ENFORC E ABLE CONSENT AGREEME NT

FOR

ENVIRONMENTAL TESTING FOR

OCTAMETHYLCYCLOTETRA SILOXANE (D4) (CASRN 556

- 67

- 2)

Docket No. EPA

- 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 n2 ENFORCEABLE CONSENT AGREEMENT FOR

ENVIRONMENTAL TESTI N G FOR:

OCTAMETHYLCYCLOTETRA SILOXANE (D4) (CASRN 556

- 67

- 2)

Docket No. EPA

- HQ

- OPPT

- 2012

- 0209

TABLE OF CONTENTS

I. INTRODUCTION

................................ ................................ ................................ ................................ ..... 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. DESCRIPTION OF TESTING PROGRAM

................................ ................................ ......................... 5

VIII. STANDARDS FOR CONDUCTING TESTING

................................ ................................ ................ 6

IX. SCHEDULE, STUDY PLANS, TESTING, AND REPORTS

................................ ............................... 6

X. MODIFICATIONS TO THE ECA

................................ ................................ ................................ .......... 8

XI. FAILURE TO COMPLY WITH ECA

................................ ................................ ................................ ... 8

XI I. EPA MONITORING OF ECA TESTING

................................ ................................ ............................ 8

XIII. SUBMISSIONS TO EPA AND CONFIDENTIALITY OF INFORMATION

................................ ... 9

XIV. PUBLICATION AND DISCLOSURE OF TESTING RESULTS

................................ ...................... 9

XV. OTHER RESPONSIBILITIES OF THE SIGNATORY COMPANIES

................................ ............. 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

................................ ................................ ................................ ............... 11

XXI. PUBLIC RECORD

................................ ................................ ................................ ............................ 11

XXII. EFFECTIVE 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

................................ ................................ ................................ .......................... 15 143

APPENDIX 1

- ENVIRONMENTAL TESTING AT D4 DIRECT DISCHARGE SITES

................... 17 16

APPENDIX 2

- ENVIRONMENTAL TESTING FOR INDIRECT DISCHARGE SITES

................... 19 18

APPENDIX 3

- ENVIRONMENTAL TESTING FOR PRIMARILY NON

- INDUSTRIAL

WASTEWATER TREATMENT PLANTS

................................ ................................ ........................... 22 21

APPENDIX 4

- TESTING STANDARD FOR THE COLLECTION, SAMPLE HANDLING,

TRANSFER AND ANALYSIS OF INFLUENT AND EFFLUENT SAMPLES FOR D4

................... 24 23

APPENDIX 5

- TESTING STANDARD FOR THE COLLECTION, SAMPLE HANDLING,

TRANSFER AND ANALYSIS OF SURFACE WATER SAMPLES FOR D4

................................ .... 30 29

APPENDIX 6

- TESTING STANDARD FOR THE COLLECTION, SAMPLE HANDLING,

TRANSFER AND ANALYSIS OF BIOSOLIDS SAMPLES FOR D4

................................ ................ 35 34

APPENDIX 7

- TESTING STANDARD FOR THE COLLECTION, SAMPLE HANDLING,

TRANSFER AND ANALYSIS OF SEDIMENT SAMPLES FOR D4

................................ ................. 40 39

APPENDIX 8

- TESTING STANDARD FOR THE COLLECTION, SAMPLE HANDLING,

TRANSFER AND ANALYSIS OF BIOTA SAMPLES FOR D4

................................ ......................... 46 454

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 Goldschmidt Corporation, Momentive Performance Materials USA Inc.,

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 “Party” shall refer i ndividually to one or the other.

II. CHEMICALS 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 E CA, EPA will issue an order under

S ection 4 of TSCA that incorporates the terms of this ECA

. The Signatory Companies agree

that all 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 VI through IX provide more details about the testing that will be accomplished under

this ECA (“ Testing Program ” )

.

IV. PRINCIPAL 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 complying with this ECA. The role of the Principal Test Sponsor is to assist in

coordinating and administering testing under this ECA and in communic ating with EPA about

study plans, protocols, analytical methods, schedules, reports , and other aspects of the testing

program

. Responsibility for complying with the ECA rests at all times 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 pathways 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 U nited 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 TESTING PROGRAM

The Testing Program is described in Section VII

. Sampling and analysis 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 TESTING 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 analyzed for D4 . Sediment

, surface water and biota (benthic and fish species) in the receiving waters will also be sampled

and analyzed for D4

. The test standards described in A ppendi 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 analysis 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 A ppendi 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

, preferably

, 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 analysis 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 A ppendi 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 analyzed for D4 at

one commercial testing laboratory that has appropriate expertise wit h the D4 analyse s of samples

of the types collected in this testing program when the testing analysis 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 delineate a test requirement to be followed or met.

2. Provisions that are not mandatory, and are therefore only recommended, are identified by the

use of “should” statements

. If such “should” provisions are not followed, the Signatory

Companies will not be deemed by 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 any, will be governed by 40 C.F.R. § 790.68.

C. As specified in the Tes t Standards in Appendices 4, 5, 6, 7, and 8, All a ll testing required by

this ECA shall be in accordance with the EPA Good Laboratory 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/analytical issues, lo gistics,

etc. ) inherent in performing the field sampling and environmental testing contemplated by this7

Testing Program. Modifications to the schedule, if any, will be made according to the

procedures set out in 40 C.F.R. § 790.68.

A. Study Plan

The Signatory Companies will submit a Study Plan prepared pursuant to this ECA to EPA at

least forty

- five ( 45 ) days prior to the initiation of testing in accordance with 40 C.F.R. § 790.62

and no more than one hundred twenty (120) days 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 by 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 by EPA.

The Signatory Companies shall submit a QAPP to EPA within one hundred eighty ( 180 ) days of

the Effective Date of this ECA and at least forty

- five ( 45 ) days 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 analyses. EPA shall approve the QAPP

within 60 days 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 ha ve been approved by EPA . The testing program shall commence no later than sixty (60)

days after the study plan and QAPP have been approved. T esting ( i.e. , collection and analysis of

all samples) shall be completed within three hundred sixty (360) days after testing commences

, unless 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 progres s of the Testing Program. A n Interim Progress Report is required one hundred eighty

( 180 ) days after the Effective Date specified in Section XX II .A of this ECA and every one

hundred eighty ( 180 ) days t hereafter 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, any proposed changes in protocols or schedule, raw data (as defined in 40

C.F.R. § 792.3) and any other matt ers 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

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

once the Interim Progress Reports and the Environmental Monitoring Report are submitted to the

A gency in a ccordance with this ECA.

D

. Final Report

No later than one hundred fifty ( 15 0 ) days following completion of the required e nvironmental

testing ( i.e.

, collection and analysis of the d ata), the Signatory Companies shall submit to EPA a n

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 analyses, 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 any, 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 by 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 constitute 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

. In addition,

noncompliance with this ECA could result in a citizen’s civil action

. The Signatory

Compan ies further acknowledge that 40 C.F.R. § 790.65 provides additional information

regarding the implications of failing to comply with an enforceable consent agreement.

XII. EPA MONITORING OF ECA TESTING

EPA may conduct monitoring activities, such as labo ratory 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 delays in the completion of any activities required under this9

ECA, the parties may seek modification in the scope of testing performed under the consent

order or test schedule in accordance with 40 C.F.R. § 790.68

.

XIII. SUBMISSIONS TO EPA AND CONFIDENTIALITY O F INFORMATION

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. Any document submitted to EPA that contains data or information for which a Signatory

Company makes a claim of confidentiality 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 respects except that all of the information

claimed as confidential shall be redacted. EPA will place only the public version in the A gency ’s

docket

. The complete version will be treated in accordance w ith 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 electronically to EPA by e

- mail. Any part or all of data or other

information claimed as CBI must b e 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

. Info rmation 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) by the su bmitter of the

information at the time of submission, the information will be deemed by 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 TESTING RESULTS

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 by 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 generat ed 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 by the Signatory Companies pursuant to this ECA

for commercial purposes in any entity that is not a Signatory Company.10

XV. OTHER RESPONS I BILITIES OF THE SIGNATORY COMPANIES

A. The Signatory Companies are bound by 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. If 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 by a TSCA S ection 4 test rule.

XVI. RESPONSIBILITY FOR THE ACTIONS OF UNRELATED THIRD PARTIES

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 held liable for any 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 by circumstances beyond its control or the control of any entity controlled by

the Signatory Company, including any contractors and subcont ractors, 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 informally and in good faith to resolve any disputes that

may arise concerning 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

unenforceable, 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.11

X X . FINAL AGENCY ACTION

For purposes of 5 U.S.C. § 704, publication of the Federal Register notice announcing the

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 any information claimed as CBI, has been established

under docket control number EPA

- HQ

- OPPT

- 2012

- 0209

.

X X 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 by 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 o f 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 any 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 XI X 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 SIGNATORY 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 any 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 any penalty assessed for alleged violations of this ECA, and12

3. the right to seek judicial review of any administrative enforcement decision pertaining to this

ECA or of any EPA ru le that imposes requirements to test D4.

XXI V . 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 . NOTICES

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.

Russell Mait, Director EHSQ

Consumer Specialties North America

Evonik Corporation

PO Box 1299

Hopewell, VA 23860

B. Any changes in the individuals or addresses referenced in Section XXV.A of this ECA shall

be made by 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 transmission.

XX V I . IDENTITY OF THE SIGNATORY 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, MI 48686 Formatted: Font: Times New Roman, 12 pt,

Not Bold

Formatted: Font: Times New Roman, 12 pt

Formatted: Font: Times New Roman, 12 pt,

Not Bold

Formatted: Font: Times New Roman, 12 pt

Formatted: Font: Times New Roman, 12 pt,

Not Bold

Formatted: Font: Times New Roman, 12 pt

Formatted: Font: Times New Roman, 12 pt,

Not Bold13

Evonik Goldschmidt Corporation

PO Box 1299

Hopewell, VA 23860

Momentive Performance Materials USA Inc.

260 Hudson River Road

Waterford, NY 121 8 814

Shin

- Etsu Silicones of America, Inc.

1150 Damar Drive

Akron, OH 44305

Wacker Chemical Corporation

3301 Sutton Road

Adrian, MI 49221 Formatted: Normal15

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 legally bind that Party to it.

Date:_______ ________________________

Jim Jones, Assistant Administrator

, Office of Chemical Safety and Pollution Prevention

United States Environmental Protection Agency

Date:_______ _______

_________________

[ Name ], [Title]

Dow Corning Corporation

PO Box 994

Midland, MI 48686

Date:_______ ________________________

Date:_______ ________________________

Reinhold Brand, Senior Vice President & General Manager

Consumer Specialties North America

Evonik Corporation

PO Box 1299

Hopewell, VA 23860

Russell Mait, Director EHSQ

Consumer Specialties North America

Evonik Corporation

PO Box 1299

Hopewell, VA 23860

[ 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 Formatted: Font: (Default) Times New

Roman, 12 pt, Not Bold

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single

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Date:_______

________________________

Jun Hamuro, President/CEO

[ 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 4922117 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 by Signatory Companies that directly 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

Friendly, 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

wastewa ter treatment system 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

analysis (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

fl ow rates from the wastewater treatment system are representative of the normal plant

operations.

