# Technical Memorandum

TO: Brenda Shine, Refining and Chemicals Group, SPPD

FROM: Eric Goehl, Environmental Protection Specialist Refining and Chemicals Group, SPPD (E143-01)

DATE: May 29, 2012

SUBJECT: Summary of Wastewater Emission Source Test Reports

I. Purpose The objective of this documen t is to provide a summary of the wastewater emission source test reports received by the EPA from the 2011 Information Collection Request (ICR) of the Petroleum Refinery industry.

II. Background On April 1, 2011, the EPA sent an ICR to facilities in the U.S. petroleum refining industry. The ICR was comprehensive and designed to collect information on processing characteristics, crude slate characteristics, emissi ons inventories and source testing to bolster our current data and fill known data gaps. The I CR had four components: (1) a questionnaire on processes and controls to be completed by all petroleum refine ries (Component 1); (2) an emissions inventory to be developed by all petr oleum refineries using the emissions estimation protocol developed for this effort (Component 2) ; (3) distillation feed sa mpling and analysis to be conducted by all petroleum refineries (Compone nt 3); and (4) emission s source testing to be completed in accordance with an EPA-approved protocol for specific sources at specific petroleum refineri es (Component 4). Component 4 of the ICR requested source test ing for twelve different types of emission sources or units: fluid catalytic cracking units (FCCU), thermal catalytic cracking units, catalytic reforming units, sulfur recovery units, delayed coking units, fluid coking units, hydrocracking units, hydrogen plants, asphalt blowing units, fuel gas systems, cooling water systems, and wastewater treatment systems. This memorandum summarizes the results of the wastewater

## treatment system source tests. A similar memora ndum is available for the other emission sources requested to be tested as a result of this ICR. Facilities often claimed specific process information as CBI, and included that
information in the CBI version of the emission sour ce test report stored in the EPA’s CBI office in Research Triangle Park, NC. This memorandum summarizes and presen ts only non-CBI data.

III. Source-specific Testing Program Below is a list of facilities required to te st their wastewater treatment systems:

• Motiva Enterprises – Convent, LA (LA3C0620, the non-CBI portions of the test report are summarized in this memorandum.)

• ConocoPhillips – Belle Chasse, LA (LA3C0690)

• Valero – Memphis, TN (TN2A1060, did not submit)

• Exxon Mobil Oil – Beaumont, TX (TX3B1170, did not submit)

• Flint Hills Resources – Corpus Christi, TX (TX3B1180, submitted data for West Refinery only, as approved by EPA.)

Owners or operators of the wastewater tr eatment systems at these facilities were requested to collect three wastewater samples: a sample from the influent stream to the biological treatment unit; a sample from within the biological treatment unit; and a sample from the effluent stream. Facility TX3B1180 performed two tests; the influent of the first test was the
influent wastewater and the infl uent of the second test was f ilter backwash. Each wastewater sample was requested to be analyzed for:

• Speciated volatile organic h azardous air pollutants (HAP);

• Speciated semi-volatile organic HAP;

• Aldehydes;

• Sulfide (as S);

• BOD5; and

• COD. Each facility was also requested to do a well- mixed assessment of the biological treatment unit and provide compound specific biodegradation rates for benzene (as the sole substrate) and for benzene, toluene, xylene, and napht halene at equal concentrations.

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## Additional detail of the sour ce testing requirements for the wastewater treatment systems
can be found at can be found at http://www.epa.gov/ttn/atw /petref/petrefpg.html

. As the wastewater sampling and biological testing methods are not currently supported by the EPA Electronic Reporting Tool (ERT), the f acility was requested to report the results in the Refinery Testing Supplement, a Microsof t® Excel spreadsheet. After completing the Refinery Testing Supplement, the refineries were also asked to submit an electronic copy of the emission test report, preferably in PDF format.

IV. Results A summary of the non-CBI test results for wastewater treatment systems are provided in Tables 1 through 4. Only three reports were su bmitted; Facility LA3C0690 performed the testing on June 2, 2011; Facility LA3C0620 performed th e testing on June 15, 2011; and Facility TX3B1180 performed the testing on August 1, 2011. Table 1 summarizes the conditions in the biological treatment unit during th e test and the results of the well-mixed assessment. Table 1 contains only partial data for Facility LA3C0620 b ecause some of the data elements in the table are CBI for this facility. Table 2 presents the biodegradation rates for Facility LA3C0690 and Table 3 presents the biodegradation rates for Facility TX3B1180. The biodegradation rates for Facility LA3C0620 are not presente d because they have been claimed as CBI by the facility. Table 4 presents the concentration data for each of the tests and again, some of the data elements in the table are CBI for Facility LA3C0620 a nd are therefore not included. Facility LA3C0690 only submitted the Refinery Testing Supplement; no te st report was provided by which to verify the summary data submitted for this facility. A limited review of the source test reports
submitted for Facilities LA3C0620 and TX3B1180 wa s performed; no revisions to the summary
data were made as a result of this review.

