Document ID: EPA-HQ-OW-2010-0192-0215
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2011-12-14T05:00Z

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, 2011 

 

 

 

 

 


 

INTRODUCTION 

 

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 following 
steps 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) comparability 
plots 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 12/21/2010 

 

2) http://www.regulations.gov/#!documentDetail;D=EPA-HQ-OW-2010-0192-0135 


a. 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 12/21/2010 

 

 

 


APPENDIX A – MATRICES RESULTS 

 


MATRIX #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 #2 Food 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 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/A39.5839.14YES4040YESBlankBLANK-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%YES


 

APPENDIX 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 AVE 

POTW 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 range 

ASTM D7575 AVE - EPA 1664 AVE (mg/L) 

ASTM D7575 DEVELOPMENT STUDIES 

NODA 

STUDY 


0.0 

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 DUP 

LCS 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 DUP 

LCS 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 STUDY 


0% 

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