To: Jan Matuszko/DC/USEPA/US@EPA From: "Fick, Alyson" <afick@astm.org>
Date: 08/14/2012 11:41AM Cc: "Morrissey, Len" <lmorriss@astm.org> , "Fick, Alyson" <afick@astm.org> Subject: D7575 EPA Questions from NODA - Task Group Response (See attached file: D7575 Task Group Response to EPA NODA Questions_Final.docx)

Hi Jan,

Attached, please find a working document that the D7575 TG has been developing to address the questions that you forwarded from the recent NODA. This continues to be an ongoing discussion at our D19 meetings but I thought that the information in the report might be useful as your staff is looking to address the issues brought up. If the EPA requires an official ASTM response to the questions, we will put this document through the necessary procedural process to make that happen.

I wanted you to get this information prior to my going on maternity leave. If you need any additional information or would like to coordinate on these issues, you can work
with Len while I’m out. He has been in the l oop on our coordination efforts and will be glad to assist as n eeded until I return.

Take care,

Alyson Alyson Fick, MPA Manager, TCO Division
ASTM International
100 Barr Harbor Drive West Conshohocken, PA 19428
Phone: 610-832-9710
Fax: 610-832-9666 afick@astm.orgTo: "Fick, Alyson" <afick@astm.org>
From: Jan Matuszko/DC/USEPA/US
Date: 07/12/2012 11:52AM Subject: A few questions about ASTM D7575

Hi Alyson,

Per our conversation the other day, there are a few technical questions that were raised during the NODA comment period for which yo ur input would be helpful. Please see the
attachment.

(See attached file: Questions for ASTM 71012.docx)

Thanks!
Jan

++++++++++++++++++++ Jan Matuszko
Branch Chief Engineering and Analyt ical Support Branch Engineering and Analys is Division (4303T)

U.S. EPA 1200 Pennsylvania Avenue, N.W. Washington, DC 20460 (202) 566-1035

Questions for ASTM on D7575

Based on Public Comments

1) Note 9 in the ASTM method mentions that co ntact mixing (i.e., a stan d mixer) is acceptable EPA has always maintained that no contact should be made with the sample because the analyte may adhere to the contacting device (e.g., stir ro d), which would change the sample integrity.
What data does ASTM have to ensure that contact mixing does not have an impact on the analytical results?

2) What data or literature does ASTM have to demonstrate that a 10 mL sample is truly representative of a 1L sample (aside from the comparability data already submitted to EPA)?

3) How does D7575 compensate for extremely turbid samples? ASTM D7575 contains a cautionary statement that for certain samples th is method may not be appropriate (e.g., because the samples contain high particulates). Is th ere a practical way for an analyst to make a determination before conducting an analysis usin g this method in a laboratory that receives a large amount of samples of different types?

## ASTM **Committee D19**  **on WATER**  **D7575 TASK GROUP:**

**RESPONSE TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS**  **DERIVED FROM**

**NOTICE OF DATA AVAILABILITY COMMENTS**

Aug ust 201 2ASTM D19 D7575 TASK GROUP TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS

DERIVED FROM NOTICE OF DATA AVAILABILITY COMMENTS

PREFAC E

On December 14, 2011, the United States Environmental Protection Agency (EPA) publishe d a Notice of Data Availability (NODA) in the Federal Register 1 , soliciting comments
on new data received from ASTM D19 on Water D7575 Task Group and EPA’s consideration of approving ASTM Standard D7575-10 as an alternative choice for the determination of oil and grease in Clean Water programs. As published in the Method Update Rule – Notice of Data Availability Fact Sheet 2 :

[ EPA described but did not propose the new ASTM method for oil and grease in the September 23, 2010 Federal Register notice. This method was not initially proposed because it uses a different extractant (a membrane rather than a solvent) and a different measurement technique (infrared absorption rather than gravimetry) from the extractant and measurement technique of currently approved methods for oil and grease... However, EPA is considering revising its regulatory requirements for oil and grease based on comments and additional data received on the new ASTM method for oil and grease (ASTM D7575 -10). After evaluating the new data, EPA finds that AS T M D7575

