### Enclosure 2 Form Approved __/__/__ OMB Control No. ____-____

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# Test Procedures, Methods and Reporting Requirements for the Information Collection Request for Petroleum Refineries

This document provides an overview of appr oved methods, target pollutants and units of measure, and reporting requirements for petroleum re fineries. All recipients must complete and submit test results within 6 months of receipt of your Section 114 letter. This document will be referred to as the ‘petroleum refinery test pr ogram.’ The document is organized as follows:

1.0 Testing Procedures and Methods 2.0 How to Report Data

3.0 How to Submit Data 4.0 Contact Information for Question s on Test Plan and Reporting



## 1.0 Testing Procedures and Methods

The EPA petroleum refinery test program require s emissions and other test data for several pollutants, including specific haza rdous air pollutants ( HAP), criteria pollutants, and potential surrogate groups. If EPA is requesting that you complete emissions tes ting, the cover letter of this packet (CAA section 114 letter) will include a list of emissions sources selected for testing. For each petroleum refinery emissions source lis ted in your Section 114 letter, you must perform an emissions test for some combination of pollutants ( i.e. , simultaneous or overlapping measurements per group) and diluents according to the test protocols presented in Sections 1.1 through 1.4 of this section.

Please refer to your Section 114 letter for additio nal testing information. As noted previously, the Section 114 letter includes th e specific sources for which we are requesting that you perform emissions testing. Please note that you do not ha ve to submit a test plan to EPA for approval prior to testing; however, we recommend that you prepare a test plan for your own use to assist in the planning and to ensure that you address all of the testing and reporting requirements. Please note that you also must report your pro cess and emissions testi ng data using the EPA Electronic Reporting Tool (ERT), where applic able. The ERT requires you to report most elements of a test plan. Enclosure 7 of this I CR provides an example of the EPA ERT test plan. You are directed to the ERT ( http://www.epa.gov/ttn/chief/ert/ert_tool.html ) for a more complete and interactive description of these test plan elements.

You must follow all of the procedures as spec ified in the test met hods, including the quality assurance and quality control m easures, and document the results in the ERT and in any test report provided to EPA. For this program, you need not obtain audit material s from your state or local agency or from EPA. Y ou may apply any third party aud it materials you have on hand and document the results, but you are not required to do so.

You may have submitted test data for some of these pollutants already. If you have conducted any of the requested groups of tests ( i.e. , any complete set of tests required to be conducted simultaneously) in the past 5 years and reported the data in Part IV of En closure 1 of this ICR, you are not required to do additiona l testing for those pollutants.Form Approved __/__/__ OMB Control No. ____-____

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### 2 of 21 1.1 Stack Test Methods

The following emissions sources must follow the st ack test method procedur es described in this section:

• Fluid catalytic cracking unit

• Thermal catalytic cracking unit

• Fluid coking unit (including flexicoking units)

• Delayed coking unit

• Catalytic hydrocracking unit

• Hydrogen production unit

• Asphalt blowing still

• Sulfur recovery unit

During a 30-day period that include s emissions testing and fuel an alysis, you should also collect relevant process data, such as: total heat inpu t; material description, co mposition, and feed rate; coke burn-off rate; emissions control devices in use during the test; control device operating or monitoring parameters (including, as appropriate to the control device, flue gas flow rate, pressure drop, scrubber liquor pH , scrubber liquor flow rate, sorb ent type and sorbent injection rate, primary and secondary voltage and current, temperature); process parameters (such as type of crude, oxygen concentration, temperature); and any pollution prevention or other hazardous air pollutant emission reduction approaches be ing implemented during the test program. You should report the above process da ta as daily averages in the Process Data spreadsheet; you can download this spreadsheet from the ICR website ( http://icr2010.rti.org , click on “Petroleum Refineries”). For process data that you record during testing, make clear, using the Notes section of the ERT or spreadsheet, the correlation be tween emissions measurements and process data ( e.g. , identify Method 23, run 1 for th e associated process data on th e process data details tab of the ERT).

The owner/operator of the petrol eum refinery must certify that th e unit tested was operating in a normal and representative manner during the perf ormance test. The owner/operator must also certify that it operated the pollu tion control equipment, if any, on the unit tested in accordance with manufacturers’ specificat ions and requirements for prope r operation during the emissions testing.

1.1.1 Sample Location and Gas Composition Analysis Methods

You must use U.S. EPA Method 1 of Appendix A-1 to 40 CFR Part 60 to select the locations and number of traverse points for sampli ng for the tests in this section. See http://www.epa.gov/ttn/emc/methods/method1.html for a copy of the method and guidance information for sampling situations not meeting Method 1 criteria.

For analysis of flue gas co mposition, including oxygen concen tration, you must use U.S. EPA Method 3A or 3B of Appendix A-2 to 40 CFR Part 60. See http://www.epa.gov/ttn/emc/methods/method3a.html for Method 3A or http://www.epa.gov/ttn/emc/methods/method3b.html for Method 3B information.Form Approved __/__/__ OMB Control No. ____-____

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### 3 of 21 1.1.2 Emissions Measurement Methods

Table 1.1 summarizes the testing required to be pe rformed for each type of process unit. Where indicated in the tables, you must conduct the tests for the indicat ed pollutants simultaneously for your process unit. If the table does not indi cate simultaneous sampling is required for multiple pollutants, you may still choose to do so. Fo r example, if you are asked to test your fluid catalytic cracking unit, you may c onduct four separate sets of tests, one set that includes all pollutants indicated with an “a”, another set that includes all pollutants ma rked with a “b,” etc., or you may choose to conduct all the test ing at the same time (if possible).

