Testing Standard f or the Collection, Sample Handling, Transfer and Analysis of Influent and Effluent 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 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 influent and effluent 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 si te

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

Requirements for s ampling influents and effluents :

Per Appendix 1, Environmental Testing at D4 Direct Discha rge Sites :

“ With respect to the wastewater treatment effluent (outfall), sampling is to occur at the compliance point in accordance with the facility ’ s discharge permit (specific IDs will be provided in the Study Plan). In addition to the concentration o f D4 in the effluent, total effluent flow rate shall be recorded and reported. ”

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

“ The concentration of D4 in the influent at the headworks of the POTW ( i.e. , regulated compliance point per the POTW ’ s discharge permit) shall be measured along with the total influent flow rate. “

“ The concentration of D4 in the effluent at the regulated compliance point per the POTW ’ s discharge permit shall be measured along with the total effluent flow rate. ”

Establishment of the location for influent sample collection :
At each POTW, influent samples should be collected at the headworks of the POTW . The exact l ocation for collection of an influent sample will be facility

- specific and specified in the POTW ’ s discharge permit

. Each site

- specific Sampling Plan shall include a description of the portions of the POTW where influent is contained , including a basis for determining the appropriate sampling location.Testing Standard f or the Collection, Sample Handling, Transfer and Analysis of Influent and Effluent Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 2 Establishment of the location for effluent sample collection:
At each site (i.e., POTW or direct discharge facility), effluent samples shall be collected at the regulated compliance point per the POTW ’ s discharge permit

. Each site

- sp ecific Sampling Plan shall include a complete description of the effluent discharge portions of the POTW, including the established sampling location.

Special considerations for the sampling and handling of influent and effluent 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 significant 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, sun

- screen, hand lotion, antiperspirants, etc.) while preparing for or conducting any field activities or during collection of samples to minimize the possibility for contam ination with cVMS materials. Appropriate requirements for collecting and handling influent and effluent samples that comply with the special considerations related to D4 shall be specified in the site

- specific Sampling Plan.

Collection of influent samples for analysis of D4:

At each site, the time that influent samples shall be collected will be chosen in consultation with the POTW operator and should reflect normal operations and conditions. The time of collection of the influent should correspon d with the time of collection of effluent, surface water, and sediment samples at each facility.
During each sampling event at a given site, four grab samples of influent (two for analysis of D4 and two for use in preparing field spikes) shall be prepared once during the day of field sampling

. Influent flow rate shall be measured at the time of sample collection. Specific requirements for collection of grab

s a mples, including sample bottle preparation, sample preservation, shipping and storage of the influ ent samples shall be specified in the Study Plan and will be based on USEPA 2013 (Wastewater Sampling, Section 4 , Sample Types and Section 6 , Manual Sampling), USEPA 2004 (NPDES Compliance Inspection Manual, Section 5B, Sampling Procedures and Techniques), Knoerr 2013 (Sample Collection section, p. 8), and APHA 1999 (Part 1060 Collection and Preservation of Samples) (see Annexes 1 to 4). The sample containers will contain LDPE that will adsorb any dissolved D4 and prevent volatilization of any D4 present. In the laboratory, the entire contents of the sample container will be extracted including LDPE sorbent and any solids present.Testing Standard f or the Collection, Sample Handling, Transfer and Analysis of Influent and Effluent Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 3 Also d uring each sampling event at a given site, two field blank s and two field spike d

- sample s will be prepared 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 an influent sample. The laboratory

- grade water sample s will be used t o evaluate contamination bias resulting from collection, processing, transport, storage, and analysis of samples. Two of the influent grab samples shall be spiked in the field with a known amount of D4. The field

- spiked influent sample s will be used to ev aluate loss of cVMS during collection, processing, transport, storage, and analysis of samples, and to evaluate analytical bias. Specific requirements for preparation, processing, and analysis of the field blank s and field spiked s ample s shall be detailed in the Study Plan a nd the Quality Assurance Project Plan (QAPP).
During the time of collection of the influent samples , two separate sample bottles shall be prepared for analysis of total organic carbon (TOC). The TOC analyses shall follow procedures equiv alent to AHPA 1999 Part 5310, Total Organic Carbon (TOC) (see Annex 5).

