ASTM D19.06 SUBCOMMITTEE STUDY REPORT FROM THE TESTING OF ADDITIONAL INDUSTRIAL WASTEWATER MATRICES IN SUPPORT OF ASTM STANDARD D7575 FOR USEPA’s RECONSIDERATION OF THIS METHOD IN THE FORTHCOMING METHOD UPDATE RULE

Prepared for: United States Environmental Protection Agency Office of Water Engineering and Analytical Support Branch

November, 2011INTRODUCTION This report is in response to the United States Environmental Protection Agency (EPA) Office of Water, Engineering and Analytical Support Branch request to conduct and provide test results from additional industrial water matrices in support of its reconsideration of ASTM Standard D7575 (Standard Test Method for Solvent-Free Membrane Recoverable Oil and Grease by Infrared Determination) for inclusion in EPA’s forthcoming Method Update Rule (MUR). The remainder of this document provides the details of the study and results that were obtained.

STUDY NAME The name of this study was: “Testing of Additional Industrial Wastewater Matrices in Support of USEPA Reconsideration of ASTM Standard D7575 in the Forthcoming Method Update Rule.”

STUDY DIRECTION AND SPONSOR This study was performed under the direction of ASTM D 19 Water. The study was sponsored and managed voluntarily by the technical members of the ASTM D19.06 Sub-committee for ASTM Standard D7575.

STUDY DESIGN
Summary The design of this study was similar to those in the previous single-laboratory studies used for standardization of ASTM D7575. In summary, wastewater from applicable industries acceptable to the study objectives were collected according to standard EPA protocols and shipped to the OSS laboratory for initial screening of oil and grease by ASTM Standard D7575 to ensure the concentration within the sample was within the range of the method. The industrial matrices that passed this screening were then sent to a designated laboratory for oil and grease determination by EPA Method 1664 and ASTM Standard D7575. Upon completion of sample analyses, ASTM D19.06 sub-committee has reviewed the results and prepared this written study report for submission to EPA’s Engineering and Analytical Support Branch.Sample Matrices Per the objective of the study plan, three specific industrial matrices were collected. The sample collection process followed the sampling procedures of EPA’s Freon replacement studies during the development of EPA 1664, whereby one large single grab was collected and sample bottles were split from that original grab while being mixed. The three specific matrices were of the following categories:• Sample #1: Petroleum Refining and Related Industries – SIC 29: The matrix obtained was from a large refinery facility that processes raw crude oil into multiple petroleum products including petroleum and grease-related products.

• Sample #2: Food and Kindred Products Manufacturers – SIC 20: The matrix obtained was from a large food and restaurant complex whose sample stream has constituents of animal greases and oils from both beef and pork sources.

• Sample #3: Chemicals and Allied Products – SIC 28: The matrix obtained here is from the process stream of a large chemical manufacturer that falls within EPA’s regulation category of organic chemicals, plastics, and synthetic fibers (OCPSF).

Study Methods The two methods used for this study were EPA Reference Method 1664 (hexane liquid/liquid extraction) and ASTM Standard D7575. It is worth noting that through the course of this study ASTM D7575-10 was updated to ASTM D7575-11. The update process (ASTM work item WK34733) included language suggestions supplied to the subcommittee by USEPA that helped strengthen the method and its procedures. The changes followed the ASTM method revision and voting process. The changes (including an editorial change from an industry member of ASTM) were unanimously approved by ASTM D19 members. Study Laboratories The laboratories identified for this study included OSS for initial screening of matrices to ensure that they were within the operating range of D7575 and a centralized commercial laboratory in New England performing EPA Method 1664 and ASTM D7575 for oil and grease on the same collected industrial matrix samples. Standardized Quality Control Tests

START-UP TESTING: The independent laboratory and independent laboratory technician chosen were already qualified to perform EPA 1664. Prior to ASTM D7575 testing, however, the independent laboratory technician had to prove to be proficient with performing ASTM D7575. Thus, the followingsteps were successfully performed: a) Training by OSS b) Calibration – per ASTM D7575 Section 12.2. a. The technician successfully calibrated the instrument and determined a linear function to convert FTIR response peak height at or near 2920 wavenumbers to oil and grease mg/L. That equation was determined to be:b. Total Oil and Grease (mg/L) = 146.295*(peak height) – 0.217 c) Determination of technician Lower Detection Limit (LDL) and Method Detection Limit (MDL) – per ASTM D7575 Section12.4. a. The technician received an LDL of 1.69 mg/L and an MDL of 5.37 mg/L. d) Demonstration of initial performance of recovery (IPR) – per ASTM D7575 Section 12.5. a. The technician successfully passed the IPR with 88.1% average recovery and relative standard deviation of 9.1%