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## Table 1. Conditions in Biologica l Treatment Unit during Test

Facility ID

Number General Description Meets def of EBU? Wellmixed Table

1 Wellmixed Table

2 Average flow rate

(m 3 /s) pH Wastewater temperature

(deg, F) VSS d in biological treatment

unit (g/L) Total air flow rate to

diffused aerators (scfm at

68°F)

LA3C0620 Staged Activated Sludge Treatment Unit a Y N Y CBI CBI CBI CBI CBI

LA3C0620 Aeration Basins with Surface Aerators a Y N Y CBI CBI CBI CBI CBI

LA3C0690 Diffused Aeration Tk b Y Y Y 0.08 6.8 101 2.45 1358

TX3B1180 Submerged Aeration Activated Sludge Unit c Y N N 0.0355 7.62 98 840 4545

TX3B1180 Submerged Aeration Activated Sludge Unit c Y N N 0.00355 7.45 94 840 4545

a Dimensions of units are CBI.

b Biological treatment unit is circular wi th a diameter of 100 feet and a height of 25 feet. No surface aeration.

c Biological treatment unit is rectangular w ith a length of 130 feet, width of 65 feet and a height of 12 feet. No surface aerat ion.

d Volatile suspended solids.



## Table 2. Fraction Biodegraded Determination for Facility LA3C0690

Compound F_bio First-order biorate, k1 (L/gMLVSS-hr) Benzene Only Spike
Benzene 0.9952 9.901 Multi-compound Spike
Benzene 0.9952 9.877
Toluene 0.9920 6.380 Xylene 0.9860 3.729 Naphthalene 0.9949 4.691



## 4

## Table 3. Fraction Biodegraded Determination for Facility TX3B1180

Compound F_bio First-order biorate, k1 (L/gMLVSS-hr) Benzene Only Spike
Benzene Less Than Reporting Limit 2.99 Multi-compound Spike
Benzene Less Than Reporting Limit 0.58
Toluene Less Than Reporting Limit 0.34 Xylene Less Than Reporting Limit Unable to Estimate Naphthalene Less Than Reporting Limit 0.39



## Table 4. Test Concentrations a

Facility ID

Number Pollutant Name Pollutant Class Test Method Influent Concentration Value Concentration within Biounit Value Effluent Concentration Value Units mg/L or ug/L

LA3C0620 b Benzene SW8260B CBI CBI <0.0005 mg/L
LA3C0620 b Xylenes SW8260B CBI CBI <0.001 mg/L
LA3C0620 b Toluene SW8270D CBI CBI <0.0005 mg/L

LA3C0620 b Naphthalene SW8260B/ SW8270D CBI CBI <0.001 mg/L
LA3C0620 b Chemical Oxygen Demand E410.4 CBI CBI 92.57 mg/L

LA3C0620 b Formaldehyde SW8315A CBI CBI 0.03 mg/L
LA3C0620 b Sulfide M4500-S CBI CBI 0.81 mg/L
LA3C0620 b Biological Oxygen Demand SM5210B CBI CBI 126.67 mg/L
LA3C0620 c Benzene SW8260B CBI CBI <0.0005 mg/L LA3C0620 c Xylenes SW8260B CBI CBI <0.001 mg/L LA3C0620 c Toluene SW8270D CBI CBI <0.0005 mg/L LA3C0620 c Naphthalene SW8260B/ SW8270D CBI CBI 0.05 mg/L
LA3C0620 c Chemical Oxygen Demand E410.4 CBI CBI 68.33 mg/L

LA3C0620 c Formaldehyde SW8315A CBI CBI 0.04 mg/L
LA3C0620 c Sulfide M4500-S CBI CBI 0.65 mg/L
LA3C0620 c Biological Oxygen Demand SM5210B CBI CBI 103.67 mg/L

LA3C0690 Benzene Volatile Organic HAP 8260B 2,980 2,720 <5 ug/L

LA3C0690 Xylenes Volatile Organic HAP 8260B 1,810 1,580 <5 ug/L

LA3C0690 Toluene Volatile Organic HAP 8260B 1,900 1,640 <5 ug/L



## 5Facility ID Number Pollutant Name Pollutant Class Test Method Influent Concentration Value Concentration within Biounit Value Units Effluent mg/L or ug/L Concentration Value

