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

D4

August 16, 2013

Silicones Environmental, Health and Safety Center 1

Synopsis: 

This testing standard provides direction for the collection and analysis of environmental samples for 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 Sampling Plans for 

the collection and analysis of sediment samples, which will be included in a Study Plan for the Testing 

Program.

Requirements for sampling sediments: 

Per Appendix 1, Environmental Testing at D4 Direct Discharge Sites, Appendix 2, Environmental 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 

wastewater 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 wastewater 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 collection 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 inquiry. 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 reconnaissance 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 16, 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 treatment 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 example, field crew shall refrain from using any personal care products (e.g. , sun-block, sunscreen, hand lotion, antiperspirant, etc.) while preparing for or conducting any field activity to minimize 

the possibility for contamination with cVMS materials. Appropriate 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: 

On 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 

wastewater outfall release point, in accordance with the sample collection procedures set out in the 

site-specific Sampling Plan. Site-specific sample collection methods 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 section, Extraction of Surface Sediments subsection, p. 12, and Quality Control, p. 14) (see Annex 3). Specific requirements for sample container

preparation, sample handling, sample preservation, shipping and storage of the samples will be detailed 

in the site-specific Sampling Plans. 

During each sampling event at a given site, two field blanks, two field spikes, as well as a duplicate 

sample will be prepared as described in Powell and Woodburn (2009). Serving as field blanks, two

reference sediment samples 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 samples will be used 

to evaluate contamination bias resulting from collection, processing, transport, storage, and analysis of 

samples. Two of the sediment samples shall be spiked in the field with a known amount of D4. The 

sediment field spiked samples will be used to evaluate loss of cVMS during collection, processing, 

transport, storage, and analysis of samples, and to evaluate analytical bias. One of the sediment samples 

shall be split into duplicate samples. The duplicate field samples shall be processed and analyzed as 

individual samples for D4. Duplicate samples are used to evaluate between-sample variability or 

precision. Specific requirements for preparation, processing, and analysis of field blanks, field spikes, 

and duplicate samples shall 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 16, 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 analyzed 

by carbon coulometry (or an equivalent method) 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 samples 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 Annex 3). The specific level of 

detection shall be based on the Practical Quantitation Limit (PQL) (USEPA 1985 and APHA 1999, Part 

1030C, see Annexes 4 and 5). The PQL is in turn based on the matrix-specific Method Detection Limit 

(MDL). These terms are defined 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 laboratory 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 defined 

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 methods 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 for 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 significant 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 16, 2013

Silicones Environmental, Health and Safety Center 4

Annex 1 – USEPA 1994. Sediment Sampling, , Sections 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 Manipulation 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 Methylsiloxane (cVMS) 

Materials in a Temperate Freshwater Lake. Dow Corning Corporation, HES Study No. 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 Works Association, Water Environment Federation.