followed. Many HAPs are suspected carcinogens or present other serious health risks. Exposure to these compounds should be avoided in all circumstances. For instructions on the safe handling of any particular compound, refer to its material safety data sheet. When using analyte standards, always ensure that gases are properly vented and that the gas handling system is leak free. (Always perform a leak check with the system under maximum vacuum and, again, with the system at greater than ambient pressure.) Refer to section 8.2 of this method for leak check procedures. This method does not address all of the potential safety risks associated with its use. Anyone performing this method must follow safety and health practices consistent with applicable legal requirements and with prudent practice for each application.
Mention of trade names or specific products does not constitute endorsement by the Environmental Protection Agency.
The equipment and supplies are based on the schematic of a sampling system shown in Figure 1. Either the batch or continuous sampling procedures may be used with this sampling system. Alternative sampling configurations may also be used, provided that the data quality objectives are met as determined in the post-analysis evaluation. Other equipment or supplies may be necessary, depending on the design of the sampling system or the specific target analytes.
6.1
6.2
6.3
6.4
6.5
6.7
6.8
6.9
6.10
6.11
6.12
6.13
6.14
6.15
6.16
6.17
6.17.1The analyte spike procedure of section 9.2 of this method, the QA spike procedure of section 8.6.2 of this method, and the validation procedure of section 13 of this method demonstrate whether the sample conditioning affects analyte concentrations. Alternatively, measurements can be made with two parallel FTIR systems; one measuring conditioned sample, the other measuring unconditioned sample.
6.17.2Another option is sample dilution. The dilution factor measurement must be documented and accounted for in the reported concentrations. An alternative to dilution is to lower the sensitivity of the FTIR system by decreasing the cell path length, or to use a short-path cell in conjunction with a long path cell to measure more than one concentration range.
7.1
7.2
7.3
Three types of testing can be performed: (1) Screening, (2) emissions test, and (3) validation. Each is defined in section 3 of this method. Determine the purpose(s) of the FTIR test. Test requirements include: (a) AU
8.1
8.1.1
8.1.2
8.1.3.
8.1.4
8.1.5
8.1.6Calculate the Minimum Analyte Uncertainty, MAU (section 1.3 of this method discusses MAU and protocol appendix D gives the MAU procedure). The MAU for each analyte, i, and each analytical region, m, depends on the RMS noise.
8.1.7
8.2Leak-Check
8.2.1
8.2.2
8.2.2.1For the evacuated sample technique, close the valve to the FTIR cell, and evacuate the absorption cell to the minimum absolute pressure P
8.2.2.2For both the evacuated sample and purging techniques, pressurize the system to about 100 mmHg above atmospheric pressure. Isolate the pump and determine the change in pressure ΔP
8.2.2.3Measure the barometric pressure, P
8.2.2.4Determine the percent leak volume %V
8.3
8.3.1Vary the power incident on the detector by modifying the aperture setting. Measure the background and CTS at three instrument aperture settings: (1) at the aperture setting to be used in the testing, (2) at one half this aperture and (3) at twice the proposed testing aperture. Compare the three CTS spectra. CTS band areas shall
8.3.2Use neutral density filters to attenuate the infrared beam. Set up the FTIR system as it will be used in the test measurements. Collect a CTS spectrum. Use a neutral density filter to attenuate the infrared beam (either immediately after the source or the interferometer) to approximately
8.3.3Observe the single beam instrument response in a frequency region where the detector response is known to be zero. Verify that the detector response is “flat” and equal to zero in these regions.
8.4
8.5
8.5.1
8.5.2Water vapor spectra can be prepared by the following procedure. Fill a sample tube with distilled water. Evacuate above the sample and remove dissolved gasses by alternately freezing and thawing the water while evacuating. Allow water vapor into the FTIR cell, then dilute to atmospheric pressure with nitrogen or dry air. If quantitative water spectra are required, follow the reference spectrum procedure for neat samples (protocol, section 4.6). Often, interference spectra need not be quantitative, but for best results the absorbance must be comparable to the interference absorbance in the sample spectra.
8.6Pre-Test Calibrations
8.6.1
8.6.2
8.7
8.7.1
8.7.2
8.8Sampling QA and Reporting
8.8.1Sample integration times shall be sufficient to achieve the required signal-to-noise ratio. Obtain an absorbance spectrum by filling the cell with N2. Measure the RMSD in each analytical region in this absorbance spectrum. Verify that the number of scans used is sufficient to achieve the target MAU.
8.8.2Assign a unique file name to each spectrum.
8.8.3Store two copies of sample interferograms and processed spectra on separate computer disks.
8.8.4For each sample spectrum, document the sampling conditions, the sampling time (while the cell was being filled), the time the spectrum was recorded, the instrumental conditions (path length, temperature, pressure, resolution, signal integration time), and the spectral file name. Keep a hard copy of these data sheets.
8.9
8.10
8.11
8.11.1Inspect the sample spectra immediately after the run to verify that the gas matrix composition was close to the expected (assumed) gas matrix.
8.11.2Verify that the sampling and instrumental parameters were appropriate for the conditions encountered. For example, if the moisture is much greater than anticipated, it may be necessary to use a shorter path length or dilute the sample.
8.11.3Compare the pre- and post-test CTS spectra. The peak absorbance in pre- and post-test CTS must be ±5 percent of the mean value. See appendix E of the FTIR Protocol.
Use analyte spiking (sections 8.6.2, 9.2 and 13.0 of this method) to verify that the sampling system can transport the analytes from the probe to the FTIR system.
9.1
9.2
9.2.1Introduce the spike/tracer gas at a constant flow rate of ≤10 percent of the total sample flow, when possible.
Use the rotameter at the end of the sampling train to estimate the required spike/tracer gas flow rate.
Use a flow device, e.g., mass flow meter (# 2 percent), to monitor the spike flow rate. Record the spike flow rate every 10 minutes.
9.2.2Determine the response time (RT) of the system by continuously collecting spectra of the spiked effluent until the spectrum of the spiked component is constant for 5 minutes. The RT is the interval from the first measurement until the spike becomes constant. Wait for twice the duration of the RT, then collect spectra of two independent spiked gas samples. Duplicate analyses of the spiked concentration shall be within 5
9.2.3Calculate the dilution ratio using the tracer gas as follows: where:
10.1
10.2
10.3
10.4
10.5
Analyte concentrations shall be measured using reference spectra from the EPA FTIR spectral library. When EPA library spectra are not available, the procedures in section 4.6 of the Protocol shall be followed to prepare reference spectra of all the target analytes.
11.1
11.2
12.1
12.2
12.2.1
12.2.2
12.2.3
12.2.4
This validation procedure, which is based on EPA Method 301 (40 CFR part 63, appendix (A), may be used to validate this method for the analytes in a gas matrix. Validation at one source may also apply to another type of source, if it can be shown that the exhaust gas characteristics are similar at both sources.
13.1Section 5.3 of Method 301 (40 CFR part 63, appendix A), the Analyte Spike procedure, is used with these modifications. The statistical analysis of the results follows section 6.3 of EPA Method 301. Section 3 of this method defines terms that are not defined in Method 301.
13.1.1The analyte spike is performed dynamically. This means the spike flow is continuous and constant as spiked samples are measured.
13.1.2The spike gas is introduced at the back of the sample probe.
13.1.3Spiked effluent is carried through all sampling components downstream of the probe.
13.1.4A single FTIR system (or more) may be used to collect and analyze spectra (not quadruplicate integrated sampling trains).
13.1.5All of the validation measurements are performed sequentially in a single “run” (section 3.26 of this method).
13.1.6The measurements analyzed statistically are each independent (section 3.22 of this method).
13.1.7A validation data set can consist of more than 12 spiked and 12 unspiked measurements.
13.2
13.2.1With a single FTIR instrument and sampling system, begin by collecting spectra of two unspiked samples. Introduce the spike flow into the sampling system and allow 10 cell volumes to purge the sampling system and FTIR cell. Collect spectra of two spiked samples. Turn off the spike and allow 10 cell volumes of unspiked sample to purge the FTIR cell. Repeat this procedure until the 24 (or more) samples are collected.
13.2.2In batch sampling, collect spectra of 24 distinct samples. (Each distinct sample consists of filling the cell to ambient pressure after the cell has been evacuated.)
13.2.3Alternatively, a separate probe assembly, line, and sample pump can be used for spiked sample. Verify and document that sampling conditions are the same in both the spiked and the unspiked sampling systems. This can be done by wrapping both sample lines in the same heated bundle. Keep the same flow rate in both sample lines. Measure samples in sequence in pairs. After two spiked samples are measured, evacuate the FTIR cell, and turn the manifold valve so that spiked sample flows to the FTIR cell. Allow the connecting line from the manifold to the FTIR cell to purge thoroughly (the
13.3Simultaneous Measurements With Two FTIR Systems. If unspiked effluent concentrations of the target analyte(s) vary significantly with time, it may be desirable to perform synchronized measurements of spiked and unspiked sample. Use two FTIR systems, each with its own cell and sampling system to perform simultaneous spiked and unspiked measurements. The optical configurations shall be similar, if possible. The sampling configurations shall be the same. One sampling system and FTIR analyzer shall be used to measure spiked effluent. The other sampling system and FTIR analyzer shall be used to measure unspiked flue gas. Both systems shall use the same sampling procedure (i.e., batch or continuous).