Samples shall be taken during typical weather conditions and not until at least three (3) days

after an un usual weather event such as a heavy rain storm. Samp les shall be collected at a time18

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 type of samples to be collected

 sampling protocols, including loss

- free methods for collection, storage, and analysis of

samples

, and standard operating procedures

 access requirements

 site characterization for benthic invertebrate and fish sampling , including the species that

are expected to be collected for analysis

The Study Plan shall address training of sample collection personnel in sampling protocols and

the special handling requirements associated with D4

, the qualifications o f contract laboratory

vendor(s)

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

.19 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 produ ct formulators) . The

WWTP location s will be chosen based on the following criteria :

 All wastewater treatment sites selected for monitoring must be currently

processing wastewater from one or more industrial sites known to be a D4 processor or

formulator as documented through industrial user surveys or by other readily available

inform ation

. T he WWTP influent shall reasonably be expected to contain D4 based on

industrial user surveys 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 wastewater 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

u nless agreed to by EPA )

.

 All wastewater treatment sites selected for monitoring shall release wastewater to

riverine systems, not the marine (ocean environment).

 Privately owned wastewater treatment works may be selected for monitoring

provided their tre a tment processes are similar to publicly o w ned 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 geography when selecting wastewate r

treatment sites for testing. Ideally, 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 ava ilable data on historical (i.e., within

previous 5 years) effluent conditions ( e.g. , annual flow, dissolved oxygen, temperature, pH,

suspended solids, biological oxygen demand, etc. ) shall be included in the Study Plan.

A description of the industrial activity at the D4 processor or formulator site s that indirectly

discharge to the WWTP s shall be provided for such sites controlled by signatory companies

.20

This information shall be requested (and reported, if obtained) from D4 processor or formulator

sit es 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 system s employed

at the WWTP s shall also be provided ( e.g. , consistent with what was provided in each facility’s

discharge permit application)

.

Prior to including a specific location in the Study Plan, the Signatory Companies shall secure, as

necessary and appropriate, a letter of cooperation/access from the pe rson 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 analyzed 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 analysis ( method dete ction 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 system are representative of the normal plant

operations.

Samples shall be taken during typical weather conditions and not until at least three (3) days

after an un usual weather event such as a heavy 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 rel ease 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 and robust experimental design

 number and type of samples to be collected

 sampling protocols including loss

- free methods for collection, s torage, and analysis 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 analysis21

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 contract

laboratory vendor(s)

, and method validation for all matrices to be sampled ( e.g. , water, sediment,

b iosolids, biota )

.22

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 specified below is to

develop a greater und erstanding of environmental releases of D4 emanating from the down

- the

drain uses of D4 in various consumer products post

- treatment by a WWTP . Testing shall be

conducted for D4 at five (5) WWTP s. The WWTP locations will be chosen based on the

following cri teria :

 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 tr eatment

unless agreed to by EPA )

.

 The influent to the WWTP shall contain less than 1 5 % of wastewater from

industrial sources by volume and , preferably, no wastewater from D4 manufacturing,

processing, or formulating sites , as documented through industrial user surveys or by

other readily available information

.

 All wastewater treatment sites selected for monitoring shall release wastewater to

riverine systems, not the marine (ocean environment).

 Wastewater treatment sites selected for monitoring should ha ve effluent discharge

rates that are relatively large when compared to the receiving bodies flow rate (low

dilution)

.

 Consideration should be given to geography when selecting wastewater

treatment sites for testing. Ideally, the sites selected should be i n 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 oxygen

, temp erature, pH, suspended solids, biological oxygen 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 system s employed at the WWTP s shall be provided ( e.g. , consistent with

what was provided in each facility’s discharge permit application)

.23

Prior to including a specific location in the Study Plan, the Signatory 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 analyzed for D4 in accordance with the Test Standards provi ded in

Appendices 4

- 8

. These appendices provide details on sampling locations, sample collection

procedures, sample handling procedures and sample analysis ( 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 system are representative of the normal plant

operations.

Samples shall be taken during typical weather conditions and not until at least three (3) days

after an un usual weather event such as a heavy 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 S tudy Plan

submitted to EPA. The Sampling 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 type of samples to be collected

 sampling protocols

, including loss

- free methods for collection, storage, and analysis of

samples

, standard operating procedures

 access requirements

 site characterization for benthic invertebra te and fish sampling , including the species that

are expected to be collected for analysis

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).24

APPENDIX 4

- Testing Standard for the Collection, Sample Handling, Transfer and Analysis of

Influent and Effluent Samples for D4

Sy n o p s i s :

T his t esting s t andard provides guidelines for t he c ollec t ion and analysis of environmen t al samples

for D4 in support of a T esting Program de t ailed in t his ECA

. T his s t andard c i t es t he requirements

for t he sampling of influent and effluent as des c ribed in Se ct ion 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 t ion of

si t e

- spe c ific Sampling Plans for t he c ollec t io n /analysis of influent and effluent samples, whi c h

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

t ions during sample c ol lec t ion t o avoid sample c ontamina t ion

4. How t o c ollect and process influent and effluent samples

5. How t o analyze influent and effluent samples for D4 and t he 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 even t s at least t hree (3) mon t

hs apar t . The

exact duration be t ween sampling even t s for each si t e shall be de t ermined in a de t 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 su c h t imes t hat

effluent flow ra t es from t

he wastewater t

reatment system are representa t ive of t he

normal plant operations.”

“Samples shall be t ak en during t ypi c al weather c ondi t ions 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 t ime when t he ra t e of D4 release is expec t ed t o be representa t ive of t he

t ypi 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 en t s w i l l be under t aken t hat are s c hedu l ed t o be a m i n i mum o f

t hree mon t

hs apart and dur i ng normal p l ant opera t i ons and weather c ondi t

i ons. N ormal

opera t i ng c ondi t

i ons w i l l be es t ab li shed by c onsul t i ng w i t h t he opera t or of e a c h WWTP

, indirect and d i re c t d i s c har g e fa c ili t y. T he c r i t er i a or means t hat are used by t

he f a c ili t i es t o

de t erm i ne normal opera t

i n g c ondi t i ons w i l l be do c umen t 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 t y i s opera t i ng under normal c ondi t

i ons

pr i or t o c ommenc i ng samp l i ng at a gi v en l o c a t i o n

. I n add i t i on, samp l i ng wou l d not t ake p l a c e25

w i t h i n t hree ( 3 ) days of unusual weather e v en t 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

. T he exa c t l o c a t i on for c o l l e c t i on of an i nf l uent samp l e w i l l be

fa c ili t y

- 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 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 bas i s for de t erm i n i ng t he appropr i a t e samp l i ng l o c a t i 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 a t ed c omp li an c e po i nt per t he

WWT P ’ s d i s c h ar g e perm i t

. E a c h s i t e

- spe c i f i c Samp l i n g P l an sha l l i n c l ude a c omp l e t e

des c r i p t i on of t he eff l uent d i s c har g e por t

i 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 a t

i 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 y c li c v o l a t i l e meth y l s il oxa n e ( c VMS) mater i a l s, su c h a s D 4

, are w i de l y used i n c onsumer

produ c t s and may be present i n personal c are produc t s, c ommer c i al produ c t s, and l ubr i c an t s

, and may be c omponen t s of a n t i foams w i de l y used i n WWTPs

. I f t hese produc t s are used by

i nd i v i dua l s dur i ng any part of t he prepara t

i on for or d u r i ng any aspe c t of t he f i e l d samp l i ng

e v en t or laboratory analysis?

, samp l e c on t am i na t i on by D4 v o l a t ili z i n g from t he user c ou l d

o c c ur. T o a v o i d t

he s ig n i f i c ant po t en t

i al for samp l e c on t am i na t i on dur i ng c o l l e c t i on,

pro c ess i n g

, s t ora g e, and ana l ys i s for D4 i n en v i ronmen t al matr i c es, pre v en t a t i v e measures

should be i m

p l emen t ed t o t he 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 and laboratory?

c rew personnel sha l l be requ i red t o refra i n from us i ng any personal c are produ c t s t hat may

c on t a i n any c VMS mater i al s (e

. g

., su n

- b l o c k, su n

- s c reen, h a nd l o t i on, an t i persp i ran t s, e t c

. )

wh il e prepar i ng for or c onduc t i ng any f i e l d a ct i v i t i es t o m i n i m i ze t he poss i b il i t y for

c o n t am i na t i on w i t

h D 4

. Sp e c i f

i c requ i remen t s for c o l l e c t i ng and hand l i ng i n f l uent and

eff l uent samp l es a i med at pre v en t i ng sam p l e c on t am i na t i on by sour c es of D4 t hat are not

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 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 :

T he exa c t method for c o l l e c t i 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 na t

i on

pr i mar i l y dependent on t

he a c c ess i b i l i t y and c onf

i g ura t i on of t he headworks of t

he WWTP for

i nf l uent samp l i n g and t

he c omp li an c e po i nt for eff l uent samp l i n 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 ig h de g ree of

v o l a t i l i za t i on of D4 from aqueous samp l es. For ea c h s i t e, pr o c edures for c o l l e c t i ng g rab

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 ct i on

4

, Samp l e T ypes and Se c t i 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 I nspe c t i on Manual, Se c t i 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 t i on se c t i o n ), and A P H A 199 9 ( P art 10 6 0 C o l l e c t i on and26

P reser v a t i on of Samp l e s

, pp

. 48

- 62 ) if appropriate given the site

- specific circumstances. T h i s

g u i dan c e i den t

i f i es t he fa ct ors i n v o lv ed i n de t erm i na t i on of the most approp r i a t e samp l i n g

methods for i nf

l uen t s and eff

l uen t s. T he exa c t c o l l e c t i 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 remen t s for samp l e container prepara t i on, samp l e hand l i n g

, samp l e prese r v a t i on,

sh i pp i ng and s t ora g e of samp l es should be essen t i a ll y t he same a c ross a l l s i t es. I m m ed i a t e l y

pr i or t o ea c h samp l i n g e v ent at ea c h s i t e, t he l abora t ory t hat w i l l ana l yze t he samp l es sha l l

prepare c l ean (new, ne v er used) gl ass sam p 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 yzed for D 4

, for a l l qua l i t y assuran c e samp l es, and for re t a i n

s a mp l e s

. T he 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 polyethylene ( L DPE ) sorbent i n t o t he container s

, prov i d i ng polytetrafluoroethylene

( P T FE ) t ape t o ass i st i n sea l i ng t he container s (as des c r i bed i n Knoerr 20 1 3 , Samp l e C o l l e c t i on

se c t i o n )

, as we l l as prov i d i ng l ab e l s. T he l abora t ory w i l l sh i p a l l samp l e container s w i t h

adequa t e pa c k i ng mater i a l s i n c oolers t o ea c h s i t e. T he c oolers w i l l a l so c on t a i n c ha i n

- o f

c u s t ody forms t

h a t w il l a cc ompany t

he samp l e container s from t he l abora t o r y t o t he f

i e l d and

ba c k t o t he l abora t 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. Influent and effluent flow rates shall be recorded at the time

of sampling and reported.