MATRICES: In this study, the three matrices of interest were subjected to the following standardized quality control (QC) and comparative tests, for each of the two methods: • Calibration verification (once per batch [e.g. 20 samples] per day of testing) – per ASTM D7575 Section 14.1 and EPA 1664 Section 9.5. • Field matrix sample in triplicate – per ASTM D7575 Section 14 and EPA 1664 Section 11. • Field matrix sample spike (hexadecane and stearic acid per EPA Method 1664 protocol) – per ASTM D7575 Section 12.8 and EPA 1664 Section 9.3. • Field matrix sample spike duplicate (hexadecane and stearic acid per EPA Method 1664 protocol) – per ASTM D7575 Section 12.8 and EPA 1664 Section 9.3. • Reagent blank (one per batch [e.g. 20 samples] per day of testing) – per ASTM D7575 Section 12.7 and EPA 1664 Section 9.4. • Laboratory Control Spike (one per batch [e.g. 20 samples] per day) – per ASTM D7575 Section 12.6 and EPA 1664 Section 9.6. • Laboratory Control Spike Duplicate (one per batch [e.g. 20 samples] per day) – per ASTM D7575 Section 12.6 and EPA 1664 Section 9.6.

Statistical Analysis and Results Precision of Triplicate Field Sample Analyses – Triplicate analyses of each matrix were tested for precision by calculating the percent relative standard deviation (standard deviation divided by the mean concentration X 100).Accuracy and Precision of Matrix Spike and Matrix Spike Duplicate Analyses - The matrix spike and matrix spike duplicate (MS/MSD) test was used to assess method performance in the sample matrix. Analytes of interest (hexadecane and stearic acid) were added to a field sample aliquot that was then thoroughly homogenized and split into two spiked replicate aliquots for analysis. One of these replicates was identified as the matrix spike sample and the other was identified as the matrix spike duplicate sample. The recovery of the analytes relative to the spike concentration was determined in each sample. Accuracy was measured from the difference in determination of the spiked sample and unspiked field sample divided by the spiked amount,multiplied by 100. The precision of the determinations was assessed by measuring the relative standard deviation of recovery. Accuracy and Precision of Laboratory Control Spike and Laboratory Control Spike Duplicate - The laboratory control spike and laboratory control spike duplicate (LCS/LCSD) test was used to assess method performance in a controlled reference matrix. Analytes of interest (hexadecane and stearic acid) were added to reagent water that was then thoroughly homogenized and split into two spiked replicate aliquots for analysis. One of these replicates was identified as the laboratory control spike sample and the other was identified as the laboratory control spike duplicate sample. The recovery of the analytes relative to the spike, were determined in each sample. Accuracy was determined from the average of the two recoveries of spiked samples divided by the spiked amount, multiplied by 100. The precision of the determinations was assessed by measuring the relative standard deviation of recovery. The statistical results for the study matrices are provided in Appendix A. Appendix A – provides the data and analysis for each of the three primary study matrices. The results include: a) Calibration Verification b) Method Blank c) Laboratory Controls d) Triplicates e) Matrix Spikes

