# Karluss T homas Senior Director UNITED STATES ENVIRONMENTAL PROTECTION AGENCY 

## WASHINGTON, D.C. 20460



# DEC 

# 04 2014

Si licones Environmental, Health. and Safety Center American Chemistry Council
700 2nd Street NE
Wash ington
, DC 20002

Re: Quality Assurance Project Plan (QAPP) OFFICE OF CHEMICAL SAFETY
AND POLLUTION PREVENTION



# Testing Consent Order for Octamethylcyclotetrasiloxane (D4) (CASRN: 556-67-2)
40 C

.F

.R. 799.5000 EPA-HQ-OPPT-20 12-0209

·rhis letter is in response to your October l, 2014, submission of a Quality Assurance Project Plan (QAPP) as identified in the April 4, 2014

, Enforceable Consent Agreement (ECA) for Environmental Testing for Octamethylcyc lotetrasi loxane (D4) between the U.S. Environmenta l Protection Agency and
five manufacturers ofthe chemical. While the QAPP as submitted has not fully fulfilled the requirement of the ECA

, desc ribed below are EPA's comments on the submission. In addition

, particu lar deficiencies
and needs for claritication are identified in the enc losed table. The D4 environmental monitoring

program may commence after all the issues in this letter and the attached table have been resolved and
EPA has approved the Study Plan and QAPP.

Major Comments:

1. Modifications to the Study Plan (including site specific sampling plans) shall follow procedure identified in the ECA and codified in 40 CFR 790.68. Although not a requirement, EPA

encourages SEHSC to develop and include in the QAPP contingency plans for (a) the major and
minor Study Plan (including site-specific sampling plans adjustments and schedule changes related to potential challenges encountered during tield work activities) and (b) criteria for determining ifpost-implementation notifications to EPA are preferable to pre-implementation
notifications.

2. Representatives from both laboratories are required to sign the QAPP; in particular, the project

manager and the QA manager from each laboratory must sign the QAPP. In addition, the
database software and how stored information will be recorded, archived and transmitted amongst the participants must be described in the QAPP with greater detail and specificity.

3

. Further detail must be provided in the QAPP to describe the data quality objectives (DQOs) for
the analytics and under what condit ions data may be rejected. A procedure for who would be responsible for determining how to handle rejected data and considerations for replacement of rejected data must be described in the QAPP. The QAPP must also identify where rejected data

I nternet Address ( URL) ·http// www epa gov Recycled/Recyclable • Pr,nted w1th Vegetable 011 Based I nks on 100% Postconsumer. Process Chlorine Free Recycled Paper

# will be discussed in the final or interim reports. Rejected data must be presented in one of the reports, not only in the bulk raw data submission. Please refer to Group A7, Quality Objective s and Criteria for Measureme nt Data and 85

, Quality Control Requirements.

4. The QAPP states that primary samp les will be disposed of by the laboratory 30 days after submitting the data package to EPA and the retained samples will be disposed of following QA

verification. Based on the frequency of Interim and Final Reports

, both of these disposal tri ggers will likely occur before EPA has an opportunity to review the raw and summary data from the analysis. The QAPP must be revised to allow EPA sufficient time to review this data.

Deficiencies and Clarifications:

Deficiencies and needs for clarification were identified by comparing the QAPP to the enclosed table of requirements in the ECA and EPA's 2002 QAPP guidance. The identified deficiencies must be
addressed in a modified QAPP covering the direct discharge and WWTP sites.

If yo u have any question s, please contact Heather Njo ormy stafTat 202-564-2574 or at njo.hcather@ epa.go v

.

Enclos ure Jeff Monis, Deput y Director for Pror:,TTams Office of Pollution Pr evention and ToxicsReview Checklist: Quality Assurance Project Plan (QAPP) D4 Environmental Testing Study Versus ECA Requirements and EPA Guidance Page 1 of 6

EPA 2002 QAPP Guidance ECA Requirement Defficiencies and Clarifications Group A: Project Management A1. Title and approval sheet - Section 2.1 - Page 9
Title: Organization name: Dated signature of project manager: Dated signature of QA officer: Note, signatures and dates will be added when QAPP is approved. It is also necessary for a representative of each of the labs to sign the QAPP.

