**ENFORC E**  **ABLE CONSENT AGREEME NT**  **FOR ENVIRONMENTAL**  **TESTING FOR**  **OCTAMETHYLCYCLOTETRA SILOXANE (D4) (CASRN**  **556 -**  **67 -**  **2)**

**Docket No.**  **EP A**  **- HQ**  **- OPPT**  **- 2012**  **- 0209**  **Available at www.regulations.gov** 

**Date: December 1**  **9 , 2013**  **DRAFT FOR 30 DAY COMMENT**  **BY INTERESTED PARTIES Contains No Confidential Business Informatio**  **n**2 **ENFORCEABLE CONSENT AGREEMENT FOR ENVIRONMENTAL**  **TESTI N**  **G FOR:**  **OCTAMETHYLCYCLOTETRA SILOXANE (D4)**  **(CASRN 556 -**  **67 -**  **2)**

**Docket No.**  **EP A**  **- HQ**  **- OPPT**  **- 2012**  **- 0209**  **TABLE OF CONTENTS** I. INTRODUCT ION ................................ ................................ ................................ ................................ ..... 4 II. CHEMICALS SUBJECT TO THE ECA ................................ ................................ ................................ . 4 III. OBLIGATIONS OF THE SIGNATORY COMPANIES ................................ ................................ ....... 4 IV . PRINCIPAL TEST SPONSOR ................................ ................................ ................................ .............. 4 V. PURPOSE OF THE TESTING PROGRAM ................................ ................................ ........................... 5 VI . SCOPE OF THE TESTING PROGRAM ................................ ................................ ............................... 5 VII. DESCRIPT ION OF TESTING PROGRAM ................................ ................................ ......................... 5 VIII. STANDARDS FOR CONDUCT ING TESTING ................................ ................................ ................ 6 IX . SCHEDULE, STUDY PLANS, TESTING, AND REPORTS ................................ ............................... 6 X. MODIFICAT IONS TO THE ECA ................................ ................................ ................................ .......... 8 XI . FAILURE TO COMPLY WITH ECA ................................ ................................ ................................ ... 8 XII. EPA MONITORING OF ECA TESTING ................................ ................................ ............................ 8 XIII. SUBMISSIONS TO EPA AND CONFIDENT IALITY OF INFORMATION ................................ ... 9 XIV. PUBLICAT ION AND DISCLOSURE OF TESTING RESULTS ................................ ...................... 9 XV. OTHER RESPONSIBILIT IES OF THE SIGNATORY CO MPANIES ................................ ............. 10 XVI. RESPONSIBILITY FOR THE ACTIONS OF UNRELATED THIRD PARTIES .......................... 10 XVII. FORCE MAJEURE ................................ ................................ ................................ .......................... 10 XVIII. DISPUTE RESOLUTION ................................ ................................ ................................ .............. 10 XIX. SEVERABILITY OF ECA PROVISIONS ................................ ................................ ....................... 10 XX. FINAL AGENCY ACTION ................................ ................................ ................................ ............... 10 XXI. PUBLIC RECORD ................................ ................................ ................................ ............................ 11 XXII. EFFECT IV E DATE AND TERM ................................ ................................ ................................ .... 11 XXIII. RIGHTS OF THE SIGNATORY COMPANIES ................................ ................................ ........... 11 XXIV. RESERVATION OF RIGHTS BY SIGNATORY COMPANIES ................................ ................. 12 XXV. NOTICES ................................ ................................ ................................ ................................ ......... 12 XXVI. IDENTITY OF THE SIGNATORY COMPANIES AND PRINCIPAL TEST SPONSOR .......... 12 XXVII. SIGNATURES ................................ ................................ ................................ .............................. 143

APPENDIX 1 - ENVIRONMENTAL TESTING AT D4 DIRECT DISCHARGE SITES ....................... 15 APPENDIX 2 - ENVIRONMENTAL TESTING FOR INDIRECT DISCHARGE SITES ....................... 17 APPENDIX 3 - ENVIRONMENTAL TESTING FOR PRIMARILY NON - INDUSTRIAL WASTEWATER TREATMENT PLANTS ................................ ................................ ............................... 20 APPENDIX 4 - TESTING STANDARD FOR THE COLLECTION, SAMPLE HANDLING, TRANSFER AND ANALYSIS OF INFLUENT AND EFFLUENT SAMPLES FOR D4 ....................... 22 APPENDIX 5 - TESTING STANDARD FOR THE COLLECTION, SAMPLE H ANDLING, TRANSFER AND ANALYSIS OF SURFACE WATER SAMPLES FOR D4 ................................ ........ 28 APPENDIX 6 - TESTING STANDARD FOR THE COLLECTION, SAMPLE HANDLIN G, TRANSFER AND ANALYSIS OF BIOSOLIDS SAMPLES FOR D4 ................................ .................... 33 APPENDIX 7 - TESTING STANDARD FOR THE COLLECTION, SAMPLE HANDLING, TRANSFER AND ANALYSIS OF SEDIMENT SAMPLES FOR D4 ................................ ..................... 38 APPENDIX 8 - TESTING STANDARD FOR THE COLLECTION, SAMPLE HANDLING, TRANSFER AN D ANALYSIS OF BIOTA SAMPLES FOR D4 ................................ ............................. 444

I. INTRODUCTION A. Under the authority

of S ection 4 of the Toxic Substances Control Act (TSCA), 15 U.S.C. § 2603, and 40 C.F.R. Part 790 of the A gency ’s implementing regulations, the United States Environmental Protection Agency [hereinafter “EPA” or “ A gency” ] and , Dow Corning Corporation, Evonik Goldschm idt Corporation, Momentive Performance Materials USA In c., Shin
- Etsu Silicones of America, Inc., and Wacker Chemical Corporation [hereinafter individually

a “ Signatory Company” and collectively “the Signatory Companies”] enter into this Enforceable Consent Agreement for certain e nvironmental t esting [hereinafter “this ECA”]
. As used in this ECA, the term “Parties” shall refer jointly to EPA and the Signatory Companies, and the term “Part y” shall refer i ndividually to one or the other. II. CHEMICAL S SUBJECT TO THE ECA T his ECA requires testing for presence of octamethylcyclotetrasiloxane, Chemical Abstracts Service Registry

Number ( CASRN ) 556 - 67 - 2 [hereinafter referred to as “D4”] in specified wastewater treatment plant (WWTP) influent and effluent discharges , r eceiving streams and environmental matrices at method detection limits specified in the test standards in Appendices 4 - 8 of this document. III. OBLIGATIONS OF THE SIGNATORY COMPANIES The Signatory Companies are responsible for complying with the terms of this ECA. The Signatory Companies recognize that to implement this ECA, EPA will issue an order under S ection 4 of TSCA that incorporates the terms of this ECA
. The Signatory Companies agree that al l terms of this ECA will take effect on the date of publication of the notice in the F ederal R egister announcing the issuance of the Order that incorporates this ECA
. All applicable time periods will be treated as beginning on that publication date
. The Signatory Companies shall submit a draft Study Plan and Quality

Assurance Project Plan (“QAPP”) to carry

out the environmental testing program set forth in Section VII and Appendices 1 - 8 . The Signatory Companies shall conduct environmental testing in accordance with the Final Study

Plan and Final QAPP that will be developed based on EPA’s review of the Signatory Compan ies ’ draft submission s . Following completion of environmental testing , the Signatory Companies shall submit a Final Report to EPA. Section s VIthrough IX provide more details about the testing that will be accomplished under this ECA (“ Testing Program ” )
. IV . PRI NCIPAL TEST SPONSOR A. To facilitate implementation of the Testing Program, the Signatory Companies have appoint ed the Silicones Environmental, Health, and Safety Center ( SEHSC ) , 700 2 nd Street NE , Washington DC 20002 , 202 - 249 - 7000 , as the Principal Test Sponsor of this Testing Program .5

B . The Signatory Companies will provide EPA with written notice should they elect to designate a different Principal Test Sponsor. C . EPA and the Signatory Companies recognize that the Principal Test Sponsor has no legal responsibility

for compl ying with this ECA. The role of the Principal Test Sponsor is to assist in coordinating and administering testing under this ECA and in communicating with EPA about study plans, protocols, analy

tical methods, schedules, reports , and other aspects of the testing program . Responsibility

for compl yi ng with the ECA rests at all time s with the individual Signatory Companies. V. PURPOSE OF THE TESTI NG PROGRAM The purpose of the Testing Program is to conduct environmental monitoring to characterize specified sources and pathway s of release of D4 to the environment and resulting exposure of aquatic and sediment dwelling organisms to D4
. Through the Testing Program, the Signatory Companies will develop environmental testing data for D4 in the vicinity

of manufacturing and processing (including product formulating ) sites and WWTP s in the United S tates . EPA believes that the T esting P rogram will generate data useful to the A gency to assess D4 exposures and risks to sediment dwelling and aquatic organism s . VI . SCOPE OF THE TESTI NG PROGRAM The Testing Program is described in Section VII . Sampling and analy sis will be conducted in accordance with the test standards described in Section VIII (“Test Standards”) and documented in the required submissions described in Section IX (i.e., Study Plan, QAPP , Interim Progress Reports, and Final Report)
. VII. DESCRIPTION OF TESTI NG PROGRAM A. As described further in Appendix 1 to this ECA, environmental testing will be conducted on samples collected at four (4) direct discharge locations operated by certain Signatory

Companies
. For each of the four locations described in Appendix 1 , there will be two ( 2 ) testing events . In particular, each facilit y ’ s WWTP ’ s effluent will be sampled and anal yz ed for D4 . Sediment , surface water and biota (benthic and fish species) in the receiving waters will also be sampled and anal yz ed for D4
. The test standards described in Appendi c es 4, 5, 7 and 8 shall be used for testing. B. As described further in Appendix 2 to this ECA, environmental testing will be conducted on samples collected at f

ive (5) WWTP locations th at use activated sludge to treat wastewater from indirect discharge sites that include D4 processors (including product formulators)
. For each of the locations described in Appendix 2 , there will be two ( 2 ) testing events involving the collection and anal ys is for D4 of samples of the following: WWTP influent , WWTP effluent , WWTP biosolids, receiving stream s urface water, receiving stream sediment, and receiving stream biota (benthic and fish species )
. T he test standards described in Appendi c es 4, 5, 6, 7 and 8 shall be used for testing.6

C. As described further in Appendix 3 to this ECA, environmental testing will be conducted on samples collected at five (5) WWTP locations receiving less than 1 5 % of wastewater from industrial facilit ies and , preferabl y , no wastewater from D4 manufacturing or processing (including product formulation) sites
. For each of the locations described in Appendix 3 , there will be two ( 2 ) testing events involving the collection and anal ys is for D4 of samples of the following: WWTP influent, WWTP effluent, WWTP biosolids , receiving stream surface water , receiving stream sediment , and receiving stream biota (benthic and fish species)
. T he test standards described in Appendi c es 4, 5, 6, 7 and 8 shall be used for testing. Following completion of the environmental testing described in paragra ph s A - C above , the Signatory Companies will provide EPA with a report summarizing the results. VIII. STANDARDS FOR CONDUCTING TESTING A. E nvironmental testing shall be conducted in accordance with the Test Standards described in Append ices 4, 5, 6, 7, and 8 to this ECA
. P referably , all samples should be anal yz ed for D4 at one commercial testing laboratory that has appropriate expertise with the D4 anal ys e s of samples of the ty pes collected in this testing program when the testing occurs , unless there are unforeseen circumstances such as lack of laboratory availability as noted in 40 C.F.R. § 790.68(b)(2)(iii)
. 1. Certain provisions of Test Standards are considered to be mandatory and are referred to as “requirements.” These requirements are identified by the use of the words “shall,” “will,” or “must” in the text of the Test Standard and del ineate a test requirement to be followed or met. 2. Provisions that are not mandatory , and are therefore onl y recommended, are identified b y the use of “should” statements
. If such “should” provisions are not followed, the Signatory Companies will not be deemed b y EPA to be in violation and will not be subject to penalties or other enforcement actions and th is will not , in and of itself, cause th e resulting data to be deemed invalid
. B. The Signatory Companies and EPA will consult in good faith to consider the need for Test Standard modifications if either EPA or the Signatory Companies desire such modifications
. Modifications to the Test Standards, if an y, will be governed b y 40 C.F.R. § 790.68. C. All testing required b y this ECA shall be in accordance with the EPA Good L aboratory Practice (GLP) regulation s found at 40 C.F.R. Part 792
. IX . SCHEDULE, STUDY PLANS, TESTING, AND REPORTS The schedule and deliverables for the Testing Program are described below
. EPA and the Signatory Companies recognize that in some instances modifications to the described schedule may be required given the uncertainties (such as weather, sampling/anal yt ical issues, logistics, etc. ) inherent in performing the fie ld sampling and environmental testing contemplated by this Testing Program. Modifications to the schedule, if any , will be made according to the procedures set out in 40 C.F.R. § 790.68.7

A. Study Plan The Signatory

Companies will submit a Study Plan prepared pursuant to this ECA to EPA at least fort y - five ( 45 ) day s prior to the initiation of testing in accordance with 40 C.F.R. § 790.62 and no more than one hundred twent y (120) day s after the effective date of the ECA . The content of the Study

Plan submitted to EPA will comply with 40 C.F.R. § 790.62(b). Modifications to the study plan will be governed b y the procedures of 40 C.F.R. § 790.62(c). The Study Plan will become part of the official record (docket number EPA
- HQ - OPPT - 2012 - 0209). EPA shall approve the Study

Plan at the same time QAPP approval is required if it meets the requirements of this ECA and 40 C.F.R. § 790.62(b). The Study Plan shall become the “Final Study Plan” when approved b y EPA. The Signatory

Companies shall submit a QAPP to EPA within one hundred eight y ( 180 ) day s of the Effective Date of this ECA and at least fort y - five ( 45 ) day s prior to the initiation of testing
. The QAPP must be prepared in accordance with EPA guidance. 1 The QAPP shall include complete information on the T est S tandards to be used. If multiple commercial testing laboratories are used for different environmental media and environmental matrices tested , the QAPP will address inter
- laboratory variability

of D4 anal ys es. EPA shall approve the QAPP within 60 day s of receipt of the QAPP if it meets the requirements of this ECA and is consistent with EPA guidance noted above. B. Testing The Testing Program shall commence (i.e., initiation of field work) af ter the Study

Plan and QAPP have been approved by EPA . The testing program shall commence no later than sixty (60) day s after the study

plan and QAPP have been approved. T esting ( i.e. , collection and anal ys is of all samples) shall be completed within three hundred sixty (360) day s after testing commences , un less the schedule is modified, as described above and in Section X
. C . Interim Progress Reports The Signatory Companies will submit Interim Progress Reports to EPA informing the A gency of the progress of the Testing Program. An Interim Progress Report is required one hundred eight y ( 180 ) day s after the Effective Date specified in Section XX II .A of this ECA and every one hundred eight y ( 180 ) day s thereafter until the Signatory Companies have fulfilled all obligations under Section VII of this ECA
. Interim Progress Reports shall include a summary of work completed to date, an y proposed changes in protocols or schedule, raw data (as defined in 40 C.F.R. § 792.3) and an y other matters affecting progress of testing
. No further reporting is required of the Signatory Companies to satisfy any potential reporting obligations that might arise under S ection 8(e) of TSCA with respect solely to the data being generated under this ECA once the Interim Progress Reports and the Environmental Monitoring Report are submitted to the A gency in a ccordance with this ECA.