Table 1.2 presents a list of the test methods to use for completing the tests required in Table 1.1. Tables 1.3 through 1.5 provide listings of target analytes for volat ile and semi-volatile organic HAP and aldehyde test methods. Table 1.6 provides a listing of target analytes for C1 through C5 hydrocarbons. For copies of the U.S. EPA test methods, continuous emissions monitoring systems (CEMS) performance sp ecifications, and additional info rmation, please refer to EPA’s Emission Measurement Center website, http://www.epa.gov/ttn/emc/ , and EPA’s Hazardous Waste website, http://www.epa.gov/waste/hazard/t estmethods/sw846/online/index.htm , as appropriate. If you would like to use a method no t on this list, please contact EPA for approval of an alternative method. Please see Section 4.0 of this document fo r a list of persons to contact with questions regarding test methods and reporting.

Report all pollutant emission data as indicated in Table 1.2. Report the results of your emissions tests according to the directions provid ed in Section 2.0 of this enclosure.

Unless otherwise specified, each pollutant emissions te st should consist of at least three test runs for the sampling duration and/or volume indicat ed for each specified unit or operation. You should collect emissions samples for the identifie d pollutants downstream of the last relevant emissions control device ( i.e. , stack or other point representing the composition of the flue gases at the exit to the atmosphere ), unless otherw ise indicated.

You must keep the following records for 3 years:

• Documentation that each emissions test was conducted in accordance with the enclosed sampling protocol; and

• The results of each emissions test.Form Approved __/__/__ OMB Control No. ____-____

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### 4 of 21 Table 1.1: Required Test Matrix for Process Units by Process Type

Process Unit

Catalytic Reforming Pollutant 1Delayed Coking2

Fluid Catalytic Cracking, Thermal Catalytic Cracking, Fluid Coking, Catalytic Hydrocracking 2PurgeVent2CokeBurnVent2HydrogenProduction2Asphalt Blowing2Sulfur Recovery2

Speciated Volatile Organic HAP a a a a a a a Speciated Semi-volatile Organic HAP a a a a a a Aldehydes a a a a a a Total hydrocarbons (THC) a a a a a a Methane and ethane a a a a a C1 through C5 hydrocarbons a Carbon Monoxide (CO) a a a a a a Dioxins and Furans (D/F), Polychlorinated biphenyls (PCB) b b b
Hydrogen chloride (HCl), chlorine gas (Cl 2 ), hydrogen fluoride (HF), and hydrogen cyanide (HCN) c e e

Hydrogen sulfide (H 2 S), carbonyl sulfide ( COS), and carbon disulfide (CS 2 ) c f f

Total reduced sulfur compounds (TRS) c f f
Mercury (Hg) d d d Hexavalent chromium (Cr +6 ) d 3
Other Metals d d d PM/PM 2.5 (filterable) d d d
PM 2.5 (condensable) d d d Ammonia (NH 3 ) d 3 Oxides of nitrogen (NO X ) d d d g g Sulfur dioxide (SO 2 ) d d d g g Gas flow rate a, b, c, d a, b, d, e a, b, d, e a, g a, f, g a, f Oxygen (O 2 ) and Carbon dioxide (CO 2 ) a, b, c, d a, b, d, e a, b, d, e a, g a, f, g a, f
Moisture a, b, c, d a, b, d, e a, b, d, e a, g a, f, g a, f

1 Three runs per test, unless otherwise noted

2 For each process unit, simultaneous sampling for pollutants marked with same letter

3 For fluid catalytic cracking uni ts and fluid coking units onlyForm Approved __/__/__ OMB Control No. ____-____

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### 5 of 21 Table 1.2: Summary of Test Methods and Alternative Methods

Pollutant Recommended Method Alternative Method Target Reported Units of Measure 1 Speciated Volatile Organic HAP 2 SW-846 Method 0031 with SW-846 Method 8260B. Collect a minimum of four sets of ad sorbent traps over each 1-hour period test run (total of three test runs). U.S. EPA Method 18. Use a minimum sample time of 1 hour
per run. lb/hr and μ g/dscm

Speciated Semivolatile Organic HAP 3 SW-846 Method 0010. Collect at least 4 cubic meters per each of three test runs. Use SW-846 Method 8270C or D for the analytical finish. lb/hr and μ g/dscm

Aldehydes 4 SW-846 Method 0011 with SW-846 Method 8315A. Collect a minimum volume of 1.3 cubic meters U.S. EPA Method 320 only if concentrations are known to be 1 ppmvd or greater. Use a minimum test run time of 2 hours. lb/hr and μ g/dscm

THC U.S. EPA Method 25A. Use a minimum sampling time of 1 hour per run. Calibrate the measuring instrument with propane. You may calibrate the measuring instrument with a mixture representing the organic compounds being emitted. Provide the chemical make-up and response factors for the alternative standards; report the results as the alternative organic mixture and as propane equivalent concentrations. lb/hr and ppmvd as
propane

Methane and ethane U.S. EPA Method 18. Use a minimum sample time of 1 hour per

run. U.S. EPA Method 320 lb/hr and ppmvd

C1 through C5 hydrocarbons 5 U.S. EPA Method 18. Use a minimum sample time of 1 hour per

run. U.S. EPA Method 320 lb/hr and ppmvd

CO 6 U.S. EPA Method 10 or 10B. Collect a minimum volume of 60 liters over a minimum sample time of 1 hour per

run. None lb/hr and ppmvd

D/F, PCB 7 U.S. EPA Method 23. Collect a minimum volume of 3 cubic meters. Use high resolution GC/MS for the analytical finish. None lb/hr and pg/dscm

HCl, Cl 2 , and HF U.S. EPA Method 26A. Collect a minimum volume of 2 cubic meters.. U.S. EPA Method 26 or U.S. EPA Method 320 if there are no entrained water droplets in the emissions stream. lb/hr and mg/dscm

HCN U.S. EPA Conditional Test Method 033 (CTM-033). Collect a minimum volume of 1 cubic meter with particular attention to maintaining the collection solution pH as per section 4.1 of the method. U.S. EPA Method 320 if there are no entrained water droplets in the emissions stream. lb/hr and μ g/dscm

Hg ASTM D6784-02 (Ontario-hydro method). Collect a minimum volume of 3 cubic meters. U.S. EPA Method 30B only if you have the knowledge and capability to speciate mercury using this method. lb/hr and μ g/dscmForm Approved __/__/__ OMB Control No. ____-____

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### 6 of 21 Table 1.2: Summary of Test Methods and Alternative Methods (cont.)