Other signatures, as needed: Must add a representative from the laboratories to the QAPP signature
list. A2. Table of Contents and Document Control Format - Section 2.2 - Page 9
Includes Table of Contents: Includes document control format: A3. Distribution List - Section 2.3 - Page 9 Includes a list of people who will receive the completed QAPP: A4. Project/Task Organization - Section 2.4 - Page 9Identifies key individuals, w/ their responsibilities (data users, decisionmakers, project QA manager, subcontractors, etc.): A5. Problem Definition/Background - Section 2.5 - Page 11 Clearly states problem or decision to be resolved: Provides historical and scientific background info.: A6. Project /Task Description - Section 2.6 - Page 11
Lists measurements to be made: Cites applicable technical, regulatory, or program-specific quality standards, criteria, or objectives: Notes special personnel or equipment requirements: Identifies the assessment tools needed:
Provides work schedule: Notes required project and QA records/reports: A7. Quality Objectives and Criteria for Measurement Data - Sect. 2.7 - P. 16 States project objectives and limits, both qualitatively and quantitatively: Table 2-6 does not provide the Data Quality Objectives (DQOs), but rather summarizes the DQO process for this program. As the QAPP and supporting documents address the DQO process for this program, Table 2-6 is redundant and unnecessary because the DQOs for this program are the performance and acceptance criteria provided in Tables 2-7 through 2-9. (1) See comments under Section B5 below regarding development of DQOs for sampling and analytical precision. (2) See EPA Comment #(2) under Section B5 below regarding developing a DQO for Relative Percent Difference (RPD) between pairs of field spikes to these tables. (3) Please provide info. on how bias will be assessed (i.e., qualitatively or quantitatively) and how sensitivity will be assessed (i.e., MDLs, LOQ, etc.). (4) EPA suggests adding depth measurement to Table 2-7. The importance of collecting samples at a certain depth was stated, thus this info. should be included in the QAPP. EPA suggests adding the instrument that will be used to perform this assessment and the instruction manual's performance criteria. Additionally, EPA suggests adding the instrumentation that will be used for all measurements and to add the sensitivity for water quality. (5) Footnote 1 in Table 2-8 indicates that field spike QC samples that do not meet the target limit "will raise questions that must be resolved prior to acceptance of the data." Please describe the types of questions that may be anticipated, the steps that will be undertaken to resolve them, and the criteria that will be considered in evaluating acceptance of the data. (6) The term "Field Blank" in Table 2-8 and throughout the QAPP is too vague and inconsistent (e.g., reference material field blank, split sample unspiked (field blank), lab water field blank, surface water field blank). A8. Special training/Certification Requirements - Section 2.8 - Page 19 Lists special training and certification requirements: A9. Documentation and Records - Section 2.9 - Page 21 1) An Interim Progress Report is required 180 days after the Effective Date of the ECA and every 180 days thereafter until all obligations are fulfilled. Interim Progress Reports shall include a summary of work completed to date, any proposed changes in protocols or schedule, raw data, and any other matters affecting progress of testing.

2) The Final Report is due no later than 150 days following completion of the required environmental testing (i.e., collection and analysis of the data). The Final Report shall include a description of monitoring performed, summary of test results, raw data, laboratory analyses, and QA/QC info., as per 40 CFR 792.185. 3) "The Signatory Companies will document all QA/QC work done as part of the Testing Program." 4) "The Signatory Companies will electronically submit all of the raw data (as defined in 40 CFR 792.3)..." Describes process and responsibilities for ensuring that the most current approved version of the QAPP is available: Specifies the level of detail of the field sampling and/or lab analysis narrative needed to completely describe difficulties encountered: Gives retention time and location for records and reports: Records shall be retained per 40 CFR 792.195. Group B: Measurement/Data Acquisition B1. Sampling Process Design (Experimental Design) - Section 3.1 - Page 26 States and characterizes measurements quality objectives as applicable action levels or criteria:

Lists info. and records to be included in data reports (eg., raw data, field logs, results of QC checks, problems encountered):Review Checklist: Quality Assurance Project Plan (QAPP) D4 Environmental Testing Study Versus ECA Requirements and EPA Guidance Page 2 of 6

EPA 2002 QAPP Guidance ECA Requirement Defficiencies and Clarifications Direct Discharge Sites: 1) Sample Types (App. 1): wastewater treatment effluent, receiving stream surface water, receiving stream sediment, receiving stream
biota.