### Qualit

y

Assura

nce

Sampl

es Lab

Water

Field

Blank Blank 1 Blank 2 Grab

Sample

1 Grab

Sample

2 Lab

Water

Field

Blank Influent/Ef

fluent

Field

Blank

(spiked)

Influent/E

ffluent

Grab

Sample 3 Influent/E

ffluent

Grab

Sample 4 Influent/E

ffluent

Grab

Sample 5 Influent/Efflu

ent

Grab Sample

6

(Retained

Sample) Influent/Efflu

ent

Grab Sample

7 (Retained

Sample) Influent/Ef

fluent

Field

Blank

(spiked) Influent/Ef

fluent

Field

Blank

(unspiked) Influent/Ef

fluent

Field

Blank

(unspiked) Split Split

T

O

C Anal

ysis

1 Ana

lysis

2 T

O

C Anal

ysis

1 Ana

lysis

2 T

O

C Anal

ysis

1 Ana

lysis

2 

### Study

Sampl

es27

Figure 1. Schematic d i agram of samples taken while monitoring for D4 in influent and effluent

at wastewater treatment p lants

.

G rab samples 3, 4 and 5 will be divided to provide two duplicates for analysis of D4. The

duplicate samples shall be processed and analyzed 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) analysis.

The TOC analyses 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 analysis of TOC, t he exact method and instrumentation that will be used

will be determined by the analytical laboratory that will conduct the analyses and documented

in the Study Plan and QAPP. G rab samples 6 and 7 will serve as retain samples

. These retain

samples would b e analyzed if a primary sample container arrives broken at the laboratory, but

otherwise would be retained in a refrigerator for later analysis 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 analyzed 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. G rab 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 analyzed 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 analysis. 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 Limit of Quantification ( LOQ ) and shall be taken into the field and processed like an

influent or effluent sam

ple. The laboratory blanks will be used to evaluate contamination bias

resulting from collection, processing, transport, storage, and analysis 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 on t a i ners w il l be pa c ked i n t o c oolers w it h b l ue

- ic e or wa t er ic e, and t aken

ba c k t o t he l abora t ory or sh i pped ba c k t o t he l abora t ory us i ng an overn ig ht express sh i p pi ng

c ompany. Al l sam

pl 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

t he 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 yzed for D4 at one c ommer c i al t es t i ng l abora t or y that has appropriate expertise with the

D4 analyses to be conducted when the testing analysis occurs , unless there are unforeseen

circumstances such as lack of laboratory availability as noted in 40 C.F.R. § 790.68(b)(2)(iii).

T he c ommer c i al l abora t or y w i l l v a l i da t 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 a na l y t i c al method spe c i f i ed i n Knoerr ( 2013 ).

T he Knoerr ( 20 1 3 ) ana l y t i c al method u t ili zes p i e c es of L DP E film t o a c t as a sorbent and par t i al28

barr i 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 wa t er samp l e i s p l a c ed i n t o a container c o n t a i n i ng p i e c es o f L DP E , wh i c h adsorbs

t he D 4

. I n t

he l abora t ory, t

he wa t er samp l e and t

he L DPE sorbent are so lv ent ex t 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 ct i on L i m i t (MD L ) is the c on c en t r a t i on of a c o ns t

i 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 repor t ed w i t h 99 %

probab i li t y t

hat i t i s g rea t er t

han 0 or s t a t i s t i c a ll y d i fferent from a b l ank. T he M D L i s a measure

of a metho d ’ s ab ili t y t o quan t i fy a c ons t

i t uent i n a samp l e matr i x. During method de v e l opmen t

,

t he Knoerr ( 20 1 3 ) ana l y t i c al method for D4 a c h i e v ed a matr i x

- spe c i f i c MD L of 0.037 μ g /

L

which shall be achieved for influent and effluent testing

. T he spe c i f i c l e v el of de t e c t

i 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 a t ed spe c i f

i c a l l y t o t he c o l l e c t i on, ha n d li n g

, and t

ransfer of i nf

l uent and

eff l uent samp l es should be c ondu c t ed i n a cc orda n c e w i t h U S E P A ’ s G L P r e g u l a t

i 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 a l 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 L P r e g u l a t i ons (see 4 0 C

. F

. R

. P art 792 ). T he Q A P P sha l l be

prepared a cc ord i ng t o U S E P A g u 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 ct i on 4 Samp l e T ypes, Se ct i on 6 Manual Samp l i n g

. O pera t i ng P ro c edure N o. S E SDPR O C

- 306

- R 3

. U S E n v i ronmen t al P ro t e c t i 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 I nspe ct i on Manu a l

, Se ct

i 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 E n v i ronmen t al P ro t e c t i on Ag en c y, J u l y, 20 0 4

.

Knoerr SM. 20 1 3

. N O N R E G U L A TE D S T U 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 Qua n t i f i c a t i on of D 4

, D 5

, and D6 i n Was t e Wa t er T rea t ment P l ant

E ff l uent a n d Surfa c e Wa t er Samp l e s . Dow C orn i ng C orpora t i on, H E S S t

udy N o. 11 9 36

- 1 0 8

, A pr i l 18

, 2013

.

A P H A 1999 . S t andard Me t hods for t he E xa m i na t i on of Wa t er and Was t ewater, P art 1 0 60

, C o l l e c t i on and P r e ser v a t i on of Samp l es. A m er i c an P ub l i c H ea l t h A sso c i a t

i on, A mer i c an

Wa t er Works A sso c i a t i on, Wa t er E n v i ronment Federa t i o n

.

A P H A 1999 . S t andard Me t hods for t he E xa m i na t i on of Wa t 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 mer i c an P ub l i c H e a l t h A sso c i a t

i on, A mer i c an Wa t er Works29

A sso c i a t i on, Wa t er E n v i ronment Federa t i on. P ub l i c H ea l t h A sso c i a t

i on, A me r i c an Wa t er

Works A sso c i a t i on, W a t er E n v i ronment Federa t i o n

.

US E P A 2002 Guidance for Qua li t y 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 E n v i ronmen t al I nforma t i on, E P A (De c ember 2002 )

-

h t t p : // www

. ep a .g o v

/ qua l i t y / qs

- do c s / g 5

- f

i na l

. pdf.30

A PPENDIX 5

- Testing Standard for the Collection, Sample Handling, Transfer and Analysis of

Surface Water Samples for D4

Sy n o p s i s :

T h i s t es t i ng s t andard prov i des g u i de li n es for t he c o l l e c t i on and ana l ys i s of en v i ronmen t al

sam p l es for D4 i n support of a T es t i ng P ro g ram de t a il ed i n t h i s ECA

. T h i s s t andard c i t es t he

requ i remen t s for t

he samp l i ng of surfa c e wa t er as de s c r i bed i n Se ct i on V I I of t

he E C A and

A ppend i c es 1

, 2 , and 3

, and i den t i f i es spe c i f i c g u i de l i nes and references t hat w i l l be used i n t

he

prepara t i 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 t i o n / ana l ys i s of surfa c e wa t 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 g ram. T h is s t andard addresse s :

1

. When t o c o l l e c t surfa c e wa t er samp l es

2

. Where t o c o l l e c t surfa c e wa t er samp l es

3

. Spe c i al c ons i dera t

i ons dur i ng samp l e c o l l e c t i on t o a v o i d samp l e c on t am i na t i on

4

. H ow t o c o l l e c t and pro c ess surf a c e wa t er samp l es

5

. H ow t o ana l yze surfa c e wa t er samp l es for D4 and t he appropr i a t 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 :

A ppend i c es 1

– 3 of t

h i s E C A s t a t e t ha t :

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

hs apar t

. T he

exa c t dura t

i on be t ween samp l i ng e v en t 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 dur i ng normal p l ant opera t i ons and dur i ng su c h t

i mes t hat

eff l uent f l ow ra t es from t he was t ewater t rea t ment system are represen t a t i v e of t he

normal p l ant opera t

i ons

. ”

“ Samp l es sha l l be t aken dur i ng t yp i c al weather c ondi t i ons and n o t un t

i l at l e a st t

hree

( 3 ) days af

t er an unusual weather e v ent su c h as a hea v y ra i n s t orm. Samp l es sh a l l be

c o l l e c t ed at a t i me when t he ra t e of D4 re l ease i s expe c t ed t o be represen t a t i v e of t he

t yp i c al ra t 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 en t s w i l l be under t aken t hat are s c hedu l ed t o be a m i n i mum of

t hree mon t

hs apart and dur i ng normal p l ant opera t i ons and weather c ondi t

i ons. N ormal

opera t i ng c ondi t

i ons w i l l be es t ab li shed by c onsul t i ng w i t h t he opera t or of e a c h WWTP

, indirect and d i re c t d i s c har g e fa c ili t y. T he c r i t er i a or means t hat are used by t

he f a c ili t i es t o

de t erm i ne normal opera t

i n g c ondi t i ons w il l be do c umen t 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 t y i s o pera t i ng under normal c ondi t

i ons31

pr i or t o c ommenc i ng samp l i ng at a gi v en l o c a t i o n

. I n add i t i 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 ) days of unusual weather e v en t 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 wa t er samp l es should be c o l l e c t ed at approximately the same location and

roughly the same time as benthic organism s are collected which is described in Append ix 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 mater i a l s, su c h a s D 4

, are w i de l y used i n c onsumer produ c t s and may be present i n

person a l c are produc t s, c ommer c i al produ c t s, and l ubr i c an t s

, and may be c omponen t s of

a n t i foams w i de l y used i n WWTPs

. I f t hese produ c t s are used by i nd i v i dua l s dur i ng any part of

t he prepara t

i on for or d u r i ng any aspe c t of t he f i e l d samp l i n g e v en t or laboratory analysis

,

samp l e c on t am i na t i on by D4 v o l a t ili z i n g from t he user c ou l d o c c ur. T o a v o i d t he po t e n t i al for

samp l e c on t am i na t

i on dur i ng c o l l e c t i on, pro c ess i n g

, s t ora g e, a nd ana l ys i s for D4 i n

en v i ronmen t al matr i c es, pre v en t a t i v e measures should be i mp l e mented t o t he ex t ent poss i b l e

i n t he f i e l d . For example, f

i e l d and laboratory c rew personnel sha l l be requ i red t o refra i n from

us i ng any personal c are produ c t s t hat may c on t a i n any c VMS mater i al s ( e

. g

., su n

- b l o c k, s u n

s c reen, hand l o t

i on, a n t i persp i ran t

, e t c

. ) wh il e prepar i ng for or c onduc t i ng any f i e l d a ct i v i t

i es

t o m i n i m i ze t

he poss i b ili t y for c on t am i na t i on w i t h D 4 . Spe c i f

i c requ i remen t s for c o l l e c t i ng

and hand l i ng surfa c e wa t er samp l es a i med a t pre v en t i ng samp l e c on t am i na t i 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 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 :

T he exa c t method for c o l l e c t i on of surfa c e wa t er samp l es i s a s i t e

- spe c i f i c de t erm i na t

i o n

. During prepara t

i on of t he s i t e

- spe c i f

i c Samp l i ng P l ans, t

he phys i c al na t

ure (e

. g

. , w i d t

h

, dep t h

, f l ow) of t he re c e i v i n g wa t er w i l l be de t erm i ned and used t o g u i de t he se l e c t i on of t he

appr o pr i a t 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 t i on pro c edures for sur f a c e wa t er

samp l es sha l l be based, as appropr i a t e t o t he c hara c t er i s t

i c s of t he r e c e i v i ng wa t e r

, on U S E P A

199 4 (S O P # 20 1 3 , Se ct

i on 7

. 3 Samp l e C o l l e c t i o n

, pp. 3

- 4 ) (USEPA 1994). T h i s g u i dan c e

i den t i f i es t he se v eral ma i n t ypes of c o l l e c t i on de v i c es t h at are used t o c o l l e c t aqueous samp l e s

. T he exa c t c o l l e c t i on met h od for surfa c e wa t 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 remen t s for samp l e container prepara t i on, samp l e hand l i n g

, sam p l e preser v a t

i on,

sh i pp i ng and s t ora g e of samp l es should be essen t i a ll y t he same a c ross a l l s i t es. I m med i a t e l y

pr i or t o ea c h samp l i n g e v ent at ea c h s i t e, t he l abora t ory t hat w i l l ana l yze 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

wa t er samp l es t o be ana l yzed for D 4 , for a l l qua l i t y assuran c e samp l e s

, and for re t a i n samp l es.

