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

Silicones Environmental, Health and Safety Center 1 Synopsis:

This testing standard provide s guidelines 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. ” An additional requirement of the ECA is to sample and analyze biosolids from each POTW.

This standard cites the requirements for the sampling of biosolids as described in Section VII of the ECA and Appendices 2 and 3 and identifies speci fic guidelines and references that will be used in the preparation of site

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

Requirements for s ampling biosolids :

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

“ Biosolids samples will be collected as close to the release point of the treatment facility as possible and the concen tration of D4 in the biosolid samples will be measured. ”

Establishment of the location for biosolid s sample collection :

At each POTW, biosolids samples shall be collected as close as possible to the biosolids release point as possible . To satisfy this requirement , detailed knowledge of each facility ’ s handling of biosolids is required. T he chosen location for sampling should be where the biosolids are prepared, staged, or stored for transportation off site. The exact location of the point of releas e should be established during preparation of the site

- specific Sampling Plans

.

Special considerations for the sampling and handling of biosolids 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 , a nd may be components of antifoams widely used in waste water treatment plants . To avoid the potential for sample contamination during collection, processing, stora ge, and analysis for D4 in environmental matrices, appropriate quality control measures should be implemented to the extent possible in theTesting Standard for the Collection, Sample Handling, Transfer and Analysis of Biosolids Samples f or D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 2 field. For example, field crew shall refrain from using any personal care products (e.g. , sun

- block, sun

screen, ha nd lotion, antiperspirants, etc.) while preparing for or conducting any field activities to minimize the possibility for contamination with cVMS materials. Appropriate requirements for collecting and handling biosolids samples that comply with the special considerations related to D4 shall be specified in the site

- specific Sampling Plan.

Collection of biosolids samples for analysis of D4:

On the day of sampling at each POTW, two (n=2) composited biosolids samples shall be collected at the established location

. The sampl e collection procedure will be based, as appropriate, on USEPA (1989
, Section 2.2 Sample Point Selection and Section 2.3 Sample Collection ) (see Annex 1)

. Once composited biosolids samples are collected, they will be processed i n prepara tion for sending to an analytical laboratory following general procedures similar to those used for sediments as given in Powell and Woodburn (2009) (Sample Collection section, p. 9
, Analysis of Cyclic Volatile Methylsiloxane (cVMS) Materials section , Extr action of Surface Sediments sub

- section , p. 12 , and Quality Control, p. 14 ) (see
A nnex 2 )

. Sample collection methods as well as specific requirements for sample container preparation, sample handling, sample pres ervation, shipping and storage of the sample s will be detailed in the site

specific Sampling Plans.

During each sampling event at a given site, two field blank s will be prepared as described in Powell and Woodburn (2009) . Serving as f ield blank s for biosolids collection and handling
, 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 biosolids sample. The reference sediment sample s will be used to evaluate contamination bias resulting from c ollection, processing, transport, storage, and analysis of samples. Specific requirements for preparation, processing, and analysis of field blanks sh all be detailed in the Study Plan and the Quality Assurance Project Plan (QAPP).

Following collection of b iosolids samples, subsamples shall be separately prepared from the composited samples for analysis of carbon and water content following procedures equivalent to those used for sediments as given in Powell and Woodburn (2009) Characterization of Sediments , p. 10 (see Annex 2 ). The biosolids samples should be analyzed 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 Biosolids Samples for D4:

All biosolids samples shall be analyzed for D4 at a commercial testing laboratory. The commercial laboratory will validate a method for the analysis of D4 in the biosolids samples that shall be adapted from the analytical method specified in Knoerr ( 2012 ) (see Annex 3 ). The specific level of detection shallTesting Standard for the Collection, Sample Handling, Transfer and Analysis of Biosolids Samples f or D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 3 be based on the Practical Quantitation Limit (PQL) (USEPA 19 85 and APHA 1999
, Part 1030C, see Annex es 4 and 5 ). The PQL is in turn based on the matrix

- sp ecific 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 l aboratory opera tions

. 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.

During method development, the Knoerr (201 2 ) analytical method for D4 did not determine a mat rix

specific Method Detection Limit (MDL) . However, since the analytical method (Knoerr 2012 , A nnex 2 ) is very similar to that of sediment (Powell and Woodburn 2009 , see Annex 3 ), the sediment MDL of 8.5 ng/g (wet weight, ww) will be the basis of the biosolids PQL . For use at a commercial laboratory, the targeted PQL for D4 in biosolids shall be ca lculated as 5 times the Powell and Woodburn (20 09 ) MDL for sediment . Therefore, when rounded to one significant figure, the PQL for D4 in biosolids 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 accor ding to USEPA guidance and shall include information on all field and laboratory quality control measures to be followed.

Annex 1

– USEPA (1989): POTW Sludge Sampling and Analysis Guidance Document
, Section 2.2 Sample Point Selection and Section 2.3 Sam ple Collection . EPA 833

- B

- 89

- 100, August, 1989.

Annex 2

– 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 3

– Knoerr SM. 2012. Non

- Regulated Study: Development of a Method for the Collection, Storage

a nd Analysis of Biosolids Obtained from a Waste Water Treatment Plant for the Quantitation of Octamethylcyclotetrasiloxane . Dow Corning Corporation Study Number 11800

- 108

.Testing Standard for the Collection, Sample Handling, Transfer and Analysis of Biosolids Samples f or D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 4 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 Wat er and Wastewater, Part 1030 C. Method Detection Level, Section 2 Determining Detection Levels. American Public Health Association, American Water Works Association, Water Environment Federation.