LA3C0690 Napthalene SemiVolatile/NonVolatile Organic HAP 8270D 230 200 <10 ug/L

LA3C0690 Acetone VOC 8260B 1,640 1,680 <25 ug/L

LA3C0690 Methanol Volatile Organic HAP 8000 22,000 22,100 1,840 ug/L

LA3C0690 Cresol SemiVolatile/NonVolatile Organic HAP 8270D 6,000 5,200 14 ug/L

LA3C0690 2,4- Dimethylphenol VOC 8260B 3,700 3,400 <10 ug/L

LA3C0690 2- Methylnaphthalene SemiVolatile/NonVolatile Organic HAP 8270D 70 64 <10 ug/L

LA3C0690 Phenol SemiVolatile/NonVolatile Organic HAP 8270D 5,700 4,400 16 ug/L

LA3C0690 Formaldehyde Volatile Organic HAP 8260B 150 420 26 ug/L

LA3C0690 Acetaldehyde Volatile Organic HAP 8315A 22 91 <100 ug/L

LA3C0690 Propanal VOC 8260B 6 <50 <50 ug/L

LA3C0690 Sulfide (as S) Surrogate 6,000 4,400 <100 ug/L

LA3C0690 BOD 5 Surrogate 511 559 95 mg/L

LA3C0690 COD Surrogate 1,230 1,190 1,180 mg/L

TX3B1180 d Benzene Volatile Organic HAP 8260B <2.8 <0.14 <0.14 ug/L

TX3B1180 d Xylenes Volatile Organic HAP 8260B 37 0.85 0.90 ug/L

TX3B1180 d Toluene Volatile Organic HAP 8260B <6.0 0.84 0.68 ug/L

TX3B1180 d Naphthalene SemiVolatile/NonVolatile Organic HAP 8260B <4.0 <0.20 <2.0 ug/L

TX3B1180 d Acetone VOC 8260B 2,200 <5 5.1 ug/L

TX3B1180 d Methyl t-butyl ether Volatile Organic HAP 8260B 51 8.3 4.6 ug/L

TX3B1180 d Aniline Volatile Organic HAP 8270C 190 <7.9 <7.9 ug/L

TX3B1180 d 2- Methylnaphthalene SemiVolatile/NonVolatile Organic HAP 8270D 5.6 <1.1 <1.1 ug/L

TX3B1180 d Sulfide (as S) Surrogate SM 4500- S2D 36 16 <13 ug/L

TX3B1180 d BOD 5 Surrogate SM 5210B 52 <2.0 <2.0 mg/L



## 6

## 7 Facility ID

Number Pollutant Name Pollutant Class Test Method Influent Concentration Value Concentration within Biounit Value Effluent Concentration Value Units mg/L or ug/L

TX3B1180 d COD Surrogate HACH 8000 110 54 53 mg/L

TX3B1180 e Benzene Volatile Organic HAP 8260B <0.14 <0.14 <0.14 ug/L

TX3B1180 e Xylenes Volatile Organic HAP 8260B 1.3 0.85 0.90 ug/L

TX3B1180 e Toluene Volatile Organic HAP 8260B 1.9 0.55 0.68 ug/L

TX3B1180 e Naphthalene SemiVolatile/NonVolatile Organic HAP 8260B <0.2 <2.0 <2.0 ug/L

TX3B1180 e Acetone VOC 8260B 7.9 <5 5.1 ug/L

TX3B1180 e Methyl t-butyl ether Volatile Organic HAP 8260B 3.6 7 4.6 ug/L

TX3B1180 e Aniline Volatile Organic HAP 8270C <8.3 <7.9 <7.9 ug/L

TX3B1180 e 2- Methylnaphthalene SemiVolatile/NonVolatile Organic HAP 8270D <1.1 <1.1 <1.1 ug/L

TX3B1180 e Sulfide (as S) Surrogate SM 4500- S2D 43 18 <13 ug/L

TX3B1180 e BOD 5 Surrogate SM 5210B <2.0 <2.0 <2.0 mg/L

TX3B1180 e COD Surrogate HACH 8000 52 50 53 mg/L

a All data reported for benzene, xylene, toluene and naphthalene . Other compounds only listed if concentrations above detection
limits.

b Staged Activated Sludge Treatment Unit.

c Aeration Basins with Surface Aerators.

d Influent is Influent Wastewater. Basin is 10 feet from influent side.

e Influent is Filter Backwash. Basin is 10 feet from Filter Backwash side.