T he 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 n t o

t he container s and prov i d i ng P T FE t ape t o ass i st i n sea l i ng t he container s (as des c r i bed i n

Knoerr 20 1 3

, Samp l e C o l l e c t i on se c t i on), as we l l as prov i d i ng l a b e l s

. T he l abora t ory w i l l sh i p32

a l l samp l e container s w i t h adequa t e pa c k i ng mater i a l s i n c oolers t o ea c h s i t e

. T he c oolers w i l l

a l so c on t a i n c ha i n

- o f

- c us t ody forms t

h a t w i l l a cc ompany t

he samp l e container s from t he

l abora t ory t o t

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

he l abora t 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 t he 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 study

samples) will be taken.

Figure 2. Schematic diagram of samples taken while m onitoring for D4 in surface water near

wastewater treatment p lants

.

G rab samp l es 3, 4 and 5 w i l l be divided to provide two dupl i c a t es for ana l ys i s of D 4

. T he

dupl i c a t e sam

p l es sha l l be pr oc essed and ana l yzed as i nd iv i dual sam p l es for D 4 . Dupl i c a t e

samp l es are used t o e v a l ua t e be t wee n

- samp l e v a r i ab i li t y and pre c i s i on. Additionally, an

aliquot of each of the three samples will be used for TOC analysis. T h e TO C ana l yses 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 r g an i c C arbon ( T O C ). Wh i l e

t h i s g u i dan c e ( APHA 1999 ) prov i des se v er a l 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

rumen t a t i on t hat w i l l be used w i l l be de t e r m i ned by t he

ana l y t i c al l abora t ory t

hat w i l l c ondu c t t

he ana l yses and do c umen t ed i n t he Study Plan and

QAPP. G rab samp l es 6 and 7 w i l l se r v e as re t a i n sa m p l es

. T hese retain samp l es wou l d be

ana l y z ed i f a pr i mary samp l e container arr i v es broken at t he l abora t ory, b u t o t

h erw i se wou l d

be re t a i ned i n a refr i g era t or for l a t 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

. T he retain samp l es w i l l be kept un t i l Qua li t y A ssuran c e has been

v er i f i ed and may be analyzed for D4 as necessary. 

### Qualit

y

Assura

nce

Sampl

es Lab

Water

Field

Blank Blank 1 Blank 2 Grab

Sample

1 Grab

Sample

2 Lab

Water

Field

Blank Surface

Water

Field

Blank

(spiked) Surface

Water

Field

Blank

(spiked)

Surface

Water

Grab

Sample

3 Surface

Water

Grab

Sample

4 Surface

Water

Grab

Sample

5 Surface

Water

Grab Sample

6 (Retained

Sample) Surface

Water

Grab Sample

7 (Retained

Sample)

T

O

C Anal

ysis

1 Ana

lysis

2 T

O

C Anal

ysis

1 Ana

lysis

2 T

O

C Anal

ysis

1 Ana

lysis

2 Surface

Water

Field

Blank

(unspiked) Surface

Water

Field

Blank

(unspiked) S

pl

it S

pl

it



### Study

Sampl

es33

In addition to the study samples used to determine D4 concentrations in surface water, several

samples will be analyzed for quality assurance purposes. G rab 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 analyzed for D4 as is (field blank) and the second part will be spiked with a known

amount o f D4 and then analyzed (field spike)

. The field blank/field spike sample s will be used to

evaluate c ontamination bias resulting from sample collection, processing, transport, storage and

analysis. D ur i ng ea c h surface water samp l i ng e v 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 abora t ory

g rade wa t er ha v i ng c on c en t ra t i ons of D 4 b e l ow t

he LOQ and sha l l be t aken i n t o t he f i e l d and

pro c essed li ke a surface water samp l e. T he laboratory blanks w i l l be used t o e v a l ua t e

c o n t am i na t

i on b i as resu l t i ng from c o l l e c t i on, pro c ess i n g

, t ranspor t , s t ora g e, and ana l ys i s of

samp l es. Spe c i f

i c requ i remen t s for prepara t i on, pro c ess i n g

, and ana l ys i s of t he quality

assurance samp l e s sh a

l l be de t a il ed i n t

he Study Plan and t

he QAPP

.

Sea l ed samp l e c on t a i ners w i l l be pa c ked i n t o c oolers w i t h b l ue

- i c e or wa t er i c e, and t aken

ba c k t o t he l abora t ory or sh i pped ba c k t o t he l abora t ory us i ng an overn ig ht express sh i p p i ng

c ompany. A l l sam

p l e c o l l e c t i 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 wa t er samp l es and a cc ompany i ng qua lit y 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 abora t o r y that has appropriate expertise with the D 4 analyses

to be conducted when the testing analysis 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 laborator y will validate a method for the analysis of D4 i n t he surfa c e wa t er

samp l es t hat sha l l be adapted from t he a na l y tic al method spe ci f i ed i n Knoerr ( 2013 ). T he

Knoerr ( 2013 ) ana l y tic al method u tili zes p i e c es of LDPE film t o a c t as a sorbe n t and pa rti al

barr i 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

. I m m ed i a t e l y af t er

c o ll e cti on, a wa t er samp l e i s p oured i n t o a container c on t a i n i ng p i e c es of L DP E , wh ic h

adsorbs t he D 4

. I n th e l abora t ory, t he wa t er samp l e and t

he LDPE sorbent are solvent

extracted and processed for analysis with GC

- MS.

T he MDL is the c on c en t

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

i 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 repor t ed w i t h 99 % probab i li t y t

hat i t i s

g rea t er t han 0 or s t a t

i s t i c a ll y d i fferent from a b l ank. T he M D L i s a measure of a metho d ’ s

ab ili t y t o quan t

i fy a c ons t

i t uent i n a samp l e matr i x. During method de v e l opmen t

, t he Knoerr

( 20 1 3 ) ana l y t i c al method for D4 a c h i e v ed a matr i 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

. T he spe c i f i c l e v el of de t e c t i 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 :34

Al l f i e l d work re l a t ed spe c i f

i c a l l y t o t he c o l l e c t i on, ha n d li n g

, and t

ransfer of surfa c e wa t 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 g u l a t

i 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 n

a c c ordan c e w i t

h U S E P A ’ s G L P re g u l a t i ons (see 4 0 C

. F

. R

. P art 7 9 2 ). T he Q A P P sha l l be

prepared a c c ord i ng t o U S E P A g u i dan c e ( U S E P A 2002 ).

REFERENCES

U S E P A 2006

. C omp il a t

i on of E P A M i x i ng Z one Do c umen t s, Model i ng Do c umen t s, pp. 9

-

13

. E P A 823

- R

- 06

- 0 0 3

, J u l y, 2006

.

U S E P A 1994 . Surfa c e Wa t er Samp l i n g

, Se ct i on 7

. 3 Samp l e C o l l e c t i on. U

. S. E n v i ron m en t al

P ro t e c t i on Ag en c y, S O P #: 2 01 3

, 11 / 1 7 / 94

, R E V. #: 0

. 0

Knoerr S M , Durham JA

. 2013

. N O N R E G U L A TE D S T U 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 t i f i c a t i on of D 4 , D 5

, and D6 i n Was t e Wa t er

T rea t ment P l ant E ff

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

udy

N o. 11 9 36

- 1 0 8

, A pr i l 18

, 2013

.

A P H A 1999 . S t andard Me t hods for t he E xa m i na t i on of Wa t er a n 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 mer i c an P ub l i c H e a l t h A sso c i a t

i on, A mer i c an Wa t er Works

A sso c i a t i on, Wa t er E n v i ronment Federa t i on.

US EPA 2002

. Guidance for Qua li t y 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 E n v i ronmen t al I nforma t i on, E P A

- h t t p : // www

. ep a .g o v

/ qua l i t y / qs

- do c s / g 5

- f

i na l

. pdf.35

A PPENDIX 6

- Testing Standard for the Collection, Sample Handling, Transfer and Analysis of

Biosolids Samples for D4

Sy n o p s i s :

T h i s t es t i ng s t andard prov i des g u i de li n es for t he c o l l e c t i on and ana l ys i s of en v i ronmen t al

sam p l es for D4 i n support of a T es t i ng P ro g ram de t a il ed i n t h i s ECA

. T h i s s t andard c i t es t he

requ i remen t s for t

he samp l i ng of b i osol i ds as des c r i bed i n Se ct i on V I I of t

he E C A and

A ppend i c es 2 and 3 and i den t i f i es spe c i f i c g u i de l i n es and references t hat w i l l be used i n t

he

prepara t i 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 t i 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 g ram. T he 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 dera t

i ons dur i ng samp l e c o l l e c t i on t o a v o i d samp l e c on t am i na t i 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 yze b i osol i ds samp l es for D4 and t he appr o pr i a t 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 :

A ppend i c es 1

- 3 of t

h i s E C A s t a t e t

ha t :

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

hs apar t

. T he

exa c t dura t

i on be t ween samp l i ng e v en t 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 dur i ng normal p l ant opera t i ons and du r i ng su c h t

i mes t hat

eff l uent f l ow ra t es from t he was t ewater t rea t ment system are represen t a t i v e of t he

normal p l ant opera t

i ons

. ”

“ Samp l es sha l l be t aken dur i ng t yp i c al weather c ondi t i ons and n o t un t

i l at l east t

hree

( 3 ) days af

t er an unusual weather e v ent su c h as a hea v y ra i n s t orm. Samp l es sh a l l be

c o l l e c t ed at a t i me when t he ra t e of D4 re l ease i s expe c t ed t o be represen t a t i v e of t he

t yp i c al ra t 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 documen t ed in the site

- specific Sampling Plans. Confirmation will be

obtained that the sub

j ect facility is operating under normal conditions prior to commencing36

sampling at a given location. In a ddition, sampling would not take place within three ( 3 ) days 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 c hosen l o c a t

i on for c o l l e c t i on of b i os o li ds sam p l es s hall be immediately after

dewatering before onsite storage , as practicable, and shall be established in the site s pecific

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 mater i a l s, su c h a s D 4

, are w i de l y used i n c onsumer produ c t s and may be present i n

personal c are p r odu c t s, c ommer c i al produ c t s, and l ubr i c an t s

, and may be c omponen t s of

a n t i foams w i de l y used i n WWTPs

. I f t hese produ c t s are used by i nd i v i dua l s dur i ng any part of

t he prepara t

i on for or d u r i ng any aspe c t of t he f i e l d samp l i ng e v en t or laboratory analysis