States sampling network design and rationale: Direct Discharge Sites: 1) Sample Locations (App. 1): The 4 direct dischargers (Dow Corning Carrollton Plant; MPM Silicones Waterford Plant; MPM Silicones Sisterville Plant; Wacker Adrian Plant). 2) Sampling Frequency (App. 1): "Samples shall be taken during two testing events at least 3 months apart. The exact duration between sampling events for each site shall be determined in a detailed Sampling Plan included in the Study Plan and QAPP." 3) Effluent Sample Locations (App. 4): "At each site, effluent samples shall be collected at the regulated compliance point per the WWTP's discharge permit." 4) Surface Water Sample Locations (App. 5): "At each site, surface water samples should be collected at approximately the same location and roughly the same time as benthic organisms are collected which is described in App. 8." 5) Sediment Sample Locations (App. 7): "At each site, sediment samples from the receiving water body shall be collected at approximately the same location where benthic organisms are collected for D4 analysis as described in App. 8."

6) Biota Sample Locations (App. 8): "At each site, benthic organisms shall be collected as close as reasonably possible to the effluent outfall provided adequate mixing of the discharge and receiving water has occurred and where adequate benthic organism sample masses are obtained." Identifies sample matrices: Direct Discharge Sites: Sample Matrices (App. 1): wastewater treatment effluent, receiving stream surface water, receiving stream sediment, receiving stream biota. Gives appropriate validation study info. for non-standard situations:

B2. Sampling Methods Requirements - Section 3.2 Influent and Effluent Samples (App. 4): 1) "Influent and effluent samples will be collected as grab samples and not composite samples due [to] the expected high degree of volatilization of D4 from aqueous samples." 2) "For each site, procedures for collecting grab samples of influent and effluent will be based on USEPA 2013 (Wastewater Sampling, Section 4, Sample Types and Section 6, Manual Sampling, pp. 14-15, 20), USEPA 2004 (NPDES Compliance Inspection Manual, Section 5B, Sampling Procedures and Techniques, pp. 5-3 to 5-7), Knoerr 2013 (Sample Collection section), and APHA 1999 (Part 1060 Collection and Preservation of Samples, pp. 48-62) if appropriate given the site-specific circumstances.

Surface Water Samples (App. 5): During preparation of the sitespecific Sampling Plans, the physical nature (e.g., width, depth, flow) of the receiving water will be determined and used to guide the selection of the appropriate method of sample collection. For each site, collection procedures for surface water samples shall be based, as appropriate to the characteristics of the receiving water, on USEPA 1994 (SOP #2013, Section 7.3 Sample Collection, pp. 3-4) (USEPA 1994). Sediment Samples (App. 7): 1) During preparation of the site-specific Sampling Plans, the physical nature (e.g., width, depth, flow) of the receiving water will be determined and used to guide the selection of the appropriate method of sample collection. For each site, collection procedures for sediment samples shall be based, as appropriate to the characteristics of the receiving water, on techniques described in USEPA 1994 (SOP #2016, Sections 2-5,7, pp. 1-7) and USEPA (2001) (Chapter 3, pp. 3-1 to 3-17)." 2) "Sample collection, storage and preparation will follow Powell and Woodburn (2009) w/ each sample being placed in a plastic bag, homogenized, then placed directly into a glass jar, and then capped.

Biota Samples (App. 8): 1) Benthic Organism Samples: During preparation of the site-specific Sampling Plans, the physical nature (e.g., width, depth, flow) of the receiving water will be determined and used to guide the selection of the appropriate method of sample collection. For each site, collection procedures for sediment samples shall be based, as appropriate to the characteristics of the receiving water, on techniques described in Powell and Woodburn (2009, Sample Collection, p. 9) and USEPA (2003a, Sections 5.2 Sampling for Community Samples and 5.3 Sampling for AnalyticalMeasurements)." 2) Fish Samples: "During preparation of the sitespecific Sampling Plans, the physical nature (e.g., width, depth, flow) of the receiving water will be determined and used to guide the selection of the appropriate method of sample collection. For each site, collection procedures will be based, as appropriate to the characteristics of the receiving water, on USEPA 2003a (Section 7.0 Procedures, pp. 3-5) and Powell and Woodburn (2009, Sample Collection, p. 8)." Gives sampling locations and sampling frequency: EPA suggests adding sampling locations for sediment and benthic as discussed in response to study plan. Not all WWTP are specified as of this date, as expected.