1 USEPA Guidance for Quality Assurance Project Plans, EPA QA/ G - 5 , prepared by: Office of Environmental Information, EPA ( December 200 2 )
- http://www.epa.gov/quality/qs
- docs/g5
- final.pdf
.8

D . Final Report No later than one hundred fifty ( 15 0 ) day s following completion of the required e nvironmental testing ( i.e. , collection and anal ys is of the d ata), the Signatory Companies shall submit to EPA an e nvironmental m onitoring r eport (“Final Report”)
. This Final Report shall include a description of monitoring performed, summary of test results, raw data, laboratory analy ses, and quality assurance/quality

control information, as per 40 C.F.R. §792.185 . R ecords shall be retained per 40 C.F.R. §792.195. This Final Report is intended to be released to the public
. I f the Signatory Companies believe that any of this information should be submitted under a confidentiality claim, then a confidential version should be submitted in accordance with Section XIII of this agreement. However, in such event EPA may

choose to initiate a review of the confidentiality claim in accordance with EPA confidentiality

regulations at 40 C
. F . R . § 2.306(d) and (e) and S ections 14(a) and 14(b) of TSCA , 15 U.S.C. § 2613 (a)
- (b) , in order to ensure that the necessary information is made available to the public
. The Signatory Companies will document all Q uality A ssurance /Q uality C ontrol work done as part of the T esting P rogram . The Signatory Companies will electronically sub mit all of the raw data ( as defined in 40 C.F.R. § 792.3 ) produced during the T esting P rogram . X. MODIFICATIONS TO THE ECA Modifications to this ECA, if an y, shall be made in accordance with the modification procedures contained in 40 C.F.R. § 790.68. Modifications to any

Study Plan under this ECA shall be governed b y the procedures of 40 C.F.R. § 790.62(c). XI . FAILURE TO COMPLY WITH ECA The Signatory Companies acknowledge that, as specified in 40 C.F.R. § 790.65, a violation of this ECA shall cons titute a “prohibited act” under section 15(1) of TSCA, 15 U.S.C. § 2614(1) and shall trigger all provisions applicable to a violation of section 15
. Inaddition, noncompliance with this ECA could result in a citizen’s civil action
. The Signatory Companies further acknowledge that 40 C.F.R. § 790.65 provides additional information regarding the implications of failing to compl y with an enforceable consent agreement. XII. EPA MONITORING OF ECA TESTING EPA may conduct monitoring activities, such as labo rato ry inspections and/or study audits of the monitoring, sampling, and/or testing conducted under this ECA in accordance with the authority

and procedures in Section 11 of TSCA, 15 U.S.C. § 2610. In the event that this monitoring contributes to delay s in the completion of any activities required under this ECA, the parties may

seek modification in the scope of testing performed under the consent order in accordance with 40 C.F.R. § 790.68 .9

XIII. SUBMISSIONS TO EPA AND CONFIDENTIALITY OF IN FORMATION A. All data submitted to EPA under this ECA will be identified by the Docket Number “ EPA HQ - OPPT - 2012 - 0209 ” and the name “ Testing Consent Order for Octamethylcyclotetrasiloxane ( D4) CASRN: 556 - 67 - 2 . ” A ll submissions under this ECA will be provided to EPA at the address specified in 40 C.F.R. § 790.5 in a readily downloadable electronic format
. B. An y document submitted to EPA that contains data or information for which a Signatory Company makes a claim of confidentialit y shall be submitted as two separate versions. One version ( the confidential business information ( CBI ) version) shall be complete, with the information being claimed as confidential marked in the manner described under 40 C.F.R. § 790.7 . The other, public version shall be identical in all re spects except that all of the information claimed as confidential shall be redacted. EPA will place only the public version in the A genc y ’s docket
. The complete version will be treated in accordance with EPA confidentiality regulations in 40 C.F.R. P art 2 and 40 C.F.R. § 790.7
. Data or other information that are considered to be CBI must not be submitted electronicall y to EPA by e
- mail. Any part or all of data or other information claimed as CBI must be so marked
. If the CBI submission is on diskette or CD ROM, the outside of the diskette or CD ROM shall be marked as CBI and the specific information that is CBI shall be identified electronically within the diskette or CD ROM. C. EPA shall not disclose information marked as CBI except in accordance with procedures set forth in 40 C.F.R. P art 2 and 40 C.F.R. § 790.7 . Any claims of confidentiality for information submitted under this Testing Program shall be made under the terms of 40 C.F.R. § 790.7
. In formation claimed as confidential shall be treated in accordance with the procedures in 40 C.F.R. P art 2 and with S ection 14 of TSCA, 15 U.S.C. § 2613
. If no claim of confidentiality is made and substantiated in accordance with 40 C .F.R. § 790.7(c) b y the submitter of the information at the time of submission, the information will be deemed b y EPA, in accordance with 40 C.F.R. § 790.7, to be public, and may be made available to the public without further notice to the submitter. XIV. PUBLICATION AND DISCLOSURE OF TESTI NG RESUL TS A. All results of testing conducted pursuant to this ECA shall be announced to the public by EPA in accordance with procedures specified in Section 4(d) of TSCA, 15 U.S.C. § 2603(d). B. Disclosure b y EPA of data generated pursuant to this ECA to the public or other government agencies shall be governed by S ection 14(b) of TSCA, 15 U.S.C. § 2613(b), and 40 C.F.R. Part 2. C. Public availability

of the Final Report and other data generated pursuant to this ECA is not intended to, and does not create an ownership interest or right to use the Final Report, the underlying data or other information provided b y the Signatory Companies pursuant to this ECA for commercial purposes in any entity that is not a Signat ory

Company .10

XV. OTHER RESPONS I BILIT IES OF THE SI GNATORY COMPANIES A. The Signatory Companies are bound b y the terms of this ECA and the provisions of 40 C.F.R. § § 790.62 and 790.65. B. The Signatory Companies shall comply with the notification requirements of S ection 12(b)(1) of TSCA, 15 U.S.C. 2611(b)(1) and 40 C.F.R. P art 707, subpart D, if they export or intend to export D4 . Any

other person who exports or intends to export D4 is subject to the above cited export notification requirements. C. I f D4 becomes subject to a rule promulgated under TSCA S ection 5(a)(2), 15 U.S.C. 2604(a)(2), governing significant new uses of D4 then the Signatory Companies will be subject to the data submission requirements imposed by se ction 5(b)(1)(A) of TSCA, 15 U.S.C. 2604(b)(1)(A), as if the testing under this ECA had been required b y a TSCA S ection 4 test rule. XVI. RESPONSIBILITY FOR THE ACTIONS OF UNRELATED THIRD PARTI ES The Signatory Companies shall make a good faith effort to secure the cooperation of third parties (such as WWTP operators) as needed to complete the Testing Program under this ECA
. H owever the Signatory Companies are not responsible for the actions of third parties and shall not be hel d liable for an y inability to secure needed cooperation and/or permission to conduct the environmental testing specified under this ECA at locations owned, operated, and/or controlled by non - parties to this ECA. XVII. FORCE MAJEURE A Signatory

Company

shall not be held liable for any failure to perform its obligations under this ECA that is caused b y circumstances beyond its control or the control of any entity controlled b y the Signatory

Company , including an y contractors and subcontractors, that the Signatory Company could not have prevented through the exercise of reasonable due diligence. XVIII. DISPUTE RESOLUTION The Parties shall use their best efforts informall y and in good faith to resolve an y disputes that may arise concern ing the interpretation or application of the provisions of this ECA , including those involving the Study Plan or QAPP
. X IX . SEVERABILITY OF ECA PROVISIONS In the event that one or more provisions of this ECA is determined by a court decision to be unen forceable, the remaining provisions of this ECA will not be presumed to be valid, and EPA will either initiate a rulemaking proceeding to require testing or publish in the Federal Register its reason for not initiating such a proceeding. XX . FINAL AGENCY ACTION For purposes of 5 U.S.C. § 704, publication of the Federal Register notice announcing the11

issuance of the Order incorporating this ECA constitutes final agency action. XX I . PUBLIC RECORD EPA has established a public record which will contain this ECA, the Order that incorporates this ECA, the Federal Register notice announcing issuance of the Order incorporating this ECA, and any and all relevant information, subject to the confidentiality provisions of section 14(b ) of TSCA , 40 C.F.R. P art 2 , and 40 C.F.R. § 790.7 . The official record for this E CA, including the public version, which does not include an y information claimed as CBI, has been established under docket control number EPA - HQ - OPPT - 2012 - 0209 . XX II . EFFECTIVE DATE AND TERM A. Effective Date : This ECA takes effect on the date of publication in the Federal Register of the notice announcing the issuance of the Order that incorporates this ECA, which shall follow final approval and signature of the ECA by the Parties. This ECA may be signed in separate counterparts . This ECA will not be effective unless signed b y each of the Signatory Companies and EPA
. EPA will codi fy a reference to the substance in the Testing Program in subpart C of 40 C.F.R. P art 799. B. Term : Obligations of the Signatory Companies under this ECA, other than record retention obligations under 40 C.F.R. § 792.1 9 5, as applicable, will cease when an y one of the following occurs: 1. The Signatory Companies have provided EPA with all of the deliverables specified under this ECA . 2. A court determines that the relevant provisions of this ECA are unenforceable as described in Section XIX of this ECA and 40 C.F.R. § 790.60(a)(14)
. 3. Non - performance of the specific obligation is excused due to Force Majeure as described in Section XVII. XX I II . RIGHTS OF THE SI GNATORY COMPANIES By signing this ECA, the Signatory Companies waive their right to challenge EPA’s authority to assess penal ties for violations of this ECA
. This waiver does not affect an y other rights that the Signatory Companies may have under TSCA with respect to this ECA or to D4 testing beyond this ECA, including, but not limited to: 1. the right to contest whether a vi olation of this ECA has occurred, 2. the right to contest the amount of an y penalt y assessed for alleged violations of this ECA, and 3. the right to seek judicial review of an y administrative enforcement decision pertaining to this ECA or of an y EPA ru le that imposes requirements to test D4.12

XXIV . RESERVATION OF RIGHTS BY SIGNATORY COMPANIES The Signatory

Companies are not admitting that the requirements of S ection 4 of TSCA for promulgating a test rule to generate the data and information required by this ECA have been satisfied
. The Signatory

Companies are also not admitting that Section 4 of TSCA provides EPA with authority

to require generation of some of the data and information the Signatory Companies will provide to EPA through this ECA
. XXV . NOT IC ES A. Whenever under the terms of this ECA notice is required to be given or a report or other document is required to be submitted to a Party , it shall be directed to the individuals and addresses specified below, unless otherwise specified in thi s ECA. B. An y changes in the individuals or addresses referenced in Section XXV.A of this ECA shall be made b y written notice to all Parties. C. A ll documents submitted pursuant to this ECA shall be deemed submitted on the date of postmark or placed in the hands of a commercial courier service for overnight delivery . Hand
delivered documents are deemed submitted upon receipt at the appropriate address specified in Section XXV. A. Electronically transmitted documents are deemed submitted upon tr ansmission. XXV I . IDENTITY OF THE SI GNATORY COMPANIES AND PRINCIPAL TEST SPONSOR A. The Princip a l Test Sponsor is the Silicones Environmental, Health and Safety Center (SEHSC), 700 2 nd Street NE Washington DC 20002
. B. The Signatory Companies subject to this ECA are: Dow Corning Corporation Corporate Center PO Box 994 Midland, MI48686 Evonik Goldschmidt Corporation PO Box 1299 Hopewell, VA 23860 Momentive Performance Materials USA Inc. 260 Hudson River Road Waterford, NY 121 8 813

Shin
- Etsu Silicones of America, Inc. 1150 Damar Drive Akron, OH 44305 Wacker Chemical Corporation 3301 Sutton Road Adrian, MI 4922114

XXV I I . SIGNATURES Each undersigned representative of the Parties to this ECA certifies that he or she is fully authorized by

the Party represented to enter into the terms and conditions of this ECA and to execute and legall y bind that Party to it. Date:_______ ________________________ Jim Jones, Assistant Administrator , Office of Chemical Safet y and Pollution Prevention United States Environmental Protection Agency Date:_______ ________________________ [ Name ], [Title] Dow Corning Corporation PO Box 994 Midland, MI48686 Date:_______

________________________ [ Name ], [Title] Evonik Goldschmidt Corporation PO Box 1299 Hopewell, VA 23860 Date:_______ ________________________ [ Name ], [Title] Momentive Performance Materials USA Inc. 260 Hudson River Road Waterford, NY 121 8 8 Date:_______ ________________________ [ Name ], [Title] Shin
- Etsu Silicones of America, Inc. 1150 Damar Drive Akron, OH 44305 Date:_______ ________________________ [ Name ], [Title] Wacker Chemical Corporation 3301 Sutton Road Adrian, MI 4922115 APPENDIX 1 - Environmental Testing at D4 Direct Discharge Sites Direct discharge sites are D4 manufacturing and/or processing sites that discharge process wastewater into the environment after on
- site treatment. The four (4) D4 direct discharge sites operated b y Signatory

Companies that directl y discharge process wastewater into the environment after onsite wastewater treatment that will be monitored for D4 under this ECA are: Dow Corning Carrollton Plant 4770 Highway

42 East Carrollton, KY 41008 MPM Silicones, LLC Waterford Plant 260 Hudson River Road Waterford, NY 12188 MPM Silicones, LLC Sistersville Plant 10851 Energy

Highway Friendl y, WV 26146 Wacker Adrian Plant 3301 Sutton Road Adrian, MI 49221 A general process description of the industrial plant operations involving D4 shall be provided. A more detailed description , including a written narrative and process flow diagram (s) of the wastewater treatment sy stem employed at the sites shall also be provided ( e.g. , at a minimum consistent with what was provided in each facility’s discharge permit application)
. At each of these sites, wastewater treatment effluent, receiving stream surface water, receiving stream sediment and receiving stream biota shall be sampled and analyzed for D4 in accordance with the Test Standards provided in Appendices 4 , 5, 7 and 8 . These appendices provide details on sampling locations, s ample collection procedures, sample handling procedures and sample anal ys is (method detection limit and limit of quantification)
. T otal effluent flow rat e shall be recorded and reported. Samples shall be taken during two testing events at least three ( 3 ) months apart. The exact duration between sampling events for each site shall be determined in a detailed Sampling P lan included in the Study

Plan and QAPP
. Samples shall be collected during normal plant operations and during such times that effluent flow rates from the wastewater treatment s ys tem are representative of the normal plant operations. Samples shall be taken during t ypical weather conditions and not until at least three (3) day s after an unusual weather event such as a heav y rain storm. Samples shall be collected at a time16

when the rate of D4 release is expected to be representative of the typical rate of release of D4 for that site. A detailed Sampling Plan shall be prepared for each site and included as part of the overall Study Plan submitted to EPA
. The Sampling Plans shall include (with appropriate reference s to Test Standards and QAPP):

 map and detailed description of testing locations  sampling grids  sampling timing and schedule  sampling objectives and robust experimental design  number and t ype of samples to be collected  sampling protocols, including loss
- free methods for collection, storage, and anal ys is of samples , and standard operating procedures  access requirements  site characterizat ion for benthic invertebrate and fish sampling , including the species that are expected to be collected for anal ys is The Study

Plan shall address training of sample collection personnel in sampling protocols and the special handling requirements associated with D4 , the qualifications of contract laboratory vendor(s) , and method validation for all matrices to be sampled ( e.g. , sediment, water, biota )
.17 APPENDIX 2 - Environmental Testing for Indirect Discharge Sites Indirect discharge sites are D4 processing sites (including product formulation sites) that discharge process wastewater to offsite WWTPs . Testing shall be conducted for D4 at five (5) WWTP location s receiving wastewater from D4 processors (including product formulators) . The WWTP location s will be chosen based on the following criteria :
 All wastewater treatment sites selected for monitoring must be currentl y processing wastewater from one or more industrial sites known to be a D4 processor or formulator as documented through industrial user survey s or b y other readily available inform ation
. T he WWTP influent shall reasonabl y be expected to contain D4 based on industrial user survey s or other readily available information. The approximate relative contribution of wastewater being treated from industrial sources and wastewater treated from residential sources shall be provided for all wastewat er treatment sites selected for monitoring.

 All wastewater treatment sites selected for monitoring shall use activated sludge for wastewater treatment. S ites selected may follow activated sludge treatment with secondary clarification and/or disinfection (but no other forms of additional treatment)
.
 All wastewater treatment sites selected for monitoring shall release wastewater to riverine s ys tems, not the marine (ocean environment).
 Privately

owned wastewater treatment works may be selected for monitoring provided their treatment processes are similar to publicly o wned treatment works
.

 Wastewater treatment sites selected for monitoring should have effluent discharge rates that are relatively

large when compared to the receiving bodies flow rate (low dilution)
.
 Consideration should be given to geograph y when selecting wastewate r treatment sites for testing. I deall y, the sites selected should be in different regions of the country
. The Study

Plan shall detail the factors that were used to select each of the sites for testing and shall provide an explanation of why D4 is expected in the influent s . A summary of each WWTP ’s NPDES permit ( e.g. , location, industrial inputs, compliance issues, changes in facility structure or operation, etc. ) as well as a summary of available data on historical (i.e., within previous 5 years) effluent conditions ( e.g. , annual flow, dissolved oxygen, temperature, pH, suspended solids, biological ox ygen demand, etc. ) shall be included in the Study Plan. A description of the industrial activity at the D4 processor or formulator site s that indirectl y discharge to the WWTP s shall be provided for such sites controlled by signatory companies
. This information shall be requested (and reported, if obtained) from D4 processor or formulator18

sites that are not controlled by the signatory

companies. A more detailed description , including a written narrative and process flow diagram (s) , of the wastewater treatment sy stem s employed at the WWTP s shall also be provided ( e.g. , consistent with what was provided in each facilit y’s discharge permit application)
. Prior to including a specific location in the Study Plan, the Signato ry

Companies shall secure, as necessary and appropriate, a letter of cooperation/access from the person with control of the location. These letters will be included in the Study Plan. At each of the five (5) WWTP locations , the WWTP influent, WWTP effluent , WWTP biosolids , receiving stream surface water, receiving stream sediment, and receiving stream biota shall be sampled and anal yz ed for D4 in accordance with the Test Standards provided in Appendices 4
- 8 . These appendices provide details on sampling locations, sample collection procedures, sample handling procedures and sample anal ys is ( method detection limit and limit of quantification)
. Samples shall be taken during two testing events at least three ( 3 ) months apart. The exact duration between sampling events for each site shall be determined in a detailed Sampling Plan included in the Study

Plan and QAPP
. Samples shall be collected during normal plant operations and during such times that effluent flow rates from the wastewater treatment s ys tem are representative of the normal plant operations. Samples shall be taken during t ypical weather conditions and not until at least three (3) day s after an unusual weather event such as a heav y rain storm. Samples shall be collected at a time when the rate of D4 release is expected to be representative of the typical rate of release of D4 for that site. A detailed Sampling Plan shall be prepared for each site and included as part of the Study Plan submitted to EPA. The Sampling Plans shall include (with appropriate reference s to Test Standards and QAPP):

 map and detailed description of testing locations  sampling grids  sampling timing and schedule  sampling objectives an d robust experimental design  number and t ype of samples to be collected  sampling protocols including loss
- free methods for collection, storage, and anal ys is of samples , standard operating procedures  access requirements  site characterization for benthic invertebrate and fish sampling , including the species that are expected to be collected for anal ys is The Study

Plan shall address the training of sample collection personnel in sampling protocols and the special handling requirements associated with D4 , the qualifications of contract19

laboratory

vendor(s) , and method validation for all matrices to be sampled ( e.g. , water, sediment, biosolids, biota)
.20

APPENDIX 3 - Environmental Testing for Primarily Non - Industrial W astewater Treatment P lants This Appendix addresses D4 testing at WWTP locations that receive less than 15% of wastewater from industrial facilities, and, preferably , no wastewater from D4 manufacturing or processing (including product formulation) sites. The intent of the testing s pecified below is to develop a greater understanding of environmental releases of D4 emanating from the down
- the
drain uses of D4 in various consumer products post
- treatment b y a WWTP . Testing shall be conducted for D4 at five (5) WWTP s. The WWTP locations will be chosen based on the following criteria :
 All wastewater treatment sites selected for monitoring shall use activated sludge for wastewater treatment. S ites selected may follow activated sludge treatment with secondary clarification and/or disinfe ction (but no other forms of additional treatment)
.
 The influent to the WWTP shall contain less than 1 5 % of wastewater from industrial sources b y volume and , preferably , no wastewater from D4 manufacturing, processing, or formulating sites , as documented through industrial user survey s or by other readily

available information
.
 All wastewater treatment sites selected for monitoring shall release wastewater to riverine s ys tems, not the marine (ocean environment).