of each study matrix. Appendix B – provides plots of the data associated with all aspects of recent ASTM D7575 versus EPA 1664 comparability studies. These plots include: Chart 1: Difference in average results between ASTM D7575 and EPA 1664. This plot includes data from ASTM D7575 development, auxiliary data provided to EPA per their request, and this Notice of Data Availability study. It should be noted that the average difference across all matrices = 0.6 mg/L. Note that in this chart the ‘industrial laundry (1664 interferent issues)’ non-point reflects that TPH measurement is used instead of total oil and grease because of a known interferent issue with surfactants in this matrix. Chart 2: ASTM D7575 vs. EPA 1664 Laboratory Control Sample (LCS) comparabilityplots from both ASTM D7575 development and this Notice of Data Availability Study. Chart 3: ASTM D7575 vs. EPA 1664 Matrix Spike (MS) plots from both ASTM D7575 development and this Notice of Data Availability Study.Conclusion ASTM D19 Subcommittee for ASTM D7575 has successfully executed a comparative study in response to the United States Environmental Protection Agency (EPA) Office of Water, Engineering and Analytical Support Branch request to conduct and provide test results from additional industrial water matrices in support of its reconsideration of ASTM Standard D7575 (Standard Test Method for Solvent-Free Membrane Recoverable Oil and Grease by Infrared Determination) for inclusion in EPA’s forthcoming Method Update Rule (MUR). The study focused on providing comparability data (ASTM D7575 versus EPA 1664) on three matrices of interest to EPA (SICS Code 29 – Petroleum Refining, SIC Code 20 – Food – including animal greases and oils, and SIC Code 28 – OCPSF). For these matrices, testing included: a) Calibration verification b) Method Blank c) Laboratory Control and Laboratory Control Duplicate d) Triplicate analysis and e) Matrix Spike and Matrix Spike Duplicate.