13.3.1If batch sampling is used, synchronize the cell evacuation, cell filling, and collection of spectra. Fill both cells at the same rate (in cell volumes per unit time).
13.3.2If continuous sampling is used, adjust the sample flow through each gas cell so that the same number of cell volumes pass through each cell in a given time (i.e. TC
13.4
13.4.1
13.4.2
13.4.3If measurements do not pass validation, evaluate the sampling system, instrument configuration, and analytical system to determine if improper set-up or a malfunction was the cause. If so, repair the system and repeat the validation.
The extracted sample gas is vented outside the enclosure containing the FTIR system and gas manifold after the analysis. In typical method applications the vented sample volume is a small fraction of the source volumetric flow and its composition is identical to that emitted from the source. When analyte spiking is used, spiked pollutants are vented with the extracted sample gas. Approximately 1.6 × 10−
Small volumes of laboratory gas standards can be vented through a laboratory hood. Neat samples must be packed and disposed according to applicable regulations. Surplus materials may be returned to supplier for disposal.
1. “Field Validation Test Using Fourier Transform Infrared (FTIR) Spectrometry To Measure Formaldehyde, Phenol and Methanol at a Wool Fiberglass Production Facility.” Draft. U.S. Environmental Protection Agency Report, EPA Contract No. 68D20163, Work Assignment I-32, September 1994.
2. “FTIR Method Validation at a Coal-Fired Boiler”. Prepared for U.S. Environmental Protection Agency, Research Triangle Park, NC. Publication No.: EPA-454/R95-004, NTIS No.: PB95-193199. July, 1993.
3. “Method 301—Field Validation of Pollutant Measurement Methods from Various Waste Media,” 40 CFR part 63, appendix A.
4. “Molecular Vibrations; The Theory of Infrared and Raman Vibrational Spectra,” E. Bright Wilson, J. C. Decius, and P. C. Cross, Dover Publications, Inc., 1980. For a less intensive treatment of molecular rotational-vibrational spectra see, for example, “Physical Chemistry,” G. M. Barrow, chapters 12, 13, and 14, McGraw Hill, Inc., 1979.
5. “Fourier Transform Infrared Spectrometry,” Peter R. Griffiths and James de Haseth, Chemical Analysis, 83, 16-25,(1986), P. J. Elving, J. D. Winefordner and I. M. Kolthoff (ed.), John Wiley and Sons.
6. “Computer-Assisted Quantitative Infrared Spectroscopy,” Gregory L. McClure (ed.), ASTM Special Publication 934 (ASTM), 1987.
7. “Multivariate Least-Squares Methods Applied to the Quantitative Spectral Analysis of Multicomponent Mixtures,” Applied Spectroscopy, 39(10), 73-84, 1985.
The purpose of this addendum is to set general guidelines for the use of modern FTIR spectroscopic methods for the analysis of gas samples extracted from the effluent of stationary emission sources. This addendum outlines techniques for developing and evaluating such methods and sets basic requirements for reporting and quality assurance procedures.
1.1Nomenclature
1.1.1Appendix A to this addendum lists definitions of the symbols and terms used in this Protocol, many of which have been taken directly from American Society for Testing and Materials (ASTM) publication E 131-90a, entitled “Terminology Relating to Molecular Spectroscopy.”
1.1.2Except in the case of background spectra or where otherwise noted, the term “spectrum” refers to a double-beam spectrum in units of absorbance vs. wavenumber (cm
1.1.3The term “Study” in this addendum refers to a publication that has been subjected to EPA- or peer-review.
2.1
2.2Analytical Principle
2.2.1In the mid-infrared band, most molecules exhibit characteristic gas phase absorption spectra that may be recorded by FTIR systems. Such systems consist of a source of mid-infrared radiation, an interferometer, an enclosed sample cell of known absorption pathlength, an infrared detector, optical elements for the transfer of infrared radiation between components, and gas flow control and measurement components. Adjunct and integral computer systems are used for controlling the instrument, processing the signal, and for performing both Fourier transforms and quantitative analyses of spectral data.
2.2.2The absorption spectra of pure gases and of mixtures of gases are described by a linear absorbance theory referred to as Beer's Law. Using this law, modern FTIR systems use computerized analytical programs to quantify compounds by comparing the absorption spectra of known (reference) gas samples to the absorption spectrum of the sample gas. Some standard mathematical techniques used for comparisons are classical least squares, inverse least squares, cross-correlation, factor analysis, and partial least squares. Reference A describes several of these techniques, as well as additional techniques, such as differentiation methods, linear baseline corrections, and non-linear absorbance corrections.
The characteristics that distinguish FTIR systems from gas analyzers used in instrumental gas analysis methods (e.g., Methods 6C and 7E of appendix A to part 60 of this chapter) are: (1) Computers are necessary to obtain and analyze data; (2) chemical concentrations can be quantified using previously recorded infrared reference spectra; and (3) analytical assumptions and results, including possible effects of interfering compounds, can be evaluated after the quantitative analysis. The following general principles and requirements of this Protocol are based on these characteristics.
3.1
3.2
The CTS may, but need not, include analytes of interest). To effect this, record the absorption spectra of the CTS (a) immediately before and immediately after recording reference spectra and (b) immediately after recording sample spectra.
3.3
3.3.1
3.3.2
Before testing, demonstrate the suitability of FTIR spectrometry for the desired application according to the procedures of this section.
4.1
4.1.1Analytes (specific chemical species) of interest. Label the analytes from i = 1 to I.
4.1.2Analytical uncertainty limit (AU
4.1.3Required detection limit for each analyte (DL
4.1.4Maximum expected concentration of each analyte (CMAX
4.2
4.3
4.4
4.5Select Calibration Transfer Standards (CTS's). Select CTS's that meet the criteria listed in sections 4.5.1, 4.5.2, and 4.5.3 of this addendum.
It may be necessary to choose preliminary analytical regions (see section 4.7 of this addendum), identify the minimum analyte linewidths, or estimate the system noise level (see section 4.12 of this addendum) before selecting the CTS. More than one compound may be needed to meet the criteria; if so, obtain separate cylinders for each compound.
4.5.1The central wavenumber position of each analytical region shall lie within 25 percent of the wavenumber position of at least one CTS absorption band.
4.5.2The absorption bands in section 4.5.1 of this addendum shall exhibit peak absorbances greater than ten times the value RMS
4.5.3At least one absorption CTS band within the operating range of the FTIR instrument shall have an instrument-independent linewidth no greater than the narrowest analyte absorption band. Perform and document measurements or cite Studies to determine analyte and CTS compound linewidths.
4.5.4For each analytical region, specify the upper and lower wavenumber positions (FFU
4.5.5Associate, whenever possible, a single set of CTS gas cylinders with a set of reference spectra. Replacement CTS gas cylinders shall contain the same compounds at concentrations within 5 percent of that of the original CTS cylinders; the entire absorption spectra (not individual spectral segments) of the replacement gas shall be scaled by a factor between 0.95 and 1.05 to match the original CTS spectra.
4.6Prepare Reference Spectra
Reference spectra are available in a permanent soft copy from the EPA spectral library on the EMTIC (Emission Measurement Technical Information Center) computer bulletin board; they may be used if applicable.
4.6.1Select the reference absorption pathlength (L
4.6.2Obtain or prepare a set of chemical standards for each analyte, potential and known spectral interferants, and CTS. Select the concentrations of the chemical standards to correspond to the top of the desired range.
4.6.2.1
4.6.2.2
4.6.3Record a set of the absorption spectra of the CTS {R1}, then a set of the reference spectra at two or more concentrations in duplicate over the desired range (the top of the range must be less than 10 times that of the bottom), followed by a second set of CTS spectra {R2}. (If self-prepared standards are used, see section 4.6.5 of this addendum before disposing of any of the standards.) The maximum accepted standard concentration-pathlength product (ASCPP) for each compound shall be higher than the maximum estimated concentration-pathlength products for both analytes and known interferants in the effluent gas. For
4.6.4Permanently store the background and interferograms in digitized form. Document details of the mathematical process for generating the spectra from these interferograms. Record the sample pressure (P
4.6.5If self-prepared chemical standards are employed and spectra of only two concentrations are recorded for one or more compounds, verify the accuracy of the dilution technique by analyzing the prepared standards for those compounds with a secondary (non-FTIR) technique in accordance with sections 4.6.5.1 through 4.6.5.4 of this addendum.
4.6.5.1Record the response of the secondary technique to each of the four standards prepared.
4.6.5.2Perform a linear regression of the response values (dependant variable) versus the accepted standard concentration (ASC) values (independent variable), with the regression constrained to pass through the zero-response, zero ASC point.
4.6.5.3Calculate the average fractional difference between the actual response values and the regression-predicted values (those calculated from the regression line using the four ASC values as the independent variable).
4.6.5.4If the average fractional difference value calculated in section 4.6.5.3 of this addendum is larger for any compound than the corresponding AU
4.7
4.8
4.9
4.10Prepare Computerized Analytical Programs
4.10.1Choose or devise mathematical techniques (e.g, classical least squares, inverse least squares, cross-correlation, and factor analysis) based on equation 4 of Reference A that are appropriate for analyzing spectral data by comparison with reference spectra.