- 10 is a good stand

alone method for the measurement of oil and grease..., and it produces results that are generally very close results using Method 1664A for those matrices
tested... ]

On May 18, 2012, EPA published the Method Update Rule 3 . In the Final Rule, EPA stated that it would, “Make a decision on the inclusion of the new method [ASTM D7575] once it reviews the public comments received in response to the NODA in a separate Federal Register notice.” As part of its diligence in reviewing the public comments solicited from the NODA,

EPA on July 12, 2012 4 requested response from ASTM D19 on Water D7575 Task Group (D7575 Task Group) on three questions concerning contact mixing and representative sampling.
The following document is the D7575 Task Group response to these questions.

Comments regarding the content of this document should be addressed to the following:

Mr. Len Morrissey
Director

, ASTM International
100 Barr Harbor Drive West Conshohocken, PA (610 ) 832-9719 lmorriss@astm.org

1 Federal Register/Vol.76, No. 240/Wednesday, December 14, 2011/Proposed Rules

2 EPA

- 820 -F- 11

- 0150

3 Federal Register /Vol. 77, No. 97/Friday, May 18, 2012/Rules and Regulations

4 Communication from USEPA Jan Matus z ko Branch Chief, Engineering and Analytical Support Branch, Engineering and Analysis Division to ASTM D19 Manager Alyson Fick July 12, 2012 including attached “Questions for ASTM 71212.docx” document.ASTM D19 D7575 TASK GROUP TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS

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3 

### QUESTION 1

USEPA Statement :

Note 9 in the ASTM method mentions that contact mixing (i.e., a stand mixer) is acceptable . EPA has always maintained that no contact should be made with the sample because the analyte may adhere to the contacting device (e.g., stir rod), which would change the sample integrity.

USEPA Question 1

–

What data does ASTM have to ensure that contact mixing does not have an impact on the analytical results?

D7575 Tas k Group Response

In many sections, D7575 references the procedures allowable in EPA Method 1664. Sections 6, 8, and 11 of the EPA reference method discus ses, describes, and allows the use of contact mixing devices such as glass stirring rods and PFTE

- coated stirring bars, etc. To address that contact mixing does not have an impact on the analytical results, ASTM Standard D7575 instructs and guides the operator through the method to ensure analytical integrity and data quality. Specifically, in th e following Sections:

Section 6. Interferences 6.1 Method interferences may be caused by contaminants in instrumentation, reagents, glassware and other apparatus producing artifacts. Routine laboratory method blanks

will demonstrate all these materials are free from interferences.

Section 14. Procedure
14.2 Sample pretreatment —If the sample to be tested is a grab sample, vigorously shake

t he sample bottle to sufficiently mix the sample. The sample bottle may require more shaking if collected seven or more days prior to testing. It is up to the operator to ensure the sample is homogeneous prior to proceeding with the measurement.

NOTE 9 —For challenging samples it has been found that: A) vigorously shaking a sample bottl e for up to 20 minutes with a paint shaker or an appropriate laboratory shaker with sample container holder accessory and B) ultrasonic vibration using an ultrasonic bath under the following suggested conditions [(a) bath is operating at a temperature o f 40 °C, (b) sample bottle cap(s) are sufficiently tightened (c) water level is sufficient to fully submerge the sample bottle(s), (d) ultrasonic vibration for up to 20 minutes], are sufficient to homogenize a sample that has been stationary for the maximum allowed holding time of 28 days in the vast majority of cases. A sample processed very soon after taking the sample or created in the lab by spiking immediately before testing may requireASTM D19 D7575 TASK GROUP TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS

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4 minimal shaking. If an inspection of the sample clearly indicates this amount of shaking
ha s not sufficiently homogenized the sample (that is, stratification in the sample container), further homogenization by the same method or a different method may be required. In general it has been found that contact mixing (that is, ultrasonic homogenization, stand mixer, etc.) of the sample does not cause any interferences for the method. If the sample is known to be problematic, it may be ideal to co llect the sample in a wide mouth jar to facilitate contact mixing.