Pollutant Recommended Method Alternative Method Target Reported Units of Measure 1
Hexavalent Chromium (Cr +6 ) SW-846 Method 0061. Collect a minimum sample volume of 3 cubic meters per run (or the maximum sample volume possible while maintaining the pH of first impinger solution above 8.5 if less than 3 cubic meters can be collected) and use a sample preconcentrator according to §4.4 and 4.5. None lb/hr and μ g/dscm

Metals 8 U.S. EPA Method 29. Collect a minimum volume of 3 cubic meters per run. Use ICAP/MS or GFAAS for the analytical finish. For stacks without entrained water droplets, determine filterable PM emissions according to §8.3.1 .1 with a filter temperature of 320°F +/- 25°F. For stacks with entrained water droplets, do not determine filterable PM with Method 29 (see PM/PM 2.5 below). For stacks without entrained water droplets, you may opt to conduct a separate EPA Method 5 or 5F test with a filter temperature of 320°F +/- 25°F in lieu of measuring PM with the Method 29 train (see PM/PM 2.5 below). lb/hr and mg/dscm

PM/PM 2.5 (filterable plus condensable) 9 from stacks without entrained water droplets ( e.g. , not from units with wet scrubbers) 9 U.S. EPA Other Test Methods 27 (OTM 27) and 28 (OTM 28). Collect a minimum volume of 2 cubic meters
per run. None lb/hr and gr/dscf

lb/hr and gr/dscf (if use Method 5F, report both total filterable catch and non-sulfate PM) PM/PM 2.5 (filterable plus condensable) 9 from stacks with entrained water droplets

AND

Total Dissolved Solids (TDS) and Total Suspended Solids (TSS) from wet scrubber recirculation liquid 9 U.S. EPA Method 5 or 5B with a filter temperature of 320°F +/- 25°F and Other Test Method 28 (OTM 28). Collect a minimum volume of 2 cubic meters per run.

AND

ASTM D5907 For TDS and TSS, Standard Methods of the Examination of Water and Wastewater Method 2540B for solids in scrubber recirculation liquid (as fed to the wet scrubber) lb/hr and gr/dscf

AND

mg solids per liter of scrubber recirculation liquid 10

NH 3 South Coast AQMD Method 207.1 U.S. EPA Conditional Test Method 027 (CTM-027) lb/hr and ppmvd

NO X 11 U.S. EPA Method 7E; 2-hr sample time U.S. EPA Method 7 lb/hr and ppmvdForm Approved __/__/__ OMB Control No. ____-____

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### 7 of 21 Table 1.2: Summary of Test Methods and Alternative Methods (cont.)

Pollutant Recommended Method Alternative Method Target Reported Units of Measure 1
SO 2 11 U.S. EPA Method 6C; 2-hr sample time U.S. EPA Method 6 lb/hr and ppmvd

H 2 S, COS, CS 2 U.S. EPA Method 15. Per method, a minimum of 16 individual samples during a period of 3 to 6 hours, per

run None lb/hr and ppmvd

TRS U.S. EPA Method 15A or 16A; 3-hr sample time per run; (one 3-hr sample per run or three 1-hr samples per run) U.S. EPA Method 16B combined with the analysis procedures of U.S. EPA Method 15. ppmvd

Gas flow rate U.S. EPA Method 2 U.S. EPA Method 2A, 2B, 2C, 2D, 2F, or 2G, as appropriate acfm, scfm, and dscfm O 2 /CO 2 U.S. EPA Method 3A U.S. EPA Method 3B percent volume, dry Moisture U.S. EPA Method 4 None percent volume

1 lb/hr = pounds per hour; μ g/dscm = micrograms per dry standard cubic meter; ppmvd = parts per million by volume, dry basis;

pg/dscm = picograms per dry standard cubic meter; mg/dscm = m illigrams per dry standard cubic meter; gr/dscf = grains per dry standard cubic foot; acfm = actual cubic feet per minute; scfm = standard cubic feet pe r minute; dscfm = dry standard cubic feet per minute.

2 Target analytes are given in Table 1.3; test runs must occu r during the test runs for speciated semi-volatile organic HAP ( i.e.
, one volatile organic HAP run conducted pe r each semi-volatile organic HAP run).

3 Target analytes are given in Table 1.4; use either SW-846 Method 8270C or 8270D for the analysis of Method 0010 samples.

Follow SW-846 Method 3542 for Method 0010 sample train compone nts extraction and preparation for analyses. This procedure will result in three separate sample fractions for analyses – the front half (filter and front half rinse), the back half (XAD-2 and back half rinse), and condensate (first impinger an d impinger rinse). You may combine the three analytical fractions collected in the Method 0010 sampling train and analy ze as one sample. If you choose this option rather than analyzing the fractions separately, you mu st track the various fractional extraction and condensate volumes carefully in order to calculate the relative in-stack concentrations correctly. Y ou may use acetone followed by MeCl for the solvent rinse in lie u of the 50/50 MeCl/MeOH rinse ( i.e. , no liquid/liquid extraction). In addition, the analytical finish for either method should also employ high resolution gas chromatography and either low resolution or high resolution mass spectrometry with selective ion monitoring (SIM) specifically for target ed polycyclic aromatic hydrocarbons (PAH).

4 Target analytes are given in Table 1.5; test runs must occur during the test runs for speciated volatile and speciated semi-vo latile

organic HAP.

5 Target analytes for C1 through C5 hydrocar bons are given in Table 1.6; test runs mu st occur during the test runs for speciated volatile and speciated se mi-volatile organic HAP.