Identifies sample collection procedures and methods: EPA suggests including info. on the headspace left w/in each of the sample bottles. Lists samples required as to type and number: EPA suggests revising the column headings in Table 2-5 to clarify that the reported numbers are per site per event (instead of per site). Labels for each of the rows at the bottom of Table 2-5 should start w/ the word "Total". Additionally, it's confusing that the numbers reported in the
columns do not sum to the totals listed in the bottom rows. EPA suggests revising the table format to better indicate the split between the top and bottom of the tables (e.g., double border or shading), and adding a footnote to explain how the totals are calculated.Review Checklist: Quality Assurance Project Plan (QAPP) D4 Environmental Testing Study Versus ECA Requirements and EPA Guidance Page 3 of 6

EPA 2002 QAPP Guidance ECA Requirement Defficiencies and Clarifications Lists equipment needed: Presently, only sampling equipment is provided in this section. However, Sect. 3.6.1 identified additional equipment that are used to determine water depth, scales, electrofishing, etc. The additional equipment provided in Sect. 3.6.1 pertain to sampling and therefore should be included in the list of equipment provided.

Identifies support facilities: Identifies individuals responsible for corrective actions: Describes process for preparation and decontamination of sampling equipment: Influent and Effluent Samples (App. 4) and Surface Water Samples (App. 5): "Immediately prior to each sampling event at each site, the laboratory that will analyze the samples shall prepare clean (new, never used) glass sample containers in sufficient numbers for all [influent and effluent or surface water] samples to be analyzed for D4, for all QA samples, and for retain samples. The sample containers will be prepared by pre-washing w/ hexane, adding low density polyethylene (LDPE) sorbent into the containers, providing polytetrafluoroethylene (PTFE) tape to assist in sealing the containers (as described in Knoerr 2013, Sample Collection section), as well as providing labels. The laboratory will ship all sample containers w/ adequate packing materials in coolers to each site. The coolers will also contain chain-of-custody forms that will accompany the sample containers from the laboratory to the field and back to the laboratory."

Sediment Samples (App. 7) and Biota Samples (App. 8): Same as above, except where underlined: "...shall prepare clean (new, never used) pre-weighed glass sample containers in sufficient numbers...The sample containers will be prepared by pre-washing w/ hexane, providing polytetrafluoroethylene (PTFE) tape to assist in sealing the containers, as well as providing labels..."

Influent and Effluent Samples (App. 4), Surface Water Samples (App. 5), and Sediment Samples (App. 7): "Sealed sample containers will be packed into coolers w/ blue-ice or water ice, and taken back to the laboratory or shipped back to the laboratory using an overnight express shipping company." Biota Samples (App. 8): 1) Benthic Organisms: "Benthic organisms will be separated from the sediment and five composite samples shall be prepared by randomly dividing the collected organisms into glass containers and freezing prior to shipment. Prior to preparing composite samples, the taxa represented in the sample will be noted at the lowest level possible. Frozen samples will be packed into coolers w/ dry ice and taken back to the laboratory or shipped back to the laboratory using an overnight express shipping company." 2) Fish Samples: "Individual fish will be doubly bagged using polyethylene bags and frozen prior to shipment. Composited fish will be placed in sample containers and frozen prior to shipment. Frozen samples will be packed into coolers w/ dry ice and taken back to or shipped back to the laboratory using an overnight express shipping company."

B3. Sample Handling and Custody Requirements - Section 3.3

Notes sample handling requirements: Special Considerations for D4 (Appendices 4, 5, 6, 7, and 8): "Specific requirements for collecting and handling...samples aimed at preventing sample contamination by sources of D4 that are not specific to the WWTP or direct discharge site shall be specified in the Study Plan and QAPP." Information is presented w/in the QAPP. However, page 31 indicates that sample container, minimum sample volume, preservation and maximum storage requirements are presented in Table 3-2. Table 3-2 shows the analytical methods. Need to make sure that tables and figures are referenced consistently throughout the document.

Notes chain of custody procedures, if required: The chain-of-custody procedures provided for Field QC samples is confusing and incomplete. Section 3.3.2.1 of the QAPP states "COC forms will not identify field QC samples, such as field blanks or field spike samples. Field QC samples will be designated following the procedures presented in Section 3.2.5.2 of the QAPP." However, Section 3.2.5.2 of the QAPP does not exist. Section 4.0 of SOP 100 (Field Sample Custody) states "COC forms will not identify field QC (QC) samples, such as field blanks or field spike samples. Field QC samples will be designated following the procedures presented in Section 3.5.1 of the QAPP." However, Section 3.5.1 of the QAPP does not discuss custody of QC samples. Please describe how custody of field QC samples will be maintained and documented.