,

samp l e c on t am i na t i on by D4 v o l a t ili z i n g from t he user c ou l d o c c ur. T o a v o i d t he po t e n t i al for

samp l e c on t am i na t

i on dur i ng c o l l e c t i on, pro c ess i n g

, s t ora g e, a nd ana l ys i s for D4 i n

en v i ronmen t al matr i c es, pre v en t a t i v e measures should be i mp l e mented t o t he ex t ent poss i b l e i n

t he f i e l d. For example, f

i e l d and laboratory personnel c rew sha l l be requ i red t o refra i n from

us i ng any personal c are produ c t s t hat m a y c on t a i n c VMS mater i a l s ( e

. g

., su n

- b l o c k, su n

- s c reen,

hand l o t i on, a n t i persp i ran t s, e t c

. ) wh il e prepar i n g for or c onduc t i ng any f i e l d a ct i v i t

i es t o

m i n i m i ze t

he poss i b il i t y for c o n t am i na t i on w i t h D 4 . Spe c i f

i c requ i remen t s for c o l l e c t i ng and

hand l i ng b i o s o l i ds sa m

p l es a i med at pre v en t

i ng s a mp l e c on t am i na t

i on by sour c es of D 4 t hat 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 :

T he exa c t method for c o l l e c t i 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 na t

i on. During

prepara t i 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 t

en c y of t he b i osol i ds w i l l be

es t ab li s h ed

. T he c ons i s t en c y of t he b i osol i ds w i l l g u 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 t i on pro c edures for b i osol i ds samp l es sha l l be based, as appropr i a t e t o t he

c hara c t er i s t i c s of t

he b i osol i ds, on t e c hn i ques des c r i bed i n U S E P A 198 9 (Se c t i on 2

. 2 Samp l e

P o i nt Se l e c t

i on and Se c t

i on 2

. 3 S a mp l e C o ll e c t i on, pp. 2

- 4 t o 2

- 1 4 ). T he g u i dan c e i den t i f i es

sam p l e c o l l e c t

i on de v i c es and t e c hn i ques for c o l l e c t i on of subsamp l es t hat w i l l make up

c ompos i t e samp l es. T he e x a c t c o l l e c t i 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 remen t s for samp l e c on t a i ner prepara t i on, samp l e hand l i n g

, samp l e prese r v a t i on,

sh i pp i ng and s t ora g e of samp l es should be essen t i a ll y t he same a c ross a l l s i t es. I m med i a t e l y

pr i or t o ea c h samp l i n g e v ent at ea c h s i t e, t he l abora t ory t hat w i l l ana l yze 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 sam p l e c on t 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 yzed f or D 4 , for a l l qua l i t y assuran c e samp l es, and for re t a i n

samp l es. T he samp l e c on t a i ners w i l l be prepared by pre

- wash i ng w i t h hexane, prov i d i n g P T FE

t ape t o a s s i st i n sea l i n g t he c on t a i ners, as we l l as prov i d i n g l abe l s

. T he l abora t ory w i l l sh i p a l l

samp l e c on t a i ners w i t

h adequa t e pa c k i ng mater i a l s i n c oolers t o ea c h s i t e. T he c oolers w i l l a l so37

c on t a i n c ha i n

- o f

- c us t ody fo r ms t

hat w i l l a cc ompany t

he samp l e c on t a i ners from t he l abora t ory

t o t he f i e l d and b a c k t o t

he l abor a t ory.

Figure 3 provides a schematic that describes the quality 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 quality assurance samples and five

D4 study samples) will be taken. During ea c h samp l i ng e v 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 r i 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 analysis

of D4

. T he d u p li c a t e samp l e s sha l l be pro c essed and ana l yzed as i nd iv i dual samp l es for D 4

. Dupl i c a t e samp l es are u sed t o e v a l ua t e be t wee n

- sam p l e v ar i a b i l i t y and pre c i s i o n

. I n add i t i on,

a separa t 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 separa t 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 wa t er c on t en t

. F o l l ow i ng t he g ener a l pro c edures of

P owe l l 2010

, t he add i t

i onal a li quo t s sha l l be ana l yzed by c arbon c ou l o m e t ry 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 t i on

for t o t al wa t er c o n t ent a n d t o t al or g an i c mat t er c on t e n t

. C ompos i t ed b i osol i ds samples 6 and 7

will serve as retain samples

. T hese retain s a mp l es wou l d be ana l yzed i f a pr i mary samp l e

c on t a i ner arr i v es at t

he l abora t 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 refr i g era t or for l a t er ana l ys i s i f a samp l e be c om e s c o m prom i sed dur i ng collection or 

### Qualit

y

Assura

nce

Sampl

es Referenc

e

Sedimen

t

Field

Blank Blank 1 Blank 2 Composi

ted

Sample

1 Composi

ted

Sample

2

T

O

C Anal

ysis

1 Ana

lysis

2 T

O

C Anal

ysis

1 Ana

lysis

2 T

O

C Anal

ysis

1 Ana

lysis

2 Referenc

e

Sedimen

t

Field

Blank Biosolids

Field

Blank

(spiked) Biosolids

Field

Blank

(spiked)

Biosolids

Composit

ed

Sample 3 Biosolids

Composit

ed

Sample 4 Biosolids

Composit

ed

Sample 5 Biosolids

Composited

Sample 6

(Retained

Sample) Biosolids

Composited

Sample 7

(Retained

Sample) 

### Study

Sampl

es Biosolid

s

Field

Blank

(unspike

d) S

pl

it S

pl

it Biosolid

s

Field

Blank

(unspike

d)38

pro c ess i n g

. T he retain samp l es w i l l be kept un t i l Qua l i t y A ssur a

n c e has been v er i f

i ed and may

be analyzed for D4 as necessary

.

In addition to the study samples used to determine D4 concentrations in biosolids, several

samples will be analyzed 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 w i t h a known amount of

D 4

. T he f

i e l d sp i ked b i osol i ds samp l es w i l l be used t o e v a l ua t e l oss of D 4 dur i ng c o l l e c t i on,

pro c ess i n g

, t

ranspor t , s t ora g e, and ana l ys i s of samp l e s

, and t o e v a l ua t e ana l y t i c al b i as

. Two

reference sed i ment samp l e s ha v i ng c on c en t r a t i ons of D4 be l ow t

he LOQ for t

h i s matr i x sha l l

be t aken i n t 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 i ment w i l l be used

be c ause of t

he expe c t a t

i on t hat any WWTP b i osol i ds may c on t a i n D 4

. T he reference s e d i ment

samp l e s w i l l be used t o e v a l ua t e c on t am i na t i on b i as resu l t

i ng from c o l l e c t

i on, pro c ess i n g

,

t ranspor t

, s t ora g e, and ana l ys i s of samp l es. Specific requirements for preparation, processing,

and analysis 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

company. 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 sam

p l es and a cc ompany i ng qua l i t y assur a n c e samp l es sha l l be ana l y z ed for D4 a t

one c ommer c i al t es t i ng l abora t o r y that has appropriate expertise w ith the D 4 analyses to be

conducted when the testing analysis occurs , unless there are unforeseen circumstances such as

lack of laboratory availability as noted in 40 C.F.R. § 790.68(b)(2)(iii). T he c ommer c i al

l abora t o r y w i l l v a l i da t 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)

T he MDL is the c o n c en t

r a t i on of a c o ns t

i 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 repor t ed w i t h 99 % probab i li t y t

hat i t i s g rea t er

t han 0 or s t a t i s t

i c a ll y d i fferent from a b l ank. T he M D L i s a measure of a metho d ’ s ab ili t y t o

quan t i fy a c ons t

i t uent i n a samp l e matr i x. Powell (2010) determined an MDL up to 3.7 n g/ g (wet

we i g h t

, ww) for sediment which shall be applied for biosolids. T he spe c i f i c l e v el of de t e c t i 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 a t ed t o t he c o l l e c t i on, hand l i n g

, and t r ansfer of b i osol i ds samp l es should be

c ondu c t ed i n a cc ordan c e w i t h U S E P A ’ s G L P r e g u l a t i on s (see 4 0 C

. F

. R

. P art 7 9 2 ). Al l39

ana l y t i c al work, i n c l ud i n g 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 g u l a t i o n s (see 4 0 C

. F

. R

. P art 792 ). T he Q A P P sha l l be prepared a cc ord i ng t o

U S E P A g u i d a

n c e ( U S E P A 2002 ).

REFERENCES

U S E P A ( 1989 ): WWTP S l ud g e Samp l i n g and A na l ys i s Gu i dan c e Do c umen t

, Se ct i on 2

. 2

Samp l e P o i nt Se l e c t i on and Se ct i on 2

. 3 Samp l e C o l l e c t i o n

. E P A 833

- B

- 8 9

- 10 0

, A u g us t

, 1989

.

Powell, D.E. 2010. Bioaccumulation and Trophic Transfer of Cyclic 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

. T rophic D i l u t i on of C y c li c Vo l a t il e Me t hy l s i l oxane

( c VMS) Ma t er i a l s i n a T empera t e Freshwa t er L ake. Dow C orn i ng C orpora t i on, H E S S t

u dy

N o. 1077 1

- 108

.

US E P A 2002. Guidance for Qua li t y 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 E n v i ronmen t al I nforma t i on, E P A (De c ember 2002 )

- h t t p : // www

. ep a .g o v

/ qua l i t y / qs

- do c s / g 5

-

f i na l

. pdf.40

APPENDIX 7

- Testing Standard for the Collection, Sample Handling, Transfer and Analysis of

Sediment Samples for D4

Sy n o p s i s :

T h i s t es t i ng s t andard prov i des d i re c t i on for t he c o l l e c t i on and ana l ys i s of en v i ronmen t al

samp l es for D4 i n support of a T es t i ng P ro g ram de t a il ed i n t h i s ECA

. T h i s s t andard c i t es t he

requ i remen t s for t

he samp l i ng of sed i ment as des c r i bed i n Se ct i on V I I of t

he E C A and

A ppend i c es 1

, 2

, and 3 , and i den t i f i es spe c i f i c g u i d e l i nes and references t hat w i l l be used i n t

he

prepara t i 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 t i 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 g ram. T he 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 dera t

i ons dur i ng samp l e c o l l e c t i on t o a v o i d samp l e c on t am i na t i 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 yze sed i ment samp l es for D4 and t he app r opr i a t 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 :

A ppend i c es 1

- 3 of t

h i s E C A s t a t e t

h a t :

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

hs apar t

. T he

exa c t dura t

i on be t ween samp l i ng e v en t 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 dur i ng normal p l ant opera t i ons and d ur i ng su c h t

i mes t hat

eff l uent f l ow ra t es from t he was t ewater t rea t ment system are represen t a t i v e of t he

normal p l ant opera t

i ons

. ”

“ Samp l es sha l l be t aken dur i ng t yp i c al weather c ondi t i ons and n o t un t

i l at l east t

hree

( 3 ) days af

t er an unusual weather e v ent su c h as a hea v y ra i n s t orm. Samp l es sh a l l be

c o l l e c t ed at a t i me when t he ra t e of D4 re l ease i s expe c t ed t o be represen t a t i v e of t he

t yp i c al ra t 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 en t s w i l l be under t aken t hat are s c hedu l ed t o b e a m i n i mum of

t hree mon t

hs apart and dur i ng normal p l ant opera t i ons and weather c ondi t

i ons. N ormal

opera t i ng c ondi t

i ons w i l l be es t ab li shed by c onsul t i ng w i t h t he opera t or of e a c h WWTP