6 If a unit has a certified CEMS installed for CO, you may report hourly averages from 30 da ys of CEMS data for the unit in lieu

of conducting a CO stack test. In order to correlate these emissions with other st ack test emissions, a portion of the CEMS data submitted should contain the emissions data collected duri ng performance of the other requested stack tests and hourly O 2 concentrations should also be provided, if continuously monitored. The CEMS must meet the requirements of Performance Specification 4 and 40 CFR 60.13 or the CE MS accuracy and ongoing QA/QC requirements of 40 CFR part 60, subpart J or Ja. Also provide the data of the most recent CEMS accuracy certification.

7 Just the 12 “dioxin-like” PCB congeners (IUPAC Numbers PCB-77, -81, -105, -114, -118, -123, -126, -156, -157, -167, -169,

and -189)

8 Metals to be tested include antimony (Sb), arsenic (As), beryll ium (Be), cadmium (Cd), chromium (Cr), cobalt (Co), lead (Pb),

manganese (Mn), nickel (Ni), and selenium (Se).

9 Conduct either the test for PM/PM 2.5 (filterable) from stacks without entrained water droplets or the PM/PM 2.5 (filterable) from

stacks with entrained water droplets (with the TDS and TSS an alysis), whichever is appropr iate for your stack.

10 Also report scrubber recirculation liquid flow rate in liters/min.

11 If a unit has a certified CEMS installed for NO X and/or SO 2 , you may report hourly averages from 30 days of CEMS data for

the unit in lieu of conducting a NO X and/or SO 2 stack test. Also provide hourly O 2 concentrations for the 30 days of CEMS data. In order to correlate these emissions with other stack test emissions, a portion of the CEMS data submitted should contain the emissions data collected during performance of th e other requested stack tests. The CEMS must meet the requirements of Performance Specification 2 and 40 CFR 60.13 or the CEMS accura cy and ongoing QA/QC requirements of 40 CFR part 60, subpart J or Ja. Al so provide the data of the most re cent CEMS accuracy certification.Form Approved __/__/__ OMB Control No. ____-____

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### 8 of 21 NOTE: Special criteria apply fo r simultaneous sampling, sampling run time, and sample volumes for the semi-continuous and batch processes rela ted to the delayed coki ng unit and cyclic and semi-regenerative catalytic reforming units. Sa mpling should be conducte d over the duration of the venting cycle. For vent cycles lasting less th an 6 hours, testing over a vent cycle constitutes a single test run. For venting cycl es shorter than the specified sampling time (or insufficient to allow collection of the required sample volume) , sampling over the duration of the vent cycle shall constitute an acceptable te st run. For semi-regenerative cat alytic reforming units (only one cycle), the anticipated venting cycle should be di vided into three roughly equivalent periods, and testing over each period would const itute a single run so that the three test runs would cover the duration of the entire venting event. Generall y, you will need to apply U.S. EPA Method 1A in sampling these locations. A sample testing plan for a delayed coking unit is provided on the ICR website ( http://icr2010.rti.org , click on “Petroleum Refineries”); th is testing plan may be used as guidance in developing testing pl an for the particular batch emissions source required to be tested.

Table 1.3: Target Volatile Analytes
Compound CAS Number Compound CAS Number Acetone 1 67-64-1 Methyl t-butyl ether 2 91-20-3 Acetonitrile 75-05-8 Methylene chloride 75-09-2 Acrolein 1 107-05-8 Naphthalene 91-20-3 Acrylonitrile 107-13-1 Nitrobenzene 98-95-3 Benzene 71-43-2 2-Nitropropane 79-46-9 1,3-Butadiene 2 106-99-0 Pentane 2 109-66-0 Carbon disulfide 75-15-0 Styrene 100-42-5 Chlorobenzene 108-90-7 Tetrachloroethene 127-18-4 Cumene (isopropylbenzene) 98-82-8 Toluene 108-88-3 1,2-Dibromoethane 106-93-4 Trichloroethene 79-01-6 Ethylbenzene 100-41-4 Triethylamine 121-44-8
Hexane 2 110-54-3 2,2,4 Trimethylpentane 2 540-84-1 Methanol 1 67-56-1 Xylenes (mixed isomers) 1330-20-7 Methyl isobutyl ketone 108-10-1

1 Analyte is not applicable to SW-846 Method 0031 sampling proce dure. Collection of samples for these compounds is required

only for hydrogen plant vent and requires collec tion in tedlar bags or evacuated canisters.

2 Not specifically listed as an analyte for SW-846 Method 8260B.Form Approved __/__/__ OMB Control No. ____-____

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### 9 of 21 Table 1.4: Target Semi-volatile Analytes
Compound CAS Number Compound CAS Number Acenaphthene 83-32-9 Dimethylaminobenzene 60-11-7 Acenaphthylene 208-96-8 7,12-Dimethylbenz(a)anthracene 57-97-6 Aniline 62-53-3 3,3’-Dimethylbenzidine 119-93-7 Anthracene 120-12-7 α , α -Dimethylphenethylamine 122-09-8 Benzidine 1 92-87-5 2,4-Dimethylphenol 105-67-9 Benz[a]anthracene 56-55-3 Fluoranthene 206-44-0 Benzo[b]fluoranthene 205-99-2 Fluorene 86-73-7 Benzo[k]fluoranthene 207-08-9 Indeno(1,2,3-cd)pyrene 193-39-5 Benzo[g,h,i]perylene 191-24-2 Isophorone 78-59-1 Benzo[a]pyrene 50-32-8 3-Methylcholanthrene 56-49-5 Benzo[e]pyrene 2 192-97-2 2-Methylnaphthalene 91-57-6 Biphenyl 2, 92-52-4 Naphthalene 91-20-3 Cresol (mixed isomers) 1319-77-3 Perylene 2 198-55-0 Chrysene 218-01-9 Phenanthrene 85-01-8 Dibenz[a,h]anthracene 53-70-3 Phenol 108-95-2 Dibenzofuran 132-64-9 1,4-Phenylenediamine 106-50-3 Dibenzo(a,e)pyrene 192-65-4 Pyrene 129-00-0 3,3’-Dimethoxybenzidine 119-90-4 o-Toluidine 95-53-4

