Testing Standard for the Collection, Sample Handling, Transfer and Analysis of Sediment Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 1 Synopsis:
This testing standard provide s direction for the collection and analysis of environmental samples f or D4 in support of a Testing Program detailed in this Enforceable Consent Agreement (ECA)

. The purpose of the Testing Program is to “... develop environmental testing data for D4 in the vicinity of manufacturing and processing (including product formulating) sites and POTWs in the U.S. so that exposures and risks to sediment and aquatic organisms can be assessed. ” This standard cites the requirements for the sampling of sediment as described in Section VII of the ECA and Appendices 1, 2, and 3, and identifies specific guidelines and references that will be used in the preparation of site

- specific S ampling Plans for the collection and analysis of sediment samples, which will be included in a Study Plan for the Testing Program.

Requirements for s ampling sediments :

Per Appendix 1, Environmental Testing at D4 Direct Discharge Sites , Appendix 2, Envir onmental Testing for Indirect Discharge Sites , and Appendix 3, POTWs Not Receiving D4 from Industrial Facilities:

“ Surface sediment samples from the receiving water body will be collected as close as possible to the
waste water outfall release point of the treatment facility. ”

Establishment of location for sediment sample collection:

At each site , (i.e., POTW and direct discharge sites) sediment samples shall be collected as close as possible to the waste water outfall release point. However, because sediments are expected to be found only in deposition zones within the receiving stream, the specific sampling location must also be within a deposition zone and be of sufficient area to allow collect ion of both sediment and benthos samples

. Accordingly, sediment samples should be collected from the deposition zone nearest the facility wastewater outfall release point.

Determination of the location of the nearest deposition zone of sufficient size to take samples of sediment is a facility

- specific inquir y

. The facility operator or permitting authority should be consulted, as appropriate, to determine if the deposition zone has been established. For cases in which the nearest deposition zone is not known, it should be determined in the field by reconnaiss ance prior to the actual collection of samples. For each site, establishment of the deposition zone by field reconnaissance shall be detailed in the site

- specific Sampling Plans.Testing Standard for the Collection, Sample Handling, Transfer and Analysis of Sediment Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 2 Special considerations for the sampling and handling of sediment samples for D4:
Cyclic volatile methyl siloxane (cVMS) materials, such as D4, are widely used in consumer products and may be present in personal care products, commercial products, and lubricants, and may be components of antifoams widely used in waste water tr eatment plants. To avoid the potential for sample contamination during collection, processing, storage, and analysis for D4 in environmental matrices, appropriate quality control measures should be implemented to the extent possible in the field. For examp le, field crew shall refrain from using any personal care products (e.g. , sun

- block, sun

screen, hand lotion, antiperspirant, etc.) while preparing for or conducting any field activity to minimize the possibility for contamination with cVMS materials. App ropriate requirements for collecting and handling sediment samples that comply with the special considerations related to D4 are introduced below and shall be specified in the study Plan.

Collection of sediment samples for analysis of D4:

O n the day of field sampling at a given site , four (n= 4 ) sediment samples (two for analysis of D4 and two for use in preparing field spikes) shall be collected from the deposition zone nearest the facility
wastew ater outfall release point , in accordance with the sampl e collection procedures set out in the site

- specific Sampling Plan. Site

- specific sample collection method s shall be based, as appropriate for D4 , on techniques described in USEPA (1994) ( SOP# 2016 , sections 2

- 5, 7 ) and USEPA (2001) ( Chapter 3 and Appendix E ) (see Annexes 1 and 2 )

. Once sediment samples are collected, they will be processed in accordance with the procedures given in Powell and Woodburn (2009) (Sample Collection section, p. 9
, Analysis of Cyclic Volatile Methylsiloxane (cVMS) Materials secti on , Extraction of Surface Sediments sub

section , p. 12 , and Quality Control, p. 14 ) (see A nnex 3). S pecific requirements for sample container preparation, sample handling, sample preservation, shipping and storage of the samples will be detailed in the sit e

- specific Sampling Plans.
During each sampling event at a given site, two field blank s, two field spike s, as well as a duplicate sample will be prepared as described in Powell and Woodburn (2009) . Serving as field blank s , two reference sediment sample s having very low or non

- detectable concentrations of cVMS materials shall be taken into the field and processed like a field sample. The reference sediment sample s will be used to evaluate contamination bias resulting from collection, processing, transpor t, storage, and analysis of samples. Two of t he sediment samples shall be spiked in the field with a known amount of D4