, indirect discharge facility and d i re c t d i s c har g e fa c ili t y. T he c r i t er i a or means t hat are used by

t he f a c ili t i es t o de t erm i ne normal opera t i n g c ondi t i ons w il l be do c umen t 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 t y i s opera t i ng under41

normal c ondi t

i ons pr i or t o c ommenc i ng samp l i ng at a gi v en l o c a t i o n

. I n add i t i 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 ) days of unusual weather e v en t 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 v i ng wa t er body sha l l be c o l l e c t e d at

approximately t

he same l o c a t

i on where ben t

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 mater i a l s, su c h a s D 4

, are w i de l y used i n c onsumer produ c t s and may be present i n

personal c are produc t s, c ommer c i al produ c t s, and l ubr i c an t s

, and may be c omponen t s of

a n t i foams w i de l y used i n WWTPs

. I f t hese produc t s are used by i nd i v i dua l s dur i ng any part

of t he prepara t

i on for or d u r i ng any aspe c t of t he f i e l d samp l i ng e v en t or laboratory analysis

,

samp l e c on t am i na t i on by D4 v o l a t ili z i n g from t he user c ou l d o c c ur. T o a v o i d t he po t e n t i al for

samp l e c on t am i na t

i on dur i ng c o l l e c t i on, pro c ess i n g

, s t ora g e, a nd ana l ys i s for D4 i n

en v i ronmen t al matr i c es, pre v en t a t i v e measures should be i mp l e mented t o t he ex t ent poss i b l e

i n t he f i e l d. For example, f

i e l d and laboratory personnel c rew sha l l be requ i red t o refra i n from

us i n g any personal c are produ c t s t hat may c on t a i n c VMS mater i a l s ( e

. g

., su n

- b l o c k, su n

s c reen, hand l o t

i on, a n t i persp i ran t

, e t c

. ) wh il e prepar i n g for or c onduc t i ng any f i e l d a ct i v i t y t o

m i n i m i ze t

he poss i b i l i t y for c o n t am i na t i on w i t h D 4 . Spe c i f

i c requ i remen t s for c o l l e c t i ng and

hand l i ng sed i ment sam

p l es a i m ed at pre v en t

i ng samp l e c on t am i na t

i 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 t he 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 :

T he exa c t method for c o l l e c t i 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 na t

i on. During

prepara t i on of t he s i t e

- spe c i f

i c Samp l i ng P l ans, t

he phys i c al na t

ure (e

. g

. , w i d t

h

, dep t h

, f l ow) of

t he re c e i v i ng wa t er w i l l be de t erm i ned and used t o g u i de t he se l e c t i on of t he appropr i a t 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 t i on pr o c edures for sed i ment samp l es sha l l be based,

as appropr i a t e t o t

he c hara c t er i s t i c s of t

he re c e i v i ng wa t e r

, on t e c h n i ques des c r i bed i n U S E P A

199 4 (S O P # 20 1 6

, S e ct

i ons 2

- 5

, 7

, pp. 1

- 7 ) and U S E P A ( 2001 ) ( C hap t er 3 , pp. 3

- 1 t o 3

- 1 7 )

. T h i s g u i dan c e i den t

i f i es t he se v eral m a i n t ypes of c o l l e c t i on de v i c es t

hat are used t o c o l l e c t

sed i ment samp l e s

. T he exa c t c o l l e c t i 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 remen t s for samp l e c on t a i ner prepara t i on, samp l e hand l i n g

, samp l e prese r v a t i on,

sh i pp i ng and s t ora g e of samp l es should be essen t i a ll y t he same a c ross a l l s i t es. I m med i a t e l y

pr i or t o ea c h samp l i n g e v ent at ea c h s i t e, t he l abora t ory t hat w i l l ana l yze 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 sam p l e c on t a i ners i n suff

i c i e n t numbers for

a l l sed i ment samp l es t o be ana l yzed for D 4 , for a l l qua l i t y assuran c e samp l es, and for re t a i n

samp l es. T he samp l e c on t a i ners w i l l be prepared by pre

- washing w i t h hexane, prov i d i ng P T FE

t ape t o ass i st i n sea l i ng t he c on t a i ners, as we l l as prov i d i ng l abe l s

. T he l abora t ory w i l l sh i p a l l

samp l e c on t a i ners w i t

h adequa t e p a c k i ng mater i a l s i n c oolers t o ea c h s i t e. T he c oolers w i l l a l so42

c on t a i n c ha i n

- o f

- c us t ody fo r ms t

hat w i l l a cc ompany t

he samp l e c on t a i ners from t he l abora t ory

t o t he f i e l d and b a c k t o t

he l abor a t ory.

Figure 4 provides a schematic that describes the quality 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 quality assurance samples and five D4 study

samples) will be taken from t he depos i t i on zone nearest t he fa c ili t y was t e w a t er ou t fa l l re l ease

po i n t

, i n a cc or d an c e w i t

h t he samp l e c o l l e c t i 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 directly into a glass jar, and

then capped.

S ediment samples 3

, 4 and 5 will be divided to provide two duplicates for analysis of D4

. The

duplicate samples shall be processed and analyzed as individual samples for D4. Dupl i c a t e

samp l es are u sed t o e v a l ua t e be t we e n

- samp l e v ar i ab i li t y 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 separa t e a li quot sha l l be t aken from ea c h samp l e and

separa t 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 wa t er c o n t en t . 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 er i za t i on of Sed i ments, p. 10 ) t hese

add i t i onal samp l es sha l l be ana l yzed by c arbon c ou l ome t ry 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 a r bon, and t o t al or g an i c c arbo n , and l os s

- o n

- ig n i t i on for t o t al wa t er

c on t e n t and t o t al or g an i c mat t er c on t en t

. S ed i ment samp l es 6 and 7 w i l l serve as re t a i n Sedimen

t

Field

Blank

(unspike

d) S

pl

it S

pl

it Sedimen

t

Field

Blank

(unspike

d) 

### Qualit

y

Assura

nce

Sampl

es Referenc

e

Sedimen

t

Field

Blank Blank 1 Blank 2 Sample

1 Sample

2

T

O

C Anal

ysis

1 Ana

lysis

2 T

O

C Anal

ysis

1 Ana

lysis

2 T

O

C Anal

ysis

1 Ana

lysis

2 Referenc

e

Sedimen

t

Field

Blank Sedimen

t

Field

Blank

(spiked) Sedimen

t

Field

Blank

(spiked)

Sediment

Sample 3 Sediment

Sample 4 Sediment

Sample 5 Sediment

Sample 6

(Retained

Sample) Sediment

Sample 7

(Retained

Sample) 

### Study

Sampl

es43

samp l e s

. T hese retain samp l es wou l d be ana l yzed i f a pr i ma r y samp l e c on t a i ner arr i v es broken

at t he l abora t ory, but o t

herw i se wou l d be re t a i ned i n a refr i g era t or for l a t er ana l ys i s i f a samp l e

be c omes c omprom i sed dur i ng collection or pro c ess i n g

. T he retain samp l es w i l l be kept un t i l

Qua l i t y A ssuran c e has been v er i f i e d and may be analyzed for D4 as necessary.

In addition to the study samples used to determine D4 concentrations in sediment, several

samples will be analyzed 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 w i t h a known amount of D 4

. T he f i e l d

sp i ked sediment samp l es w i l l be used t o e v a l ua t e l oss of D 4 dur i ng c o l l e c t i on, pro c ess i n g

,

t ranspor t , s t ora g e, and ana l ys e s of samp l e s

, and t o e v a l ua t e ana l y t i c al b i as. Spe c i f i c

requ i re m en t s for prepara t 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 a t e

samp l es sh a

l l be de t a il ed i n t

he S t udy P l an and t

he Q A PP

. T wo reference sed i ment samp l e s

ha v i ng c on c en t

r a t i ons of D4 be l ow t

he LOQ for t

h i s matr i x sha l l be t aken i n t o t he f i e l d and

pro c essed li ke sediment samp l e s

. T he reference s e d i ment samp l e s w i l l be used t o e v a l ua t e

c on t am i na t i on b i as resu l t i ng from c o l l e c t i on, pro c ess i n g

, t ranspor t

, s t ora g e, and ana l ys i s of

samp l es.

Sea l ed samp l e c on t a i ners w i l l be pa c ked i n t o c oolers w i t h b l ue

- i c e or wa t er i c e and t aken

ba c k t o t he l abora t ory or sh i pped ba c k t o t he l abora t ory us i ng an overn ig ht express sh i p p i ng

c ompany. A l l sam

p l e c o l l e c t i 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 d i ment sam

p l es and a cc ompany i ng qua l i t y assur a n c e samp l es sha l l be ana l y z ed for D4 a t

one c ommer c i al t es t i ng l abora t o r y that has approp riate expertise with D4 analyse 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). T he c ommer c i al l abora t o r y w i l l

v a l i da t 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).

T he MDL is the c on c en t

r a t i on of a c o ns t

i 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 u r ed and repor t ed w i t h 99 % probab i li t y t

hat i t i s g rea t er

t han 0 or s t a t i s t

i c a ll y d i fferent from a b l ank. T he M D L i s a measure of a metho d ’ s ab ili t y t o

quan t i fy a c ons t

i t uent i n a samp l e matr i x. The method for analyzing D4 in sediment reported by

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 LOQ 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 signa tory 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 :44

Al l f i e l d work re l a t ed spe c i f

i c a l l y t o t he c o l l e c t i on, ha n 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 L P r e g u l a t i 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 on t en t

, 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 L P r e g u l a t i ons (see 4 0 C .F. R

. P art 792 ). T he Q A P P sha l l be

prepared a cc ord i ng t o U S E P A g u i dan c e ( U S E P A 2002 ).45 R EFERENCES

U S E P A 1994 . Sed i ment Samp l i n g

, Se c t i ons 2

- 5 and 7

. U

. S. E n v i ronmen t al P ro t e c t i on

Ag en c y, S O P #: 201 6

, 1 1 / 17 / 94 , R E V. #: 0

. 0

– See a tt a c hed

U S E P A 2001 . Me t

hods for C o l l e c t

i on, S t ora g e and Manipu l a t i 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 A ppend i x E

. U S

E n v i ronmen t al P ro t e c t

i 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 Cyclic 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

. T rophic D i l u t i on of C y c li c Vo l a t il e Me t hy l s i l oxane

( c VMS) Ma t er i a l s i n a T empera t e Freshwa t er L ake. Dow C orn i ng C orpora t i on, H E S S t

u dy

N o. 1077 1

- 108

.