1 Notes non-reproducible chromatographic performance in SW-846 Method 8270D

2 Not specifically listed as an analyte for SW-846 Method 8270D



### Table 1.5: Aldehydes
Compound CAS Number Formaldehyde 100-41-4 Acetaldehyde 106-99-0 Propanal 123-38-6Form Approved __/__/__ OMB Control No. ____-____

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### 10 of 21 Table 1.6: C1 through C5 Hydrocarbons
Description Compound CAS No. C1 Alkanes Methane 74-82-8 C2 Alkanes Ethane 74-84-0 C3 Alkanes Propane 74-98-6 C4 Alkanes n-Butane 106-97-8 Isobutane 75-28-5 C5 Alkanes n-Pentane 109-66-0 2-Methylbutane 78-78-4 Cyclopentane 287-92-3 C2 Olefins Ethylene 74-85-1 C2 Alkynes Acetylene 74-86-2 C3 Olefins Propylene 115-07-1 C4 Olefins 1-Butene 106-98-9 2-Butene 107-01-7 Isobutene 115-11-7 C5 Olefins 1-Pentene 109-67-1 Cis-2-pentene 627-20-3 Trans-2-pentene 646-04-8 2-Methyl-1-butene 563-46-2 3-Methyl-1-butene 563-45-1 2-Methyl-2-butene 513-35-9 Cylcopentene 142-29-0 C3 Alkadienes Propadiene 463-49-0 C4 Alkadienes 1,2-Butadiene 590-19-2 1,3-Butadiene 106-99-0 C5 Alkadienes 1,2-Pentadiene 591-95-7 1-cis-3-Pentadiene 1574-41-0 1-trans-3-Pentadiene 2004-70-8 1,4-Pentadiene 591-93-5 2,3-Pentadiene 591-96-8 3-Methyl-1,2-butadiene 598-25-4 2-Methyl-1,3-butadiene 78-79-5 Cyclopentadiene 542-92-7



### 1.2 Fuel Gas Analysis Methods

Table 1.7 describes the tests and pr ocedures required fo r the analysis of your fuel gas. In addition to providing the results of the tests indicated in this section, you should also indicate whether the fuel gas system you test ed includes gas from a coking unit.

You will find copies of EPA methods at http://www.epa.gov/ttn/emc/tmethods.html . You can find instructions on how to obtain ASTM methods at http://www.astm.org/

.Form Approved __/__/__ OMB Control No. ____-____

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### 11 of 21 Table 1.7: Summary of Test Methods and Alt ernative Methods for Organic Compounds, Reduced Sulfur, and Other Parameters for Refinery Fuel Gas

Pollutant Recommended Method Alternative Method Target Reported Units of Measure 1 C1 through C5 hydrocarbons plus benzene 2 ASTM D1945-03. Use a minimum sample time of 2 hours per run. U.S. EPA Method 18; U.S. EPA Method 320; ASTM D1946-90; GPA 2261-00; ASTM/UOP539- 97 lb/hr and ppmvd

H 2 S, COS, CS 2 3 U.S. EPA Method 15. Per method, a minimum of 16 individual samples during a period of 3 to 6 hours, per run. lb/hr and ppmvd

TRS U.S. EPA Method 15A or 16A; 3-hr sample time per run; (one 2-hr sample per run or three 40-minute samples per run) U.S. EPA Method 16B combined with the analysis procedures U.S. EPA Method 15. ppmvd

Inorganics/other 4 ASTM D1945-03 ASTM D1946-90; GPA 2261-00; ASTM/UOP 539-97 Higher Heating Value Any of the following methods, as appropriate: ASTM D240-02 (Reapproved 2007), Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter; ASTM D1826-94 (Reapproved 2003), Standard Test Method for Calorific (Heating) Value of Gases in Natural Gas Range by Continuous Recording Calorimeter; ASTM D3588-98 (Reapproved 2003), Standard Practice for Calculating Heat Value, Compressibility Factor, and Relative Density of Gaseous Fuels ASTM D4809-06, Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter (Precision Method) ASTM D4891-89 (Reapproved 2006), Standard Test Method for Heating Value of Gases in Natural Gas Range by Stoichiometric Combustion Gas Processors Association Standard 2172-09, Calculation of Gross Heating Value, Relative Density, Compressibility and Theoretical Hydrocarbon Liquid Content for Natural Gas Mixtures for Custody Transfer Calculated based on detailed gas compositional analysis using: ASTM D1945-03, Standard Method for Analysis of Natural Gas by Gas Chromatography; ASTM D1946-90 (Reapproved 2006), Standard Method for Analysis of Reformed Gas by Gas Chromatography; GPA 2261-00, Analysis for Natural Gas and Similar Gaseous Mixtures by Gas Chromatography; or ASTM/UOP 539-97, Refinery Gas Analysis by Gas Chromatography Any of the methods specified in section 2.2.7 of Appendix D to part 75 MMBtu/scf

Gas flow rate ASME MFC-3M, - 4M, -6M, -7M, -11M, -14M, or -18M; or AGA Report No. 11 (Measurement of Natural Gas by Coriolis Meter) U.S. EPA Method 2, 2A, 2B, 2C, 2D, 2F, or 2G, as appropriate acfm, scfm, and dscfm

Moisture U.S. EPA Method 4 None percent volume

1 lb/hr = pounds per hour; ppmvd = parts per million by volume, dry basis; MMBtu/scf = million British thermal units per

standard cubic foot; acfm = actual cubic fe et per minute; scfm = standard cubic feet per minute; dscfm = dry standard cubic feet per minute.Form Approved __/__/__ OMB Control No. ____-____

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### 12 of 21 2 Target analytes are given in Table 1.6, but include benzene (CAS No. 71-43-02) as a specific analyte.