 Wastewater treatment sites selected for mo nitoring should have effluent discharge rates that are relatively

large when compared to the receiving bodies flow rate (low dilution)
.
 Consideration should be given to geograph y when selecting wastewater treatment sites for testing. Id eall y, the sites se lected should be in different regions of the country
. The Study

Plan shall detail the factors that were used to select each of the sites for testing . A summary of each WWTP ’s NPDES permit ( e.g. , location, industrial inputs, compliance issues, changes in facility

structure or operation, etc. ) as well as a summary of publicly available d ata on historical (i.e., within previous 5 years) effluent conditions ( e.g. , annual flow, di s solved ox ygen , temp erature, pH, suspended solids, biological ox ygen demand, etc. ) shall be included in the Study Plan. A detailed description, including a written narrative and process flow diagram (s) of the wastewater treatment sy stem s employed at the WWTP s shall be provided ( e.g. , consistent with what was provided in each facility ’s discharge permit application)
.21

Prior to including a specific location in the Study Plan, the Signatory

Companies shall secure, as necessary and appropriate, a letter of cooper ation/access from the person with control of the location. These letters will be included in the Study Plan. At each of the five (5) WWTP locations , the WWTP influent , WWTP effluent, WWTP biosolids , receiving stream surface water, receiving stream sediment , and receiving stream biota shall be sampled and anal yz ed for D4 in accordance with the Test Standards provided in Appendices 4
- 8 . These appendices provide details on sampling locations, sample c ollection procedures, sample handling procedures and sample anal ys is ( method detection limit and limit of quantification)
. Samples shall be taken during two testing events at least three ( 3 ) months apart. The exact duration between sampling events for each site shall be determined in a detailed Sampling Plan included in the Study

Plan and QAPP
. Samples shall be collected during normal plant operations and during such times that effluent flow rates from th e wastewater treatment s ys tem are representative of the normal plant operations. Samples shall be taken during t ypical weather conditions and not until at least three (3) day s after an unusual weather event such as a heav y rain storm. Samples shall be col lected at a time when the rate of D4 release is expected to be representative of the typical rate of release of D4 for that site. A detailed Sampling Plan shall be prepared for each site and included as part of the Study Plan submitted to EPA. The Samplin g Plans shall include (with appropriate reference to Test Standards and QAPP):

 map and detailed description of testing locations  sampling grids  sampling timing and schedule  sampling objectives and robust experimental design  number and t ype of samples to be collected  sampling protocols , including loss
- free methods for collection, storage, and anal ys is of samples , standard operating procedures  access requirements  site characterization for benthic invertebrate and fish sampling , including the species that are expected to be collected for anal ys is The Study

Plan shall address training of sample collection personnel in sampling protocols and the special handling requirements associated with D4 , the qualif ications of contract laboratory vendor(s) , and method validation for all matrices to be sampled ( e.g. , water, sediment, biosolids, biota).22

APPENDIX 4 - Testing Standard for the Collection, Sample Handling, Transfer and Anal ys is of In fluent and Effluent Samples for D4 **Sy n**  **o p**  **s i**  **s :**  This t esting s t andard provides guidelines for t he c ollec tion and anal ys is of environment al samples for D4 in support of a T esting Program det ailed in this ECA . T his s t andard c i t es t he requirements for t he sampling of influent and effluent as des cribed in Se ction VII of t he E CA and Appendices 1, 2, and 3, and identifies specific guidelines and references that will be used in the prepara tion of si t e - spe c ific Sampling Plans for t he c ollec tio n

/anal ysis of influent and effluent samples, whi ch will be included in a Study Plan and QAPP for t

he T esting Program. T his s t andard addresses: 1. When t o c ollect influent and effluent samples 2. Where t o c ollect influent and effluent samples 3. Special c onsidera

tions during sample c ollec tion to avoid sample c ontamina tion 4. How to c ollect and process influent and effluent samples 5. How to analy

ze influent and effluent samples for D4 and the appropria t e method detection limit and limit of quantification **Requirements for sampling influents and effluents:** Appendi c es 1

– 3 of t

his E CA s t a

t e tha t : “Samples shall be t aken during t wo t esting event s at least three (3) mont hs apar t . The exact duration between sampling event s for each si t e shall be det ermined in a det ailed Samp l ing Plan in c luded in t he Study Plan and QAPP.” “Samples shall be c ollec t ed during normal plant operations and during such times t hat effluent flow ra

t es from the wastewater t

reatment sy stem are representa tive of t he normal plant operations.” “Samples shall be t aken during typi c al weather c ondi tions and not until at least t hree (3) days af t er an unusual weather event su c h as a heavy rain storm. Samples shall be c ollec t ed at a time when the ra t e of D4 release is expec t ed t o be representa tive of t he typi c al ra t e of release of D4 for t

hat si t e.” **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **app r** **op r** **i a**  **te t**  **i me**  **fo r**  **s a**  **mp li**  **n g**  **e v**  **e n**  **t s**  **:** A t ea c h s i t e, t

wo samp l i ng e v ent s w i l l be undert aken t hat are s chedu l ed to be a m i n i mum o f t hree mont

hs apart and duri ng normal p l ant operat i ons and weather c ondi ti ons. N ormal operati ng c ondi ti ons w i l l be es t ab li shed by c onsul ti ng w i t h t he operator of e a ch WWTP , indirect and d i re c t d i s char g e fa c ili ty. The cri t eri a or means t hat are used by t

he f a c ili ti es t o de t erm i ne normal operati ng c ondi ti ons w i l l be do cument ed i n t he s i t e - spe c i f

i c Samp l i ng P l an s . C onf i r mat i on w i l l be ob t a i ned t

hat t he subje c t fa c ili ty i s operati ng under normal c ondi ti ons pri or t o c ommenc i ng samp l i ng at a gi v en l o c ati o n . I n add i ti on, samp l i ng wou l d not t ake p l a c e23

w i t h i n t hree ( 3 ) day s of unusual weather e v ent s. The date and time of the most recent precipitation occurrence for each sampling event will be recorded. **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **l o**  **c a**  **t i**  **o n**  **f o**  **r i**  **nf l**  **u e**  **n t**  **s a**  **mp l**  **e c**  **o ll**  **ect i**  **on :**  For t he s i t e s where influent is to be tested, i nf l uent samp l es should be c o l l e c t ed at t he headworks of t

he WWT P . The exa c t l o c a ti on for c o l l e c ti on of an i nf l uent samp l e w i l l be fa c ili ty - spe c i f

i c and spe c i f

i ed i n t he WWT P ’ s d i s c har g e perm i t . E a ch s i t e - spe c i f i c Samp l i ng P l an sha l l i n c l ude a bas i s for de t erm i n i ng t he appropri at e samp l i ng l o c ati on. **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **l o**  **c a**  **t i**  **o n**  **f o**  **r e**  **ff l**  **u e**  **n t**  **s a**  **mp l**  **e c**  **o l**  **l ect**  **i on**  **:** A t ea c h s i t e, eff

l uent samp l es sha l l be c o l l e c t ed at t he re g u l at ed c omp li an c e po i nt per t he WWT P ’ s d i s c h arg e perm i t . E a c h s i t e - spe c i f i c Samp l i ng P l an sha l l i n c l ude a c omp l e t e des c ri p ti on of t

he eff l uent d i s char g e porti ons of t he WWTP , i n c l ud i ng t

he es t ab li shed samp l i ng l o c ati on. **S p**  **ec i**  **a l**  **c o**  **n s**  **i d**  **e r**  **a t**  **i on**  **s fo**  **r t**  **h e**  **s a**  **mp li**  **n g**  **a n**  **d h**  **a nd**  **li n**  **g o**  **f i**  **nf l**  **u e**  **n t**  **a n**  **d e ff** 

**l u**  **e n**  **t s**  **a mp**  **l es**  **fo r**  **D 4**  **:** C yc li c v o l ati l e meth y

l s il oxane ( c VMS) materi a l s, su ch a s D 4 , are w i de l y used i n c onsumer produ ct s and may be present i n personal c are produc t s, c ommerc i al produ ct s, and l ubri c ant s , and may be c omponent s of anti foams w i de l y used i n WWTPs . I f t hese produc t s are used by i nd i vi dua l s duri ng an y part of t he preparati on for or d

u ri ng an y aspe c t of t

he f i e l d samp l i ng e v ent , samp l e c ont am i nat i on by D4 v o l atili z i ng from t he user c ou l d o c c ur. T o av o i d t he s ign i f i c ant po t enti al for samp l e c ont am i nati on duri ng c o l l e c ti on, pro c ess i n g , s t ora g e, and ana l ys i s for D4 i n env i ronment al matri c es, pre v ent ati v e measures should be i mp l emented to the ex t ent p oss i b l e i n t

he f i e l d. For examp l e, f

i e l d crew sha l l be requ i red to refra i n from us i ng any personal c are produ c t s t hat may c ont a i n an y c VMS materi al s (e
. g ., sun - b l o c k, sun - s creen, h and l o ti on, anti persp i rant s, e t c . ) wh il e prepari ng for or c onduc ti ng an y f i e l d a cti v i ti es to m i n i m i ze t

he poss i b il i ty for c o nt am i nati on w i t h D 4 . Sp e c i f

i c requ i rement s for c o l l e c ti ng and hand l i ng i n f

l uent and eff

l uent samp l es a imed at pre v enti ng samp l e c ont am i nati on by sour c es of D4 t hat are not spe c i f

i c to t he WWTP or d i re c t d i s char g e s i t e sha l l be spe c i f i ed i n t he Study Plan and QAPP. **C o**  **ll ect**  **i o**  **n o**  **f i**  **nf**

**l u**  **e n**  **t a**  **n d e**  **f**

**f l**  **u e**  **n t**  **s a**  **mp l**  **es fo**  **r a**  **n a**  **l y**  **s i**  **s o**  **f D**  **4 :**  The exa c t method for c o l l e c ti on of i nf l uent and eff

l uent samp l es i s a s i t e - spe c i f i c de t erm i nati on pri mari l y dependent on the a c c ess i b i l i ty and c onf i gurati on of t

he headworks of t

he WWTP for i nf l uent samp l i ng and t

he c omp li an c e po i nt for eff l uent samp l in g . I nf

l uent and eff

l uent samp l es w i l l be c o l l e c t ed as g rab samp l es and not c ompos i t e samp l es due t he e xpe c t ed h igh de g ree of v o l ati l i zati on of D4 from aqueous samp l es. For ea c h s i t e, pro c edures for c o l l e c ti ng grab samp l es of i nf

l uent and eff

l uent w i l l be based on U S E P A 201 3 (Wastewater Samp l i n g , Se cti on 4 , Samp l e T ypes and Se c ti on 6 , Manual Samp l i n g , pp. 14 - 15 , 20 ) , U S E P A 200 4 (N P D E S C omp li an c e Inspe cti on Manual, Se c ti on 5 B, Samp l i ng P ro c e dures and T e c hn i ques, pp. 5 - 3 t o 5 - 7 ), Knoerr 201 3 (Samp l e C o l l e c ti on se c ti o n), and A P H A 199 9 ( P art 10 6 0 C o l l e c ti on and24

P reserv ati on of Samp l e s , pp . 48 - 62 ) if appropriate given the site
- specific circumstances. Th i s gu i dan c e i denti f

i es t he fa ct ors i nv o lv ed i n de t erm i nati on of the most approp ri at e samp l i ng methods for i nf

l uent s and eff

l uent s. The exa c t c o l l e c ti on methods for i nf l uent and eff

l uent samp l es w i l l be de t a il ed i n t he Study Plan and QAPP. Spe c i f i c requ i rement s for samp l e container preparati on, samp l e hand l i n g , samp l e prese r v ati on, sh i pp i ng and s t ora g e of samp l es should be essent i a ll y t he same a c ross a l l s i t es. I mm ed i at e l y pri or t o ea c h samp l i ng e v ent at ea c h s i t e, t he l aborat ory that w i l l ana l yz e t he samp l es sha l l prepare c l ean (new, ne v er used) gl ass samp l e container s i n suff i c i ent numbers for a l l i nf

l uent and eff l uent samp l es t o be ana l yz ed for D 4 , for a l l qua l i ty assuran c e samp l es, and for re t a i n s a mp l e s . The samp l e container s w i l l be prepared by pre - wash i ng w i t h hexane, add i ng low density pol yeth yl ene ( L DPE ) sorbent i nt o t he container s , prov i d i ng poly tetrafluoroethylene ( P T FE ) t ape t o ass i st i n sea l i ng t he container s (as des c ri bed i n Knoerr 20 1 3 , Samp l e C o l l e c ti on se c ti o n) , as we l l as prov i d i ng l ab e l s. The l aborat ory w i l l sh i p a l l samp l e container s w i t h adequat e pa c ki ng mater i a l s i n c oolers t o ea c h s i t e. The c oolers w i l l al so c ont a i n c ha i n - o f
cu s t ody forms t

h a t w il l a cc ompan y t

he samp l e container s from t he l aborat o ry t o the f

i e l d and ba c k t o t he l aborat ory . Figure 1 provides a schematic that describes the quality assurance and D4 study samples to be taken at each influent and effluent sampling location o n t he day of samp l i ng at a gi v en s i t e. At each influent and effluent location seven grab samples (two quality assurance samples and five D4 study samples) will be taken. In fluent and effluent flow rates shall be recorded at the time of sampling and reported.