4.10.2Following the general recommendations of Reference A, prepare a computer program or set of programs that analyzes all of the analytes and known interferants, based on the selected analytical regions (section 4.7 of this addendum) and the prepared reference spectra (section 4.6 of this addendum). Specify the baseline correction technique (e.g., determining the slope and intercept of a linear baseline contribution in each analytical region) for each analytical region, including all relevant wavenumber positions.
4.10.3Use programs that provide as output [at the reference absorption pathlength (L
4.11
4.12
5.1
5.2
5.3Determine the Sample Absorption Pathlength
Record a background spectrum. Then, fill the absorption cell with CTS at the pressure P
5.4
Multiple sample spectra may be recorded according to the procedures of section 5.4 of this addendum before performing sections 5.5 and 5.6 of this addendum.
5.5
5.6
5.6.1Perform instrumental checks and adjust the instrument to restore its performance to acceptable levels. If adjustments are made, repeat sections 5.3, 5.4 (except for the recording of a sample spectrum), and 5.5 of this addendum to demonstrate that acceptable uncertainties are obtained in all analytical regions.
5.6.2Apply appropriate mathematical transformations (e.g., frequency shifting, zero-filling, apodization, smoothing) to the spectra (or to the interferograms upon which the spectra are based) generated during the performance of the procedures of section 5.3 of this addendum. Document these transformations and their reproducibility. Do not apply multiplicative scaling of the spectra, or any set of transformations that is mathematically equivalent to multiplicative scaling. Different transformations may be applied to different analytical regions. Frequency shifts shall be less than one-half the minimum instrumental linewidth, and must be applied to all spectral data points in an analytical region. The mathematical transformations may be retained for the analysis if they are also applied to the appropriate analytical regions of all sample spectra recorded, and if all original sample spectra are digitally stored. Repeat sections 5.3, 5.4 (except the recording of a sample spectrum), and 5.5 of this addendum to demonstrate that these transformations lead to acceptable calculated concentration uncertainties in all analytical regions.
Estimate the overall accuracy of the analyses performed in accordance with sections 5.1 through 5.6 of this addendum using the procedures of sections 6.1 through 6.3 of this addendum.
6.1
6.2
6.2.1Using appendix I of this addendum, determine the fractional model error (FMU) for each analyte.
6.2.2Provide statistically determined uncertainties FMU for each analyte which are equivalent to two standard deviations at the 95 percent confidence level. Such determinations, if employed, must be based on mathematical examinations of the pertinent sample spectra (not the reference spectra alone). Include in the report of the analysis (see section 7.0 of this addendum) a complete description of the determination of the concentration uncertainties.
6.3
(A) Standard Practices for General Techniques of Infrared Quantitative Analysis (American Society for Testing and Materials, Designation E 168-88).
(B) The Coblentz Society Specifications for Evaluation of Research Quality Analytical Infrared Reference Spectra (Class II); Anal. Chemistry 47, 945A (1975); Appl. Spectroscopy 444, pp. 211-215, 1990.
(C) Standard Practices for General Techniques for Qualitative Infrared Analysis, American Society for Testing and Materials, Designation E 1252-88.
(D) “EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards,” U.S. Environmental Protection Agency Publication No. EPA/600/R-93/224, December 1993.
A.1
The quantitative result for a single analyte may be based on data from more than one analytical region.
The term “double-beam” is used elsewhere to denote a spectrum in which the sample and background interferograms are collected simultaneously along physically distinct absorption paths. Here, the term denotes a spectrum in which the sample and background interferograms are collected at different times along the same absorption path.
When FTIR spectrometers are interfaced with other instruments, a slash should be used to denote the interface; e.g., GC/FTIR; HPCL/FTIR, and the use of FTIR should be explicit; i.e., FTIR not IR.
The term “single-beam” is used elsewhere to denote any spectrum in which the sample and background interferograms are recorded on the same physical absorption path; such usage differentiates such spectra from those generated using interferograms recorded along two physically distinct absorption paths (see “double-beam spectrum” above). Here, the term applies (for example) to the two spectra used directly in the calculation of transmission and absorbance spectra of a sample.
The equivalent ISO term is “certified reference material.”
The usual unit of wavenumber is the reciprocal centimeter, cm
Performing the FT of a zero-filled interferogram results in correctly interpolated points in the computed spectrum.
A.2
(1) A, absorbance = the logarithm to the base 10 of the reciprocal of the transmittance (T).
(2) AAI
(3) AAV
(4) ASC, accepted standard concentration = the concentration value assigned to a chemical standard.
(5) ASCPP, accepted standard concentration-pathlength product = for a chemical standard, the product of the ASC and the sample absorption pathlength. The units “centimeters-ppm” or “meters-ppm” are recommended.
(6) AU
(7) AVT
(8) CKWN
(9) CMAX
(10) CPOT
(11) DL
(12) FC
(13) FAU
(14) FCU
(15) FFL
(16) FFU
(17) FL
(18) FMU
(19) FN
(20) FN
(21) FRU
(22) FU
(23) IAI
(24) IAV
(25) ISC
(26) kPa = kilo-Pascal (see Pascal).
(27) L
(28) L
(29) L
(30) MAU
(31) MAU
(32) MIU
(33) MIU
(34) MIL, minimum instrumental linewidth = the minimum linewidth from the FTIR system, in wavenumbers.
The MIL of a system may be determined by observing an absorption band known (through higher resolution examinations) to be narrower than indicated by the system. The MIL is fundamentally limited by the retardation of the interferometer, but is also affected by other operational parameters (e.g., the choice of apodization).
(35) N
(36) N
(37) N
(38) N
(39) OFU
(40) Pascal (Pa) = metric unit of static pressure, equal to one Newton per square meter; one atmosphere is equal to 101,325 Pa; 1/760 atmosphere (one Torr, or one millimeter Hg) is equal to 133.322 Pa.
(41) P
(42) P
(43) P
(44) P
(45) RMS
(46) RMSD, root mean square difference = a measure of accuracy determined by the following equation:
The RMSD value “between a set of n contiguous absorbance values (A
(47) RSA
(48) RSI
(49) t
(50) t
(51) t
(52) t
(53) T
(54) T
(55) TP, Throughput = manufacturer's estimate of the fraction of the total infrared power transmitted by the absorption cell and transfer optics from the interferometer to the detector.
(56) V
(57) W
B.1.1Assume a fixed absorption pathlength equal to the value L
B.1.2Use band area calculations to compare the relative absorption strengths of the analytes and potential interferants. In the m
B.1.3Use the average total absorbance of the analytes and potential interferants in each analytical region to determine whether the analytical region is suitable for analyte concentration determinations.
The average absorbance in an analytical region is the band area divided by the width of the analytical region in wavenumbers. The average total absorbance in an analytical region is the sum of the average absorbances of all analytes and potential interferants.
B.2.1Prepare spectral representations of each analyte at the concentration CL
B.2.2Prepare spectral representations of each potential interferant at its expected concentration (CPOT
B.2.3Repeat the calculation for each analytical region, and record the band area results in matrix form as indicated in Figure B.1.
B.2.4If the band area of any potential interferant in an analytical region is greater than the one-half the band area of any analyte (i.e., IAI
B.2.5Calculate the average total absorbance (AVT
C.1.1The root-mean-square (RMS) noise level is the standard measure of noise in this addendum. The RMS noise level of a contiguous segment of a spectrum is defined as the RMS difference (RMSD) between the absorbance values which form the segment and the mean value of that segment (see appendix A of this addendum).
C.1.2The RMS noise value in double-beam absorbance spectra is assumed to be inversely proportional to: (a) the square root of the signal integration period of the sample single beam spectra from which it is formed, and (b) the total infrared power transmitted through the interferometer and absorption cell.
C.1.3Practically, the assumption of C.1.2 allows the RMS noise level of a complete system to be estimated from the quantities described in sections C.1.3.1 through C.1.3.4:
C.1.3.1RMS
C.1.3.2t
C.1.3.3t
C.1.3.4TP, the manufacturer's estimate of the fraction of the total infrared power transmitted by the absorption cell and transfer optics from the interferometer to the detector.
C.2.1Obtain the values of RMS
C.2.2Calculate the noise value of the system (RMS
Estimate the minimum concentration measurement uncertainties for the i
For a single analytical region, the MAU or MIU value is the concentration of the analyte or interferant for which the band area is equal to the product of the analytical region width (in wavenumbers) and the noise level of the system (in absorbance units). If data from more than one analytical region are used in the determination of an analyte concentration, the MAU or MIU is the mean of the separate MAU or MIU values calculated for each analytical region.
D.2.1For each analytical region, set RMS = RMS
D.2.2For each analyte associated with the analytical region, calculate MAU
D.2.3If only the m
D.2.4If more than one analytical region is used to calculate the concentration of the i
D.2.5Repeat sections D.2.1 through D.2.4 of this appendix to calculate the analogous values MIU
To estimate the reproducibility of the spectroscopic results of the system, compare the CTS spectra recorded before and after preparing the reference spectra. Compare the difference between the spectra to their average band area. Perform the calculation for each analytical region on the portions of the CTS spectra associated with that analytical region.