Further, if there is observance of non

- homogeneity [as outlined in ASTM D7575 -10 Note 9.], and the operator determines a sample does not adequately homogenize using the
conventional non -c ontact techniques (e.g. shaking, ultrasonic bath) and requires special treatment, then:

The operator may consider other contact homogenization techniques such as those described in EPA Method 1664 Revision A, using appropriate safeguards and
considerat ion of data quality objectives. These procedures are described below:

EPA 1664 Equipment:
6.4 Equipment for sample extraction
6.4.2 Glass stirring rod

6.7 Equipment for removal of adsorptive materials
6.7.1 Magnetic stirrer
6.7.2 PTFE

- coated magnetic stirring bars

EPA 1664 Procedures:
8.0 Sample Collection, Preservation, and Storage
8.3 The high probability that extractable matter may adhere to sampling equipment and result in measurements that are biased low precludes the collection of composite samples for determination of oil and grease. ... Alternatively, samples can be collected in the field and composited in the laboratory. For example, collect four individual 250- mL samples over the course of a day. In the laboratory, pour each 250- mL sample into the separatory funnel, rinse each of the four bottles (and caps) sequentially with 30 mL of n-hexane, and use the 30 mL of n-hexane for the extraction (Section 11.3).

11.2 pH verification
11.2.1.1 Dip a glass stirring rod into the well mixed sample.
11.2.1.3 Rinse the stirring rod with a small portion of n -hexane that will be used for extraction (to ensure that no extractable material is lost on the stirring rod).
11.3 Extraction
11.3.5 Allow the organic phase to separate from the aqueous phase for a minimum of 10minutes. If an emulsion forms between the phases and the emulsion is greater than onethird the volume of the solvent layer, the laboratory must em ploy emulsion

- breaking techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring

...ASTM D19 D7575 TASK GROUP TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS

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5 11.5 SGT

- HEM D etermination
11.5.3.2 Add a fluoropolymer-coated stirring bar to the flask and stir the solution on a magnetic stirrer for a minimum of 5 minutes.

With consideration to the above as it relates to contact homogenization, the operator should perform an equivalence testing study to ensure against impacting sample results (as per ASTM D7575 Section 2.2 Referenced Document EPA Method 1664 – see Section 9.2.3).

The operator should consider appropriate options based on the sample matrix. ASTM D7575 states that the method (as with all methods) may not be appropriate for all matrices and, in the case of concern, other alternative methods may be more appropriate.

As was pointed out in the “ASTM International D19 Water and Orono Spectral Solutions, Inc. Response to United States Environmental Protection Agency Questions Concerning
ASTM Standard D7575” in June of 2011:

“to our knowledge, there is no single stand

- alone method or Standard approved by USEPA and ASTM D19 that is completely robust to all NPDES regulated industries and discharge matrices for a given set of monitoring parameters. The USEPA is well aware of this gap in method robustness (deficiencies) and identifies and builds sufficient safeguards into method requirements for the laboratory and regulator who enforces the requirements of the method.”

As an example, the method deficiencies and safeguards written in to ASTM D7575 referenced document 2.2 ‘USEPA Method 1664, Revision A’, sections 1.3, 1.4, 1.7, 1.9, 9.1, and Note of 11.2 point out the following:

Method Deficiencies [this header added for clarity] Section 1.3 – [ This method is not applicable to measurement of materials that volatilize

at tempera tures below approximately 85oC. Petroleum fuels from gasoline through #2 fuel oil may be partially lost in the solvent removal process .]

Section 1.4 – [ Some crude oils and heavy oils contain significant percentage of materials that are not soluble in n-hexane. Accordingly, recoveries of these materials may be low .]

Method Safeguards [this header added for clarity]
Section 1.7 – [ The laboratory is permitted to modify the method to overcome interferences or lower the cost of measurements, provided that a ll performance criteria in this method are met. The requirements for establishing method equivalency are given
in Sections 9.1.2 and 9.2.3 .]