Figure 1. Schematic d i agram of samples taken while monitoring for D4 in influent and effluent at wastewater treatment p lants
.25

Grab samples 3, 4 and 5 will be divided to provide two duplicates for analy sis of D4. The duplicate samples shall be processed and anal yz ed as individual samples for D4. Duplicate samples are used to evaluate between
- sample variability and precision. Additionally , an aliquot of each of the three samples will be used for Total Organic Carbon (TOC) anal ys is. The TOC anal ys es shall follow procedures equivalent to APHA 1999 Part 5310, Total Organic Carbon (TOC). While this guidance (APHA 1999) provides several methods that could be used for the analy sis of TOC, the exact method and instrumentation that will be used will be determined b y the anal yt ical laboratory that will conduct the anal ys es and documented in the Study

Plan and QAPP. Grab samples 6 and 7 will serve as retain samples
. These retain samples would b e anal yz ed if a primary sample container arrives broken at the laboratory , but otherwise would be retained in a refrigerator for later analy sis if a sample becomes compromised during collection or processing. The retain samples will be kept until Quality A ssurance has been verified and may b e anal yz ed for D4 as necessary
. In addition to the study samples used to determine D4 concentrations in influent and effluent, several samples will be analyzed for quality assurance purposes. Grab samples 1 and 2 will serve as field blank

/field spike samples . The field blank /field spike sample s will be split into two parts. One part will be anal yz ed for D4 as is (field blank) and the second part will be spiked with a known amount of D4 and then analyzed (field s pike) . The field blank/field spike sample s will be used to evaluate contamination bias resulting from sample collection, processing, transport, storage and anal ys is. During each influent and effluent sampling event at a given site, two laboratory blanks w ill also be prepared. The two laboratory blanks shall be created from two samples of laboratory
- grade water having concentrations of D4 below the Li mit of Quantification ( LOQ ) and shall be taken into the field and processed like an influent or effluent sample. The laboratory blanks will be used to evaluate contamination bias resulting from collection, processing, transport, storage, and anal ys is of samples. Specific requirements for preparation, processing, and analysis of the quality assurance samples shal l be detailed in the Study

Plan and the QAPP. Sea l ed samp l e c ont a i ners w il l be pa c ked i nt o c oolers w ith b lue - ic e or wat er ic e, and t aken ba c k t o the l aborat ory or sh i pped ba c k t o the l aborat ory us i ng an overn ight express sh ip pi ng c ompan y. Al l sampl e c o ll e cti on methods and samp l e hand li ng pro c edures w il l be de t a il ed i n the Study Plan and QAPP
. **A n**  **a l** **y s**  **i s**  **o f**  **i nf** 

**l u**  **e n**  **t an**  **d e**  **ff**

**l u**  **e n**  **t s**  **a mp**  **l es**  **fo r**  **D 4**  **:** A l l i nf l uent and eff

l uent samp l es and accompanying quality assurance samples sha l l be ana l yz ed for D4 at one c ommerc i al t es t i ng l aborat ory that has appropriate expertise with the D4 analy ses to be conducted when the testing occurs , unless there are unforeseen circumstances such as lack of laboratory availability as noted in 40 C.F.R. § 790.68(b)(2)(iii). The c ommerc i al l aboratory w i l l v a l i dat e a method for t he ana l ys i s of D4 i n t

he i nf l uent and eff l uent samp l es t

hat sha l l be adapted from t he ana l y t i c al method spe c i f

i ed i n Knoerr ( 2013 ). The Knoerr ( 20 1 3 ) ana l y

t i c al method utili zes p i e c es of LDP E film to a c t as a sorbent and parti al barri er t o pre v ent l oss of ana l y t e t o t he headspa c e of t

he samp l e container
. Immediately after collection, a wat er samp l e i s p l a c ed i nto a container c o nt a i n i ng p i e c es o f L DP E , wh i ch adsorbs26

t he D 4 . I n t

he l aborat ory , t

he wat er samp l e and t

he L DPE sorbent are so lv ent ext ra ct ed and p r o c essed for ana l ys i s w i t h G C - MS. The Me t hod De t e cti on L i m i t (MD L) is the c on c entr a ti on of a c o ns ti t uent i n a samp l e, t

h a t when pr o c essed t

hrough t he c omp l e t e ana l y

t i c al method, c an be mea s ured and report ed w i t h 99 % probab i li ty t

hat i t i s g reat er t

han 0 or s t ati s ti c a ll y d i fferent from a b l ank. The M D L i s a measure of a metho d ’ s ab ili ty t o quanti fy a c ons ti t uent i n a samp l e matri x. During method de v e l opment , t he Knoerr ( 20 1 3 ) ana l y

t i c al method for D4 a ch i e v ed a matri x - spe c i f i c MD L of 0.037 μ g/ L which shall be achieved for influent and effluent testing
. The spe c i f i c l e v el of de t e c ti on sha l l be based on t

he LOQ which shall be 3 times the MDL . EPA recognizes that a laboratory may have difficulties achieving the specified MDL. In this event, the signatory companies shall seek a modification as per 40 C
. F . R . § 790.68. **C o**  **mp li**  **an ce**  **w i** **th Go o**  **d L**  **abo r**  **a t** **o r** **y Pr**  **a ct**  **i ce**  **Re qu**  **i r**  **e m**  **e n**  **t s**  **:** Al l f i e l d work re l at ed spe c i f

i c a l l y to t he c o l l e c ti on, han d li n g , and t ransfer of i nf

l uent and eff l uent samp l es should be c ondu ct ed i n a cc ordan c e w i t h U S E P A ’ s G LP r e gu l ati ons (see 4 0 C . F . R . P art 792 ). Al l ana l y t i c al work, i n c l ud i ng an al ys i s of D4 and TO C , sha l l be c onduc t ed i n a c c ordan c e w i t

h U S E P A ’ s G LP r e gu l ati ons (see 4 0 C . F . R . P art 792 ). The Q A P P sha l l be prepared a cc ord i ng t o U S E P A gu i dan c e (U S E P A 2002 ).

REFERENCES U S E P A 2013 . Was t ewater Samp l i n g , Se cti on 4 Samp l e T yp es, Se cti on 6 Manual Samp l i n g . Operati ng P ro c edure N o. S E SDPR O C - 306 - R3 . U S Env i ronment al P ro t e c ti on Ag en c y, Re g i on 4 . February , 2013 . U S E P A 2004 . N P D E S C omp li an c e Inspe cti on Manu al , Se cti on 5 B , Samp l i ng P ro c edures and T e c hn i ques . E P A 305 - X - 04 - 001 , U S Env i ronment al P ro t e c ti on Ag en c y, J ul y, 20 0 4 . Knoerr SM. 20 1 3 . N ON RE GU LA TE D S TU D Y : De v e l opment of C o l l e c t i on, S t ora g e and A na l ys i s P ro c edures for t he Quan ti f

i c ati on of D 4 , D 5 , and D6 i n Was t e Wat er Treatment P l ant E ff l uent an d Surfa c e Wat er Samp l e s . Dow C orn i ng C orporati on, H E S S t udy N o. 11 9 36 - 1 0 8 , Apri l 18 , 2013 . A P H A 1999 . S t andard Me t hods for t he E xam i nati on of Wat er and Was t ewater, P art 1 0 60 , C o l l e c ti on and P r e ser

v ati on of Samp l es. A m eri c an P ub l i c H ea l t h A sso c i ati on, A meri c an Wat er Works A sso c i ati on, Wat er Env i ronment Federat i o n . A P H A 1999 . S t andard Me t hods for t he E xam i nati on of Wat er and Was t ewater, P art 5 3 1 0 C . T o t al O r g an i c C arbon ( T O C ). A meri c an P ub l i c H e al t h A sso c i ati on, A meri c an Wat er Works A sso c i ati on, Wat er Env i ronment Federat i on. P ub l i c H ea l t h A sso c i ati on, A me ri c an Wat er Works A sso c i ati on, W at er Env i ronment Federat i o n .27

US E P A 2002 Guidance for Qua li ty A ssuran c e P r o je c t P l ans, E P A Q A/ G - 5 , prepared by : O ff i c e of Env i ronment al I nformati on, E P A (De c ember 2002 )
- h tt p : //www . ep a .g o v

/ qua l i ty / qs - do c s / g 5 - f

i na l
. pdf.28

A PPENDIX 5 - Testing Standard for the Collection, Sample Handling, Transfer and Anal ys is of Surface Water Samples for D4 **Sy n**  **o p**  **s i**  **s :**  Th i s t es t i ng s t andard prov i des gu i de li nes for t he c o l l e c ti on and ana l ys i s of env i ronment al samp l es for D4 i n support of a T es t i ng P ro gram de t a il ed i n t h i s ECA . Th i s s t andard c i t es t he requ i rement s for t

he samp l i ng of surfa c e wat er as de s cri bed i n Se cti on V I I of t he E C A and Append i c es 1 , 2 , and 3 , and i denti f i es spe c i f i c gu i de l i nes and references t hat w i l l be used i n t

he preparati on of s i t e - spe c i f i c Samp l i ng P l ans for t

he c o l l e c ti o n

/ ana l ys i s of surfa c e wat er samp l e s , wh i c h w i l l be i n c l uded i n a S t udy P l an for t

he T es t i ng P ro gram. Th is s t andard addresse s : 1 . When t o c o l l e c t surfa c e wat er samp l es 2 . Where t o c o l l e c t surfa c e wat er samp l es 3 . Spe c i al c ons i derati ons duri ng samp l e c o l l e c ti on t o av o i d samp l e c ont am i nati on 4 . H ow t o c o l l e c t and pro c ess surf a c e wat er samp l es 5 . H ow t o ana l yz e surfa c e wat er samp l es for D4 and t he appropri at e method detection limit and limit of quantification (LOQ) **Re qu**  **i r**  **eme n**  **ts fo**  **r s**  **a mp**  **li n**  **g s**  **u r**  **fa ce**  **( r**  **ece i** **v i**  **n g**  **) w**  **a te**  **r s**  **:** Append i c es 1

– 3 of t

h i s E C A s t at e that :

“ Samp l es sha l l be t aken duri ng t wo t es t i ng e v ent s at l e ast t hree ( 3 ) mo n t

hs apart . T he exa c t durati on be t

ween samp l i ng e v ent s for ea c h s i t e sha l l b e de t erm i ned i n a de t a il ed Samp l i ng P l an i n c l uded i n t he S t udy P l an and QAPP
. ”

“ Samp l es sha l l be c o l l e c t ed duri ng normal p l ant operati ons and duri ng su c h ti mes t hat eff l uent f l ow rat es from t

he was t ewater t

reatment sy stem are represent ati v e of t he normal p l ant operati ons . ”

“ Samp l es sha l l be t aken duri ng typ i c al weather c ondi ti ons and n o t unti l at l e a st t hree ( 3 ) day s af

t er an unusual weather e v ent su ch as a heav y ra i n s t orm. Samp l es sh al l be c o l l e c t ed at a ti me when t he rat e of D4 re l ease i s expe c t ed to be represent ati v e of t he typ i c al rat e of re l ease of D4 for t hat s i t e . ” **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **app r** **op r** **i a**  **te t**  **i me**  **fo r**  **s a**  **mp li**  **n g**  **e v**  **e n**  **t s**  **:** A t ea c h s i t e, t

wo samp l i ng e v ent s w i l l be undert aken t hat are s chedu l ed to be a m i n i mum of t hree mont

hs apart and duri ng normal p l ant operat i ons and weather c ondi ti ons. N ormal operati ng c ondi ti ons w i l l be es t ab li shed by c onsul ti ng w i t h t he operator of e a ch WWTP , indirect and d i re c t d i s char g e fa c ili ty. The c ri t eri a or means t hat are used by t

he f a c ili ti es to de t erm i ne normal operati ng c ondi ti ons w il l be do cument ed i n t he s i t e - spe c i f

i c Samp l i ng P l an s . C onf i r mat i on w i l l be ob t a i ned t

hat t he subje c t fa c ili ty i s o perati ng under normal c ondi ti ons29

pri or t o c ommenc i ng samp l i ng at a gi v en l o c ati o n . I n add i ti on, samp l i ng wou l d not t ake p l a c e w i t h i n t hree ( 3 ) day s of unusual weather e v ent s. The date and time of the most recent precipitation occurrence for each sampling event will be recorded. **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **l o**  **c a**  **t i**  **o n**  **f o**  **r s**  **u r** **fa ce**  **w a**  **ter s**  **a mp**  **l e**  **c o**  **ll ect**  **i on**  **:** A t ea c h s i t e, surfa c e wat er samp l es should be c o l l e c t ed at the same location and roughl y the same time as benthic organism s are collected which is described in Appendix 8 **S p**  **ec i**  **a l**  **c o**  **n s**  **i d**  **e r**  **a t**  **i on**  **s fo**  **r t**  **h e**  **s a**  **mp li**  **n g**  **a n**  **d h**  **a nd**  **li n**  **g o**  **f w**  **a ter**  **s a**  **mp l**  **es fo**  **r D**  **4 :**  c VMS materi a l s, su ch a s D 4 , are w i de l y used i n c onsumer produ ct s and may be present i n person a l c are produc t s, c ommerc i al produ ct s, and l ubri c ant s , and may be c omponent s of anti foams w i de l y used i n WWTPs . I f t hese produ c t s are used by i nd i vi dua l s duri ng an y part of t he preparati on for or d

u r i ng an y aspe c t of t

he f i e l d samp l i n g e v ent , samp l e c ont am i nati on by D4 v o l atili z i ng from t

he user c ou l d o c c ur. T o av o i d the po t e n ti al for samp l e c ont am i nati on duri ng c o l l e c ti on, pro c ess i n g , s t ora g e, and ana l ys i s for D4 i n env i ronment al matri c es, pre v ent ati v e measures should be imp l emented to the ex t ent poss i b l e i n t he f i e l d . For example, f i e l d c rew sha l l be requ i red t o refra i n from us i ng any personal c are produ ct s t hat may c ont a i n any c VMS materi al s ( e . g ., sun - b l o c k, s un - s creen, hand l o ti on, an ti persp i rant , e t c . ) wh il e prepari ng for or c onduc ti ng an y f i e l d a cti v i ti es to m i n i m i ze t he poss i b ili ty for c ont am i nati on w i t h D 4 . Spe c i f

i c requ i rement s for c o l l e c ti ng and hand l i ng surfa c e wat er samp l es a imed a t pre v enti ng samp l e c ont am i nati on by sour c es of D4 t h a t are n o t spe c i f

i c to t he WWTP or d i re c t d i s c har g e s i t e sha l l be spe c i f i ed i n t he S t udy P l an. **C o**  **ll ect**  **i o**  **n o**  **f s**  **u r**  **fa ce**  **w a**  **ter s**  **a mp**  **l es**  **fo r**  **ana l** **y s**  **i s**  **o f**  **D 4**  **:** The exa c t method for c o l l e c ti on of surfa c e wat er samp l es i s a s i t e - spe c i f i c de t erm i nati o n . During preparati on of t

he s i t e - spe c i f

i c Samp l i ng P l ans, t

he phy s i c al nat

ure (e
. g . , w i dt

h , dep t h , f l ow) of the re c e i v i ng wat er w i l l be de t erm i ned and used t o gu i de the se l e c t i on of t he appro pri at e method of samp l e c o l l e c ti on. For ea c h s i t e, c o l l e c ti on pro c edures for sur f a c e wat er samp l es sha l l be based, as appropri at e to t he chara c t eri s ti c s of t

he r e c e i v i ng wat e r , on U S E P A 199 4 (S O P # 20 1 3 , Se cti on 7 . 3 Samp l e C o l l e c ti o n , pp. 3 - 4 ) (USEPA 1994). Th i s gu i dan c e i denti f i es t he se v eral ma i n typ es of c o l l e c ti on de v i c es t h at are used to c o l l e c t aqueous samp l e s . The exa c t c o l l e c ti on meth od for surfa c e wat er samp l es w i l l be de t a il ed i n t he S t udy P l an and QAPP . Spe c i f i c requ i rement s for samp l e container preparati on, samp l e hand l i n g , samp l e preser v ati on, sh i pp i ng and s t ora g e of samp l es should be essent i a ll y t he same a c ross a l l s i t es. Immed i at e l y pri or t o ea c h samp l i ng e v ent at ea c h s i t e, t he l aboratory that w i l l ana l yz e t he samp l es sha l l prepare c l ean (new, ne v er used) gl ass samp l e container s i n suff i c i ent numbe r s for a l l surfa c e wat er samp l es t o be ana l yz ed for D 4 , for a l l qua l i ty assuran c e samp l e s , and for re t a i n samp l es. The samp l e container s w i l l be prepared by pre - washing w i t h hexane, add i ng L DPE sorbent i nto t he container s and prov i d i ng P T FE t ape to ass i st i n sea l i ng t he container s (as des cri bed i n Knoerr 20 1 3 , Samp l e C o l l e c ti on se c ti on), as we l l as prov i d i ng l a b e l s . The l aborat ory w i l l sh i p a l l samp l e container s w i th adequat e pa c ki ng mater i a l s i n c oolers to ea c h s i t e . The c oolers w i l l30

a l so c ont a i n c ha i n - o f

- cus t ody forms t

h a t w i l l a cc ompany t

he samp l e container s from the l aborat ory t o t

he f i e l d and ba c k t o t

he l aborat ory . Figure 2 provides a schematic that describes the quality assurance and D4 study samples to be taken at each surface water sampling location o n the day of samp l i ng at a gi v en s i t e. At each surface water location seven grab samples (two quality assurance samples and five D4 stud y samples) will be taken.