US E P A 2002. Guidance for Qua li t y 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 E n v i ronmen t al I nforma t i on, E P A (De c ember 2002 )

- h t t p : // www

. ep a .g o v

/ qua l i t y / qs

- do c s / g 5

-

f i na l

. pdf.46

A PPENDIX 8

- Testing Standard for the Collection, Sample Handling, Transfer and Analysis of

Biota Samples for D4

Sy n o p s i s :

T h i s t es t i ng s t andard prov i des g u i de li n es for t he c o l l e c t i on and ana l ys i s of en v i ronmen t al

sam p l es for D4 i n support of a T es t i ng P ro g ram de t a il ed i n t h i s ECA

. T h i s s t andard c i t es t he

requ i remen t s for t

he samp l i ng of b i o t a as des c r i bed i n Se c t i on V I I of t

he E C A and A ppend i c es

1

, 2 and 3 , and i den t

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

he prepara t

i 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 t i o n / ana l ys i s of b i o t a 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 g ram. T he s t andard addresse s :

1

. When t o c o l l e c t b i o t a 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 dera t

i ons dur i ng samp l e c o l l e c t i on t o a v o i d samp l e c on t am i na t i 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 yze b i o t a samp l es for D4 and t he appropr i a t 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 ben t h i c spe c i es c o l l e c t ed i n sed i ment of t he re c e i v i ng

wa t er body a n 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 wa t er bod y

. ”

A ppen d i c es 1

- 3 of t

h i s E C A s t a t e t

ha t :

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

hs apar t

. T he

exa c t dura t

i on be t ween samp l i ng e v en t 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 dur i ng normal p l ant opera t i ons and dur i ng su c h t

i mes t hat

eff l uent f l ow ra t es from t he was t ewater t rea t ment system are represen t a t i v e of t he

normal p l ant opera t

i ons

. ”

“ Samp l es sha l l be t aken dur i ng t yp i c al weather c ondi t i ons and n o t un t

i l at l east t

hree

( 3 ) days af

t er an unusual weather e v ent su c h as a hea v y ra i n s t orm. Samp l es sh a l l be

c o l l e c t ed at a t i me when t he ra t e of D4 re l ease i s expe c t ed t o be represen t a t i v e of t he

t yp i c al ra t e of re l ease of D4 for t hat s i t e

. ”47

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 en t s w i l l be under t aken t hat are s c hedu l ed t o be a m i n i mum of

t hree mon t

hs apart and dur i ng normal p l ant opera t i ons and weather c ondi t

i ons. N ormal

opera t i ng c ondi t

i ons w i l l be es t ab li shed by c onsul t i ng w i t h t he opera t or of e a c h WWTP,

indirect and d i re c t d i s c har g e fa c ili t y

. T he c r i t er i a or means t hat are used by t

he f a c ili t i es t o

de t erm i ne normal opera t

i n g c ondi t i ons w il l be do c u mented 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 t y i s opera t i ng under normal c ondi t

i ons

pr i or t o c ommenc i ng samp l i ng at a gi v en l o c a t i on. I n add i t i 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 ) days of unusual weather e v en t 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 adequa t e m i x i ng of t he d i s c har g e and re c e i v i n g wa t er has o c c urred and where

adequate benthic organism sample masses are obtained. Each site specific sampling plan will

identify where the eff

luent and receiving stream are adequately mixed and the basis for the

determination

. At each site fish

, surface water and sediment s hall also be collected at

approximately 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 mater i a l s, su c h a s D 4

, are w i de l y used i n c onsumer produ c t s and may be present i n

personal c are produc t s, c ommer c i al produ c t s, and l ubr i c an t s

, and may be c omponen t s of

a n t i foams w i de l y used i n WWTPs

. I f t hese produc t s are used by i nd i v i dua l s dur i ng any part

of t he prepara t

i on for or d u r i ng any aspe c t of t he f i e l d samp l i ng e v en t or laboratory analysis

,

samp l e c on t am i na t i on by D4 v o l a t ili z i n g from t he user c ou l d o c c ur. T o a v o i d t he po t e n t i al for

samp l e c on t am i na t

i on dur i ng c o l l e c t i on, pro c ess i n g

, s t ora g e, a nd ana l ys i s for D4 i n

en v i ronmen t al matr i c es, pre v en t a t i v e measures should be i mp l e mented t o t he 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 and laboratory personnel c rew sha l l be requ i red t o refra i n from

us i ng any personal c are produ c t s t hat may c on t a i n c VMS mater i a l s ( e

. g

., su n

- b l o c k, su n

s c reen, hand l o t

i on, a n t i persp i ran t s, e t c

. ) wh il e prepar i n g for or c onduc t i ng any f i e l d a ct i v i t i es

t o m i n i m i ze t

he poss i b il i t y for c o n t am i na t i on w i t h D 4 . Spe c i f

i c requ i remen t s for c o l l e c t i ng

and hand l i ng b i o t a samp l e s a i med at pre v en t i ng samp l e c on t am i na t i on by sour c es of D 4 t h a t

are n o t spe c i f

i c t o t he WWTP or d i r e c t d i s c har 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:

T he exa c t method for c o l l e c t i on of sed i ment samp l es from wh i c h ben t h i c i n v er t ebra t 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 na t i on. During prepara t i on o f t he s i t e

- spe c i f

i c Samp l i n g

P l ans, t he phys i c al na t

ure (e

. g.

, w i d t

h

, dep t h , f l ow) of t he re c e i v i ng wa t er w i l l be de t erm i ned

and used t o g u i de t

he se l e c t i on of t

he appropr i a t 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 t i on pr o c edures for sed i ment samp l es sha l l be based, as appropr i a t e t o t h e c hara c t er i s t

i c s

of t he re c e i v i ng wa t e r

, on t e c hn i ques des c r i bed i n P owe l l and Woodburn ( 200 9 , Samp l e

C o ll e c t i on, p. 9 ) and U S E P A ( 2003 a , Se ct i ons 5

. 2 Samp l i ng for C ommun i t y Sam p l es and 5

. 348

Samp l i n g for A na l y t i c al Measur e ments )

. T h i s g u i dan c e i den t i f i es c o l l e c t i on pro c edures t

hat

may be used t o c o l l e c t sed i ment samp l es from wh i c h ben t h i c i n v er t ebra t 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 t i ng ben t h 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 remen t s for samp l e c on t a i ner prepara t i on, samp l e hand l i n g

, samp l e prese r v a t i on,

sh i pp i ng and s t ora g e of samp l es should be e ssen t i a ll y t he same a c ross a l l s i t es. I m med i a t e l y

pr i or t o ea c h samp l i n g e v ent at ea c h s i t e, t he l abora t ory t hat w i l l ana l yze 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 sam p l e c on t a i ners i n suff

i c i e n t numbers for

a l l ben t h i c or g an i sm samp l es t o be ana l yzed for D 4

. T he samp l e c on t 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. T he l abora t ory w i l l sh i p a l l sam p l e c on t a i ners w i t

h adequa t e pa c k i ng mater i a l s

i n c oolers t o ea c h s i t e. T he c oolers w i l l a l so c on t a i n c ha i n

- o f

- c us t ody forms t

hat w i l l a cc ompany

t he samp l e c o nt a i ners from t he l abora t ory t o t

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

he l abora t 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 in to three parts. Two of the parts will serve as duplicates for D4 analysi s and one part

will be analyzed 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 analysis as needed. T hese retain samp l es

wou l d be ana l y z ed i f a pr i mary samp l e container arr i v es broken at t he l abora t 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 a t er ana l ys i s i f a samp l e be c omes c omprom i sed

dur i n g collection or processing

. T he retain samp l es w i l l be kept un t i l Qua li t y A ssuran c e has

been v er i f

i ed and may be analyzed for D4 as necessary.



### Qualit

y

Assur

ance

Sampl

es Rainbow

Trout

Field

Blank Blank 1 Blank 2 Spike 1 Spike 2 Lipid 1 Lipid 2



# Grab

If grab does not yield sufficient sample mass, then repeat effort in an

adjacent location.

Total mass ≥ 100 g from

composite sample

≥ 20 g

composi

te

sample

1

Li

pi

d Anal

ysis

1 Ana

lysis

2 ≥ 20 g

composi

te

sample

2

Li

pi

d Anal

ysis

1 Ana

lysis

2 ≥ 20 g

composi

te

sample

3

Li

pi

d Anal

ysis

1 Ana

lysis

2 ≥ 20 g

composite

sample

(Retained

Sample)

sample 4 ≥ 20 g

composite

sample

(Retained

Sample)

sample 5 Rainbow

Trout

Field

Blank Rainbow

Trout

Field

Blank Rainbow

Trout

Field

Blank Rainbow

Trout

Field

Blank Rainbow

Trout

Field

Blank



### Study

Sampl

es49

Figure 5. Schematic d i 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 analyses. Ben t h i c or g an i sms w i l l be separa t 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 v i d i n g t he c o l l e c t ed

o r g an i sms i n t o gl ass c on t a i ners and freez i ng pr i or t o sh i pmen t

. P r i or t o prepar i ng c ompos i t e

samp l es, t h e t axa represen t 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 n t o 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 abora t ory or sh i pped

ba c k t o t he l abora t ory us i ng an overn ig ht 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 ben t

h i c or g an i sms t o

b o t h ana l yze for c hem i c al c on c en t ra t i on and t o prepare qu a li t y 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 surroga t e

mater i al t o use t o prepare qua l i t y assuran c e samp l es t o use dur i ng prepara t i on of ben t

hos

samp l es.

During ea c h samp l i ng e v 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 pu r c hased from a c ommer c i al fish hatchery w i l l be

g round i n t o a homo ge nous m i x t ure. Sam

p l es of t he g round rainbow trout w i l l be prepared i n t he

l abora t ory pr i or t o samp l e c o l l e c t i on and sh i pped t o t

he f i e l d. P r i or t o sh i pp i ng t o t he f i e l d, t he

g round rainbow trout samp l es w i l l be ana l yzed and shown t o ha v e c on c en t ra t i ons of D4 be l ow

t he LOQ for t

h i s matr i x. Ser vi ng as f

i e l d b l anks, t

wo reference g round rainbow trout samp l e s

w i l l be opened dur i ng prepara t i on of t he c ompos i t e samp l es of ben t h i c or g an i sm s

. T he

reference rainbow trout samp l e s w i l l be used t o e v a l ua t e c o n t am i na t i on b i as re s u l t i ng from

c o l l e c t i on, pro c ess i n g

, t

ranspo r t , s t ora g e, and a n a l ys i s of ben t hos samp l es. I n add i t

i o n

, t wo of

t he g round 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

. T he

f i e l d sp i ked samp l e s of g round rainbow trout w i l l be used t o e v a l ua t e l oss of D 4 dur i ng

c o l l e c t i on, pro c ess i n g

, t

ranspor t

, s t ora g e, and ana l ys i s of t he ben t hos samp l es, and t o e v a l ua t e

ana l y t i c al b i as. Samp l e c o l l e c t i on pro c edures as we l l as spe c i f i c requ i remen t s for samp l e

c on t a i ner prepara t

i o n, samp l e preser v a t

i 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 analysis will be performed on two ground rainbow trout field blanks. T he method for

a na l ys i s of li p i d c on t ent of t he c ompo s i t ed ben t h i c or g an i sm samp l es w i l l be t he same as used

for f i sh. P ro c edures equ i v a l ent t o P owe l l and Woodburn ( 20 0 9 ) C hara c t er i za t i on of F i sh and

Ben t h i c Ma c ro i n v er t ebra t es, p. 1 1 sha l l be used t o measure li p i d c on t en t s i n t he ben t h i c

or g an i sm sam

p l e s

.

Spe c i f i c requ i remen t s for monitoring site location prepara t 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 k es, and dupl i c a t 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 :50

T he exa c t method for c o l l e c t i on of f i sh i s a s i t e

- spe c i f

i c de t erm i na t

i on. During prepara t

i on of

t he s i t e

- spe c i f

i c Samp l i n g P l ans, t

he phys i c al n a t

ure (e

. g.