3 If your fuel gas system has a certified continuous monitoring system (CMS) installed to measure H 2 S concentrations, you may

report daily averages from 30 days of data from that CMS in lieu of conducting a H 2 S test. In order to correlate these emissions with other emissions tests, a portion of the monito ring data submitted should contain the data collected during performance of the other requested tests. The CMS must meet the requirements of Performance Specification 7 or the accuracy and ongoing QA/QC requirements of 40 CFR part 60, subpart J or Ja.

4 Target analytes are given in Table 1.8.



### Table 1.8: Analytes for “Inorganics/Other” in Fuel or Flare Gas
Compound CAS No. Hydrogen 1333-74-0 Carbon monoxide 630-08-0 Carbon dioxide 124-38-9 Nitrogen 7727-37-9 Oxygen 7782-44-7Form Approved __/__/__ OMB Control No. ____-____

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### 13 of 21 1.3 Sampling and Analysis Methods for Cooling Water Systems

Collect a sample from each cooli ng water system return line prio r to exposure to air using “Air Stripping Method (Modified El Pa so Method) for Determination of Volatile Organic Compound Emissions from Water Sources.” a



### Table 1.9 describes the tests and procedures required for the an alysis of your cooling water system sample. You will find copies of EPA methods at http://www.epa.gov/ttn/emc/tmethods.html . You can find instructions on how to obtain Standard Methods for the Examination of Water and Wastewater at http://www.standardmethods.org/

. Table 1.9: Summary of Test Methods for Analysis via Texas El Paso Stripping Column

Pollutant Recommended Method Alternative Method Target Reported Units of Measure 1 Speciated Volatile Organic HAP 2 Standard Methods 6200 for water U.S. EPA Method TO-15 for stripping air U.S. EPA Method TO-14A for stripping air ppmvd in air (as measured) and ppmw in cooling water

Speciated Semivolatile Organic HAP 3 Standard Methods 6410 for water U.S. EPA Method TO-13A for stripping air None ppmvd in air (as measured) and ppmw in cooling water

Formaldehyde U.S. EPA Method TO-5 for stripping air. U.S. EPA Method TO-11A for stripping air ppmvd in air (as measured) and ppmw in cooling water (back-calculated) THC U.S. EPA Method TO-12 for stripping air. None ppmvd in air (as measured) and ppmw in cooling water (back-calculated) CH 4 U.S. EPA Method 18. U.S. EPA Method 320 ppmvd in air (as measured) and ppmw in cooling water (back-calculated) HCl, Cl 2 U.S. EPA Method 26 U.S. EPA Method 26A ppmvd in air (as measured) and ppmw in cooling water (back-calculated)

1 ppmvd = parts per million by volume, dry ba sis; ppmw = parts per million by weight

2 Target analytes are given in Table 1.3.

3 Target analytes are given in Table 1.4.

a “Air Stripping Method (Modified El Paso Method) for Determination of Volatile Organic Compound Emissions from Water Sources” Revision Number One, dated January 2003, Sampling Procedures Manual, Appendix P: Cooling Tower Monitoring, prepared by Texas Commission on Environmental Quality, January 31, 2003.Form Approved __/__/__ OMB Control No. ____-____

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### 14 of 21 1.4 Sampling and Analysis Methods for Enhanced Biodegradation Units (EBU)

Table 1.10 lists the procedures required for the an alysis of your EBU(s). You will find copies of EPA methods at http://www.epa.gov/ttn/emc/tmethods.html and copies of EPA SW-846 methods
at http://www.epa.gov/waste/hazard/t estmethods/sw846/online/index.htm . You can find instructions on how to obtain Sta ndard Methods for the Examinati on of Water and Wastewater at http://www.standardmethods.org/

. 1.4.1 Sampling Methods

You should follow the sampling methods described in the EPA document “Handbook for Sampling and Sample Preservation of Wa ter and Wastewater” (EPA-600/4-82-029). Additionally, you should conduct samp le collection and preservati on in accordance to 40 CFR Part 136, which can be accessed at: http://www.epa.gov/regi on9/qa/pdfs/40cfr136_03.pdf

. The sample chain-of-custody should al so include the volumetric flow (m 3 

### /s), pH, and temperature of each sample. You should include th is information with the results of this study.

1.4.2 Sampling Location

Influent: One (1) grab sample of each influent stream to the EBU

EBU: One (1) grab sample within te n (10) feet of each influent location

Effluent: One (1) grab sample of each effluent stream of the EBU

1.4.3 Sampling Times

The sampling and testing events ( e.g. , well-mixed assessment and F bio 

### determination) should occur at the same time and duri ng normal operating conditions.Form Approved __/__/__ OMB Control No. ____-____

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### 15 of 21 Table 1.10: Summary of Analytical Methods a nd Alternative Methods for Wastewater Treatment Systems

Pollutant Recommended Method Alternative Method Target Reported Units of Measure 1 Speciated Volatile Organic HAP 2 SW-846 Method 8260B Standard Methods 6200 μ g/L

Speciated Semivolatile Organic HAP 3 SW-846 Method 8270C or D Standard Methods 6410 μ g/L

Aldehydes 4 SW-846 Method 8315A Standard Methods 6252 μ g/L Sulfide (as S) EPA Method 376.1 Standard Methods 4500-S 2- μ g/L BOD5 5 EPA Method 405.1 Standard Methods 5210 mg/L COD 5 EPA Method 410.1 Standard Methods 5220 mg/L Well-mixed
assessment Technical Support Document for Evaluation of Thoroughly Mixed Biological Treatment Units, 1998. 6 None N/A

Site-specific biodegradation rates Appendix C to 40 CFR Part 63 – Aerated reactor batch test with oxygen addition (BOX test). Do one test using benzene as the sole substrate and perform a second test using benzene, toluene, xylene, and naphthalene at equal concentrations. Technical Support Document for the Evaluation of Aerobic Biological Treatment Units with Multiple Mixing Zones. 7 (F bio )

1 μ g/L = micrograms per liter; mg/L = milligrams per liter; F bio = site-specific fraction of organic compounds biodegraded

2 Target analytes are given in Table 1.3.

3 Target analytes are given in Table 1.4.

4 Target analytes are given in Table 1.5.

5 BOD5 = 5-day biological oxygen dema nd; COD = chemical oxygen demand.

6 A copy of this document is located at http://www.epa.gov/ttncaaa1/t3/reports/guidfn.pdf

. 7 A copy of this document is located at http://www.epa.gov/ttn/ca aa/t3/reports/mulmix5.pdf

.