Figure 2. Schematic diagram of samples taken while m onitoring for D4 in surface water near wastewater treatment p lants
. Grab samp l es 3, 4 and 5 w i l l be divided to provide two dupl i c at es for ana l ys i s of D 4 . The dupl i c at e samp l es sha l l be pr oc essed and ana l yz ed as i nd iv i dual samp l es for D 4 . Dupl i c at e samp l es are used t o e v a l uat e be t wee n - samp l e v ari ab i li ty and pre c i s i on. Additionally, an aliquot of each of the three samples will be used for TOC analys is. Th e TO C ana l ys es sha l l fo l l ow pro c edures equ i v a l ent t o A P H A 199 9 P art 5 310 , T o t al O rg an i c C arbon ( T O C ). Wh i l e t h i s gu i dan c e ( APHA 1999 ) prov i des se v er al methods t hat c ou l d be used for t

he a na l ys i s of TO C , t he exa c t method and i ns t

rument ati on t

hat w i l l be used w i l l be de t e rm i ned by t he ana l y t i c al l aborat ory t

hat w i l l c ondu ct t

he ana l ys es and do cument ed i n t he Study Plan and QAPP. Grab samp l es 6 and 7 wi l l se r v e as re t a i n sam

p l es . These retain samp l es wou l d be ana l yz ed i f a pri mary

samp l e container arri v es broken at t he l aborat ory , b u t o t

h erw i se wou l d be re t a i ned i n a refri g erat or for l at er ana l ys i s i f a samp l e be c omes c omprom i sed during collection or pro c ess i n g . The retain samp l es w i l l be kept unti l Qua li ty A ssuran c e has been v eri f i ed and may

be analyzed for D4 as necessary. In addition to the study samples used to determine D4 concentrations in surface water, several samples will be analy

zed for quality

assurance purposes. Grab samples 1 and 2 will serve as field31

blank /field spike samples . The field blank /field spike sample s will be split into two parts. One part will be analy

zed for D4 as is (field blank) and the second part will be spiked with a known amount o f D4 and then analy zed (field spike)
. The field blank/field spike sample s will be used to evaluate contamination bias resulting from sampl e collection, processing, transport, storage and analysis. D uri ng ea c h surface water samp l i ng ev ent at a gi v en s i t e, t wo laboratory b l anks w i l l also be prepared. The two laboratory b l anks shall be created from t wo samp l e s of l aborat ory grade wat er hav i ng c on c ent rati ons of D 4 b e l ow t

he LOQ and sha l l be t aken i nt o t he f i e l d and pro c essed li ke a surface water samp l e. The laboratory blanks wi l l be used to e v a l uat e c o nt am i nati on b i as resu l ti ng from c o l l e c ti on, pro c ess i n g , t ransport , s tora g e, and ana l ys i s of samp l es. Spe c i f

i c requ i rement s for preparati on, pro c ess i n g , and ana l ys i s of t he quality assurance samp l e s sh al l be de t a il ed i n t he Study Plan and t

he QAPP . Sea l ed samp l e c ont a i ners w i l l be pa c ked i nt o c oolers w i t h b l ue - i c e or wat er i c e, and t aken ba c k t o t he l aborat ory or sh i pped ba c k to the l aborat ory us i ng an overn ight express sh i p p i ng c ompan y. A l l samp l e c o l l e c ti on methods and samp l e hand l i ng pro c edures w i l l be de t a i l ed i n t he Study Plan and QAPP **. A**  **n a**  **l y**  **s i**  **s o**  **f s**  **u r**  **fa ce**  **w a**  **ter s**  **a mp**  **l es**  **fo r**  **D 4**  **:** A l l surfa c e wat er samp l es and a cc ompanyi ng qua lity a s suran c e samp l es sha l l be ana l y z ed for D4 at one c ommer ci al t es ti ng l aborat o ry that has appropriate expertise with the D 4 anal ys es to be conducted when the testing occurs , unless there are unforeseen circumstances such as lack of laboratory

availability as noted in 40 C.F.R. § 790.68(b)(2)(iii) . The commercial laboratory will validate a method for the analy sis of D4 i n the surfa c e wat er samp l es that sha l l be adapted from the ana l y tic al method spe ci f

i ed i n Knoerr ( 2013 ). T he Knoerr ( 2013 ) ana l y tic al method utili zes p i e c es of LDPE film t o a c t as a sorbe nt and parti al barri er t o pre v ent l oss of ana l y

t e t o the headspa c e of the samp l e container
. Imm ed i at e l y af t er c o ll e cti on, a wat er samp l e i s p oured i nt o a container c ont a i n i ng p i e c es of L DP E , wh ic h adsorbs the D 4 . In th e l aborat ory , the wat er samp l e and the LDPE sorbent are solvent extracted and processed for anal ys is with GC
- MS. The MDL is the c on c ent

r a ti on of a c o n s ti t

uent i n a samp l e, t

h a t when pro c essed t

hrough t he c omp l e t e ana l y

t i c al method, c an be mea s ured and report ed w i t h 99 % probab i li ty t

hat i t i s great er t han 0 or s t ati s ti c a ll y d i fferent from a b l ank. The M D L i s a measure of a metho d ’ s ab ili ty t o quanti fy a c ons t i t uent i n a samp l e matri x. During method de v e l opment , t he Knoerr ( 20 1 3 ) ana l y

t i c al method for D4 a ch i e v ed a matri x - spe c i f i c MD L of 0 . 03 7 μ g/ L and which s hall be achieved for surface water testing
. The spe c i f i c l e v el of de t e c ti on sha l l be based on t he LOQ which shall be 3 times the MDL . EPA recognizes that a laboratory may have difficulties achieving the specified MDL . In this event, the signatory companies shall seek a modification as per 40 C . F . R . § 790.68. **C o**  **mp li**  **an ce**  **w i** **th Go o**  **d L**  **abo r**  **a t** **o r** **y Pr**  **a ct**  **i ce**  **Re qu**  **i r**  **e m**  **e n**  **t s**  **:** Al l f i e l d work re l at ed spe c i f

i c a l l y to t he c o l l e c ti on, han d li n g , and t ransfer of surfa c e wat er samp l es should be c ond

u ct ed i n a c c ordan c e w i t

h U S E P A ’ s G L P r e gu l ati ons (see 4 0 C . F . R . P art 792 ). Al l ana l y

t i c al work, i n c l ud i ng ana l y s i s of D4 and TO C , sha l l be c o nd u ct ed i n32

a c c ordan c e w i t

h U S E P A ’ s G LP re gu l ati ons (see 4 0 C . F . R . P art 7 9 2 ). The Q A P P sha l l be prepared a c c ord i ng to U S E P A gu i dan c e (U S E P A 2002 ). REFERENCES U S E P A 2006 . C omp il ati on of E P A M i x i ng Z one Do cument s, Model i ng Do cument s, pp. 9 - 13 . E P A 823 - R - 06 - 0 0 3 , Ju l y, 2006 . U S E P A 1994 . Surfa c e Wat er Samp l i n g , Se cti on 7 . 3 Samp l e C o l l e c ti on. U . S. Env i ronment al P ro t e c ti on Ag en c y, S O P #: 2 01 3 , 11 / 1 7 / 94 , R EV. #: 0 . 0 Knoerr S M , Durham JA . 2013 . N ON RE GU LA TE D S TU D Y : De v e l opment of C o l l e c ti on, S t ora g e and A na l ys i s P ro c edures for t he Quanti f

i c ati on of D 4 , D 5 , and D6 i n Was t e Wa t er Treatment P l ant E ff

l uent and Surfa c e Wat er Samp l es. Dow C orn i ng C o r porati on, H E S S t

udy N o. 11 9 36 - 1 0 8 , Apri l 18 , 2013 . A P H A 1999 . S t andard Me t hods for t he Exam i nati on of Wat er an d Was t ewater, P art 5 3 1 0 C . T o t al O r g an i c C arbon ( T O C ). A meri c an P ub l i c H e al t h A sso c i ati on, A meri c an Wat er Works A sso c i ati on, Wat er Env i ronment Federat i on. US EPA 2002 . Guidance for Qua li ty A ssuran c e P r o je c t P l ans, E P A Q A/ G - 5 , prepared by : O ff i c e of Env i ronment al I nformati on, E P A - h tt p : //www . ep a .g o v/ qua l i ty

/ qs - do c s / g 5 - f

i na l
. pdf.33

A PPENDIX 6 - Testing Standard for the Collection, Sample Handling, Transfer and Anal ys is of Biosolids Samples for D4 **Sy n**  **o p**  **s i**  **s :**  Th i s t es t i ng s t andard prov i des gu i de li nes for t he c o l l e c ti on and ana l ys i s of env i ronment al samp l es for D4 i n support of a T es t i ng P ro gram de t a il ed i n t h i s ECA . Th i s s t andard c i t es t he requ i rement s for t

he samp l i ng of b i osol i ds as des c ri bed i n Se cti on V I I of t he E C A and Append i c es 2 and 3 and i denti f i es spe c i f i c gu i de l i nes and references t hat w i l l be used i n t

he preparati on of s i t e - spe c i f i c Samp l i ng P l ans for t

he c o l l e c ti o n

/ ana l ys i s of b i osol i ds s a

mp l es, wh i c h w i l l be i n c l uded i n a S t udy P l an and QAPP for t

he T es t i ng P ro gram. The s t andard addresse s : 1 . When t o c o l l e c t b i osol i ds samp l es 2 . Where t o c o l l e c t b i osol i ds samp l es 3 . Spe c i al c ons i derati ons duri ng samp l e c o l l e c ti on t o av o i d samp l e c ont am i nati on 4 . H ow t o c o l l e c t and pro c ess b i osol i ds samp l es 5 . H ow t o ana l yz e b i osol i ds samp l es for D4 and t he appro pri at e method detection limit and limit of quantification **Re qu**  **i r**  **eme n**  **ts fo**  **r s**  **a mp**  **li n**  **g b**  **i o**  **s o**  **li d**  **s :**  Append i c es 1 - 3 of t

h i s E C A s t at e t

hat :

“ Samp l es sha l l be t aken duri ng t wo t es t i ng e v ent s at l e ast t hree ( 3 ) mo n t

hs apart . T he exa c t durati on be t

ween samp l i ng e v ent s for ea c h s i t e sha l l b e de t erm i ned i n a de t a il ed Samp l i ng P l an i n c l uded i n t he S t udy P l an and QAPP
. ”

“ Samp l es sha l l be c o l l e c t ed duri ng normal p l ant operati ons and duri ng su c h ti mes t hat eff l uent f l ow rat es from t

he was t ewater t

reatment sy stem are represent ati v e of t he normal p l ant operati ons . ”

“ Samp l es sha l l be t aken duri ng typ i c al weather c ondi ti ons and n o t unti l at l east t hree ( 3 ) day s af

t er an unusual weather e v ent su ch as a heav y ra i n s t orm. Samp l es sh al l be c o l l e c t ed at a ti me when t he rat e of D4 re l ease i s expe c t ed to be represent ati v e of t he typ i c al rat e of re l ease of D4 for t hat s i t e . ” **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **app r** **op r** **i a**  **te t**  **i me**  **fo r**  **s a**  **mp li**  **n g**  **e v**  **e n**  **t s**  **:** At ea c h site, two sampling events will be undertaken that are scheduled to be a minimum of three months apart and during normal plant operations and weather conditions. Normal operating conditions will be es t ablished by consulting with the operator of each WWTP to be tested. The criteria or means that are used by the facilities to determine normal operating conditions will be document ed in the site
- specific Sampling Plans. Confirmation will be obtained that the sub

j ect facility is operating under normal condi tions prior to commencing34

sampling at a given location. Inaddition, sampling would not take place within three ( 3 ) day s of unusual weather events. **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **l o**  **c a**  **t i**  **o n**  **f o**  **r b**  **i o**  **s o**  **li d**  **s s**  **a mp**  **l e**  **c o**  **l l**  **ect i**  **on :**  A t ea c h s i t e , t

he chosen l o c ati on for c o l l e c ti on of b i os o li ds samp l es s hall be immediatel y after dewatering before onsite storage and shall be established in the site specific S ampling P lans , as practicable
. **S p**  **ec i**  **a l**  **c o**  **n s**  **i d**  **e r**  **a t**  **i on**  **s fo**  **r t**  **h e**  **s a**  **mp li**  **n g**  **a n**  **d h**  **a nd**  **li n**  **g o**  **f b**  **i o**  **s o**  **li d**  **s s**  **a mp**  **l es**  **fo r**  **D 4**  **:** c VMS materi a l s, su ch a s D 4 , are w i de l y used i n c onsumer produ ct s and may be present i n personal c are p r odu c t s, c ommerc i al produ ct s, and l ubri c ant s , and may be c omponent s of anti foams w i de l y used i n WWTPs . I f t hese produ c t s are used by i nd i vi dua l s duri ng an y part of t he preparati on for or d

u r i ng an y aspe c t of t

he f i e l d samp l i ng e v ent , samp l e c ont am i nati on by D4 v o l atili z i ng from t

he user c ou l d o c c ur. T o av o i d the po t e n ti al for samp l e c ont am i nati on duri ng c o l l e c ti on, pro c ess i n g , s t ora g e, and ana l ys i s for D4 i n env i ronment al matri c es, pre v ent ati v e measures should be imp l emented to the ex t ent poss i b l e i n t he f i e l d. For example, f i e l d c rew sha l l be requ i red t o refra i n from us i ng any personal c are produ ct s t hat m a y c ont a i n c VMS materi a l s ( e . g ., sun - b l o c k, sun - s creen, hand l o ti on, an t i persp i rant s, e t c . ) wh il e prepari ng for or c onduc ti ng an y f

i e l d a cti v i ti es to m i n i m i ze t he poss i b il i ty for c o nt am i nati on w i t h D 4 . Spe c i f i c requ i rement s for c o l l e c ti ng and hand l i ng b i o s o l i ds sam p l es a i med at pre v enti ng s a mp l e c ont am i nati on by sour c es of D 4 that are n o t spe c i f i c t o t he WWTP sha l l be spe c i f i ed i n t he S t udy P l an and QAPP
. **C o**  **ll ect**  **i o**  **n o**  **f b**  **i o**  **s o**  **li d**  **s s**  **a mp**  **l es**  **fo r**  **ana l** **y s**  **i s**  **o f**  **D 4**  **:** The exa c t method for c o l l e c ti on of b i osol i ds samp l es i s a s i t e - spe c i f i c de t erm i nati on. During preparati on of t

he s i t e - spe c i f

i c Samp l i ng P l ans, t

he g eneral c ons i s ten c y of the b i osol i ds w i l l be es t ab li s hed
. The c ons i s t en c y of t he b i osol i ds w i l l gu i de t

he methods used for samp l i n g . For ea c h s i t e, c o ll e c ti on pro c edures for b i osol i ds samp l es sha l l be based, as appropri at e t o t he c hara c t eri s ti c s of t

he b i osol i ds, on t e c hn i ques des c ri bed i n U S E P A 198 9 (Se c ti on 2 . 2 Samp l e P o i nt Se l e c ti on and Se c ti on 2 . 3 S amp l e C o ll e c ti on, pp. 2 - 4 t o 2 - 1 4 ). The gu i dan c e i denti f i es samp l e c o l l e c ti on de v i c es and t e c hn i ques for c o l l e c ti on of subsamp l es t hat w i l l make up c ompos i t e samp l es. The e x a c t c o l l e c ti on method for b i osol i ds samp l es w i l l be de t a i l ed i n t he S t udy P l an and QAPP
. Spe c i f i c requ i rement s for samp l e c ont a i ner preparati on, samp l e hand l i n g , samp l e prese r v ati on, sh i pp i ng and s t ora g e of samp l es should be essent i a ll y t he same a c ross a l l s i t es. Immed i at e l y pri or t o ea c h samp l i ng e v ent at ea c h s i t e, t he l aboratory that w i l l ana l yz e t he samp l es sha l l prepare c l ean (new, ne v er used) pre - we i ghed g l ass samp l e c ont a i ners i n suff i c i e n t numbers for a l l b i osol i ds samp l e s t o be ana l yz ed f or D 4 , for a l l qua l i ty assuran c e samp l es, and for re t a i n samp l es. The samp l e c ont a i ners w i l l be prepared by pre - wash i ng w i t h hexane, prov i d i ng P T FE t ape t o a s s i st i n sea l i ng the c ont a i ners, as we l l as prov i d i ng l abe l s . The l aboratory w i l l sh i p a l l samp l e c ont a i ners w i t

h adequat e pa c ki ng materi a l s i n c oolers to ea c h s i t e. The c oolers w i l l a l so35

c ont a i n c ha i n - o f

- c us t ody fo rms t

hat w i l l a cc ompany t

he samp l e c ont a i ners from t he l aborat ory t o t he f i e l d and b a c k t o t

he l abor at ory . Figure 3 provides a schematic that describes the qualit y assurance and D4 study

samples to be taken at each biosolids sampling location on the day of sampling at a given site. At each biosolids location , seven composited biosolids samples (two qualit y assurance samples and five D4 study samples) will be taken. During ea c h samp l i ng ev ent for b i osol i ds at a gi v en s i t e , all quality assurance samples and D4 samples w i l l be prepared as des c ri bed i n P owe l l and Woodburn ( 20 09 )
.