E.2.1The CTS spectra {R1} consist of N spectra, denoted by S
E.2.2Each analytical region m is associated with a portion of the CTS spectra S
E.2.3For each m and the associated i, calculate the band area of S
E.2.4For each m and the associated i, calculate the RMSD of S
E.2.5For each analytical region m, calculate FM
E.2.6If only the m
E.2.7If a number p
F.1.1The concentrations yielded by the computerized analytical program applied to each single-compound reference spectrum are defined as the indicated standard concentrations (ISC's). The ISC values for a single compound spectrum should ideally equal the accepted standard concentration (ASC) for one analyte or interferant, and should ideally be zero for all other compounds. Variations from these results are caused by errors in the ASC values, variations from the Beer's law (or modified Beer's law) model used to determine the concentrations, and
F.1.2When the calibration error appears non-systematic, apply the procedures of sections F.2.1 through F.2.3 of this appendix to estimate the fractional calibration uncertainty (FCU) for each compound. The FCU is defined as the mean fractional error between the ASC and the ISC for all reference spectra with non-zero ASC for that compound. The FCU for each compound shall be less than the required fractional uncertainty specified in section 4.1 of this addendum.
F.1.3The computerized analytical programs shall also be required to yield acceptably low concentrations for compounds with ISC = 0 when applied to the reference spectra. The ISC of each reference spectrum for each analyte or interferant shall not exceed that compound's minimum measurement uncertainty (MAU or MIU).
F.2.1Apply each analytical program to each reference spectrum. Prepare a similar table to that in Figure F.1 to present the ISC and ASC values for each analyte and interferant in each reference spectrum. Maintain the order of reference file names and compounds employed in preparing Figure F.1.
F.2.2For all reference spectra in Figure F.1, verify that the absolute values of the ISC's are less than the compound's MAU (for analytes) or MIU (for interferants).
F.2.3For each analyte reference spectrum, calculate the quantity (ASC-ISC)/ASC. For each analyte, calculate the mean of these values (the FCU
The root-mean-square (RMS) noise level is the standard measure of noise. The RMS noise level of a contiguous segment of a spectrum is the RMSD between the absorbance values that form the segment and the mean value of the segment (see appendix A of this addendum).
G.2.1Evacuate the absorption cell or fill it with UPC grade nitrogen at approximately one atmosphere total pressure.
G.2.2Record two single beam spectra of signal integration period t
G.2.3Form the double beam absorption spectrum from these two single beam spectra, and calculate the noise level RMS
Reference spectra recorded at absorption pathlength (L
H.1.1Before sampling, determine the sample absorption pathlength using least squares analysis. Determine the ratio L
H.1.2Determine the fractional analysis uncertainty (FAU) for each analyte by comparing a scaled CTS spectral set, recorded at L
H.2.1
H.2.2
The fractional analytical uncertainty, FAU, is given by equation H.4,
To prepare analytical programs for FTIR analyses, the sample constituents must first be assumed. The calculations in this appendix, based upon a simulation of the sample spectrum, shall be used to verify the appropriateness of these assumptions. The simulated spectra consist of the sum of single compound reference spectra scaled to represent their contributions to the sample absorbance spectrum; scaling factors are based on the indicated standard concentrations (ISC) and measured (sample) analyte and interferant concentrations, the sample and reference absorption pathlengths, and the sample and reference gas pressures. No band-shape correction for differences in the temperature of the sample and reference spectra gases is made; such errors are included in the FMU estimate. The actual and simulated sample spectra are quantitatively compared to determine the fractional model uncertainty; this comparison uses the reference
I.2.1For each analyte (with scaled concentration RSA
I.2.2For each interferant, select a reference spectrum SI
I.2.3For each analytical region, determine by visual inspection which of the spectra SAC
I.2.4For each analytical region m, calculate the RMSD of SUB
I.2.5For each analyte i, calculate FM
I.2.6If only the m
I.2.7If a number of analytical regions are used to calculate the concentration of the i
The calculations in this addendum estimate the measurement uncertainties for various FTIR measurements. The lowest possible overall concentration uncertainty (OCU) for an analyte is its MAU value, which is an estimate of the absolute concentration uncertainty when spectral noise dominates the measurement error. However, if the product of the largest fractional concentration uncertainty (FRU, FCU, FAU, or FMU) and the measured concentration of an analyte exceeds the MAU for the analyte, then the OCU is this product. In mathematical terms, set OFU
This method should be performed by those persons familiar with the operation of Fourier Transform Infrared (FTIR) instrumentation in the application to source sampling. This document describes the sampling procedures for use in the application of FTIR spectrometry for the determination of vapor phase hydrogen chloride (HCl) concentrations both before and after particulate matter control devices installed at portland cement kilns. A procedure for analyte spiking is included for quality assurance. This method is considered to be self validating provided that the requirements listed in section 9 of this method are followed. The analytical procedures for interpreting infrared spectra from emission measurements are described in the “Protocol For The Use of Extractive
1.1Scope and Application
This method is specifically designed for the application of FTIR Spectrometry in extractive measurements of gaseous HCl concentrations in portland cement kiln emissions.
This method applies to the measurement of HCl [CAS No. 7647-01-0]. This method can be applied to the determination of HCl concentrations both before and after particulate matter control devices installed at portland cement manufacturing facilities. This method applies to either continuous flow through measurement (with isolated sample analysis) or grab sampling (batch analysis). HCl is measured using the mid-infrared spectral region for analysis (about 400 to 4000 cm
1.3Method Range and Sensitivity
1.3.1The analytical range is determined by the instrumental design and the composition of the gas stream. For practical purposes there is no upper limit to the range because the pathlength may be reduced or the sample may be diluted. The lower detection range depends on (1) the absorption coefficient of the compound in the analytical frequency region, (2) the spectral resolution, (3) the interferometer sampling time, (4) the detector sensitivity and response, and (5) the absorption pathlength.
1.3.2The practical lower quantification range is usually higher than the instrument sensitivity allows and is dependent upon (1) the presence of interfering species in the exhaust gas including H
1.4Data Quality Objectives
1.4.1In designing or configuring the analytical system, data quality is determined by measuring of the root mean square deviation (RMSD) of the absorbance values within a chosen spectral (analytical) region. The RMSD provides an indication of the signal-to-noise ratio (S/N) of the spectral baseline. Appendix D of the FTIR Protocol (the addendum to Method 320 of this appendix) presents a discussion of the relationship between the RMSD, lower detection limit, DL
1.4.2Data quality is determined by measuring the root mean square (RMS) noise level in each analytical spectral region (appendix C of the FTIR Protocol). The RMS noise is defined as the root mean square deviation (RMSD) of the absorbance values in an analytical region from the mean absorbance value in the same region. Appendix D of the
2.1Principle
See Method 320 of this appendix. HCl can also undergo rotation transitions by absorbing energy in the far-infrared spectral region. The rotational transitions are superimposed on the vibrational fundamental to give a series of lines centered at the fundamental vibrational frequency, 2885 cm-
2.2
2.3
See appendix A of the FTIR Protocol.
This method will not measure HCl under conditions: (1) where the sample gas stream can condense in the sampling system or the instrumentation, or (2) where a high moisture content sample relative to the analyte concentrations imparts spectral interference due to the water vapor absorbance bands. For measuring HCl the first (sampling) consideration is more critical. Spectral interference from water vapor is not a significant problem except at very high moisture levels and low HCl concentrations.
4.1
4.1.1
4.1.2
4.2
5.1Hydrogen chloride vapor is corrosive and can cause irritation or severe damage to respiratory system, eyes and skin. Exposure to this compound should be avoided.
5.2This method may involve sampling at locations having high positive or negative pressures, or high concentrations of hazardous or toxic pollutants, and can not address all safety problems encountered under these diverse sampling conditions. It is the responsibility of the tester(s) to ensure proper safety and health practices, and to determine the applicability of regulatory limitations before performing this test method. Leak-check procedures are outlined in section 8.2 of Method 320 of this appendix.
Mention of trade names or specific products does not constitute endorsement by the Environmental Protection Agency.
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
6.10
6.11
6.12
6.13
6.14
6.14.1Delivery of calibration gas directly to the analytical instrumentation;
6.14.2Delivery of calibration gas to the sample probe (system calibration or analyte spike) via a heated traced sample line;
6.14.3Delivery of sample gas (kiln gas, spiked kiln gas, or system calibrations) to the analytical instrumentation;
6.14.4Delivery (optional) of a humidified nitrogen sample stream.
6.15
HCl can be purchased in a standard compressed gas cylinder. The most stable HCl cylinder mixture available has a concentration certified at ±5 percent. Such a cylinder is suitable for performing analyte spiking because it will provide reproducible samples. The stability of the cylinder can be monitored over time by periodically performing direct FTIR analysis of cylinder samples. It is recommended that a 10-50 ppm cylinder of HCl be prepared having from 2-5 ppm SF6 as a tracer compound. (See sections 7.1 through 7.3 of Method 320 of this appendix for a complete description of the use of existing HCl reference spectra. See section 9.1 of Method 320 of this appendix for a complete discussion of standard concentration selection.)
See also Method 320 of this appendix.