## 2.0 How to Report Data

The method for reporting the resu lts of any testing and monitoring requests depend on the type of tests and the type of methods used to complete th e test requirements. This section discusses the requirements for reporting the data.

2.1 Reporting stack test data

If you conducted testing using one of the methods listed in Table 2.1 you must report your data using the EPA Electronic Reporting Tool (ERT) Version 3. ERT is a Microsoft ® 

### Access database application. Two versions of the ER T application are available. If you are not a registered owner of Microsoft ® 

### Access, you can install the runtime version of the ERT Application. Both versions of the ERT are available at http://www.epa.gov/ttn/chief/ert/ert_tool.html . The ERT supports a Microsoft ® 

### Excel spreadsheet application (which is included in the files downloa ded with the ERT) to documentForm Approved __/__/__ OMB Control No. ____-____

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### 16 of 21 the collection of the field sampling data. After completing the ERT, you will also need to attach an electronic copy of the emissi on test report (PDF format pref erred) to the Attachments module of the ERT.

Table 2.1: List of Test Methods Supported by ERT

EPA Test Methods (40 CFR parts 60 and 61; EMC website, http://www.epa.gov/tt n/emc/tmethods.html ; and SW 846, http://www.epa.gov/waste/hazard/tes tmethods/sw846/online/index.htm ) Methods 1 through 4 (testing locations, velocity, moisture, dilution gases) Method 3A (O 2 and CO 2 ) Method 5 (filterable PM) Other test method (OTM) 27 (formerly Conditional test method (CTM) 40) (filterable PM 2.5 ) OTM 28 (revised Method 202, formerly CTM 39) (condensable PM) Method 6C (SO 2 ) Method 7E (NO X ) Method 10 (CO) Method 17 (in-stack filterable PM) Method 23 (PCDD and PCDF) Method 25A (THC) Method 26A (HCl and HF) Method 29 (multiple metals including Hg) Method 101 (Hg) Method 101A (Hg) Method 201A Method 202
CT Method 39 CT Method 40



### At present, only the methods shown in Tabl e 2.1 are supported by the ERT. If you conducted testing using a method not currently supported by the ERT, you must report the results of this test in a Microsoft ® 

### Excel Emission Test Template. The Excel templates are specific to each pollutant and type of emissions source and th ey can be downloaded from the ICR website ( http://icr2010.rti.org , click on “Petroleum Refineries”). Yo u must report the results of each test on the appropriately labeled worksheet correspon ding to the specific te sts requested at your emissions source. If you conducted testing at more than one source at your refinery using methods not currently supported by the ERT, you mu st make a copy of the worksheet and revise the unit ID in order to distinguish between each separate test. After completing the worksheet, you must also submit an electronic copy of the emission test report (PDF format preferred).

If you have a CO Continuous Emissions Monito ring System (CEMS) that meets Performance Specification 4 (or other specified procedures) or a SO 2 

### and/or NO X 

### CEMS that meets Performance Specification 2 (or other specified procedures) installed on the exhaust of your emissions unit, and you used CEMS data to meet CO, SO 2 

### and/or NO X 

### test requirements as noted in the footnotes of specifi c tables, you must report daily av erages from the last 30 days (including those days where manual testing wa s conducted) of CEMS data in a Microsoft ® 

### Excel CEMS Template. Similarly, if you have an H 2 

### S continuous monitoring system (CMS) that meets Performance Specification 7, and you used CMS data to meet the H 2 

### S testing requirements asForm Approved __/__/__ OMB Control No. ____-____

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### 17 of 21 noted in the footnotes of specifi c tables, you must report daily av erages from the last 30 days (including those days where manual testing wa s conducted) of CMS data in a Microsoft ® 

### Excel CMS Template. The Excel spreadsheet templates are specific to each pollutant and type of emissions source, and they can be downloaded from the ICR website ( http://icr2010.rti.org , click on “Petroleum Refineries”).

2.2 Required Fields for ERT Reporting

The list of fields within the ERT with notes expl aining whether or not the field is required or optional can be found on the ICR website ( http://icr2010.rti.org , click on “Petroleum Refineries”).

2.3 Calculating and Reporting Values Measured Below Detection Levels

See Appendix A to this enclosure for guidance on calculating and reporting measurements less than detection levels for emissions data collection (ICR) programs.



## 3.0 How to Submit Data

As explained in the previous section, where app licable, you must report your data using the ERT. If the ERT does not support a part icular pollutant or method, you mu st report your data using the data reporting spreadsheet we provide. When you are ready to submit your data to EPA, use one of three transmittal ways listed below. In order to avoid duplicate data and keep all data for a particular facility together, we request that you su bmit all of the data requested from your facility in the same way. * 

### To submit your data:

• Use the ICR website to upload your files. De tailed directions for uploading your files are provided on the ICR website ( http://icr2010.rti.org , click on “Petroleum Refineries”).

• E-mail an electronic copy of all requested files to refineryicr@epa.gov

.

• Mail a CD or DVD containing an electronic copy of all requested files to the EPA address shown in your Section 114 letter. If no electronic c opy is available, mail a hard copy of all requested files to the EPA address shown in your Section 114 letter.