, w i d t

h, dep t h

, f l ow) of t he re c e i v i ng

wa t er w i l l be de t erm i ned and used t o g u i de t he se l e c t i on of t

he ap p ropr i a t 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 t i on pro c edures w i l l be based, as appropr i a t e t o t he

c hara c t er i za t i on of t

he re c e i v i ng wa t e r , on U S E P A 2003 a (Se c t i 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 t i on, p. 8 ). T h i s g u i dan c e i den t i f i es t wo ma i n

t ypes of f i sh c o l l e c t i on methods for re l a t i v e l y sha l l ow and s l ow mo vi n g wa t er and gi v es

d i r e c t i on on c ho i c e of meth o d, g eneral pra c t i c es, and o t

her c ons i dera t

i 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 t i 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 remen t s for samp l e c o nt a i ner prepara t i on, samp l e hand l i n g

, samp l e prese r v a t i on,

sh i pp i ng and s t ora g e of samp l es should be essen t i a ll y t he same a c ross a l l s i t es. I m med i a t e l y

pr i or t o ea c h samp l i n g e v ent at ea c h s i t e, t he l abora t ory t hat w i l l ana l yze t he samp l es sha l l

prepare c l e an (new, ne v er used) pre

- we i g hed g l ass sam p l e c on t a i ners and po l yethy l 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 sam p l es t o be ana l yzed for D 4 , for a l l qua l i t y

assuran c e samp l es, and for re t a i n samp l es. T he samp l e c on t a i ners w i l l be prepared by pre

washing 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 n g t he c on t a i ners, as we l l as

prov i d i n g l abe l s

. T he l abora t ory w i l l s h i p a l l sam p l e c on t a i ners and po l yethy l ene ba g s w i t h

adequa t e pa c k i ng mater i a l s i n c oolers t o ea c h s i t e. T he c o o l ers w i l l a l so c on t a i n c ha i n

- o f

c us t ody forms t

hat w i l l a cc ompany t

he samp l e c on t a i ners from t he l abora t ory t o t

he f i e l d and

ba c k t o t he l abora t ory.

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 sor t ed by spe c i es. T he

t axonom i c i den t

i f i c a t i on of ea c h f

i sh species shall be no t ed

. T wo 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 c h 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 nforma t i on about t he 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 repor t s.

T he 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 g h t

.

Figure 6 provide s a schematic that describes fish samples to be taken at each sampling location.

For ea c h of t

he t wo 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

. In the laboratory t hree of the samples shall be thawed, homogenized and divided in to

three parts. Two of the parts will serve as duplicates for D4 analysis and one part will be

analyzed 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

.51

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

analyzed 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 wil l be kept un t i l Qua li t y A ssuran c e has been v er i f i ed and may

be analyzed for D4 as necessary

.

During ea c h samp l i ng e v 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 a

i nbow t rout pu r c hased from a c ommer c i al f i sh ha tc hery w i l l be g round 

### Quali

ty

Assur

ance

Samp

les Rainbo

w Trout

Field

Blank Unspik

ed

Blank 1 Rainbo

w Trout

Field

Blank Unspik

ed

Blank 2 Rainbo

w Trout

Field

Blank Spike 1 Rainbo

w Trout

Field

Blank Spike 2 Rainbo

w Trout

Field

Blank Lipid 1 Rainbo

w Trout

Field

Blank Lipid 2



# Catch Species 1 (Trophic

guild 1) If catch does not yield sufficient sample, then repeat effort in

adjacent location. Total mass ≥ 250 g from single

fish or composite sample

≥ 50 g

from

single

fish or

compo

site

Sample

1 Li

p

i

d An

aly

sis

1 An

aly

sis

2 ≥ 50 g

from single

fish or

composite

(Retained

Sample)

sample 4



# Catch Species 2 (Trophic guild

2) If catch does not yield sufficient sample, then repeat effort in

adjacent location.

≥ 50 g from

single fish

or

composite

(Retained

Sample)

sample 4 ≥ 50 g from

single fish

or

composite

(Retained

Sample)

sample 5 Total mass ≥ 250 g from single

fish or composite sample ≥ 50 g

from

single

fish or

compo

site

sample

2 Li

p

i

d An

aly

sis

1 An

aly

sis

2 ≥ 50 g

from

single

fish or

compo

site

sample

3 Li

p

i

d An

aly

sis

1 An

aly

sis

2 ≥ 50 g

from single

fish or

composite

(Retained

Sample)

sample 5 

### Study

Samples

≥ 50 g

from

single

fish or

compo

site

sample

1 Li

p

i

d An

aly

sis

1 An

aly

sis

2 ≥ 50 g

from

single

fish or

compo

site

sample

2 Li

p

i

d An

aly

sis

1 An

aly

sis

2 ≥ 50 g

from

single

fish or

compo

site

sample

3 Li

p

i

d An

aly

sis

1 An

aly

sis

2 

### Study

Samples52

i n t o a homo g enous m i x t ure. Sam p l es of t he g round f

i sh w i l l be prepared i n t

he l abora t ory pr i or

t o samp l e c o l l e c t

i on and sh i pped t o t

he f i e l d. P r i 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 yzed and shown t o ha v e c on c en t ra t i ons of D4 be l ow t

he LOQ for t

h i s

matr i x. Ser vi 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 d

samp l e s

. T he reference f

i sh samp l e s w i l l be used t o e v a l ua t e c o n t am i na t i on b i as resu l t i ng from

c o l l e c t i on, pro c ess i n g

, t

ranspo r t , s t ora g e, and ana l ys i s of fish samp l es. In addition, two of the

ground fish sam

p l es sha l l be sp i ked i n t

he f i e l d w i t h a known amount of D 4

. T he f i e l d sp i ked

samp l es of g round f

i sh w i l l be used t o e v a l ua t e l oss of D4 dur i ng c o l l e c t i on, pro c ess i n g

,

t ranspo r t , s t ora g e, and ana l ys i s of fish samp l es, and t o e v a l ua t e ana l y t i c al b i as. Spe c i f i c

requ i remen t s for prepara t 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 v i dual f

i sh w i l l be doub l y ba g g ed us i ng po l y e t hy l e n e ba g s and frozen pr i or t o sh i pmen t

. C ompos i t ed f

i sh w i l l be p l a c ed i n samp l e c on t a i ners and frozen pr i or t o sh i pmen t. Frozen

samp l es w i l l be pa c ked i n t o c oolers w i t h dry i c e and t aken b a c k t o or sh i pped ba c k t o t he

l abora t ory us i ng an overn ig ht express sh i pp i n g c ompany. Samp l e c o l l e c t i on methods as we l l

as spe c i f i c requ i re m en t s for samp l e c on t a i ner prepara t i on, samp l e hand l i n g

, samp l e

prese r v a t i 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 abora t ory, as part of t he p r o c ess i ng of t

he f i sh s amp l es pr i or t o ana l ys i s, f i sh w i l l be

g round up and homo g en i zed. L i p i d c on t ent sha l l be ana l yzed 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 er i za t i on of F i sh and Ben t h i c Ma c ro i n v er t ebra t 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 sam

p l es and accompanying quality assurance samples sha l l be ana l yzed for D4 at one

c ommer c i al t es t i ng l a b ora t o r y that has appropriate expertise with the D4 analyses to be conducted

when the testing analysis occurs , unless there are unforeseen circumstances such as lack of

laboratory availability as noted in 40 C.F.R. § 790.68(b)(2)(iii)

. T he c ommer c i al l abora t o r y w i l l

v a l i da t e a method for t he 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 t i c al method spe c i f

i ed i n P owe l l and Woodburn ( 2 0 09

, A na l ys i s of C y c l i c Vo l a t il e

Me t hy l s il oxa n e ( c VMS) Ma t er i a l s se c t i o n

, E x t ra ct i on of F i sh and Ben t

h i c M a c ro i n v er t ebra t es

su b

- se c t i o n

, p. 1 3

, and Qua li t y C on t ro l

, p. 14 )

. T he P owe l l and Woodburn ( 2009 ) ana l y t i c al

method i n v o lv es ex t

ra ct i 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 t y assuran c e

samp l es fo l l owed by quan t i f i c a t i on us i ng G C

- MS.

The MDL is the c on c en t

r a t i on of a c o ns t

i 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 repor t ed w i t h 99 % probab i li t y t

hat i t i s g rea t er

t han 0 or s t a t i s t

i c a ll y d i fferent from a b l ank. T he M D L i s a measure of a metho d ’ s ab ili t y t o

quan t i fy a c ons t

i t uent i n a samp l e matr i x. T he m e t hod for a na l yz i ng D4 i n b i o t a repor t 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 appropr i a t e method for an MDL of 0.2 to 3.0 ng/g (wet we i g h t

,

w w ) . An MDL up to a value not exceeding 3.0 ng/g (wet weight, ww) shall be applied for b i o t a.

T he spe c i f

i c l e v el of de t e c t i 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

. § 790.68.53

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 a t ed spe c i f

i c a l l y t o t he c o l l e c t i on, ha n 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 L P r e g u l a t

i 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 on t en t

, 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 L P r e g u l a t i o n s (see 4 0 C

. F

. R

. P art 792 ). T he Q A P P sha l l be

prepared a cc ord i ng t o U S E P A g u 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 Cyclic Volatile

Methylsiloxanes (cVMS) in Fish and Other Biota Obtained from Svalbard and Bear Islands,

Norway. HES Study No: 1106 1

- 108. Health and Environmental Sciences, Dow Corning

Corporation, Auburn, MI.

Durham, J.A. 2010b. Testing to Determine the Concentration of Cyclic Volatile

Methylsiloxanes (cVMS) in Sediment, Fish and Zooplankton Obtained from Svalbard, Norway.

HES S tudy 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. Gle sne, A. Lundgren.

2005. Siloxanes in the Nordic Environment. Norden.

Powell, D.E. 2010a. Bioaccumulation and Trophic Transfer of Cyclic 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 Op eongo, 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 a t

i on of E P A M i x i ng Z one Do c umen t s, Model i ng Do c umen t s, pp. 9

-

13

. E P A 823

- R

- 06

- 0 0 3

, J u l y, 2006

.

U S E P A 2003 a. F i sh C o l l e c t i 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

O per a t i ng P ro c edure S O P # E H

- 06

, S e ct i on 7

, pp. 3

- 5 , Sep t ember, 2003

.54

P owe l l D E

, Woodburn KB. 2 0 09

. T rophic D i l u t i on of C y c li c Vo l a t il e Me t hy l s i l oxane

( c VMS) Ma t er i a l s i n a T empera t e Freshwa t er L ake. Dow C orn i ng C orpora t i on, H E S S t

u dy

N o. 1077 1

- 108

.

U S E P A 2003 b. Ben t

h i c M a c ro i n v er t ebra t e S amp l i n g and P ro c ess i n g

, T e c hn i c al S t andard

O pera t i ng P ro c edure S O P # E H

- 04

, S e ct i on 5

, pp. 3

- 6 , Sep t ember, 2003

.

US E P A 2002. Guidance for Qua li t y 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 E n v i ronmen t al I nforma t i on, E P A (De c ember 2002 )

-

h t t p : // www

. ep a .g o v

/ qua l i t y / qs

- do c s / g 5

- f

i na l

. pdf.