8.1
8.2
8.3
8.4
8.5
8.6Sampling
8.6.1
8.6.2
8.6.3
8.6.4
8.7Sample Conditioning
8.7.1
8.7.2
8.8
8.9
8.10
8.11
Use analyte spiking to verify the effectiveness of the sampling system for the target compounds in the actual kiln gas matrix. QA spiking shall be performed before and after each sample run. QA spiking shall be performed after the pre- and post-test CTS direct and system calibrations. The system biases calculated from the pre- and post-test dynamic analyte spiking shall be within ±30 percent for the spiked surrogate analytes for the measurements to be considered valid. See sections 9.3.1 through 9.3.2 for the requisite calculations. Measurement of the undiluted spike (direct-to-cell measurement) involves sending dry, spike gas to the FTIR cell, filling the cell to 1 atmosphere and obtaining the spectrum of this sample. The direct-to-cell measurement should be performed before each analyte spike so that the recovery of the dynamically spiked analytes may be calculated. Analyte spiking is only effective for assessing the integrity of the sampling system when the concentration of HCl in the source does not vary substantially. Any attempt to quantify an analyte recovery in a variable concentration matrix will result in errors in the expected concentration of the spiked sample. If the kiln gas target analyte concentrations vary by more than ±5 percent (or 5 ppm, whichever is greater) in the time required to acquire a sample spectrum, it may be necessary to: (1) Use a dual sample probe approach, (2) use two independent FTIR measurement systems, (3) use alternate QA/QC procedures, or (4) postpone testing until stable emission concentrations are achieved. (See section 9.2.3 of this method). It is recommended that a laboratory evaluation be performed before attempting to employ this method under actual field conditions. The laboratory evaluation shall include (1) performance of all applicable calculations in section 4 of the FTIR Protocol; (2) simulated analyte spiking experiments in dry (ambient) and humidified sample matrices using HCl; and (3) performance of bias (recovery) calculations from analyte spiking experiments. It is not necessary to perform a laboratory evaluation before every field test. The purpose of the laboratory study is to demonstrate that the actual instrument and sampling system configuration used in field testing meets the requirements set forth in this method.
9.1
9.1.1An HCl standard of approximately 50 ppm in a balance of ultra pure nitrogen is recommended. The SF
9.1.2The ideal spike concentration may not be achieved because the target concentration cannot be accurately predicted prior to the field test, and limited calibration standards will be available during testing. Therefore, practical constraints must be applied that allow the tester to spike at an anticipated concentration. For these tests, the analyte concentration contributed by the HCl standard spike should be 1 to 5 ppm or should more closely approximate the native concentration if it is greater.
9.2Spike Procedure
9.2.1A spiking/sampling apparatus is shown in Figure 2. Introduce the spike/tracer gas mixture at a constant flow (±2 percent) rate at approximately 10 percent of the total sample flow. (For example, introduce the surrogate spike at 1 L/min 20 cc/min, into a total sample flow rate of 10 L/min). The spike must be pre-heated before introduction into the sample matrix to prevent a localized condensation of the gas stream at the spike introduction point. A heated sample transport line(s) containing multiple transport tubes within the heated bundle may be used to spike gas up through the sampling system to the spike introduction point. Use a calibrated flow device (e.g., mass flow meter/controller), to monitor the spike flow as indicated by a calibrated flow meter or controller, or alternately, the SF
9.2.2Perform a direct-to-cell measurement of the dry, undiluted spike gas. Introduce the spike directly to the FTIR cell, bypassing the sampling system. Fill cell to 1 atmosphere and collect the spectrum of this sample. Ensure that the spike gas has equilibrated to the temperature of the measurement cell before acquisition of the spectra. Inspect the spectrum and verify that the gas is dry and contains negligible CO
9.2.3
9.2.3.1Adjust the spike flow rate to approximately 10 percent of the total flow by metering spike gas through a calibrated mass flowmeter or controller. Allow spike flow to equilibrate within the sampling system before analyzing the first spiked kiln gas samples. A minimum of two consecutive spikes are required. Analysis of the spectral band area used for quantification should agree to within ±5 percent or corrective action must be taken.
9.2.3.2After QA spiking is completed, the sampling system components shall be purged with nitrogen or dry air to eliminate traces of the HCl compound from the sampling system components. Acquire a sample spectra of the nitrogen purge to verify the absence of the calibration mixture.
9.2.3.3Analyte spiking procedures must be carefully executed to ensure that meaningful measurements are achieved. The requirements of sections 9.2.3.3.1 through 9.2.3.3.4 shall be met.
9.2.3.3.1The spike must be in the vapor phase, dry, and heated to (or above) the kiln gas temperature before it is introduced to the kiln gas stream.
9.2.3.3.2The spike flow rate must be constant and accurately measured.
9.2.3.3.3The total flow must also be measured continuously and reliably or the dilution ratio must otherwise be verified before and after a run by introducing a spike of a non-reactive, stable compound (i.e., tracer).
9.2.3.3.4The tracer must be inert to the sampling system components, not contained in the effluent gas, and readily detected by the analytical instrumentation. Sulfur hexafluoride (SF
9.3Calculations
9.3.1
9.3.2Bias. The bias may be determined by the difference between the observed spike value and the expected response (i.e., the equivalent concentration of the spiked material plus the analyte concentration adjusted for spike dilution). Bias is defined by section 6.3.1 of EPA Method 301 of this appendix (Reference 8) as,
10.1
10.2
10.3
10.4
10.5
A full description of the analytical procedures is given in sections 4.6-4.11, sections 5, 6, and 7, and the appendices of the FTIR Protocol. Additional description of quantitative spectral analysis is provided in References 10 and 11.
Data analysis is performed using appropriate reference spectra whose concentrations can be verified using CTS spectra. Various analytical programs (References 10 and 11) are available to relate sample absorbance to a concentration standard. Calculated concentrations should be verified by analyzing spectral baselines after mathematically subtracting scaled reference spectra from the sample spectra. A full description of the data analysis and calculations may be found in the FTIR Protocol (sections 4.0, 5.0, 6.0 and appendices).
12.1Calculated concentrations in sample spectra are corrected for differences in absorption pathlength between the reference and sample spectra by
12.2The temperature correction in equation 5 is a volumetric correction. It does not account for temperature dependence of rotational-vibrational relative line intensities. Whenever possible, the reference spectra used in the analysis should be collected at a temperature near the temperature of the FTIR cell used in the test to minimize the calculated error in the measurement (FTIR Protocol, appendix D). Additionally, the analytical region chosen for the analysis should be sufficiently broad to minimize errors caused by small differences in relative line intensities between reference spectra and the sample spectra.
A description of the method performance may be found in the FTIR Protocol. This method is self validating provided the results meet the performance specification of the QA spike in sections 9.0 through 9.3 of this method.
This is a gas phase measurement. Gas is extracted from the source, analyzed by the instrumentation, and discharged through the instrument vent.
Gas standards of HCl are handled according to the instructions enclosed with the material safety data sheet.
1. “Laboratory and Field Evaluation of a Methodology for Determination of Hydrogen Chloride Emissions From Municipal and Hazardous Waste Incinerators,” S.C.
2. “Evaluation of HCl Measurement Techniques at Municipal and Hazardous Waste Incinerators,” S.A. Shanklin, S.C. Steinsberger, and L. Cone, Entropy, Inc. Prepared for U.S. Environmental Protection Agency, Research Triangle Park, NC. NTIS Report No. PB90-221896. (1989).
3. “Fourier Transform Infrared (FTIR) Method Validation at a Coal Fired-Boiler,” Entropy, Inc. Prepared for U.S. Environmental Protection Agency, Research Triangle Park, NC. EPA Publication No. EPA-454/R95-004. NTIS Report No. PB95-193199. (1993).
4. “Field Validation Test Using Fourier Transform Infrared (FTIR) Spectrometry To Measure Formaldehyde, Phenol and Methanol at a Wool Fiberglass Production Facility.” Draft. U.S. Environmental Protection Agency Report, Entropy, Inc., EPA Contract No. 68D20163, Work Assignment I-32.
5. Kinner, L.L., Geyer, T.G., Plummer, G.W., Dunder, T.A., Entropy, Inc. “Application of FTIR as a Continuous Emission Monitoring System.” Presentation at 1994 International Incineration Conference, Houston, TX. May 10, 1994.
6. “Molecular Vibrations; The Theory of Infrared and Raman Vibrational Spectra,” E. Bright Wilson, J.C. Decius, and P.C. Cross, Dover Publications, Inc., 1980. For a less intensive treatment of molecular rotational-vibrational spectra see, for example, “Physical Chemistry,” G.M. Barrow, chapters 12, 13, and 14, McGraw Hill, Inc., 1979.
7. “Laboratory and Field Evaluations of Ammonium Chloride Interference in Method 26,” U.S. Environmental Protection Agency Report, Entropy, Inc., EPA Contract No. 68D20163, Work Assignment No. I-45.
8. 40 CFR 63, appendix A. Method 301—Field Validation of Pollutant Measurement Methods from Various Waste Media.
9. “Fourier Transform Infrared Spectrometry,” Peter R. Griffiths and James de Haseth, Chemical Analysis, 83, 16-25, (1986), P.J. Elving, J.D. Winefordner and I.M. Kolthoff (ed.), John Wiley and Sons.
10. “Computer-Assisted Quantitative Infrared Spectroscopy,” Gregory L. McClure (ed.), ASTM Special Publication 934 (ASTM), 1987.
11. “Multivariate Least-Squares Methods Applied to the Quantitative Spectral Analysis of Multicomponent Mixtures,” Applied Spectroscopy, 39(10), 73-84, 1985.