Figure 3. Schematic diagram of samples taken while m onitoring for D4 in biosolids near wastewater treatment p lants
. C ompos i t ed b i osol i ds samp l es 3, 4 and 5 will be divided to provide two duplicates for analys is of D4
. The dup li c at e samp l e s sha l l be pro c essed and ana l yz ed as i nd iv i dual samp l es for D 4 . Dupl i c at e samp l es are u sed t o e v a l uat e be t wee n - samp l e v ari a

b i l i ty and pre c i s i o n . In add i ti on, a separat e a li quot sha l l be t aken from ea c h of the three b i osol i ds samp l e s and separat e l y s t ored for ana l ys i s of t o t al or g an i c c ar b on and wat er c on t ent . F o l l ow i ng t he g ener al pro c edures of P owe l l 2010 , the add i ti onal a li quo t s sha l l be ana l yz ed by c arbon c ou l o m e try or an equ i v a l ent method for t o t al c ar

b on, t o t al i norgan i c c arbon, and t o t al or g an i c c arbo n , and l os s - o n - ig n i ti on for t o t al wat er c o n t ent an d t o t al or g an i c matt er c ont e n t . C ompos i t ed b i osol i ds samples 6 and 7 will serve as retain samples
. These retain s a mp l es wou l d be ana l yz ed i f a pr i mary samp l e c ont a i ner arri v es at t

he l aborat ory c omprom i sed or b r oken, but o t herw i se wou l d be re t a i ned i n a refri g erat or for l at er ana l ys i s i f a samp l e be c om e s c o m prom i sed duri ng collection or pro c ess i n g . The retain samp l es w i l l be kept unti l Qua l i ty A ssur a n c e has been v eri f

i ed and may be anal yz ed for D4 as necessary
.36

In addition to the study

samples used to determine D4 concentrations in biosolids, several samples will be anal yz ed for quality assurance purposes. C ompos i t ed b i osol i ds samp l es 1 and 2 sha l l be split, one half of each sample shall be sp i ked i n t he f i e l d wi t h a known amount of D 4 . The f

i e l d sp i ked b i osol i ds samp l es w i l l be used to e v a l uat e l oss of D 4 duri ng c o l l e c ti on, pro c ess i n g , t

ransport , s t ora g e, and ana l ys i s of samp l e s , and to e v a l uat e ana l y t i c al b i as . Two reference sed i ment samp l e s hav i ng c on c ent r a ti ons of D4 be l ow t

he LOQ for t

h i s matri x sha l l be t aken i nt o t

he f i e l d and pro c essed li ke b i osol i ds samp l e s . Reference sed iment w i l l be used be c ause of t

he expe c t ati on t

hat an y WWTP b i osol i ds may c ont a i n D 4 . The reference s e d i ment samp l e s wi l l be used t o e v a l uat e c ont am i nati on b i as resu l ti ng from c o l l e c ti on, pro c ess i n g , t ransport , s t ora g e, and ana l ys i s of samp l es. Specific requirements for preparation, processing, and anal ys is of the quality assurance samples shall be detailed in the Study Plan and the QAPP. Sealed sample containers will be packed into coolers with blue
- ice or water ice, and taken back to the lab oratory

or shipped back to the laboratory using an overnight express shipping compan y. All sample collection methods and sample handling procedures will be detailed in the Study Plan and QAPP
. **A n**  **a l** **y s**  **i s**  **o f**  **Bi o**  **s o**  **li d**  **s S**  **a mp**  **l es**  **fo r**  **D 4**  **:** A l l b i os o li ds samp l es and a cc ompan yi ng qua l i ty assur a n c e samp l es sha l l be ana l yz ed for D4 a t one c ommer c i al t es t i ng l aborat o ry that has appropriate expertise w ith the D 4 analyses to be conducted when the testing occurs , unless there are unforeseen circumstances such as lack of laboratory

availability as noted in 40 C.F.R. § 790.68(b)(2)(iii). The c ommerc i al l aborato ry w i l l v a l i dat e a method for t

he ana l ys i s of D4 i n t

he b i osol i ds samp l es t

hat sha l l be adapted from t he ana l y t i c al method used in Powell (2010) The MDL is the c o n c entr a ti on of a c o ns ti t uent i n a samp l e, t

h a t when pro c essed t

hrough t he c omp l e t e ana l y

t i c al method, c an be mea s ured and report ed w i t h 99 % probab i li ty t

hat i t i s great er t han 0 or s t ati s ti c a ll y d i fferent from a b l ank. The M D L i s a measure of a metho d ’ s ab ili ty to quanti fy a c ons ti t

uent i n a samp l e matri x. Powell (2010) determined an MDL up to 3.7 n g/ g (wet we i ght , ww) for sediment which shall be applied for biosolids. The spe c i f i c l e v el of de t e c ti on sha l l be based on t

he LOQ which shall be 3 times the MDL . All measurements of D4 concentration in biosolids shall include sufficient information to perform a wet weight to dry weight conversion and shall report concentrations in terms of dry weight. EPA recognizes that a laboratory may

have difficulties achieving the specified MDL. In this event, the signatory companies shall seek a modification as per 40 C
. F . R . § 790.68. **C o**  **mp li**  **an ce**  **w i** **th Go o**  **d L**  **abo r**  **a t** **o r** **y Pr**  **a ct**  **i ce**  **Re qu**  **i r**  **e m**  **e n**  **t s**  **:** Al l f i e l d work re l at ed t o the c o l l e c ti on, hand l i n g , and t r ansfer of b i osol i ds samp l es should be c ondu ct ed i n a cc ordan c e w i t h U S E P A ’ s G L P r e gu l ati on s (see 4 0 C . F . R . P art 7 9 2 ). Al l ana l y t i c al work, i n c l ud i ng ana l y s i s of D4 and TO C , sha l l be c onduc t ed i n a c c ordan c e w i t h U S E P A ’ s G L P r e gu l ati o n s (see 4 0 C . F . R . P art 792 ). The Q A P P sha l l be prepared a cc ord i ng to U S E P A gu i d a

n c e (U S E P A 2002 ).37 REFERENCES U S E P A ( 1989 ): WWTP S l ud g e Samp l i ng and Ana l ys i s Gu i dan c e Do cument , Se cti on 2 . 2 Samp l e P o i nt Se l e c ti on and Se cti on 2 . 3 Samp l e C o l l e c ti o n . E P A 833 - B - 8 9 - 10 0 , Au gus t , 1989 . Powell, D.E. 2010. Bioaccumulation and Trophic Transfer of C yclic Volatile Methylsiloxane (cVMS) Materials in the Aquatic Marine Food Webs of the Inner and Outer Oslofjord, Norway. HES Study No: 11060 - 108. Health and Environmental Sciences, Dow Corning Corporation, Auburn, MI. P owe l l D E , Woodburn KB. 2 0 09 . Trophic D i l uti on of C yc li c Vo l atil e Me thyl s i l oxane ( c VMS) Mat er i a l s i n a T emperat e Freshwat er L ake. Dow C orn ing C orporati on, H E S S t u dy N o. 1077 1 - 108 . US E P A 2002. Guidance for Qua li ty A ssuran c e P r o je c t P l ans, E P A Q A/ G - 5 , prepared by : O ff i c e of Env i ronment al I nformati on, E P A (De c ember 2002 )
- h tt p : //www . ep a .g o v

/ qua l i ty / qs - do c s / g 5 - f i na l
. pdf.38

APPENDIX 7 - Testing Standard for the Collection, Sample Handling, Transfer and Anal ys is of Sediment Samples for D4 **Sy n**  **o p**  **s i**  **s :**  Th i s t es t i ng s t andard prov i des d i re c ti on for t he c o l l e c ti on and ana l ys i s of env i ronment al samp l es for D4 i n support of a T es t i ng P ro gram de t a il ed i n t h i s ECA . Th i s s t andard c i t es t he requ i rement s for t

he samp l i ng of sed i ment as des c ri bed i n Se cti on V I I of t he E C A and Append i c es 1 , 2 , and 3 , and i denti f i es spe c i f i c gu i de l i nes and references t hat w i l l be used i n t

he preparati on of s i t e - spe c i f i c Samp l i ng P l ans for t

he c o l l e c ti o n

/ ana l ys i s of sed i m ent samp l es, wh i c h w i l l be i n c l uded i n a S t udy P l an and QAPP for t

he T es t i ng P ro gram. The s t andard addresse s : 1 . When t o c o l l e c t sed i ment samp l es 2 . Where t o c o l l e c t sed i ment samp l es 3 . Spe c i al c ons i derati ons duri ng samp l e c o l l e c ti on t o av o i d samp l e c ont am i nati on 4 . H ow t o c o l l e c t and pro c ess sed i ment samp l es 5 . H ow t o ana l yz e sed i ment samp l es for D4 and t he app r opri at e method detection limit and limit of quantification **Re qu**  **i r**  **eme n**  **ts fo**  **r s**  **a mp**  **li n**  **g s**  **e d**  **i ment**  **s :**  Append i c es 1 - 3 of t

h i s E C A s t at e t

h a t :

“ Samp l es sha l l be t aken d uri ng t wo t es t i ng e v ent s at l e ast t hree ( 3 ) mo n t

hs apart . T he exa c t durati on be t

ween samp l i ng e v ent s for ea c h s i t e sha l l b e de t erm i ned i n a de t a il ed Samp l i ng P l an i n c l uded i n t he S t udy P l an and QAPP
. ”

“ Samp l es sha l l be c o l l e c t ed duri ng normal p l ant operati ons and d uri ng su c h ti mes t

hat eff l uent f l ow rat es from t

he was t ewater t

reatment sy stem are represent ati v e of t he normal p l ant operati ons . ”

“ Samp l es sha l l be t aken duri ng typ i c al weather c ondi ti ons and n o t unti l at l east t hree ( 3 ) day s af

t er an unusual weather e v ent su ch as a heav y ra i n s t orm. Samp l es sh al l be c o l l e c t ed at a ti me when t he rat e of D4 re l ease i s expe c t ed to be represent ati v e of t he typ i c al rat e of re l ease of D4 for t hat s i t e . ” **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **app r** **op r** **i a**  **te t**  **i me**  **fo r**  **s a**  **mp li**  **n g**  **e v**  **e n**  **t s**  **:** A t ea c h s i t e, t

wo samp l i ng e v ent s w i l l be undert aken t hat are s chedu l ed to b e a m i n i mum of t hree mont

hs apart and duri ng normal p l ant operat i ons and weather c ondi ti ons. N ormal operati ng c ondi ti ons w i l l be es t ab li shed by c onsul ti ng w i t h t he operator of e a ch WWTP , indirect discharge facility and d i re c t d i s char g e fa c ili ty. The c ri t eri a or means t hat are used by t he f a c ili ti es t o de t erm i ne normal operati ng c ondi ti ons w il l be do cument ed i n t he s i t e - spe c i f

i c Samp l i ng P l an s . C onf

i r mat i on w i l l be ob t a i ned t

hat t he subje c t fa c ili ty i s operati ng under3 9

normal c ondi ti ons pri or t o c ommenc i ng samp l i ng at a gi v en l o c ati o n . I n add i ti on, samp l i ng wou l d not t ake p l a c e w i th i n t hree ( 3 ) day s of unusual weather e v ent s. **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **l o**  **c a**  **t i**  **o n**  **f o**  **r s**  **e d**  **i ment**  **s a**  **mp l**  **e c**  **o ll**  **ect i**  **on :**  A t ea c h s i t e, sed i ment samp l es from t he re c e i vi ng wat er body sha l l be c o l l e c t e d at t he same l o c ati on where bent

h i c or g an i sms are c o l l e c t ed for D4 ana l ys i s as described in Appendix 8
. **S p**  **ec i**  **a l**  **c o**  **n s**  **i d**  **e r**  **a t**  **i on**  **s fo**  **r t**  **h e**  **s a**  **mp li**  **n g**  **a n**  **d h**  **a nd**  **li n**  **g o**  **f s**  **e d**  **i ment**  **s a**  **mp l**  **es fo**  **r D**  **4 :**  c VMS materi a l s, su ch a s D 4 , are w i de l y used i n c onsumer produ ct s and may be present i n personal c are produc t s, c ommerc i al produ ct s, and l ubri c ant s , and may be c omponent s of anti foams w i de l y used i n WWTPs . I f t hese produc t s are used by i nd i vi dua l s duri ng an y part of t he preparati on for or d

u ri ng an y aspe c t of t

he f i e l d samp l i ng e v ent , samp l e c ont am i nati on by D4 v o l atili z i ng from t

he user c ou l d o c c ur. T o av o i d the po t e n ti al for samp l e c ont am i nati on duri ng c o l l e c ti on, pro c ess i n g , s t ora g e, and ana l ys i s for D4 i n env i ronment al matri c es, pre v ent ati v e measures should be imp l emented to the ex t ent poss i b l e i n t he f i e l d. For example, f i e l d c rew sha l l be requ i red t o refra i n from us i n g any personal c are produ ct s t hat may c ont a i n c VMS materi a l s ( e . g ., sun - b l o c k, sun - s creen, hand l o ti on, an t i persp i rant , e t c . ) wh il e prepari ng for or c onduc ti ng an y f

i e l d a cti v i ty t o m i n i m i ze t he poss i b i l i ty for c o nt am i nati on w i t h D 4 . Spe c i f i c requ i rement s for c o l l e c ti ng and hand l i ng sed i ment samp l es a i m ed at pre v enti ng samp l e c ont am i nati on by sour c es of D4 t h a t are n o t spe c i f

i c t o t he WWTP or d i re c t d i s c har g e s i t e sha l l be spe c i f

i ed i n the S t

udy P l an and QAPP
. **C o**  **ll ect**  **i o**  **n o**  **f s**  **e d**  **i ment**  **s a**  **mp l**  **es fo**  **r ana**  **l y**  **s i**  **s o**  **f D**  **4 :**  The exa c t method for c o l l e c ti on of sed i ment samp l es i s a s i t e - spe c i f i c de t erm i nati on. During preparati on of t

he s i t e - spe c i f

i c Samp l i ng P l ans, t

he phy s i c al nat

ure (e
. g . , w i dt

h , dep t h , f l ow) of the re c e i v i ng wat er w i l l be de t erm i ned and used t o gu i de t he se l e c ti on of the appropri at e method of samp l e c o l l e c ti on. For ea c h s i t e, c o l l e c ti on pr o c edures for sed i ment samp l es sha l l be based, as appropri at e to t

he c hara c t eri s ti c s of t

he re c e i v i ng wat e r , on t e c h n i ques des cri bed i n U S E P A 199 4 (S O P # 20 1 6 , S e cti ons 2 - 5 , 7 , pp. 1 - 7 ) and U S E P A ( 2001 ) ( C hap t er 3 , pp. 3 - 1 to 3 - 1 7 )
. Th i s gu i dan c e i denti f

i es t he se v eral m ai n types of c o l l e c ti on de v i c es t hat are used to c o l l e c t sed i ment samp l e s . The exa c t c o l l e c ti on method for sed i ment s a mp l es w i l l be de t a i l ed i n t he S t udy P l an and QAPP
. Spe c i f i c requ i rement s for samp l e c ont a i ner preparati on, samp l e hand l i n g , samp l e prese r v ati on, sh i pp i ng and s t ora g e of samp l es should be essent i a ll y t he same a c ross a l l s i t es. Immed i at e l y pri or t o ea c h samp l i ng e v ent at ea c h s i t e, t he l aboratory that w i l l ana l yz e t he samp l es sha l l prepare c l ean (new, ne v er used) pre - we i ghed g l ass samp l e c ont a i ners i n suff i c i e n t numbers for a l l sed i ment samp l es to be ana l yz ed for D 4 , for a l l qua l i ty assuran c e samp l es, and for re t a i n samp l es. The samp l e c ont a i ners w i l l be prepared by pre - washing wi t h hexane, prov i d i ng P T FE t ape t o ass i st i n sea l i ng the c ont a i ners, as we l l as prov i d i ng l abe l s . The l aboratory w i l l sh i p a l l samp l e c ont a i ners w i t

h adequat e p a c ki ng materi a l s i n c oolers to ea c h s i t e. The c oolers w i l l a l so c ont a i n c ha i n - o f

- c us t ody fo rms t

hat w i l l a cc ompany t

he samp l e c ont a i ners from t he l aborat ory t o t he f i e l d and b a c k to t

he l abor atory .40

Figure 4 provides a schematic that describes the qualit y assurance and D4 study

samples to be taken at each sediment sampling location on the day of sampling at a given site. At each sediment location seven sediment samples (two qualit y assurance samples and five D4 study samples) will be taken from t he depos i ti on zone nearest t he fa c ili ty was t e w at er out fa l l re l ease po i nt , i n a cc or d an c e w i t

h t he samp l e c o l l e c ti on pro c edures set out i n t he S t udy P l an.

Figure 4. Schematic diagram of samples taken while m onitoring for D4 in sediment near wastewater treatment p lants
. Sample collection, storage and preparation will follow Powell and Woodburn ( 200 9 ) with each sample being placed in a plastic bag, homogenized , then placed directl y into a glass jar, and then capped. S ediment samples 3 , 4 and 5 will be divided to provide two duplicates for analy sis of D4
. The duplicate samples shall be processed and anal yz ed as individual samples for D4. Dupl i c at e samp l es are u sed t o e v a l uat e be t we e n - samp l e v ari ab i li ty and pre c i s i o n . A f t er ea c h sed i ment samp l e i s homo g en i z ed i n t he f i e l d, a separat e a li quot sha l l be t aken from ea c h samp l e and separat e l y s t ored for ana l ys i s of t o t al or g an i c c arbon ( TO C ) and wat er c o n t ent . Fo l l ow i ng t he g eneral pro c edures of P owe l l and Woodburn ( 200 9 , C hara c t eri zati on of Sed i ments, p. 10 ) t hese add i ti onal samp l es sha l l be ana l yz ed by c arbon c ou l ome try or an equ i v a l ent method for t o t al c arbo n , t o t al i norgan i c c arbon, and t o t al or g an i c c arbo n , and l os s - o n - ig n i ti on for t o t al wat er c ont e n t and t o t al or g an i c matt er c ont ent . S ed i ment samp l es 6 and 7 w i l l serve as re t a i n samp l e s . These retain samp l es wou l d be ana l yz ed i f a pri mary samp l e c ont a i ner arri v es broken at t he l aborat ory , but o t

herw i se wou l d be re t a i ned i n a refri g erat or for l at er ana l ys i s i f a samp l e be c omes c omprom i sed duri ng collection or pro c ess i n g . The retain samp l es w i l l be kept unti l Qua l i ty A ssuran c e has been v eri f i e d and may

be analy zed for D4 as necessary.41

In addition to the study

samples used to determine D4 concentrations in sediment, several samples will be anal yz ed for quality assurance purposes. S ediment samp l es 1 and 2 sha l l be split, one half of each sample shall be sp i ked i n t he f i e l d wi t h a known amount of D 4 . The f i e l d sp i ked sediment samp l es w i l l be used to e v a l uat e l oss of D 4 duri ng c o l l e c ti on, pro c ess i n g , t ransport , s t ora g e, and ana l ys e s of samp l e s , and to e v a l uat e ana l y t i c al b i as. Spe c i f

i c requ i re m ent s for preparat i on, pro c ess i n g , and ana l ys i s of f i e l d b l anks, f

i e l d sp i kes, and dupl i c at e samp l es sh al l be de t a il ed i n t he S t udy P l an and t

