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