For
The purpose of this appendix is to define the procedures for an owner or operator to use to calculate the site specific fraction of organic compounds biodegraded (F
The determination of F
Unless otherwise specified, the procedures presented in this appendix are designed to be applied to thoroughly mixed treatment units. A thoroughly mixed treatment unit is a unit that is designed and operated to approach or achieve uniform biomass distribution and organic compound concentration throughout the aeration unit by quickly dispersing the recycled biomass and the wastewater entering the unit. Detailed discussion on how to determine if a biological treatment unit is thoroughly mixed can be found in reference 7. Systems that are not thoroughly mixed treatment units should be subdivided into a series of zones that have uniform characteristics within each zone. The number of zones required to characterize a biological treatment system will depend on the design and operation of the treatment system. Detailed discussion on how to determine the number of zones in a biological treatment unit and examples of determination of f
Biological treatment unit = wastewater treatment unit designed and operated to promote the growth of bacteria to destroy organic materials in wastewater.
The first step in the analysis to determine if a biological treatment unit may be used without being covered and vented through a closed-vent system to an air pollution control device is to determine the compound-specific f
(1) The EPA Test Method 304A or 304B (appendix A, part 63)—Method for the Determination of Biodegradation Rates of Organic Compounds,
(2) Performance data with and without biodegradation,
(3) Inlet and outlet concentration measurements,
(4) Batch tests,
(5) Multiple zone concentration measurements.
All procedures must be executed so that the resulting f
Select one or more appropriate procedures from the five listed above based on the availability of site specific data and the type of mixing that occurs in the unit (thoroughly mixed or multiple mixing zone). If the facility does not have site-specific data on the removal efficiency of its biological treatment unit, then Procedure 1 or Procedure 4 may be used. Procedure 1 allows the use of a benchtop bioreactor to determine the first-order biodegradation rate constant. An owner or operator may elect to assume the first order biodegradation rate constant is zero for any regulated compound(s) present in the wastewater. Procedure 4 explains two types of batch tests which may be used to estimate the first order biodegradation rate constant. An owner or operator may elect to assume the first order biodegradation rate constant is zero for any regulated compound(s) present in the wastewater. Procedure 3 would be used if the facility has, or measures to determine, data on the inlet and outlet individual organic compound concentration for the biological treatment unit. Procedure 3 may only be used on a thoroughly mixed treatment unit. Procedure 5 is the concentration measurement test that can be used for units with multiple mixing zones. Procedure 2 is used if a facility has or obtains performance data on a biotreatment unit prior to and after addition of the microbial mass. An example where Procedure 2 could be used is an activated sludge unit where measurements have been taken on inlet and exit concentration of organic compounds in the wastewater prior to seeding with the microbial mass and startup of the unit. The flow chart in figure 1 outlines the steps to use for each of the procedures.
If the first procedure is selected, follow the instructions in appendix A of part 63 Method 304A “Method for the Determination of Biodegradation Rates of Organic Compounds (Vented Option)” or Method 304B “Method for the Determination of Biodegradation Rates of Organic Compounds (Scrubber Option).” Method 304A or 304B provides instruction on setting up and operating a self-contained benchtop bioreactor system which is operated under conditions representative of the target full-scale system. Method 304A uses a benchtop bioreactor system with a vent, and uses modeling to estimate any air emissions. Method 304B uses a benchtop bioreactor system which is equipped with a scrubber and is not vented.
There are some restrictions on which method a source may use. If the facility is measuring the rate of biodegradation of compounds that may tend to react or hydrolyze in the scrubber of Method 304B, this method shall not be used and Method 304A is the required method. If a Henry's law value is not available to use with Form V, then Method 304A shall not be used and Method 304B is the required method. When using either method, the feed flow to the benchtop bioreactor shall be representative of the flow and concentration of the wastewater that will be treated by the full-scale biological treatment unit after the collection and treatment system has been enclosed as required under the applicable subpart.
The conditions under which the full-scale biological treatment unit is run establish the operating parameters of Method 304A or 304B. If the biological treatment unit is operated under abnormal operating conditions (conditions outside the range of critical parameters examined and confirmed in the laboratory), the EPA believes this will adversely affect the biodegradation rate and is an unacceptable treatment option. The facility would be making multiple runs of the test method to simulate the operating range for its biological treatment unit. For wide ranges of variation in operating parameters, the facility shall demonstrate the biological treatment unit is achieving an acceptable level of control, as required by the regulation, across the ranges and not only at the endpoints.
If Method 304A is used, complete Form V initially. Form V is used to calculate K1 from the Method 304A results. Form V uses the Henry's law constant to estimate the fraction lost from the benchtop reactor vent. The owner or operator shall use the Henry's law values in Table I. Form V also gives direction for calculating an equivalent KL. Note on Form V if the calculated number for line 11 is greater than the calculated value for line 13, this procedure shall not be used to demonstrate the compound is biodegradable. If line 11 is greater than line 13, this is an indication the fraction emitted from the vent is greater than the fraction biodegraded. The equivalent KL determined on Form V is used in Form II (line 6). Estimation of the Fe and f
If Method 304B is used, perform the method and use the measurements to determine K1, which is the first-order biodegradation rate constant. Form I lists the sequence of steps in the procedure for calculating K1 from the Method 304B results. Once K1 is determined, KL must be calculated by use of mass transfer equations. Form II outlines the procedure to follow for use of mass transfer equations to determine KL. A computer program which incorporates these mass transfer equations may be used. Water7 is a program that incorporates these mass transfer equations and may be used to determine KL. Refer to Form II-A to determine KL, if Water7 or the most recent update to this model is used. In addition, the Bay Area Sewage Toxics Emission (BASTE) model version 3.0 or equivalent upgrade and the TOXCHEM (Environment Canada's Wastewater Technology Centre and Environmega, Ltd.) model version 1.10 or equivalent upgrade may also be used to determine KL for the biological treatment unit with several stipulations. The programs must be altered to output a KL value which is based on the site-specific parameters of the unit modeled, and the Henry's law values listed in Table I must be substituted for the existing Henry's law values in the programs. Input values used in the model and corresponding output values shall become documentation of the f
Procedure 2 uses site-specific performance data that represents or characterizes operation of the unit both with and without biodegradation. As previously mentioned, proper determination of f
Procedure 3 uses measured inlet and outlet organic compound concentrations for the unit. This procedure may only be used on a thoroughly mixed treatment unit. Again, proper determination of f
Two types of batch tests which may be used to determine kinetic parameters are: (1) The aerated reactor test and (2) the sealed reactor test. The aerated reactor test is also known as the BOX test (batch test with oxygen addition). The sealed reactor test is also known as the serum bottle test. These batch tests should be conducted only by persons familiar with procedures for determining biodegradation kinetics. Detailed discussions of batch procedures for determining biodegradation kinetic parameters can be found in references 1-4.
For both batch test approaches, a biomass sample from the activated sludge unit of interest is collected, aerated, and stored for no more than 4 hours prior to testing. To collect sufficient data when biodegradation is rapid, it may be necessary to dilute the biomass sample. If the sample is to be diluted, the biomass sample shall be diluted using treated effluent from the activated sludge unit of interest to a concentration such that the biodegradation test will last long enough to make at least six concentration measurements. It is recommended that the tests not be terminated until the compound concentration falls below the limit of quantitation (LOQ). Measurements that are below the LOQ should not be used in the data analysis. Biomass concentrations shall be determined using standard methods for measurement of mixed liquor volatile suspended solids (MLVSS) (reference 5).
The change in concentration of a test compound may be monitored by either measuring the concentration in the liquid or in the reactor headspace. The analytical technique chosen for the test should be as sensitive as possible. For the batch test procedures described in this section, equilibrium conditions must exist between the liquid and gas phases of the experiments because the
To determine biodegradation kinetic parameters in a batch test, it is important to choose an appropriate initial substrate (compound(s) of interest) concentration for the test. The outcome of the batch experiment may be influenced by the initial substrate (S
For the batch tests described in this section, the S
1.
Before conducting experiments with biomass, it is necessary to verify the equilibrium assumption. The equilibrium assumption can be verified by conducting a stripping experiment using the effluent (no biomass) from the activated sludge unit of interest. Effluent is filtered with a 0.45 um or smaller filter and placed in the draft tube reactor. Air is sparged into the system and the compound concentration in the liquid or headspace is monitored over time. This test with no biomass may provide an estimate of the Henry's law constant. If the system is at equilibrium, the Henry's law constant may be estimated with the following equation:
A plot of—ln(C/C
The concentration of a compound decreases in the bioreactor due to both biodegradation and stripping. Biodegradation processes are typically described with a Monod model. This model and a stripping expression are combined to give a mass balance for the aerated draft tube reactor ):
Equation App. C-3 can be integrated to obtain the following equation:
This equation is used along with the substrate concentration versus time data to determine the best fit parameters (Q
The compound-specific biorate constants are then measured using Form XII. The stripping constant that was determined from Form XI and a headspace correction factor of 1 are entered on Form XII. The aerated reactor biotest may then be run, measuring concentrations of each compound of interest as a function of time. If headspace concentrations are measured instead of liquid concentrations, then the corresponding liquid concentrations are calculated from the headspace measurements using the K
The concentration data on Form XII may contain scatter that can adversely influence the data interpretation. It is possible to curve fit the concentration data and enter the concentrations on the fitted curve instead of the actual data. If curve fitting is used, the curve-fitting procedure must be based upon the Equation App. C-4. When curve fitting is used, it is necessary to attach a plot of the actual data and the fitted curve to Form XII.