Section 1.9 – [ Each laboratory [bold / underline added for emphasis ] that uses this
method must demonstrate [ added for emphasis ] the ability to generate acceptable results using the procedures in Section 9.2. ]ASTM D19 D7575 TASK GROUP TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS

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6 Se ction 9.1 – [ Each laboratory that uses this method is required to operate a formal quality assurance program (Reference 16.8)... Laboratory performance is compared to established performance criteria to determine if the results of analyses meet performance characteristics of the method. ]

Section 11.2 Note – [ NOTE: The procedure detailed below is for separatory funnel liquid -liquid extraction. Solid-phase extraction (SPE) may be used at the discretion of the discharger/generator and its laboratory. However, if SPE is used, it is the responsibility of discharger/generator and laboratory to assure [underline added for emphasis] that results produced are equivalent to results produced by the procedure below ].”

Proper operational practices, consideration, and techniques as outlined above will verify contact mixing performance (if so chosen) and ensure sample integrity.ASTM D19 D7575 TASK GROUP TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS

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7 

### QUESTION 2

USEPA Question 2

–

What data or literature does ASTM have to demonstrate that a 10 mL sample is truly representative of a 1L sample (aside from the comparability data already submitted to EPA)?

D7575 Task Group Response

ASTM D19 D7575 Task Group follows the EPA direction and its data and documentation (EPA Method 1664, Revision B) which describes and d emonstrates how a 1L sample can be representative of a larger source of water . As an example, EPA sites in Method 1664, Revision B, Sections 1.7.15 and 4.5 the following:

Section 1.7.15 [ Collection and analysis of a smaller sample volume is permitted provided all the quality control requirements of Section 9 are met. If smaller sample volumes are used, all QC and initial and ongoing demonstration of performance samples must use the same volume as the smaller volume samples. To achieve a proportionately smaller matrix spike at the recommended OPR concentration of 40 mg/L, i.e., spike 0.1 mL of the 4 mg/mL PAR standard for every 10 mL of proportionately smaller sample volume or fraction thereof. To report the most accurate HEM and SGT-HEM values in mg/L, subtract the smaller volume method blank value from the smaller volume sample value provided the recovery value of the smaller volume matrix spike is equal to or greater than the MDL for the modified method. Multiply this proportionately smaller sample value by the appropriate dilution factor and express the final sample result in mg/L. For example, if 4.4 mg/100 mL was the result for the proportionately smaller sample and 0.6 mg/100mL was the result for the method blank, the reported concentration of the sample should be 38.0 mg/L ([4.4 mg/100 mL – 0.6 mg/100 mL] x 10 = 38.0 mg/L). Additionally, all samples must be associated with an uncontaminated, 1-L method blank before the r esults may be reported for regulatory compliance purposes .]

Section 4.5 [ Interferences extracted from samples will vary considerably from source to source, depending upon the diversity of the site being sampled. For those instances in which samples are thought to consist of complex matrices containing substances (such as particulates or detergents) that may interfere with the extraction procedure, a smaller sample may need to be collected for analysis. ]

ASTM Method D7575

- 10 provides similar guidance as in EPA Method 1664 for sub

sampling in Section 14, Note:ASTM D19 D7575 TASK GROUP TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS

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8 Note 10 [ If the amount of particulate in the sample clogs the extractor and precludes processing a 10 mL sample, repeat the procedure of Section 14 except using a smaller volume of sample; alternatively dilute the sample and re

- run the analysis, making sure to account for the dilution in the final calculation of sample oil and grease concentration. It is recommended that a new MDL study be performed to determine the MDL and lower limit of th e reporting range for processing a volume other than 10 mL. If performing multiple replicates on the same sample bottle, shake the bottle by hand for 10 seconds between syringe draws .]