B4. Analytical Methods Requirements - Section 3.4 - Page 38

Influent, Effluent, and Surface Water Sample Analysis for D4 (Appendices 4 and 5) "The commercial laboratory will validate a method for the analysis of D4 in the...samples that shall be adapted from the analytical method specified in Knoerr (2013)...the water sample and the LDPE sorbent are solvent extracted and processed for analysis w/ GC-MS."

"During method development, the Knoerr (2013) analytical method for D4 achieved a matrix-specific MDL of 0.037 μg/L which shall be achieved for influent and effluent testing. The specific level of detection shall be based on the LOQ which shall be 3 times the MDL.

"Influent, Effluent, and Surface Water Sample Analysis for TOC (Appendices 4 and 5): "The TOC analyses shall follow procedures equivalent to APHA 1999 Part 5310, Total Organic Carbon (TOC)." Describes selection and preparation of sample containers and sample
volumes:

Sample hold time is not provided in this section, however, it is mentioned as a stability study in section 3.4.4. EPA suggests providing how long each sample will be stored from sampling until analysis in this
section. Describes preservation methods and maximum holding times:

Identifies analytical methods to be followed (w/ all options) and required equipment: As previously mentioned under QAPP Element B2 Sampling Methods Requirements, EPA suggests including info. on sample headspace. Specifically, will there be headspace in the extracted sample vial ready for analysis and how long will the sample wait in the autosampler before being analyzed. Any effects to the measurements caused by wait time in the auto sampler before analysis shall be described.Review Checklist: Quality Assurance Project Plan (QAPP) D4 Environmental Testing Study Versus ECA Requirements and EPA Guidance Page 4 of 6

EPA 2002 QAPP Guidance ECA Requirement Defficiencies and Clarifications Sediment Sample Analysis for D4 (Appendix 7): "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 (2010)." "The method for analyzing D4 in sediment reported by Powell (2010) is deemed the appropriate method for achieving an MDL up to 3.7 ng/g (wet weight, ww) and shall be achieved for sediment. The specific level of detection shall be based on the LOQ which shall be 3 times the MDL. All measurements of D4 concentration in sediment shall include sufficient info. to perform a wet weight to dry weight conversion and shall report concentrations in terms of dry weight."

Sediment Sample Analysis for TOC (Appendix 7): "Following the general procedures of Powell and Woodburn (2009, Characterization of Sediments, p. 10) these additional samples shall be analyzed by carbon coulometry or an equivalent method for totalcarbon, total inorganic carbon, and total organic carbon, and loss-onignition for total water content and total organic matter content."

Biota Sample Analysis for D4 (Appendix 8): "The commercial laboratory will validate a method for the analysis of D4 in biota samples that shall be adapted from the analytical method specified in Powell and Woodburn (2009, Analysis of Cyclic Volatile Methylsiloxane (cVMS) Materials section, Extraction of Fish and Benthic Macroinvertebrates sub-section, p. 13, and QC, p. 14). The Powell and Woodburn (2009) analytical method involves extraction of aliquots of homogenized biota samples and QA samples followed by quantification using GC-MS."

"The method for analyzing D4 in biota reported by Campbell 2010; Durham 2010a and 2010b; Kaj 2005; Powell 2010a and 2010b; and Powell and Woodburn (2009) is deemed the appropriate method for an MDL of 0.2 to 3.0 ng/g (wet weight, ww). An MDL up to a value not exceeding 3.0 ng/g (wet weight, ww) shall be applied for biota. The specific level of detection shall be based on the LOQ which shall be 3
times the MDL." Biota Sample Analysis for Lipids (Appendix 8): "Lipid analysis will be performed on two ground rainbow trout field blanks. The method for analysis of lipid content of the composited benthic organism samples will be the same as used for fish. Procedures equivalent to Powell and Woodburn (2009) Characterization of Fish and Benthic Macroinvertebrates, p. 11 shall be used to measure liquid contents in the benthic organism samples."