If the stripping rate constant is relatively large when compared to the biorate at low concentrations, it may be difficult to obtain accurate evaluations of the first-order biorate constant. In these cases, either reducing the stripping rate constant by lowering the aeration rate, or increasing the biomass concentrations should be considered.
The final result of the batch testing is the measurement of a biorate that can be used to estimate the fraction biodegraded, f
2.
The equilibrium assumption must be verified for the batch reactor system. In this case, K
The concentration of a compound decreases in the bioreactor due to biodegradation according to Equation App. C-5:
Equation App. C-5 can be solved analytically to give:
This equation is used along with the substrate concentration versus time data to determine the best fit parameters (Q
If the sealed reactor test is used, Form X is used to determine the headspace correction factor. The disappearance of a compound in the sealed reactor test is slowed because a fraction of the compound is not available for biodegradation because it is present in the headspace. If the compound is almost entirely in the liquid phase, the headspace correction factor is approximately one. If the headspace correction factor is substantially less than one, improved mass transfer or reduced headspace may improve the accuracy of the sealed reactor test. A preliminary sealed reactor test must be conducted to test the equilibrium assumption. As the compound of interest is degraded, simultaneous headspace and liquid samples should be collected and Form X should be used to evaluate K
The compound-specific biorate constants are then calculated using Form XII. For the sealed reactor test, a stripping rate constant of zero and the headspace correction factor that was determined from Form X are entered on Form XII. The sealed reactor test may then be run, measuring the concentrations of each compound of interest as a function of time. If headspace concentrations are measured instead of liquid concentrations, then the corresponding liquid concentrations are calculated from the headspace measurements using K
The concentration data on Form XII may contain scatter that can adversely influence the data interpretation. It is possible to
If a sealed collapsible reactor is used that has no headspace, the headspace correction factor will equal 1, but the stripping rate constant may not equal 0 due to diffusion losses through the reactor wall. The ratio of the rate of loss of compound to the concentration of the compound in the reactor (units of per hour) must be evaluated. This loss ratio has the same units as the stripping rate constant and may be entered as the stripping rate constant on line 1 of Form XII.
If the loss due to diffusion through the walls of the collapsible reactor is relatively large when compared to the biorate at low concentrations, it may be difficult to obtain accurate evaluations of the first-order biorate constant. In these cases, either replacing the materials used to construct the reactor with materials of low permeability or increasing the biomass concentration should be considered.
The final result of the batch testing is the measurement of a biorate that can be used to estimate the fraction biodegraded, f
The number on Form XII line 9 will equal the Monod first-order biorate constant if the full-scale system is operated in the first-order range. If the full-scale system is operated at concentrations above that of the Monod first-order range, the value of the number on line 9 will be somewhat lower than the Monod first-order biorate constant. With supporting biorate data, the Monod model used in Form XII may be used to estimate the effective biorate constant K1 for use in Form III.
If a reactor with headspace is used, analysis of the data using equation App. C-6 is valid only if V
If there is no headspace (e.g., a collapsible reactor), equation App. C-6 is independent of V
3.
1. A description of the apparatus used (e.g., size, volume, method of supplying air or oxygen, mixing, and sampling procedures) including a simplified schematic drawing.
2. A description of how biomass was sampled from the activated sludge unit.
3. A description of how biomass was held prior to testing (age, etc.).
4. A description of what conditions (DO, gas-liquid equilibrium, temperature, etc.) are important, what the target values are, how the factors were controlled, and how well they were controlled.
5. A description of how the experiment was conducted, including preparation of solutions, dilution procedures, sampling procedures, monitoring of conditions, etc.
6. A description of the analytical instrumentation used, how the instruments were calibrated, and a summary of the precision for that equipment.
7. A description of the analytical procedures used. If appropriate, reference to an ASTM, EPA or other procedure may be used. Otherwise, describe how the procedure is done, what is done to measure precision, accuracy, recovery, etc., as appropriate.
8. A description of how data are captured, recorded, and stored.
9. A description of the equations used and their solutions, including a reference to any software used for calculations and/or curve-fitting.
Procedure 5 is the concentration measurement method that can be used to determine the f
Reference 8 “Technical Support Document for the Evaluation of Aerobic Biological Treatment Units with Multiple Mixing Zones,” is a source for further information concerning how to interpolate the biorates for multiple zones. In units with well-characterized concentration measurements obtained in an initial evaluation of the unit, it may be possible to demonstrate that there is a good correlation of the component concentrations with the locations in the multiple-zone unit. With this good correlation, it may be possible to accurately predict the concentrations in selected zones without actually testing each selected zone. This correlation method may be used for units that have many zones (greater than 5) or where one of the interior zones is not readily accessible for sampling. To use this correlation method of estimating zone concentrations, it is necessary to measure the concentrations in the inlet unit, the exit unit, and sufficient interior units to obtain a correlation of component concentrations with the locations. You cannot use this correlation method of estimating selected zone concentrations if monitoring of each zone is required, or if the accuracy and precision of the correlation is inferior to actual individual sampling error. The accuracy and precision of the correlation may be improved by increasing the number of locations tested. Because the correlation is based on many samples, it should provide an accurate representation of a stable operating system.
The estimated mass transfer coefficient for each compound in each zone is obtained from Form II using the characteristics of each zone. A computer model may be used. If the Water7 model or the most recent update to this model is used, then use Form II-A to calculate KL. The TOXCHEM or BASTE model may also be used to calculate KL for the biological treatment unit, with the stipulations listed in Procedure 304B. Compound concentration measurements for each zone are used in Form XIII to calculate the f
At this point, the individual f
The F
1. Rajagopalan, S. et al. “Comparison of Methods for Determining Biodegradation Kinetics of Volatile Organic Compounds.” Proceedings of Water Environment Federation. 67th Annual Conference, October 15-19, 1994.
2. Ellis, T.G. et al. “Determination of Toxic Organic Chemical Biodegradation Kinetics Using Novel Respirometric Technique”. Proceedings Water Environment Federation, 67th Annual Conference, October 15-19, 1994.
3. Pitter, P. and J. Chudoba. Biodegradability of Organic Substances in
4. Grady, C.P.L., B. Smets, and D. Barbeau. Variability in kinetic parameter estimates: A review of possible causes and a proposed terminology. Wat. Res. 30 (3), 742-748, 1996.
5. Eaton, A.D., et al. eds., Standard Methods for the Examination of Water and Wastewater, 19th Edition, American Public Health Association, Washington, DC, 1995.
6. Chudoba P., B. Capdeville, and J. Chudoba. Explanation of biological meaning of the So/Xo ratio in batch cultivation. Wat. Sci. Tech. 26 (3/4), 743-751, 1992.
7. Technical Support Document for Evaluation of Thoroughly Mixed Biological Treatment Units. November 1998.
8. Technical Support Document for the Evaluation of Aerobic Biological Treatment Units with Multiple Mixing Zones. July 1999.
This procedure is to be applied exclusively to Environmental Protection Agency methods developed by the Office of Water and the Office of Solid Waste. Alternative methods developed by any other group or agency shall be validated according to the procedures in Sections 5.1 and 5.3 of Test Method 301, 40 CFR Part 63, Appendix A. For the purposes of this appendix, “waste” means waste and wastewater.
This procedure shall be applied once for each waste matrix. Waste matrix in the context of this procedure refers to the target compound mixture in the waste as well as the formulation of the medium in which the
2.1. Sampling and Analysis
2.1.1. For each waste matrix, collect twice the number of samples required by the applicable regulation. Designate and label half the sample vials the “spiked” sample set, and the other half the “unspiked” sample set. Immediately before or immediately after sampling (immediately after in the context of this procedure means after placing the sample into the sample vial, but before the sample is capped, cooled, and shipped to the laboratory for analysis), inject, either individually or as a solution, all the target compounds into each spiked sample.
2.1.2. The mass of each spiked compound shall be 40 to 60 percent of the mass expected to be present in the waste matrix. If the concentration of the target compounds in the waste are not known, the mass of each spiked compound shall be 40 to 60 percent of the limit allowed in the applicable regulation. Analyze both sets of samples (spiked and unspiked) with the chosen method.
For each pair of spiked and unspiked samples, determine the fraction of spiked compound recovered (R) using the following equations.
3.1.Method Evaluation
In order for the chosen method to be acceptable for a compound, 0.70≤R≤1.30 (R in this case is an average value of all the spiked and unspiked sample set R values). If the average R value does not meet this criterion for a target compound, the chosen method is not acceptable for that compound, and therefore another method shall be evaluated for acceptance (by repeating the procedures outlined above with another method).