he Q A PP . Two reference sed i ment samp l e s hav i ng c on c ent

r a ti ons of D4 be l ow t

he LOQ for t

h i s matri x sha l l be t aken i nt o t he f i e l d and pro c essed li ke sediment samp l e s . The reference s e d i ment samp l e s wi l l be used to e v a l uat e c ont am i nati on b i as resu l ti ng from c o l l e c ti on, pro c ess i n g , t ransport , s t ora g e, and ana l ys i s of samp l es. Sea l ed samp l e c ont a i ners w i l l be pa c ked i nt o c oolers w i t h b l ue - i c e or wat er i c e and t aken ba c k t o t he l aboratory or sh i pped ba c k t o the l aborat ory us i ng an overn ight express sh i p p i ng c ompan y. A l l samp l e c o l l e c ti on methods and samp l e hand l i ng pro c edures w i l l be de t a i l ed i n t he S t udy P l an and QAPP
. **A n**  **a l** **y s**  **i s**  **o f**  **S e**  **d i**  **ment S**  **a mp**  **l es**  **fo r**  **D 4**  **:** Al l se di ment samp l es and a cc ompan yi ng qua l i ty assur a n c e samp l es sha l l be ana l yz ed for D4 a t one c ommer c i al t es t i ng l aborat o ry that has approp riate expertise with D4 analy se s to be conducted when the testing occurs , unless there are unforeseen circumstances such as lack of laboratory

availability as noted in 40 C.F.R. § 790.68(b)(2)(iii). The c ommerc i al l aborat o ry w i l l v a l i dat e a method for t

he ana l ys i s of D4 i n sed i ment samp l es t hat sha l l be adap t ed from t he ana l y t i c al method spe c i f

i ed i n P owe l l (2010). The MDL is the c on c ent

r a ti on of a c o ns ti t

uent i n a samp l e, t

h a t when pro c essed t

hrough t he c omp l e t e ana l y

t i c al method, c an be mea s ur ed and report ed w i t h 99 % probab i li ty t

hat i t i s great er t han 0 or s t ati s ti c a ll y d i fferent from a b l ank. The M D L i s a measure of a metho d ’ s ab ili ty to quanti fy a c ons ti t

uent i n a samp l e matri x. The method for anal yz ing D4 in sediment reported b y Powell ( 2010 ) is deemed the appropriate method for achieving an MDL up to 3.7 ng/g (wet weight , ww) and shall be achieved for sediment. The specific level of detection shall be based on the L OQ which shall be 3 times the MDL . All measurements of D4 concentration in sed iment shall include sufficient information to perform a wet weight to dry weight conversion and shall report concentrations in terms of dry weight. EPA recognizes that a laboratory may have difficulties achieving the specified MDL. In this event, the signatory companies shall seek a modification as per 40 C
. F . R . § 790.68. **C o**  **mp li**  **an ce**  **w i** **th Go o**  **d L**  **abo r**  **a t** **o r** **y Pr**  **a ct**  **i ce**  **Re qu**  **i r**  **e m**  **e n**  **t s**  **:** Al l f i e l d work re l at ed spe c i f

i c a l l y to t he c o l l e c ti on, han d li n g , and t ransfer of sed i ment samp l es should be c onduc t ed i n a c c ordan c e w i t h U S E P A ’ s G LP r e gu l ati ons (see 4 0 C . F . R . P art 792 ). Al l ana l y t i c al work, i n c l ud i ng ana l ys i s of D4 and li p i d c ont ent , sha l l be c o n du c t ed i n42

a c c ordan c e w i t

h U S E P A ’ s G LP r e gu l ati ons (see 4 0 C .F. R . P art 792 ). The Q A P P sha l l be prepared a cc ord i ng t o U S E P A gu i dan c e (U S E P A 2002 ).43 REFERENCES U S E P A 1994 . Sed i ment Samp l i n g , Se c ti ons 2 - 5 and 7 . U . S. Env i ronment al P ro t e c ti on Ag en c y, S O P #: 201 6 , 1 1 / 17 / 94 , REV. #: 0 . 0

– See att a ched U S E P A 2001 . Me t

hods for C o l l e c ti on, S tora g e and Manipu l ati on of Sed i ments for C hem i c al and T ox i c o l o g i c al A na l y s i s: T e c hn i c al Manual, C hap t er 3 and Append i x E . U S Env i ronment al P ro t e c ti on Ag en c y, E P A 823 - B - 01 - 0 0 2 , Oc t ober, 2001 . Powell, D.E. 2010. Bioaccumulation and Trophic Transfer of C yclic Volatile Methylsiloxane (cVMS) Materials in the Aquatic Marine Food Webs of the Inner and Outer Oslofjord, Norway
. HES Study

No: 11060 - 108. Health and Environmental Sciences, Dow Corning Corporation, Auburn, MI. P owe l l D E , Woodburn KB. 2 0 09 . Trophic D i l uti on of C yc li c Vo l atil e Me thyl s i l oxane ( c VMS) Mat er i a l s i n a T emperat e Freshwat er L ake. Dow C orn ing C orporati on, H E S S t u dy N o. 1077 1 - 108 . US E P A 2002. Guidance for Qua li ty A ssuran c e P r o je c t P l ans, E P A Q A/ G - 5 , prepared by : O ff i c e of Env i ronment al I nformati on, E P A (De c ember 2002 )
- h tt p : //www . ep a .g o v

/ qua l i ty / qs - do c s / g 5 - f i na l
. pdf.44

A PPENDIX 8 - Testing Standard for the Collection, Sample Handling, Transfer and Anal ys is of Biota Samples for D4 **Sy n**  **o p**  **s i**  **s :**  Th i s t es t i ng s t andard prov i des gu i de li nes for t he c o l l e c ti on and ana l ys i s of env i ronment al samp l es for D4 i n support of a T es t i ng P ro gram de t a il ed i n t h i s ECA . Th i s s t andard c i t es t he requ i rement s for t

he samp l i ng of b i o t a as des c ri bed i n Se c ti on V I I of t he E C A and Append i c es 1 , 2 and 3 , and i denti f

i es spe c i f i c gu i de l i n e s and references t hat w i l l be used i n t

he preparati on of s i t e - spe c i f

i c Samp l i ng P l ans for t

he c o l l e c ti o n

/ ana l ys i s of b i o t a samp l es, wh i ch w i l l be i n c l uded i n a S t

udy P l an and QAPP for t

he T es t i ng P ro gram. The s t andard addresse s : 1 . When t o c o l l e c t b i o ta samp l es 2 . Where t o c o l l e c t b i o t a samp l es 3 . Spe c i al c ons i derati ons duri ng samp l e c o l l e c ti on t o av o i d samp l e c ont am i nati on 4 . H ow t o c o l l e c t and pro c ess b i o t a samp l es 5 . H ow t o ana l yz e b i o t a samp l es for D4 and t he appropri at e method detection limit and limit of quantification **Re qu**  **i r**  **eme n**  **ts fo**  **r s**  **a mp**  **li n**  **g b**  **i o**  **t a**  **:** B i o t a samp l ed sha l l i n c l ude bent h i c spe c i es c o l l e c t ed in sed i ment of t he re c e i v i ng wat er body

an d t wo spe c i es of f

i sh, if practicable of different trophic guilds, i n t he re c e i v i ng wat er body . ” Appen di c es 1 - 3 of t

h i s E C A s t at e t

hat :

“ Samp l es sha l l be t aken duri ng t wo t es t i ng e v ent s at l e ast t hree ( 3 ) mo n t

hs apart . T he exa c t durati on be t

ween samp l i ng e v ent s for ea c h s i t e sha l l b e de t erm i ned i n a de t a il ed Samp l i ng P l an i n c l uded i n t he S t udy P l an and QAPP
. ”

“ Samp l es sha l l be c o l l e c t ed duri ng normal p l ant operati ons and duri ng su c h ti mes t hat eff l uent f l ow rat es from t

he was t ewater t

reatment sy stem are represent ati v e of t he normal p l ant operati ons . ”

“ Samp l es sha l l be t aken duri ng typ i c al weather c ondi ti ons and n o t unti l at l east t hree ( 3 ) day s af

t er an unusual weather e v ent su ch as a heav y ra i n s t orm. Samp l es sh al l be c o l l e c t ed at a ti me when t he rat e of D4 re l ease i s expe c t ed to be represent ati v e of t he typ i c al rat e of re l ease of D4 for t hat s i t e . ”45

**Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **app r** **op r** **i a**  **te t**  **i me**  **fo r**  **s a**  **mp li**  **n g**  **e v**  **e n**  **t s**  **:** A t ea c h s i t e, t

wo samp l i ng e v ent s w i l l be undert aken t hat are s chedu l ed to be a m i n i mum of t hree mont

hs apart and duri ng normal p l ant operat i ons and weather c ondi ti ons. N ormal operati ng c ondi ti ons w i l l be es t ab li shed by c onsul ti ng w i t h t he operator of e a ch WWTP, indirect and d i re c t d i s char g e fa c ili ty . The c ri t eri a or means t hat are used by t

he f a c ili ti es to de t erm i ne normal operati ng c ondi ti ons w il l be do cumented i n t he s i t e - spe c i f

i c Samp l i ng P l an s . C onf i r mat i on w i l l be ob t a i ned t

hat t he subje c t fa c ili ty i s operati ng under normal c ondi ti ons pri or t o c ommenc i ng samp l i ng at a gi v en l o c ati on. In add i ti on, samp l i ng wou l d not t ake p l a c e w i t h i n t hree ( 3 ) day s of unusual weather e v ent s. **Es t**  **ab li**  **s h**  **ment o**  **f t**  **h e**  **l o**  **c a**  **t i**  **o n**  **f o**  **r c**  **o ll**  **ect i**  **o n**  **o f**  **benthic organisms and f**  **i s**  **h :**  A t ea c h s i t e, benthic organisms s hall be c o l l e c t ed as c l ose as reaso n ab l y poss i b l e t o t he effluent outfall prov i ded adequat e m i x i ng of t he d i s char g e and re c e i v i ng wat er has o c curred and where adequate benthic organism sample masses are obtained. Each site specific sampling plan will identify where the eff

luent and receiving stream are adequatel y mixed and the basis for the determination
. At each site fish , surface water and sediment s hall also be collected at the same location. **S p**  **ec i**  **a l**  **c o**  **n s**  **i d**  **e r**  **a t**  **i on**  **s fo**  **r t**  **h e**  **s a**  **mp li**  **n g**  **a n**  **d h**  **a nd**  **li n**  **g o**  **f b**  **i o**  **t a**  **s a**  **mp l**  **es fo**  **r D**  **4 :**  c VMS materi a l s, su ch a s D 4 , are w i de l y used i n c onsumer produ ct s and may be present i n personal c are produc t s, c ommerc i al produ ct s, and l ubri c ant s , and may be c omponent s of anti foams w i de l y used i n WWTPs . I f t hese produc t s are used by i nd i vi dua l s duri ng an y part of t he preparati on for or d

u ri ng an y aspe c t of t

he f i e l d samp l i ng e v ent , samp l e c ont am i nati on by D4 v o l atili z i ng from t

he user c ou l d o c c ur. T o av o i d the po t e n ti al for samp l e c ont am i nati on duri ng c o l l e c ti on, pro c ess i n g , s t ora g e, and ana l ys i s for D4 i n env i ronment al matri c es, pre v ent ati v e measures should be imp l emented to the ex t ent p o ss i b l e i n t he f i e l d. For example, f i e l d c rew sha l l be requ i red t o refra i n from us i ng any personal c are produ ct s t hat may c ont a i n c VMS materi a l s ( e . g ., sun - b l o c k, sun - s creen, hand l o ti on, an t i persp i rant s, e t c . ) wh il e prepari ng for or c onduc ti ng an y f

i e l d a cti v i ti es to m i n i m i ze t he poss i b il i ty for c o nt am i nati on w i t h D 4 . Spe c i f i c requ i rement s for c o l l e c ti ng and hand l i ng b i o t a samp l e s a i med at pre v enti ng samp l e c ont am i nati on by

sour c es of D 4 t

h a t are n o t spe c i f

i c to t he WWTP or d i r e c t d i s char g e sha l l be spe c i f i ed i n t he S t udy P l an and QAPP
. **C o**  **ll ect**  **i o**  **n o**  **f b**  **e n**  **t h**  **i c**  **o r**  **g a**  **n i**  **s m**  **s a**  **mp l**  **es fo**  **r ana**  **l y**  **s i**  **s o**  **f D4**  **an d**  **li p**  **i d c**  **o n**  **te n**  **t:** The exa c t method for c o l l e c ti on of sed i ment samp l es from wh i ch bent h i c i nv ert ebrat es w i l l be c o l l e c t ed i s a s i t e - spe c i f

i c de t erm i nati on. During preparati on o f t he s i t e - spe c i f

i c Samp l i ng P l ans, t he phy s i c al nat

ure (e
. g. , w i dt

h , dep t h , f l ow) of t he re c e i v i ng wat er w i l l be de t erm i ned and used t o gu i de t

he se l e c ti on of t

he appropri at e method of samp l e c o l l e c t i on. For ea c h s i t e, c o l l e c ti on pr o c edures for sed i ment samp l es sha l l be based, as appropri at e to t h e chara c t eri s ti c s of t he re c e i v i ng wat e r , on t e c hn i ques des cri bed i n P owe l l and Woodburn ( 200 9 , Samp l e C o ll e c ti on, p. 9 ) and U S E P A ( 2003 a , Se cti ons 5 . 2 Samp l i ng for C ommun i ty Samp l es and 5 . 3 Samp l i ng for A na l y

t i c al Measur ements )
. Th i s gu i dan c e i denti f i es c o l l e c ti on pro c edures t hat46

may be used t o c o l l e c t sed i ment samp l es from wh i c h bent h i c i nv ert ebrat es w i l l be c o l l e ct ed. For ea c h s i t e, t

he exa c t method for c o l l e c ti ng benth i c or g an i sms w i l l be de t a i l ed i n t he s i t e spe c i f i c Samp l i n g P l an s and QAPP. Spe c i f i c requ i rement s for samp l e c ont a i ner preparati on, samp l e hand l i n g , samp l e prese r v ati on, sh i pp i ng and s t ora g e of samp l es should be e ssent i a ll y t he same a c ross a l l s i t es. Immed i at e l y pri or t o ea c h samp l i ng e v ent at ea c h s i t e, t he l aborat ory that w i l l ana l yz e t he samp l es sha l l prepare c l ean (new, ne v er used) pre - we i g hed g l ass samp l e c ont a i ners i n suff i c i e n t numbers for a l l bent h i c or g an i sm samp l es t o be ana l yz ed for D 4 . The samp l e c ont a i ners w i l l be prepar e d by pre - wash i ng w i t

h hexane and prov i d i ng P T FE t ape t o ass i st i n sea l i ng t he c o n t a i ners, as we l l as prov i d i ng l ab e l s. The l aborat ory w i l l sh i p a l l samp l e c ont a i ners w i t h adequat e pa c ki ng mater i a l s i n c oolers t o ea c h s i t e. The c oolers w i l l a l so c ont a i n c ha i n - o f
- cus t ody forms t

hat w i l l a cc ompan y t he samp l e c o nt a i ners from t he l aborat ory t o t

he f i e l d and ba c k t o t

he l aborat ory . Figure 5 provides a schematic that describes benthic organism samples to be taken at each sampling location. Five composited samples shall be prepared. S amples 1, 2 and 3 shall be divided into three parts. Two of the parts will serve as duplicates for D4 analysi s and one part will be anal yz ed for lipid content. The duplicate s shall be processed and analyzed as individual samples for D4. Duplicate samples are used to evaluate between
- sample variability and precision. S amples 4 and 5 will be retained for anal ys is as needed. These retain samp l es wou l d be ana l y

z ed i f a pr i mary

samp l e container arri v es broken at t he l aborat ory , b u t o t h erw i se wou l d be re t a i ned i n a freezer for l at er ana l ys i s i f a samp l e be c omes c omprom i sed duri ng collection or processing
. The retain samp l es w i l l be kept unti l Qua li t y A ssuran c e has been v er i f

i ed and may

be anal yz ed for D4 as necessary
.47

Figure 5. Schematic di agram of samples taken while m onitoring for D4 in benthic organisms near wastewater treatment p lants
. Sediment containing benthic organisms will be obtained such that sufficient mass of benthic organisms are obtained for the required analy ses. Bent h i c or g an i sms w i l l be separat ed from t he sed i ment and five c ompos i t e samp l es sha l l be prepared by random l y d i vi d i ng t he c o l l e c t ed o rg an i sms i nt o gl ass c ont a i ners and freez i ng pri or to sh i pment . P ri or to prepari ng c ompos i t e samp l es, t h e t axa represent e d i n t

he samp l e w i l l be no t ed at t he l owest l e v el poss i b l e. Frozen samp l e s w i l l be pa c ked i nto c o o l ers w i t h dry i c e and t aken b a c k t o t he l aboratory or sh i pped ba c k t o the l aborat ory us i ng an overn ight express sh i p p i ng c ompany . I t should be no t ed t