Provides available validation and/or performance info. for non-standard
methods: Identifies individuals responsible for corrective actions: This is not covered in the QAPP. EPA suggests adding text that specifies the responsible party for corrective actions. Specifies needed laboratory turnaround time if important to project
schedule: This is not covered in the QAPP. EPA suggests adding text that specifies the lab analysis turnaround time. B5. QC Requirements - Section 3.5 - Page 41 Influent, Effluent, and Surface Water Samples (Appendices 4 & 5): 1) "Grab samples 3, 4 and 5 will be divided to provide two duplicates for analysis of D4. The duplicate samples shall be processed and analyzed as individual samples for D4. Duplicate samples are used to evaluate between-sample variability and precision." 2) "Grab samples 6 and 7 will serve as retain samples." 3) "Grab samples 1 and 2 will serve as field blank/field spike samples. The field blank/field spike samples will be split into two parts. One part will be analyzed for D4 as is (field blank) and the second part will be spiked w/ a known amount of D4 and then analyzed (field spike). The field blank/field spike samples will be used to evaluate contamination bias resulting from sample collection, processing, transport, storage and analysis. During each...sampling event at a given site, two laboratory blanks will also be prepared. The two laboratory blanks shall be created from two samples of laboratory-grade water having concentrations of D4 below the Limit of Quantification (LOQ) and shall be taken into the field and processed like [a]...sample. The laboratory blanks will be used to evaluate contamination bias resulting from collection, processing, transport, storage, and analysis of samples."

Sediment Samples (Appendix 7): 1) "Sediment samples 3, 4 and 5 will be divided to provide two duplicates for analysis of D4." 2) "Sediment samples 6 and 7 will serve as retain samples." 3) "Sediment samples 1 and 2 shall be split, one half of each sample shall be spiked in the field w/ a known amount of D4...Two reference sediment samples having concentrations of D4 below the LOQ for this matrix shall be taken into the field and processed like sediment samples." Identifies analytical methods to be followed (w/ all options) and required equipment: As previously mentioned under QAPP Element B2 Sampling Methods Requirements, EPA suggests including info. on sample headspace. Specifically, will there be headspace in the extracted sample vial ready for analysis and how long will the sample wait in the autosampler before being analyzed. Any effects to the measurements caused by wait time in the auto sampler before analysis shall be described.

Identifies QC procedures and frequency for each sampling, analysis, or measurement technique, as well as associated acceptance criteria and corrective action: (1) EPA suggests adding a discussion of QC requirements for duplicate investigative samples, including the development of DQOs for sampling and analytical precision, as appropriate. Section IX.A of the ECA requires the submission of a QAPP prepared in accordance w/ EPA guidance (USEPA Guidance for QA Project Plans, QA/G-5). Section 2.2.5 of EPA QA/G-5 describes the purpose of QC and provides guidance on the content for QC for field sampling programs including blanks, spikes, and split samples. For example, Section 2.2.5 of EPA QA/G-5 states "Replicate samples and split samples are commonly used to denote the level of precision in the measurement or collection system." Duplicate investigative samples are clearly a critical QC element of the sampling process design for this program regardless of their identification as "Study Samples" versus "QA Samples" w/in the ECA. For example, per the ECA, "Duplicate samples are used to evaluate between-sample variability and precision." (Note that Section 5 of the SOPs prepared for this program correctly identify the following as Field QA/QC Samples: split (duplicate) samples, unspiked field blanks, and spiked field blanks.)

(2) Section 3.5.1.2 of the QAPP (Field Spikes) states "the RPD for each pair of field spikes will then be calculated by using the results of the spiked samples. The calculated %R and RPD will be compared to the target QC limits in Tables 2-8 and 3-4." EPA suggests adding the acceptance criterion for RPD between pairs of field spikes to these
tables.

(3) Overall the QAPP must clearly discuss acceptance criteria, DQO, criteria for rejecting data and corrective actions.Review Checklist: Quality Assurance Project Plan (QAPP) D4 Environmental Testing Study Versus ECA Requirements and EPA Guidance Page 5 of 6

EPA 2002 QAPP Guidance ECA Requirement Defficiencies and Clarifications Biota Sample Analysis for D4 (Appendix 8): Benthic Organism Samples 1) "Samples 1, 2 and 3 shall be divided into three parts. Two of the parts will serve as duplicates for D4 analysis and one part will be analyzed for lipid content." 2) "Samples 4 and 5 will be retained for analysis as needed." Fish Samples 1) "For each of the two species, five individual fish or composited samples shall be prepared and frozen. In the laboratory three of the samples shall be thawed, homogenized and divided into three parts. Two of the parts will serve as duplicates for D4 analysis and one part will be analyzed for lipid content." 2) "Two of the five samples will be retained for analysis as needed."