* 

### Please Note : If you are submitting Confidential Business Information (CBI), DO NOT use one of the methods listed above to submit your CBI. You must mail a separate CD, DVD, or hard copy package containing only the CBI porti on of your data to the EPA address shown in your Section 114 letter.Form Approved __/__/__ OMB Control No. ____-____

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### 18 of 21 

## 4.0 Contact Information for Questions on Test Plan and Reporting

For questions on how to report data using the ERT, contact: Ron Myers U.S. EPA (919) 541-5407 myers.ron@epa.gov

OR

Barrett Parker U.S. EPA (919) 541-5635 parker.barrett@epa.gov

For questions on the test methods, including the use of alternat ive methods, contact: Peter Westlin U.S. EPA (919) 541-1058 westlin.peter@epa.gov

OR

Robin Segall U.S. EPA (919) 541-0893 segall.robin@epa.gov

OR

Jason DeWees U.S. EPA (919) 541-9724 dewees.jason@epa.gov

For questions on the petroleum refinery test pl an, including emissions sources selected for testing and reporting mechanisms other than the ERT, contact: Brenda Shine U.S. EPA (919) 541-3608 shine.brenda@epa.gov

For questions on uploading files to the HTTP site , please visit the ICR website ( http://icr2010.rti.org , click on “Petroleum Refineries”) and use the toll free technical support hotline or technical support email address.Form Approved __/__/__ OMB Control No. ____-____

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### 19 of 21 

## Appendix A

Guidance For Calculating And Repo rting Measurements Less Than In-Stack Method Detection Levels For Emissions Data Submitted in Response to Informatio n Collection Request (ICR) Programs

Identify the status of measured values relative to detection levels on the spreadsheet or in the ERT using the following descriptions:

• BDL (below detection level) – a ll analytical values used to calculate and report an instack emissions value are less than the la boratory’s reported de tection level(s);

• DLL (detection level limited) – at least one but not all values used to calculate and report an in-stack emissions value are less than the laboratory’s reported detection level(s); or

• ADL (above detection level) – all analytical va lues used to calculate and report an instack emissions value are greater than the laboratory’s reported detection level(s).

For each reported emissions value, insert the appropriate flag (BDL, DLL, or ADL) in the Note line of the Microsoft ® 

### Excel emission test spreadsheet template or in the Comments line of the Electronic Reporting Tool (ERT).

When reporting and calculati ng individual test run data:

• For analytical data reported from the lab as “nondetect” or “below detection level”:

− Include a brief description of the procedures used to determine the analytical detection and in-stack detection levels:

o In the Note line of Excel emission test spreadsheet template; or

o In the Comments line of Lab Data tab in the Run Data Details in the ERT

.

− Describe these procedures completely in a separate attachment including the measurements made, the standards used, and the statistical procedures applied.

− Calculate in-stack emissions rate for a ny analytical measurem ent below detection level using the relevant detection level as the “reported” value.

− Report the calculated emissions concentration or rate result:

o As a bracketed “less than ” detection level value ( e.g. , [<0.0105]) in the Excel emission test spreadsheet templa te and include the appropriate flag in the Note line; or

o As a numerical value in the ERT with the appropriate general flag in the Flag column and as a bracketed “les s than” detection level value ( e.g. , [<0.0105]) followed by a space and any sp ecific flag identifier in the Comments column. The following specific flag identifiers are commonly used by laboratories: B, E, J, Int, R, DPE.

− Report as numerical values ( i.e. , no brackets or < symbol) any analytical data measured above the detection level, in cluding any data between the analytical detection level and a laboratory-specifi c reporting or quant ification level ( i.e. , flag as ADL).

− Apply these reporting and calculation pro cedures to measurements made with Method 23 :Form Approved __/__/__ OMB Control No. ____-____

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### 20 of 21 o Report data in the Excel emission test spreadsheet template for each of the D/F congeners measured with Meth od 23 below the detection level as [< detection level]

o Do not report emissions as zero as described in the method

• For pollutant measurements composed of multiple components or fractions ( e.g. , Hg and other metals sampling trains) when the re sult for the value for any component is measured below the analytical detection level;

− Calculate in-stack emissions rate or c oncentrations as outlined above for each component or fraction;

− Sum the measured and detection level values as outlined above using the in-stack emissions rate or concentrations for all of the components or fractions; and

− Report the sum of all co mponents or fractions:

o As a bracketed “less than ” detection level value ( e.g. , [<0.0105]) in the Excel emission test spreadsheet templa te and include the appropriate flag in the Note line; or

o As a numerical value in the ERT with the appropriate flag in the Comments line.

− Report also the individual component or fr action values for each run if the Excel emission test spreadsheet template or ERT format allows; if not ( i.e. , the format allows reporting only a single sum value):

o For the Excel emission test spreadsheet template, next to the sum reported as above, report in the Notes line the appropriate flag along with the values for the measured or detection level value for each component or fraction as used in the calculations ( e.g. , 0.036, [<0.069], 1.239, [<0.945] for a four fraction sample)

o For the ERT , next to the sum reported as above, report in the Flag column the appropriate genera l flag and in the Comments column the measured or detection level value for each compon ent or fraction as used in the calculations followed by a space and any specific flag identifier provided by the laboratory ( e.g. , 0.036, [<0.069] J, 1.239, [<0.945] B for a four fraction sample).

• For measurements conducted using instrumental test methods ( e.g. , Methods 3A, 6C, 7E, 10, 25A)

− Record gaseous concentration values as measured including negative values and flag as ADL; do not report as BDL

− Calculate and report in-stack emissions rates using these measured values

− Include relevant informati on relative to calibration gas values or other technical qualifiers for measured values in Comments line in the ERT

• When reporting and calculating average emissions rate or concentration for a test when some results are reported as BDL

− Sum all of the test run values including those indicated as BDL or DLL as “real” values

− Calculate the average emissions rate or concentration ( e.g. , divide the sum by 3 for a three-run test)Form Approved __/__/__ OMB Control No. ____-____

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### 21 of 21 − Report the average emissions rate or concentration average:

o As a bracketed “less than ” detection level value ( e.g. , [<20.06]) in the Excel emission test spreadsheet templa te and include the appropriate flag in the Note line

o As a numerical value in the ERT and include the appropriate flag in the Comments line.