hat i t i s of

t en n ot p oss i b l e t o ob t a i n suff i c i ent mass of bent

h i c or g an i sms to b o t h ana l yz e for chem i c al c on c ent rati on and t o prepare qu a li ty assuran c e samp l e s . Be c ause of t h i s, rainbow trout purchased from a commercial fish hatchery w i l l be used as surrogat e materi al t o use t o prepare qua l i ty assuran c e samp l es t o use duri ng preparati on of bent hos samp l es. During ea c h samp l i ng ev ent at a gi v en s i t e, t wo f i e l d b l anks and t

wo f i e l d sp i k e s w i l l be prepared as fo l l ows. R ainbow trout tissue pur chased from a c ommerc i al fish hatchery w i l l be ground i nt o a homo ge nous m i x ture. Samp l es of t he g round rainbow trout w i l l be prepared i n t he l aborat ory pri or to samp l e c o l l e c ti on and sh i pped to t he f i e l d. P ri or t o sh i pp i ng t o t he f i e l d, the ground rainbow trout samp l es w i l l be ana l yz ed and shown to hav e c on c ent rati ons of D4 be l ow t he LOQ for t

h i s matri x. Ser

vi ng as f i e l d b l anks, two reference ground rainbow trout samp l e s w i l l be opened dur i ng preparati on of t he c ompos i t e samp l es of bent h i c or g an i sm s . The reference rainbow trout samp l e s wi l l be used to e v a l uat e c o nt am i nati on b i as re s u l ti ng from c o l l e c ti on, pro c ess i n g , t

ranspo rt , s tora g e, and an a l ys i s of bent hos samp l es. I n add i ti o n , t wo of t he ground rainbow trout samp l es sha l l be sp i ked i n t he f i e l d w i t h a k nown amount of D 4 . The f i e l d sp i ked samp l e s of g round rainbow trout w i l l be used to e v a l uat e l oss of D 4 duri ng c o l l e c ti on, pro c ess i n g , t

ransport , s t ora g e, and ana l ys i s of t he bent hos samp l es, and to e v a l uat e ana l y t i c al b i as. Samp l e c o l l e c ti on pro c edures as we l l as spe c i f i c requ i rement s for samp l e c ont a i ner preparati on, samp l e preser v ati on, sh i pp i ng and s t ora g e of t he samp l es w i l l be de t a il ed i n S t udy P l an and QAPP
. Lipid anal ys is will be performed on two ground rainbow trout field blanks. T he method for ana l ys i s of li p i d c ont ent of the c ompo s i t ed bent h i c or g an i sm samp l es wi l l be t he same as used for f i sh. P ro c edures equ i v a l ent to P owe l l and Woodburn ( 20 0 9 ) C hara c t eri zati on of F i sh and Bent h i c Ma c ro i nv ert ebrat es, p. 1 1 sha l l be used t o measure li p i d c ont ent s i n t he bent h i c or g an i sm samp l e s . Spe c i f i c requ i rement s for monitoring site location preparati on, pro c ess i n g , and ana l ys i s of f i e l d b l anks, f i e l d sp i kes, and dupl i c at e samp l es sha l l be de t a i l ed i n t he S t udy P l an and QAPP . **C o**  **ll ect**  **i o**  **n o**  **f f** 

**i s**  **h s**  **a mp**  **l es**  **fo r**  **ana l** **y s**  **i s**  **o f**  **D 4**  **:** The exa c t method for c o l l e c ti on of f i sh i s a s i t e - spe c i f

i c de t erm i nati on. During preparati on of t he s i t e - spe c i f

i c Samp l i ng P l ans, t

he phy s i c al n at

ure (e
. g. , w i dt

h, dep t h , f l ow) of t he re c e i v i ng48

wat er w i l l be de t erm i ned and used to gu i de t he se l e c ti on of t

he ap p ropri at e method of samp l e c o l l e c ti on. For ea c h s i t e, c o l l e c ti on pro c edures w i l l be based, as appropri at e t o t he c hara c t eri zati on of t

he re c e i v i ng wat e r , on U S E P A 2003 a (Se c ti on 7 . 0 P ro c edures, pp. 3 - 5 ) and P owe l l and Woodburn ( 2 0 09 , Samp l e C o l l e c ti on, p. 8 ). Th i s gu i dan c e i denti f i es t wo ma i n types of f i sh c o l l e c ti on methods for re l ati v e l y sha l l ow and s l ow mo vi ng wat er and gi v es d i re c ti on on c ho i c e of meth o d, g eneral pra c ti c es, and o t her c ons i derati ons for t

he f i e l d work. For ea c h s i t e, t

he exa c t c o l l e c ti on method for f i sh samp l es w i l l be de t a il ed i n t he s i t e - spe c i f

i c Samp l i ng P l ans and QAPP
. Spe c i f i c requ i rement s for samp l e c o nt a i ner preparati on, samp l e hand l i n g , samp l e prese r v ati on, sh i pp i ng and s t ora g e of samp l es should be essent i a ll y t he same a c ross a l l s i t es. Immed i at e l y pri or t o ea c h samp l i ng e v ent at ea c h s i t e, t he l aboratory that w i l l ana l yz e t he samp l es sha l l prepare c l e an (new, ne v er used) pre - we i ghed g l ass samp l e c ont a i ners and po l yeth yl ene food s t ora g e ba g s i n suff

i c i ent numbers for a l l f

i sh samp l es to be ana l yz ed for D 4 , for a l l qua l i ty assuran c e samp l es, and for re t a i n samp l es. The samp l e c ont a i ners w i l l be prepared by pre washing wi t

h hexane and prov i d i ng P T FE t ape t o ass i st i n sea l i ng t he c ont a i ners, as we l l as prov i d i ng l abe l s . The l aboratory w i l l s hi p a l l samp l e c ont a i ners and po l yethyl ene ba g s wi t h adequat e pa c ki ng materi a l s i n c oolers to ea c h s i t e. The c o o l ers w i l l a l so c ont a i n c ha i n - o f
cus t ody forms t

hat w i l l a cc ompan y t

he samp l e c ont a i ners from t he l aborat ory t o t

he f i e l d and ba c k t o t he l aboratory . O n t he day of f

i e l d samp l i ng at a gi v en s i t e, f i sh shall be c o l l e c t ed and sort ed by spe c i es. The t axonom i c i denti f

i c ati on of ea c h f

i sh species shall be no t ed
. Two spe c i es of f i sh from different trophic guilds , if practicable, c o l l e c t ed i n suff i c i ent mass su ch t

hat i nd iv i dual or c ompos i t e samp l es c an be prepared for t he ana l ys i s of D4 , shall be se l e ct ed. If adequate quantities of fish from different trophic guilds are not available the two most abundant species will be selected. I nformati on about the li fe h i s t ory of t he t wo spe c i es se l e c t ed sha l l be i n c l uded i n s t udy report s. The i nd iv i du a

l f i sh w i l l be measured for l en g t h and we i ght . Figure 6 provide s a schematic that describes fish samples to be taken at each sampling location. For ea c h of t

he two spe c i es, five i nd iv i dual f i sh or composited samp l e s sha l l be prepared and frozen
. Inthe laboratory

t hree of the samples shall be thawed, homogenized and divided into three parts. Two of the parts will serve as duplicates for D4 anal ys is and one part will be anal yz ed for lipid content. The duplicate s shall be processed and anal yz ed as individual samples for D4. Duplicate samples are used to evaluate between
- sample variability and precision
.49

Figure 6. Schematic d i agram of samples taken while m onitoring for D4 in fish near wastewater treatment p lants
. Two of the five samples will be retained for analysis as needed. These retain samples would be anal yz ed if a primary

sample container arrives broken at the laboratory, but otherwise would be retained in a freezer for later analysis if a sample becomes compromised during collection or processing. The retain samples will be kept unti l Qua li ty A ssuran c e has been v eri f i ed and may be anal yz ed for D4 as necessary
. During ea c h samp l i ng ev ent at a gi v en s i t e, t wo f i e l d b l anks and t

wo f i e l d sp i k e s w i l l be prepared as fo l l ows. R ai nbow t rout pur c hased from a c ommer c i al f i sh hatc hery w i l l be g round i nt o a homo g enous m i xture. Samp l es of t he g round f

i sh w i l l be prepared i n t

he l aborat ory pri or t o samp l e c o l l e c ti on and sh i pped t o t he f i e l d. P ri or t o sh i pp i ng t o t he f i e l d, t he g round f

i sh samp l es w i l l be ana l yz ed and shown t o hav e c on c ent rati ons of D4 be l ow t

he LOQ for t

h i s matri x. Servi ng as f

i e l d b l anks, t

wo reference g round f

i sh samp l e s w i l l be pro c essed l i ke f i e l d50

samp l e s . The reference f

i sh samp l e s w i l l be used t o e v a l uat e c o nt am i nati on b i as resu l ti ng from c o l l e c ti on, pro c ess i n g , t

ranspo rt , s tora g e, and ana l ys i s of fish samp l es. In addition, two of the ground fish samp l es sha l l be sp i ked i n t he f i e l d w i th a known amount of D 4 . The f i e l d sp i ked samp l es of ground f

i sh w i l l be used to e v a l uat e l oss of D4 duri ng c o l l e c ti on, pro c ess i n g , t ranspo rt , s t ora g e, and ana l ys i s of fish samp l es, and to e v a l uat e ana l y t i c al b i as. Spe c i f

i c requ i rement s for preparat i on, pro c ess i n g , and ana l ys i s of quality assurance samp l es sha l l be de t a i l ed i n t

he S t udy P l an and t

he QAPP . Ind i vi dual f

i sh w i l l be doub l y ba g g ed us i ng po l ye thyl e n e ba g s and frozen pri or t o sh i pment . C ompos i t ed f

i sh w i l l be p l a c ed i n samp l e c ont a i ners and frozen pri or to sh i pment. Frozen samp l es w i l l be pa c ked i nt o c oolers w i t h dry i c e and t aken b a c k to or sh i pped ba c k to t he l aborat ory us i ng an overn ight express sh i pp i ng c ompany . Samp l e c o l l e c ti on methods as we l l as spe c i f i c requ i re m ent s for samp l e c ont a i ner preparati on, samp l e hand l i n g , samp l e prese r v ati on, sh i pp i ng and s t ora g e of t he samp l es w i l l be de t a i l ed i n t he S t udy P l an and QAPP
. I n t he l aborat ory , as part of t he p r o c ess i ng of t

he f i sh s amp l es pri or to ana l ys i s, f i sh w i l l be ground up and homo g en i zed. L i p i d c ont ent sha l l be ana l yz ed us i ng pro c edures equ i v a l ent t o P owe l l and Woodburn ( 2 009 ) C hara c t eri zati on of F i sh and Bent h i c Ma c ro i nv ert ebrat es, p . 1 1. **A n**  **a l** **y s**  **i s**  **o f**  **Bi o**  **ta S**  **a mp**  **l es**  **fo r**  **D 4**  **:** A l l b i o t a samp l es and accompanying quality assurance samples sha l l be ana l yz ed for D4 at one c ommer c i al t es t i ng l a

b orato ry that has appropriate expertise with the D4 analyses to be conducted when the testing occurs , unless there are unforeseen circumstances such as lack of laboratory availability as noted in 40 C.F.R. § 790.68(b)(2)(iii)
. The c ommer c i al l aborat o ry wi l l v a l i dat e a method for the ana l ys i s of D4 i n b i o t a samp l es t hat sha l l be adapted from t he ana l y ti c al method spe c i f i ed i n P owe l l and Woodburn ( 2 0 09 , Ana l ys i s of C yc l i c Vo l atil e Me thyl s il oxane ( c VMS) Mat eri a l s se c ti o n , E x tra ct i on of F i sh and Bent h i c M a cro i nv ert ebrat es sub
- se c ti o n , p. 1 3 , and Qua li ty C ont

ro l , p. 14 )
. The P owe l l and Woodburn ( 2009 ) ana l y t i c al method i nv o lv es ex tra cti on of a li quo t s of homo g en i zed b i o t a samp l es and qua l i ty assuran c e samp l es fo l l owed by quanti f i c ati on us i ng G C - MS. The MDL is the c on c entr a ti on of a c o ns ti t uent i n a samp l e, t

h a t when pr o c es s ed t

hrough t he c omp l e t e ana l y

t i c al method, c an be mea s ured and report ed w i t h 99 % probab i li ty t

hat i t i s great er t han 0 or s t ati s ti c a ll y d i fferent from a b l ank. The M D L i s a measure of a metho d ’ s ab ili ty to quanti fy a c ons ti t

uent i n a samp l e matri x. The m e t hod for ana l yz i ng D4 i n b i o t a report ed by Campbell 2010; Durham 2010a and 2010 b; Kaj 2005; Powell 2010a and 2010 b; and P o w e l l and Woodburn ( 2009 ) i s deemed t he appropri at e method for an MDL of 0.2 to 3.0 ng/g (wet we i ght , ww ) . An MDL up to a value not exceeding 3.0 ng/g (wet weight, ww) shall be applied for b i o t a. The spe c i f

i c l e v el of de t e c ti on sha l l be based on t he LOQ which shall be 3 times the MDL . EPA recognizes that a laboratory may have difficulties achieving the specified MDL . In this event, the signatory companies shall seek a modification as per 40 C
. F . R . § 790.68.51

**C o**  **mp li**  **an ce**  **w i** **th Go o**  **d L**  **abo r**  **a t** **o r** **y Pr**  **a ct**  **i ce**  **Re qu**  **i r**  **e m**  **e n**  **t s**  **:** Al l f i e l d work re l at ed spe c i f

i c a l l y to t he c o l l e c ti on, han d li n g , and t ransfer of b i o t a samp l es should be c onduc t ed i n a c c ordan c e w i t h U S E P A ’ s G LP r e gu l ati o n s (see 4 0 C . F . R . P art 792 ). Al l ana l y

t i c al work, i n c l ud i ng ana l ys i s of D4 and li p i d c ont ent , sha l l be c o n du c t ed i n a c c ordan c e w i t

h U S E P A ’ s G LP r e gu l ati o n s (see 4 0 C . F . R . P art 792 ). The Q A P P sha l l be prepared a cc ord i ng t o U S E P A gu i dan c e (U S E P A 2002 ). REFERENCES Campbell, R.A. 2010. A Collaborative Assessment of Cyclic Volatile Methylsiloxanes (D4, D5, D6) Concentrations in the Norwegian Environment. HES Study No: 11061 - 108. Health and Environmental Sciences, Dow Corning Corporation, Auburn, MI. Durham, J.A. 2010a. Testing to Determine the Concentration of C yclic Volatile Methylsiloxanes (cVMS) in Fish and Other Biota Obtained from Svalbard and Bear Islands, Norway . HES Study

No: 11061 - 108. Health and Environmental Sciences, Dow Corning Corporation, Auburn, MI. Durham, J.A. 2010b. Testing to Determine the Concentration of C yclic Volatile Methylsiloxanes (cVMS) in Sediment, Fish and Zooplankton Obtained from Svalbard, Norway. HES Study

No: 11340 - 108. Health and Environmental Sciences, Dow Corning Corporation, Auburn, MI. Kaj, L ., M. Schlabach, J. Andersson, A.P. Cousins, N. Schmidbauer, E. Brorström
- Lundén, B. Bügel Mogensen, M. Dam, J.P. Hirvi, A.S. Sigurdsson, B. Hedlund, O. Glesne, A. Lundgren. 2005. Siloxanes in the Nordic Environment. Norden. Powell, D.E. 2010a. Bioaccumulation and Trophic Transfer of C yclic Volatile Methylsiloxane (cVMS) Materials in the Aquatic Marine Food Webs of the Inner and Outer Oslofjord, Norway
. HES Study

No: 11060 - 108. Health and Environmental Sciences, Dow Corning Corporation, Auburn, MI. Powell, D.E. 2010b. Preliminary Assessment of Cyclic Volatile Methylsiloxane (cVMS) Materials in Surface Sedimnets, Cores, Zooplankton and Fish of Lake Opeongo, Ontario, Canada. HES Study

No: 10806 - 108. Health and Environmental Sciences, Dow Corning Corporation, Auburn, MI. U S E P A 2006 . C omp il ati on of E P A M i x i ng Z one Do cument s, Model i ng Do cument s, pp. 9 - 13 . E P A 823 - R - 06 - 0 0 3 , Ju l y, 2006 . U S E P A 2003 a. F i sh C o l l e c ti on by Se i n i ng or E l e c t rof i sh i n g . T e c hn i c al S t andard Oper a ti ng P ro c edure S O P # E H - 06 , S e cti on 7 , pp. 3 - 5 , Sep t ember, 2003 . P owe l l D E , Woodburn KB. 2 0 09 . Trophic D i l uti on of C yc li c Vo l atil e Me thyl s i l oxane ( c VMS) Mat er i a l s i n a T emperat e Freshwat er L ake. Dow C orn ing C orporati on, H E S S t u dy N o. 1077 1 - 108 .52

U S E P A 2003 b. Bent

h i c M a c ro i nv ert ebrat e S amp l i ng and P ro c ess i n g , T e c hn i c al S t andard Operati ng P ro c edure S O P # E H - 04 , S e cti on 5 , pp. 3 - 6 , Sep t ember, 2003 . US E P A 2002. Guidance for Qua li ty A ssuran c e P r o je c t P l ans, E P A Q A/ G - 5 , prepared by : O ff i c e of Env i ronment al I nformati on, E P A (De c ember 2002 )
- h tt p : //www . ep a .g o v

/ qua l i ty / qs - do c s / g 5 - f

i na l
. pdf.