Testing Standard for the Collection, Sample Handling, Transfer and Analysis of Surface Water Samples for 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. ” This standard cites the requirements for the sampling of surface water 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

- speci fic Sampling Plans for the collection and analysis of surface water samples , which will be included in a Study Plan for the Testing Program.

Requirements for s ampling s urface ( r eceiving) w aters:

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

“ Surface water shall be collected from the receiving water as close as possible to the release point from the tr eatment facility and measured for the concentration of D4, provided that adequate mixing of the discharge from the site with the receiving stream has occurred. ”

Establishment of the location for surface water sample collection :
At each site (i.e., POTW or direct discharge facility), surface water s amples should be collected as close as possible to the discharge point provided adequate mixing of the discharge and receiving water has occurred. To satisfy these two requirements, surface water samples shall be collected at the end of the mixing zone at a point nearest the facility release point.
Determination of a mixing zone is a facility

- specific inquiry . For each facility , the mixing zone may have been established with the applicable wastewater permittin g authority

. The facility operator and permitting authority should be consulted, as appropriate, to determine if a mixing zone has been established. For cases in which the mixing zone is not known to the facility operator , it should be determined in the field using appropriate measurement or modeling techniques prior to the actual collection of samples

. Methods for the analysis of mixing zones are presented in USEPA ( 1991, Section 4.4 Mixing Zone Analyses ) and USEPA ( 2006 , Modeling Documents section, pp. 9

- 13 ) (see Annex es 1 and 2 ) and should be utilized, as appropriate

. Each site

- specific S ampling Plan shall include a discussion of the mixing zone in the receiving water , including the basis for the establishment of the specified zone

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

Silicones Environmental, Health and Safety Center 2 Special considera tions for the sampling and handling of water 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 imple mented to the extent possible in the field . For example, f ield 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 activities to minimize the possibility for contamination with cVMS materials. Appropriate requirements for collecting and handling surface water samples that comply with the special considerations related to D4 are introduced below and shall be specified in the site

- specific Sampli ng Plan.

Collection of surface water samples for analysis of D4:

O n the day of field sampling at a given site , at the end of the established mixing zone, four (n= 4 ) water samples ( two for analysis of D4 and two for use in preparing field spikes ) shall be collected from the center of the receiving water at mid

- depth in accordance with the sampl e collection procedures set out in the site

- specific Sampling Plan

. The sample collection procedures will be based, as appropriate, on U SEPA (1994 , Section 7.3 Sa mple Collection ) (see Annex 3 )

. S pecific requirements for sample bottle preparation, sample preservation, shipping and storage of the samples shall be based on Knoerr 2013, Sample Collection section, p. 8 ) ( see Annex 4). All sample collection methods and sample handling procedures will be detailed in the site

- 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 prepare d as described below

. Serving as field blank s , two sample s of laboratory

- grade
water having very low or non

- detectable concentrations of cVMS materials shall be taken into the field and processed like a field sample. The laboratory

- grade water sample s wil l be used to evaluate contamination bias resulting from collection, processing, transport, storage, and analysis of samples. Two of the s urface water samples shall be spiked in the field with a known amount of D4 , then processed like field sample s . The fi eld

- spiked surface water sample s 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 s urface water 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 spi kes, 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 Surface Water Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 3 During the time of collection of surface water samples, two separate sample bottles shall be prepared for analysis of total organic carbon (TOC). The TOC analyses shall follow procedures equivalent to AHPA 1999 Part 5310, Total Organic Carbon (TOC) (see Annex 5).

Analysis of s urface w ater s amples for D4:
All water 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 surface water samples that shall be adapted from the analytical method specified in Knoerr (2013) (see Annex 4 ). The specific level of detection shall be based on the Practical Quantitation Limit (PQL) (USEPA 1985 and APHA 1999 , Part 1030C, see Annex es 6 and 7 ). 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 concentrat ion 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 ana lytical 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 measu red 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 (2013) analytical method for D4 achieved an average matrix

specific Method Detection Limit (MDL) of 0.037 μg/L. For use at the commercial laboratory, the targeted PQL for D4 in aqueous matrices shall be calculated as 5 times the Knoerr (2013) MDL. Therefore, when rounded to one s ignificant figure, the PQL for D4 in aqueous matrices shall be 0.20 μg/L.

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 o n all field and laboratory quality control measures to be followed.Testing Standard for the Collection, Sample Handling, Transfer and Analysis of Surface Water Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 4 Annex 1

– USEPA 1991. Technical Support Document for Water Quality

- based Toxics Control, Section 4.4: Mixing Zone Analyses. EPA 505

- 290

- 001. U.S. Environmental Protection Agency, Office of Water, Washington, DC.

Annex 2

– USEPA 2006. Compilation of EPA Mixing Zone Documents , Modeling Documents, pp. 9

- 13

. EPA 823

- R

- 06

- 003, July, 2006.

Annex 3

– USEPA 1994. Surface Water Sampling, Section 7.3 Sample Collection. U.S. Environmental Protection Agency, SOP#: 2013, 11/17/94, REV. #: 0.0

Annex 4

– Knoerr SM , Durham JA . 2013. NON REGULATED STUDY: Development of Collection, Storage and Analysis Procedures for the Quantification of D4, D5, and D6 in Waste Water Treatmen t Plant Effluent and Surface Water Samples. Dow Corning Corporation, HES Study No. 11936

- 108, April 18, 2013.

Annex 5

– AHPA 1999. Standard Methods for the Examination of Water and Wastewater, Part 5310 C. Total Organic Carbon (TOC) . American Public Health Association, American Water Works Association, Water Environment Federation.

Annex 6

– 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 7

– 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 Environme nt Federation.