3.2.Records and Reports
Report the average R value in the test report and correct all reported measurements made with the method with the calculated R value for that compound by using the following equation:
3.3.Optional Correction Step
If the applicable regulation allows for correction of the mass of the compound in the waste by a published f
This procedure is required to be performed in subpart S of this part, entitled National Emission Standards for Hazardous Air Pollutants from the Pulp and Paper Industry. Subpart S requires this procedure in § 63.453(p)(3) to be followed during unsafe sampling conditions when it is not practicable to obtain representative samples of hazardous air pollutants (HAP) concentrations from an open biological treatment unit. It is assumed that inlet and outlet HAP concentrations from the open biological treatment unit may be obtained during the unsafe sampling conditions. The purpose of this procedure is to estimate the concentration of HAP within the open biological treatment unit based on information obtained at inlet and outlet sampling locations in units that are not thoroughly mixed and, therefore, have different concentrations of HAP at different locations within the unit.
Biological treatment unit = wastewater treatment unit designed and operated to promote the growth of bacteria to destroy organic materials in wastewater.
This test procedure is used under unsafe sampling conditions that do not permit practicable sampling of open biological treatment units within the unit itself, but rather relies on sampling at the inlet and outlet locations of the unit. This procedure may be used only under unsafe sampling conditions to estimate f
The steps in the estimation procedure include data collection, the estimation of concentrations within the unit, and the use of Form 1 to estimate f
This method is based upon modeling the nonthoroughly mixed open biological treatment unit as a series of well-mixed zones with internal recycling between the units and assuming that two Monod biological kinetic parameters can be used to characterize the biological removal rates in each unit. The data collection procedure consists of two separate components. The first data collection component is part of the initial performance test, and the second data collection component is used during unsafe sampling conditions.
The objective of the first data collection component is to demonstrate that the open biological treatment unit can be represented by Monod kinetics and to characterize the performance of the open biological treatment unit. An appropriate value of the biorate constant, Ks, is determined using actual sampling data from the open biological treatment unit. This is done during the initial performance test when the open biological treatment unit is operating under normal conditions. This specific Ks value obtained during the initial performance test is used in the calculation procedure to characterize the open biological treatment unit during unsafe sampling conditions. The following open biological treatment unit characterization information is obtained from the first component of the data collection procedure:
(1) The value of the biorate constant, Ks;
(2) The number and characteristics of each zone in the open biological treatment unit (depth, area, characterization parameters for surface aeration, submerged aeration rates, biomass concentration, concentrations of organic compounds, dissolved oxygen (DO), dissolved solids, temperature, and other relevant variables); and
(3) The recycle ratio of internal recirculation between the zones. The number of zones and the above characterization of the zones are also used to determine the performance of the unit under the unsafe sampling conditions of concern.
In the second data collection component obtained under unsafe sampling conditions, the measured inlet and outlet HAP concentrations and the biomass concentration are obtained for the open biological treatment unit. After the site specific data collection is completed on the day a parameter excursion occurs, the inlet and outlet concentrations are used with the prior open biological treatment unit characterization to estimate the concentrations of HAP in each zone. The following information on the open biological treatment unit must be available in the second data collection component:
(1) Basic unit variables such as inlet and recycle wastewater flow rates, type of agitation, and operating conditions;
(2) The value of the inlet and outlet HAP concentrations; and
(3) The biomass concentration in the open biological treatment unit.
A single value of Ks is calculated using Form 3 for each data set that is collected during the initial performance test. A single composite value of Ks, deemed to be representative of the biological unit, is subsequently selected so that the f
(1) Determine the median of the Ks values calculated for each data set;
(2) Estimate f
(3) Calculate f
(4) Compare the f
(1) Confirmation that the unit can be represented by Monod kinetics is made by identifying the following two items:
(i) The zone methanol concentrations measured during the initial performance test; and
(ii) The zone methanol concentrations estimated by the Multiple Zone Concentrations Calculations Procedure based on inlet and outlet concentrations (Column A of Form 2). For each zone, the concentration in item 1 is compared to the concentration in item 2.
(2) For each zone, the estimated value of item 2 must be:
(i) Within 25 percent of item 1 when item 1 exceeds 8 mg/L; or
(ii) Within 2 mg/L of item 1 when item 1 is 8 mg/L or less.
(3) Successful demonstration that the calculated zone concentrations meet these criteria must be achieved for 80 percent of the performance test data sets.
(4) If negative values are obtained for the values of K1 and Ks, then these negative kinetic constants may not be used with the Monod model, even if the criteria are met. If negative values are obtained, this test procedure cannot be used for evaluating the performance of the open biological treatment unit.
(1) A site-specific liquid-phase mass transfer coefficient (KL) must be obtained for each zone during the unsafe sampling conditions. Do not use a default value for KL. The KL value for each zone must be based on the site-specific parameters of the specific unit. The first step in using this procedure is to calculate KL for each zone in the unit using Form 4. Form 4 outlines the procedure to follow for using mass transfer equations to determine KL. Form 4 identifies the appropriate form to use for providing the detailed calculations to support the estimate of the value of KL. Forms 5 and 6 are used to provide individual compound estimates of KL for quiescent and aerated impoundments, respectively. A computer model may be used to perform the calculations. If the WATER8 model or the most recent update to this model is used, then report the computer model input parameters that you used as an attachment to Form 4. In addition, the Bay Area Sewage Toxics Emission (BASTE) model, version 3.0, or equivalent upgrade and the TOXCHEM (Environment Canada's Wastewater Technology Centre and Environmega, Ltd.) model, version 1.10, or equivalent upgrade may also be used to determine KL for the open biological treatment unit with the following stipulations:
(i) The programs must be altered to output a KL value that is based on the site-specific parameters of the unit modeled; and
(ii) The Henry's law value listed in Form 4 must be substituted for the existing Henry's law values in the models.
(2) The Henry's law value listed in Form 4 may be obtained from the following sources:
(i) Values listed by EPA with temperature adjustment if needed;
(ii) Measured values for the system of concern with temperature adjustment; or
(iii) Literature values of Henry's law values for methanol, adjusted for temperature if needed.
(3) Input values used in the model and corresponding output values shall become part of the documentation of the f
(4) Report the input parameters that you used in the computer model on Forms 5, 6, and 7 as an attachment to Form 4. If you have submerged air flow in your unit, you must add the value of KL estimated on Form 7 to the value of KL obtained with Forms 5
Form 2 is used to estimate the zone concentrations of HAP based on the inlet and outlet data. The value of Ks entered on the form is that single composite value of Ks discussed in section III.C of this appendix. This value of Ks is calculated during the Initial Performance Test (and subsequently updated, if necessary). A unique value of the biorate K1 is entered on line 5 of Form 2, and the inlet concentration is estimated in Column A of Form 2. The inlet concentration is located in the row of Form 2 corresponding to zone 0. If there are three zones in the system, n-3 equals 0 for the inlet concentration row. These estimated zone concentrations are then used in Form 1 to estimate f bio for the treatment unit.
A QA/QC plan outlining the procedures used to determine the measured inlet and outlet concentrations during unsafe conditions and how the zone characterization data were obtained during the initial performance test shall be prepared and submitted with the initial performance test report. The plan should include, but may not be limited to:
(1) A description of each of the sampling methods that were used (method, procedures, time, method to avoid losses during sampling and holding, and sampling procedures) including simplified schematic drawings;
(2) A description of how that biomass was sampled from the biotreatment unit, including methods, locations, and times;
(3) A description of what conditions (DO, temperature, etc.) are important, what the target values are in the zones, how the factors were controlled, and how they were monitored. These conditions are primarily used to establish that the conditions of the initial performance test correspond to the conditions of the day in question;
(4) A description of how each analytical measurement was conducted, including preparation of solutions, dilution procedures, sampling procedures, monitoring of conditions, etc;
(5) A description of the analytical instrumentation used, how the instruments were calibrated, and a summary of the accuracy and precision for each instrument;
(6) A description of the test methods used to determine HAP concentrations and other measurements. Section 63.457(c)(3) specifies the test methods that must be used to determine HAP concentrations. During unsafe sampling conditions, you do not have to sample over an extended period of time or obtain more than one sample at each sample point.
(7) A description of how data are captured, recorded, and stored; and
(8) A description of the equations used and their solutions for sampling and analysis, including a reference to any software used for calculations and/or curve-fitting.
Use Form 1 with your zone concentration information to estimate the value of f bio under unsafe sampling conditions. Form 1 uses measured concentrations of HAP in the unit inlet and outlet, and Form 1 also uses the estimated concentrations in each zone of the unit obtained from Form 2. This procedure may be used on an open biological treatment unit that has defined zones within the unit. Use Form 1 to determine f
A list of CFR titles, subtitles, chapters, subchapters and parts and an alphabetical list of agencies publishing in the CFR are included in the CFR Index and Finding Aids volume to the Code of Federal Regulations which is published separately and revised annually.
Material Approved for Incorporation by Reference
Table of CFR Titles and Chapters
Alphabetical List of Agencies Appearing in the CFR
List of CFR Sections Affected
The Director of the Federal Register has approved under 5 U.S.C. 552(a) and 1 CFR Part 51 the incorporation by reference of the following publications. This list contains only those incorporations by reference effective as of the revision date of this volume. Incorporations by reference found within a regulation are effective upon the effective date of that regulation. For more information on incorporation by reference, see the preliminary pages of this volume.
All changes in this volume of the Code of Federal Regulations that were made by documents published in the
Title 40 was established at 36 FR 12213, June 29, 1971. For the period before January 1, 2001, see the “List of CFR Sections Affected, 1964-1972, 1964-1972, 1973-1985, and 1986—2000” published in 10 separate volumes.