Other than what has been demonstrated through the ASTM D19 D7575 Task Group round robin and NODA validation studies, the guidance in ASTM Standard D7575, and the guidance in EPA Method 1664, Revision A, ASTM D19 D7575 Task Group is not aware of a better way to demonstrate sample r epresentativeness

.

Finally, it should be noted that with ASTM Standard D7575, multiple representative aliquots can be obtained from a single collected sample for processing and analysis. Whereas with EPA Method 1664, Revision A, unless multiple 1- L samples are collected and composited, only one f ull 1

- L sample can be processed and analyzed.ASTM D19 D7575 TASK GROUP TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS

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9 

### QUESTION 3

US EPA Question 3 – Part 1

H ow does D7575 compensate for extremely turbid samples?

D7575 Task Group Response

ASTM Standard D7575 addresses turbid samples in two specific N otes :

N ote 2 [ It is important to note that the partition of solid matter on to the extractor does not preclude IR measurement; in the majority of cases there is sufficient IR throughput to still perform the measurement as described herein. This is the case with most metal- oxide materials (that is, clay or sand) and biological material (that is, algae or cellulose). There may of course be samples encountered wherein the solid matter is not sufficiently IR transmitting; one example may be a sample containing a large concen tration of metal particulate. In these instances an alternative measurement technique may be necessary .]

Note 10 [ If the amount of particulate in the sample obstructs the extractor and precludes processing a 10 mL sample, repeat the procedure of Section 14 except using a smaller volume of sample; alternatively dilute the sample and re-run the analysis, making sure to account for the dilution in the final calculation of sample oil and grease concentration... ]

USEPA Question 3

– Part 2

ASTM D7575 contains a cautionary statement that for certain samples this method may not be appropriate (e.g., because the samples contain high particulates). Is there a practical way for an analyst to make a determination before conducting an analysis using
this method in a lab oratory that receives a large amount of samples of different types?

D7575 Task Group Response

The practical way to determine if there is a matrix issue prior to actual sample analysis is through the homogenization step in the ASTM Standard D7575 procedure. Should homogenization of the sample aliquot fail (i.e. high particulate matter), it may be determined that ASTM Standard D7575 is not be appropriate for that specific matrix and
that the alternative EPA Method 1664 need be employed.

As a note, homogenization and sample extraction failures are an exception to the number
of different matrices that were tested in the ASTM D19 D7575 Task Group round robin and NODA validation studies. The vast majority of sample matrices tested with this method experienced no failures and produced equally effective results to that of theASTM D19 D7575 TASK GROUP TO UNITED STATES ENVIRONMENTAL PROTECTION AGENCY QUESTIONS

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10 reference method . An add ed benefit to ASTM Standard D7575 is that the method allows volume corrections to be made if the entire 10 mL aliquot cannot be processed. If this is due to pressure, the user will see indications such as failure of the syringe, or stalling of the syringe pum p. If failure of the device itself occurs, t he companion Standard Operating Procedure 5 guides and instructs the user through the sample preparation

process , as described below:

Standard Operating Procedure [ NOTE: While the sample is being processed, watch carefully for leaking in the syringe. This is an indication that Extractor membrane has clogged and is no longer processing sample. In some cases the pressure from the Extractor will become great enough to stall the syringe pump. If the syringe pump is unable to process the entire 10 mL volume through the extractor, record the total volume that has been processed, and proceed with drying. A correction will be made to the measured value to accommodate for this loss of volume. If another analysis of this matrix is necessary, the syringed pump should be stopped before the point that it stalled, and this volume should be recorded ...]

Similarly , as cited in Section 11.3.5 of the EPA Method 1664, Revision A, “ an analyst is expected to use judgment to iden tify if an emulsion has formed in the two

- phase system, and determine the proper way of breaking it. In any instance that the end user is not familiar with the sample, or is unsure of the accuracy of the volume correction procedure, they are advised to show equivalency using matrix spikes...”

5 Standard Operating Procedure for: ASTM D7575 “Standard Test Method for Solvent

- Free Membrane Recoverable Oil and Grease by Infrared Determination”