Comparability data between ASTM D7575 and EPA 1664 has been provided in Appendix A. With the exception that EPA 1664 failed to adequately capture matrix spikes for the petroleum refining matrix, both methods demonstrated documented QC test performance. Consistent with previous ASTM D7575 versus EPA 1664 testing and as concluded in previous statistical comparisons, results from this study (see Appendix B plots) show comparability between ASTM D7575 and EPA 1664. These previous comparisons can be found at the EPA Docket site: 1) http://www.regulations.gov/#!documentDetail;D=EPA-HQ-OW-2010-0192-0163 a. Document ID: EPA-HQ-OW-2010-0192-0163 b. Attached file #1: “Supplemental Data and Statistical Analysis in Support of Method Equivalence of ASTM D7575 Solventless Oil and Grease and EPA Method 1664A”, c. Document Type: Public Submission d. This is comment on Proposed Rule: Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act; Analysis and Sampling Procedures e. Docket ID: EPA-HQ-OW-2010-0192 f. Submitted to Docket 12/21/20102) http://www.regulations.gov/#!documentDetail;D=EPA-HQ-OW-2010-0192-0135a. Document ID: EPA-HQ-OW-2010-0192-0135 b. Attached file #1 0900006480bba5b3.pdf. “ASTM D19.06 Sub-committee, D-19 Water Inter-Laboratory Study to Establish Precision Statements for ASTM WK23240 – Standard Test Method for Solvent-Free Membrane Recoverable Oil and Grease by Infrared Determination” c. Document Type: Public Submission d. This is comment on Proposed Rule: Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act; Analysis and Sampling Procedures e. Docket ID: EPA-HQ-OW-2010-0192 f. Submitted to Docket 12/21/2010APPENDIX A – MATRICES RESULTSMATRIX #1 Petroleum Refining and Related Industry - SIC 29 - Large Refinery Facility that Processes Raw Crude Oil into Multiple Petroleum Products including Grease ProductsCALIBRATION VERIFICATIONMETHOD BLANKLABORATORY CONTROLTRIPLICATESMATRIX SPIKEASTM D7575EPA 1664ASTM D7575EPA 1664ASTM D7575EPA 1664ASTM D7575EPA 1664ASTM D7575EPA 1664BOTTLECalibration Verification Value (mg/L) Calibration Standard Value (mg/L)Pass? Calibration Verification Value (mg/L) Calibration Standard Value (mg/L)Pass? Blank Value (mg/L) < LDL (1.69 mg/L) Pass? Blank Value (mg/L) < LDL (1.69 mg/L) Pass? LCS Value (mg/L) Recovery % 79%-113% Pass? LCS Value (mg/L) Recovery % 78%-114% Pass? Triplicate Value (mg/L) Triplicate Value (mg/L) Matrix Spike Value (mg/L) Recovery % 70%-126% Pass? Matrix Spike Value (mg/L) Recovery % 78%-114% Pass? Cal. Ver.N/A39.1439.14YES4040YESBlankBLANK-1.14YES0.3YESLCSLCS41.537LCSDLCSD39.435.5LCS AVE40.5101.13%YES36.390.63%YESLCS SD1.451.06Triplicate #1T010115.613.6Triplicate #2T010215.315.0Triplicate #3T010316.619.2Triplicate Ave15.815.9Triplicate RSD4.37%18.26% MST010464.431.1MSDT010558.228.8MS AVE61.329.9MS AVE RECOVERY113.7%YES35.0%NOMATRIX #2Food and Kindred Product Manufacturers - SIC 20 - Large Food and Restaurant Complex Sample Containing Animal Greases and Oils from both Beef and PorkCALIBRATION VERIFICATIONMETHOD BLANKLABORATORY CONTROLTRIPLICATESMATRIX SPIKEASTM D7575EPA 1664ASTM D7575EPA 1664ASTM D7575EPA 1664ASTM D7575EPA 1664ASTM D7575EPA 1664BOTTLECalibration Verification Value (mg/L) Calibration Standard Value (mg/L)Pass? Calibration Verification Value (mg/L) Calibration Standard Value (mg/L)Pass? Blank Value (mg/L) < LDL (1.69 mg/L) Pass? Blank Value (mg/L) < LDL (1.69 mg/L) Pass? LCS Value (mg/L) Recovery % 79%-113% Pass? LCS Value (mg/L) Recovery % 78%-114% Pass? Triplicate Value (mg/L) Triplicate Value (mg/L) Matrix Spike Value (mg/L) Recovery % 70%-126% Pass? Matrix Spike Value (mg/L) Recovery % 78%-114% Pass? Cal. Ver.N/A39.5839.14YES4040BlankBLANK-0.51YES0.3YESLCSLCS33.937.0LCSDLCSD31.736.0LCS AVE32.881.93%YES36.591.25%YESLCS SD1.550.71Triplicate #1R010145.437.6Triplicate #2R010251.637.2Triplicate #3R010348.838.5Triplicate Ave48.637.8Triplicate RSD6.33%1.69% MSR010495.8987773.0MSDR0105101.311773.8MS AVE98.673.4MS AVE RECOVERY125.0%YES89.2%YESMATRIX #3 Chemicals and Allied Products - SIC 28 - Large Chemical Manufacturer that Falls within EPA's Regulation Category for OCPSFCALIBRATION VERIFICATIONMETHOD BLANKLABORATORY