Applies to both Benthic and Fish Samples: "During each sampling event at a given site, two field blanks and two field spikes will be prepared as follows. Rainbow trout tissue purchased from a commercial fish hatchery will be ground into a homogeneous mixture. Samples of the ground rainbow trout will be prepared in the laboratory prior to sample collection and shipped to the field. Prior to shipping to the field, the ground rainbow trout samples will be analyzed and shown to have concentrations of D4 below the LOQ for this matrix. Serving as field blanks, two reference ground rainbow trout samples will be opened during preparation of the composite samples of benthic organisms...In addition, two of the ground rainbow trout samples shall be spiked in the field w/ a known amount of D4."

Referenced procedures used to calculate QC statistics (precision and bias or accuracy): B6. Instrument/Equipment Testing, Inspection and Maintenance Requirements - Section 3.6 - Page 44 Identifies acceptance testing of sampling and measurement systems:

Describes equipment preventive and corrective maintenance: Notes availability and location of spare parts: B7. Instrument Calibration and Frequency - Section 3.7 - Page 45

Identifies equipment needing calibration and frequency for such
calibration: Notes required calibration standard and/or equipment: Cites calibration records and manner traceable to equipment: B8. Inspection/Acceptance Requirements for Supplies and Consumables - Section 3.8 - Page 46 States acceptance criteria for supplies and consumables: Notes responsible individuals: B9. Data Acquisition Requirements for Non-direct Measurements - Section 3.9 - Page 47 Identifies type of data needed from non-measurement sources (eg., computer databases and literature files) along w/ acceptance criteria for their use: Direct Discharge Sites: Sample Timing (Appendix 1): 1) "Samples shall be collected during normal plant operations and during such times that effluent flow rates from the wastewater treatment system are representative of the normal plant operations." 2) "Samples shall be taken during typical weather conditions and not until at least 3 days after an unusual weather event such as a heavy rain storm. Samples shall be collected at a time when the rate of D4 release is expected to be representative of the typical rate of release of D4 for that site."

Additional Measurements: 1) "Total effluent flow rate shall be recorede and reported." (Appendix 1) 2) "The date and time of the most recent precipitation occurrence for each sapling event will be recored" (Appendices 4 and 5) Sufficient info. is not provided in the QAPP regarding data quality, acceptance criteria, use of data, and data limitations. EPA recommends addressing uncertainties surrounding how the team will determine if the timing of a sampling event is acceptable, plant operations are "normal", and weather conditions are "typical". Please provide historical plant operation data, including process upsets for each plant. Please provide weather data for each plant . Please include a statement and sufficient supporting summary data to indicate what are considered "normal" plant operations.

“Samples shall be collected during normal plant operations and during such times that effluent flow rates from the wastewater treatment system are representative of the normal plant operations.” This need would be met if SEHSC submitted info. that both plant operations relevant to D4 were normal, effluent flow rates were representative preceding (by three days) and during the time of each sampling event. This could be accomplished by a succinct, written narrative of the associated process operations along w/ strictly necessary supporting process data. Any abnormal equipment or operating conditions that might have an impact on D4 effluent concentrations or flows should be clearly identified and explained.

Describes any limitations of such data: B10. Data Management - Section 3.10 - Page 47 Describes standard record keeping, data storage, and retrieval requirements: Further details on the database software and how the electronically stored data will be transmitted to the participants is needed. A version number for the database software and a description of how it will meet record keeping needs should be included in the QAPP.

Checklists of standard forms attached to QAPP: Describes data handling equipment and procedures used to process, compile, and analyze data (e.g., required computer hardware and software): Describes process for assuring that applicable info. resource management requirements are satisfied: Group C: Assessment/Oversight C1. Assessments and Response Actions - Section 4.1 - Page 51