. The sed iment field spike d sample s will be used to evaluate loss of cVMS during collection, processing, transport, storage, and analysi s of samples, and to evaluate analytical bias. One of the sediment samples shall be split into duplicate samples. The d u plicate field samples shall be processed and analyzed as individual samples for D4

. Duplicate samples are u sed to evaluate between

- sampl e variability or precision

. Specific requirements for preparation, processing, and analysis of field blanks, field spikes, and duplicate samples sh all be detailed in the Study Plan and the Quality Assurance Project Plan (QAPP).Testing Standard for the Collection, Sample Handling, Transfer and Analysis of Sediment Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 3 Following collection of sediment samples, subsamples shall be separately prepared for analysis of carbon and water content following procedures equivalent to Powell and Woodburn (2009) Characterization of Sediments, p. 10 (see Annex 3). The surface sediment samples should be an alyzed by carbon coulometry ( or an equivalent met hod ) for total carbon, total inorganic carbon, and total organic carbon , and loss

- on

- ignition for total water content and total organic matter content.

Analysis of Sediment Samples for D4:

All sediment sa mples shall be analyzed for D4 at a commercial testing laboratory. The commercial laboratory will validate a method for the analysis of D4 in sediment samples that shall be adapted from the analytical method specified in Powell and Woodburn (2009) (see Ann ex 3). The specific level of detection shall be based on the Practical Quantitation Limit (PQL) (USEPA 1985 and APHA 1999 , Part 1030C, see Annex es 4 and 5 ). The PQL is in turn based on the matrix

- specific Method Detection Limit (MDL). These terms are defin ed as follows:
Practical Quantitation Limit (PQL): Minimum concentration of a constituent in a sample that can be measured among laboratories within specified limits during routine l aboratory operations

. The PQL is proposed because different laboratories may produce different MDLs even though they may be using the same analytical procedures, instruments and sample matrices. The PQL is typically d efined as 5 to 10 times the MDL.
Method Detection Limit ( MDL): Concentration of a constituent in a sample, that when processed through the complete analytical method, can be measured and reported with 99% probability that it is greater than 0 or statistically different from a blank. The MDL is a measure of a m ethods ability to quantify a constituent in a sample matrix.
The method for analyzing D4 in sediment reported by Powell and Woodburn (2009) is deemed the appropriate method f or transferring to a commercial testing laboratory and is capable of achieving an MDL of at least 8.5 ng/g (wet weight, ww) for sediment. For use at the commercial laboratory, the targeted PQL for D4 in all sediment shall be calculated as 5 times the Powell and Woodburn (2009) MDL of 8.5 ng/g, ww. Therefore, when rounded to one signific ant figure, the PQL for D4 in sediment shall be 40 ng/g,ww.

Compliance with Good Laboratory Practices:
Sample collection, handling, and transfer activities should be conducted in accordance with GLP requirements, as applicable. The analytical laboratory conducting the analyses of D4 shall be a GLP certified facility and all analytical work shall be conducted in accordance with GLP requirements. The QAPP shall be prepared according to USEPA guidance and shall include information on all field and laboratory quality control measures to be followed.Testing Standard for the Collection, Sample Handling, Transfer and Analysis of Sediment Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 4 Annex 1

– USEPA 1994. Sediment Sampling, , S ections 2

- 5 and 7

. U.S. Environmental Protection Agency, SOP#: 2016, 11/17/94, REV. #: 0.0

– See attached

Annex 2

– USEPA 2001. Methods for Collection, Storage and Manipu lation of Sediments for Chemical and Toxicological Analysis: Technical Manual , Chapter 3 and Appendix E . US Environmental Protection Agency, EPA 823

- B

- 01

- 002, October, 2001.

Annex 3

– Powell DE, Woodburn KB. 2009. Trophic Dilution of Cyclic Volatile Methyl siloxane (cVMS) Materials in a Temperate Freshwater Lake. Dow Corning Corporation , HES Study N o. 10771

- 108.

Annex 4

– USEPA 1985. National primary water drinking standards: synthetic organics, inorganics, and bacteriologicals. 40 CFR Part 141; Federal Register 50: No. 219, November 13. 1985.

Annex 5

– APHA 1999. Standard Methods for the Examination of Water and Wastewater, Part 1030 C. Method Detection Level, Section 2 Determining Detection Levels. American Public Health Association, American Water Work s Association, Water Environment Federation.