Collection of effluent samples for analysis of D4:

At each site, the time that effluent samples shall be collected will be chosen in consultation with the POTW operator and should r eflect normal operations and conditions. The time of collection of the effluent should correspond with the time of collection of influent, surface water, and sediment samples at each facility. If any facility has more than one outfall, then each outfall sh all be sampled.
During each sampling event at a given site, four grab samples of effluent (two for analysis of D4 and two for use in preparing field spikes) shall be prepared once during the day of field sampling

. Effluent flow rate shall be measured at t he time of sample collection. Specific requirements for collection of grab samples, sample bottle preparation, sample preservation, shipping and storage of the effluent samples shall be based on USEPA 2013 ( Wastewater Sampling, Section 4 Sample Types and Section 6 Manual Sampling ), USEPA 2004 ( NPDES Compliance Inspection Manual, Section 5B, Sampling Procedures and Techniques ), Knoerr 2013 ( Sample Collection section, p. 8 ), and APHA 1999 ( Part 1060 Collection and Preservation of Samples) (see Annexes 1 to 4). The composite sample containers will contain LDPE that will adsorb any dissolved D4 and prevent volatilization of any D4 present. In the laboratory, the entire contents of the composited sample container will be extracted including LDPE sorbent and an y solids present.

Also d uring each sampling event at a given site, two field blank s and two field spike d

- sample s will be prepared as described below . Serving as field blank s , two sample s of laboratory

- grade water having very low or non

- detectable concentra tions of cVMS materials shall be taken into the field and processed like

an ef fluent sample. The laboratory

- grade water sample s will be used to evaluate contamination bias resulting from collection, processing, transport, storage, and analysis of samples. Two of the ef fluent composite samples shall be spiked in the field with a known amount of D4. The field

- spiked ef fluentTesting Standard f or the Collection, Sample Handling, Transfer and Analysis of Influent and Effluent Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 4 sample s will be used to evaluate loss of cVMS during collection, processing, transport, storage, and analysis of samples, and to evalu ate analytical bias. Specific requirements for preparation, processing, and analysis of the field blank s and field spiked s ample s shall be detailed in the Study Plan and the Quality Assurance Project Plan (QAPP).
During the time of collection of the efflue nt 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 influent and effluent s amples for D4:

All influent and effluent 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 influent and effluent samples that shall be adapted from the anal ytical method specified in Knoerr ( 2013) (see Annex 3)

. The specific level of detection shall be based on the Practical Quantitation Limit (PQL) ( USEPA 19 85 and APHA 1999, see Annex es 6 and 7 )

. The PQL is in turn based on the matrix

- specific Method Detect ion Limit (MDL). These terms are defined as follows :
Practical Quantitation Limit (PQL): M inimum concentration of a constituent in a sample that can be measured among laboratories within specified limits during ro utine laboratory operations

. The PQL is p roposed 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): Concentr ation 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 (2013) analytical method for D4 achiev ed a n average matrix

specific Method Detection Limit (MDL) of 0.037 μ g/L

. For use at the commercial laboratory, the targeted PQL for D 4 in aqueous matrices shall be calculated as 5 times the Knoerr (2013) MDL. Therefore, when rounded to one significant figure, the PQL for D4 in aqueous matrices shall be 0.20 μg/L.

Compliance with Good Laboratory Practices:
Sample collection, handling, a nd 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. TheTesting Standard f or the Collection, Sample Handling, Transfer and Analysis of Influent and Effluent Samples for D4 August 1 6 , 2013

Silicones Environmental, Health and Safety Center 5 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 2013. Wastewater Sampling , Section 4 Sample Types, Section 6 Manual Sampl ing

. Operating Procedure No. SESDPROC

- 306

- R3. US Environmental Protection Agency, Region 4. February, 2013.

Annex 2

– USEPA 2004. NPDES Compliance Inspection Manual , Section 5B, Sampling Procedures and Techniques . EPA 305

- X

- 04

- 001, US Environmental Protection Agency, July, 2004.

Annex 3

– Knoerr SM. 2013

. NON REGULATED STUDY: Development of Collection, Storage and Analysis Procedures for the Quantification of D4, D5, and D6 in Waste Water Treatment Plant Effluent and Surface Water Samples . Dow Corning Corporation, HES Study No. 11936

- 108, April 18, 2013.

Annex 4

– APHA 1999. Standard Methods for the Examination of Water and Wastewater, Part 1060, Collection and Preservation of Samples. American Public Health Association, American Water Works Association, Water Environment Federation

.

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. Met hod Detection Level, Section 2 Determining Detection Levels. American Public Health Association, American Water Works Association, Water Environment Federation

.