(1) EPA recommends including info. regarding how the assessment of compliance w/ the SOPs will be recorded (i.e., checklist or other recording mechanism). The checklists provided in App. J for each event do not have a place to indicate compliance w/ each of the SOP bullets; only compliance w/ SOP 102 and 30 are recorded in the checklist. EPA suggests adding the other SOPs to the checklist. Lists required number, frequency, and type of assessments w/ approximate dates and names of responsible personnel (assessment include but are not limited to peer review, management systems review, technical systems audits, performance evaluations and audits of data quality): Identifies QC procedures and frequency for each sampling, analysis, or measurement technique, as well as associated acceptance criteria and corrective action: (1) EPA suggests adding a discussion of QC requirements for duplicate investigative samples, including the development of DQOs for sampling and analytical precision, as appropriate. Section IX.A of the ECA requires the submission of a QAPP prepared in accordance w/ EPA guidance (USEPA Guidance for QA Project Plans, QA/G-5). Section 2.2.5 of EPA QA/G-5 describes the purpose of QC and provides guidance on the content for QC for field sampling programs including blanks, spikes, and split samples. For example, Section 2.2.5 of EPA QA/G-5 states "Replicate samples and split samples are commonly used to denote the level of precision in the measurement or collection system." Duplicate investigative samples are clearly a critical QC element of the sampling process design for this program regardless of their identification as "Study Samples" versus "QA Samples" w/in the ECA. For example, per the ECA, "Duplicate samples are used to evaluate between-sample variability and precision." (Note that Section 5 of the SOPs prepared for this program correctly identify the following as Field QA/QC Samples: split (duplicate) samples, unspiked field blanks, and spiked field blanks.)

(2) Section 3.5.1.2 of the QAPP (Field Spikes) states "the RPD for each pair of field spikes will then be calculated by using the results of the spiked samples. The calculated %R and RPD will be compared to the target QC limits in Tables 2-8 and 3-4." EPA suggests adding the acceptance criterion for RPD between pairs of field spikes to these
tables.

(3) Overall the QAPP must clearly discuss acceptance criteria, DQO, criteria for rejecting data and corrective actions.Review Checklist: Quality Assurance Project Plan (QAPP) D4 Environmental Testing Study Versus ECA Requirements and EPA Guidance Page 6 of 6

EPA 2002 QAPP Guidance ECA Requirement Defficiencies and Clarifications (2) EPA recommends having a checklist for performing GLP audits prior to going into the field to ensure that audits are performed consistently and to have documentation of this. The checklist should be included in the QAPP appendices and contain a description of expectations, similar to the info. provided in Tables 5-1 and 5-2.

(3) Sect. 4.1.1.2 does not describe how an internal laboratory audit will be performed and what methods will be used to perform the audit. EPA suggests including a checklist of what systems will be audited as well as a description of the expectations, similar to the info. provided in Tables 5-1 and 5-2.
Identifies individuals responsible for corrective actions: C2. Reports to Management - Section 4.2 - Page 56 1) An Interim Progress Report is required 180 days after the Effective Date of the ECA and every 180 days thereafter until all obligations are fulfilled.

2) The Final Report is due no later than 150 days following completion of the required environmental testing (i.e., collection and analysis of the data). Results of performance evaluations and audits: The Signatory Companies will document all QA/QC work done as part of the Testing Program. EPA suggests adding the frequency.

Results of periodic data quality assessments: The Signatory Companies will document all QA/QC work done as part of the Testing Program. EPA suggests adding the frequency.

Any significant QA problems: The Signatory Companies will document all QA/QC work done as part of the Testing Program. EPA suggests adding the frequency.

Preparers and recipients of reports: EPA suggests specifying who will prepare the documents and who will receive them in a table or list w/in the document. Group D: Data Validation and Usability D1. Data Review, Validation, and Verification - Section 5.1 - Page 58 States criteria for accepting, rejecting, or qualifying data: EPA suggests adding a statement that specifies if analytical data does not fall w/in the acceptance criteria, the data will be reported but flagged. The flags that will be used should be specified w/in the document. EPA also suggests including references to the table(s) that contain the acceptance criteria. Add discussion on corrections if min. sample size problems arise from rejected or destroyed samples.

Includes project-specific calculations or algorithms: D2. Validation and Verification Methods - Section 5.2 - Page 59

Describes process for data validation and verification: Identifies issue resolution and responsible individuals: Identifies method for conveying these results to data users: D3. Reconciliation w/ User Requirements - Section 5.3 - Page 60

Describes process for reconciling project results w/ DQOs and reporting limitations on use of data: Although it's mentioned who communicates/reports to whom, it is not clear how ERM is going to provide project status reports (e.g., monthly reports or monthly meetings). This info. should be included in this
section. Project status: Lists required number, frequency, and type of assessments w/ approximate dates and names of responsible personnel (assessment include but are not limited to peer review, management systems review, technical systems audits, performance evaluations and audits of data quality):