CONTROLTRIPLICATESMATRIX SPIKEASTM D7575EPA 1664ASTMD7575EPA 1664ASTM D7575EPA 1664ASTM D7575EPA 1664ASTM D7575EPA 1664BOTTLECalibration Verification Value (mg/L) Calibration Standard Value (mg/L)Pass? Calibration Verification Value (mg/L) Calibration Standard Value (mg/L)Pass? Blank Value (mg/L) < LDL (1.69 mg/L) Pass? Blank Value (mg/L) < LDL (1.69 mg/L) Pass? LCS Value (mg/L) Recovery % 79%-113% Pass? LCS Value (mg/L) Recovery % 78%-114% Pass? Triplicate Value (mg/L) Triplicate Value (mg/L) Matrix Spike Value (mg/L) Recovery % 70%-126% Pass? Matrix Spike Value (mg/L) Recovery % 78%-114% Pass? Cal. Ver.N/A39.5839.14YES4040YESBlankBLANK-0.51YES0.3YESLCSLCS33.937.0LCSDLCSD31.736.0LCS AVE32.881.93%YES36.591.25%YESLCS SD1.550.71Triplicate #1U010136.429.2Triplicate #2U010234.531.0Triplicate #3U010335.930.7Triplicate Ave35.630.3Triplicate RSD2.80%3.21% MSU010471.4674365.1MSDU010564.1526563.4MS AVE67.864.3MS AVE RECOVERY80.6%YES84.9%YESAPPENDIX B – ASTM D7575 VS EPA 1664 COMPARABILITY CHARTS-50.0 -40.0 -30.0 -20.0 -10.0 0.0 10.0 20.0 30.0 40.0 50.0 POTW 7 Rep AVE GUNSMITH 7 Rep AVE AUTO GARAGE 3 Rep AVE DAIRY 3 Rep AVE MACHINE SHOP 3 Rep AVE SALVAGE YARD 3 Rep AVE FISH PROCESSOR 3 Rep AVE POTW DAY 1 - 3 Rep AVE POTW DAY 2 - 3 Rep AVE POTW DAY 3 - 3 Rep AVE POTW DAY 4 - 3 Rep AVEPOTW DAY 5 - 3 Rep AVE POTW DAY 6 - 3 Rep AVE POTW DAY 7 - 3 Rep AVE BILGE WATER (Sea) 3 Rep AVE PEANUT PROCESSOR 3 Rep AVE LUNCHMEAT PROCESSOR 3 Rep AVE Restaurant (dilution - out of range) Bottle 1 - 1 Rep AVE Restaurant (dilution - out of range) Bottle 2 - 1 Rep AVE Restaurant (dilution - out of range) Bottle 3 - 1 Rep AVE Car Wash Bottle 1 - 1 Rep AVE Car Wash Bottle 2 - 1 Rep AVE Restaurant Bottle 1 - 1 Rep AVE Restaurant Bottle 2 (out of range D7575) - 1 Rep AVE Industrial Laundry (1664 Interferent Issues) - 1 Rep AVE Aluminum Can Manufacturer - 1 Rep AVE Petroleum Refiner (T) - 3 Rep AVE Multi-Restaurant Complex (R) - 3 Rep AVE Chemical Manufacturer (U) - 3 Rep AVE DIFFERENCE IN RESULTS (mg/L) MATRIX TYPE AND REPLICATE ALL COMPARATIVE STUDIES: D7575 vs. EPA 1664 Differences in Results (mg/L) (average difference across all matrices = 0.6 mg/L) does not include data from test results out of ASTM D7575 rangeASTM D7575 AVE - EPA 1664 AVE (mg/L) ASTM D7575 DEVELOPMENT STUDIES NODA STUDY0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 0% 20% 40% 60% 80% 100% 120% LCS POTW 7 REP SET LCS POTW 7 REP SET DUP LCS GUNSMITH 7 REP SET LCS GUNSMITH 7 REP SET DUPLCS AUTO GARAGE AND DAIRY SET LCS AUTO GARAGE AND DAIRY SET DUP LCS MACHINE SHOP SET LCS MACHINE SHOP SET DUP LCS AUTOSALVAGE LCS AUTOSALVAGE DUP LCS FISH PROCESSOR LCS FISH PROCESSOR DUP LCS 7 DAY POTW SERIES BATCH 1 LCS 7 DAY POTW SERIES BATCH 1 DUP LCS 7 DAY POTW SERIES BATCH 2 LCS 7 DAY POTW SERIES BATCH 2 DUP LCS 7 DAY POTW SERIES BATCH 3 LCS 7 DAY POTW SERIES BATCH 3 DUP LCS 7 DAY POTW SERIES BATCH 4 LCS 7 DAY POTW SERIES BATCH 4 DUP NODA TESTING LCS 1 NODA TESTING LCS 1 DUP NODA TESTING LCS 2 NODA TESTING LCS 2 DUP NODA TESTING LCS 3 NODA TESTING LCS 3 DUPLCS RESULT (PPM) LCS RECOVERY (%) ASTM D7575 vs EPA 1664 Comparative Study Laboratory Control Samples ASTM D7575 (ave=88.4% recovery) EPA 1664 (ave=86.5% recovery) EPA 1664 % Rec ASTM D7575 % Rec EPA 1664 LCS PPM D7575 LCS PPM ASTM D7575 SINGLE LAB STUDY NODA STUDY0% 20% 40% 60% 80% 100% 120% 140% 160% 180% 200% MS Test 1 (POTW 7 Rep Set) MS Test 2 (Gunsmith 7 Rep Set) MS Test 3 (Auto Garage & Dairy Rep Set) MS Test 4 (Machine Shop Rep Set) MS Test 5 (Autosalvage Rep Set) MS Test 6 (Fish Processor) MS Test 7 (Day 1 POTW Rep Set) MS Test 8 (Day 2 POTW Rep Set) MS Test 9 (Day 3 POTW Rep Set) MS Test 10 (Day 7 POTW Rep Set) NODA Primary Matrix 1 (Petroleum Refinery)NODA Primary Matrix 1 (Petroleum Refinery) DUP NODA Primary Matrix 2 (Animal Oil and Grease) NODA Primary Matrix 2 (Animal Oil and Grease) DUP NODA Primary Matrix 3 (Chemical OCPSF) NODA Primary Matrix 3 (Chemical OCPSF) DUP MS RECOVERY (%) ASTM D7575 vs EPA 1664 Comparative Study Matrix Spike Recovery ASTM D7575 (ave=98% recovery) >> EPA 1664 (ave=71% recovery) EPA 1664 MS % Recovery ASTM D7575 MS % Recovery ASTM D7575 SINGLE LAB STUDY NODA STUDY