SAMPLING AND ANALYSIS PLAN · Finally, quality assurance/quality control (QA/QC) procedures are necessary to ensure that valid and representative data is obtained and reported. 3.2

SAMPLING AND ANALYSIS PLAN: ASSESSMENT OF PER- AND POLYFLUOROALKYL SUBSTANCES (PFAS) IN ENVIRONMENTAL MEDIA AT CHROME PLATING FACILITIES

Issued: 15 May 2020

Prepared for: National Association for Surface Finishing (NASF)

GSI Environmental Inc.

9600 Great Hills Trail, Suite 350, Austin, TX 78759 T: 512.346.4474 � www.gsi-net.com

GSI Job No.: 5265 Issued: 15 May 2020

National Association for Surface Finishing (NASF) i Sampling and Analysis Plan

TABLE OF CONTENTS

1.0 INTRODUCTION ................................................................................................................. 1 2.0 ANALYTE LISTS AND LABORATORY ANALYTICAL METHODS .................................... 1

2.1 Laboratory Analytical Methods and Certified Labs ........................................................................ 1 2.2 Analyte Lists and Detection Limits ................................................................................................ 1

2.2.1 PFAS Compounds .............................................................................................................. 1 2.2.2 Field Parameters and General Chemistry Analytes for Groundwater ................................ 5

2.3 Analytical Method Modification and Attention to Matrix Interferences .......................................... 6

3.0 REPORTING REQUIREMENTS .......................................................................................... 6 3.1 Site Investigation Work Plan ......................................................................................................... 6 3.2 Investigation and Final Report ....................................................................................................... 7

4.0 GENERAL FIELD INVESTIGATION AND PFAS SAMPLING GUIDELINES ....................... 7 4.1 Precautions for Minimizing Contamination from External Materials .............................................. 7 4.2 Sample Containers and Holding Times ....................................................................................... 10 4.3 Effluent Wastewater and Influent Water ...................................................................................... 10

4.3.1 Locations ........................................................................................................................... 10 4.3.2 Process Effluent Wastewater Sampling ............................................................................ 10

4.4 Stormwater Runoff ....................................................................................................................... 10 4.4.1 Locations ........................................................................................................................... 11 4.4.2 Qualified Storm Event ....................................................................................................... 11 4.4.3 Sample Collection ............................................................................................................. 11

4.5 Soil Sampling ............................................................................................................................... 12 4.5.1 Locations ........................................................................................................................... 12 4.5.2 Surface Soil Sampling ....................................................................................................... 12 4.5.3 Subsurface Soil Sampling ................................................................................................. 12

4.6 Groundwater Sampling ................................................................................................................ 13 4.6.1 Locations ........................................................................................................................... 13 4.6.2 Existing Groundwater Monitoring Wells ............................................................................ 13 4.6.2.1 Depth to Water Measurements .................................................................................. 13 4.6.3 Low-Flow Sampling Procedures ....................................................................................... 13 4.6.4 Grab Samples Using Direct Push Technology (DPT) Drilling Rig .................................... 14

4.7 Decontamination .......................................................................................................................... 14 4.8 Investigation Derived Waste ........................................................................................................ 15 4.9 Sample Documentation, Handling, and Shipping ........................................................................ 15

4.9.1 Labeling ............................................................................................................................. 15 4.9.2 Daily Field Notes ............................................................................................................... 15 4.9.3 Sample Handling and Packaging ...................................................................................... 16 4.9.4 Chain of Custody ............................................................................................................... 16

5.0 QA/QC SAMPLING AND DATA VALIDATION ................................................................. 18 5.1 Field Quality Control Samples ..................................................................................................... 18

5.1.1 Blank Samples .................................................................................................................. 19 5.1.2 Duplicates ......................................................................................................................... 19

5.2 Laboratory Quality Control Checks ............................................................................................. 20 5.3 Data Validation ............................................................................................................................ 20

5.3.1 Procedures Used to Validate Field Data ........................................................................... 20 5.3.2 Procedures Used to Validate Laboratory Data ................................................................. 21

5.4 Procedures to Assess Data Quality Objectives ........................................................................... 21


National Association for Surface Finishing (NASF) ii Sampling and Analysis Plan

5.4.1 Accuracy Assessment ....................................................................................................... 21 5.4.2 Precision Assessment ....................................................................................................... 22 5.4.3 Completeness Assessment .............................................................................................. 22

REFERENCES ......................................................................................................................... 23

TABLES Table 1A: PFAS Compounds Likely to be Required for Analysis ................................................ 3 Table 1B: Analytes that may help evaluate PFAS Transport ...................................................... 4 Table 2: List of Field Parameters for Groundwater Samples ...................................................... 5 Table 3: List of General Chemistry Parameters Required for Groundwater Samples ................. 5 Table 4: Sampling Equipment and Sample Collection Materials (CA SWQCB, 2019) ................ 8 Table 5: Personal Protective Equipment, Clothing, Insect Repellants, and

Sunscreens (CA SWQCB, 2019) .............................................................................. 9 Table 6: Summary of QA/QC Sampling Program ......................................................................18


National Association for Surface Finishing (NASF) iii Sampling and Analysis Plan

LIST OF ACRONYMS CAS .................... Chemical Abstract Service CoC .................... Chain of Custody DL ....................... Detection Limits DO ...................... Dissolved Oxygen DoD .................... Department of Defense EC ....................... Electrical Conductivity EDD .................... Electronic Data Deliverable ETFE .................. Ethylene-tetrafluoro-ethylene FEP ..................... Fluorinated ethylene propylene GSI ..................... GSI Environmental Inc. HDPE .................. High Density Polyethylene IDW ..................... Investigation-Derived Waste LC/MS/MS .......... Liquid Chromatography/Tandem Mass Spectrometry LCS ..................... laboratory control samples LDPE .................. Low Density Polyethylene MS/MSD ............. matrix spike/matrix spike duplicates NASF .................. National Association for Surface Finishing NOAA ................. National Oceanographic and Atmospheric Administration P.E. ..................... Professional Engineer PFAS .................. Per- And Polyfluoroalkyl Substances P.G. .................... Professional Geologist PPE .................... Personal Protective Equipment PTFE .................. Polytetrafluoroethylene PVC .................... Polyvinyl Chloride PVDF .................. Polyvinylidene Fluoride QA ...................... Quality Assurance QC ...................... Quality Control QSE .................... Qualified Storm Event RF ....................... Response Factor RL ....................... Reporting Limit RPD .................... Relative Percent Difference RPM .................... Remedial Project Manager RSD .................... Relative Standard Deviation SAP .................... Sampling and Analysis Plan SPE .................... Solid-Phase Extraction USEPA ............... United States Environmental Protection Agency DL ....................... Detection Limit/Method Detection Limit


National Association for Surface Finishing (NASF) 1 Sampling and Analysis Plan

1.0 INTRODUCTION

GSI Environmental Inc. (GSI) prepared this Sampling and Analysis Plan (SAP) at the request of the National Association for Surface Finishing (NASF) for the assessment of per- and polyfluoroalkyl substances (PFAS) at Chrome Plating Facilities. This SAP includes sampling guidelines per the latest technical understanding and recommended industry practices.

This document is organized into the following sections:

x Section 1.0: Introduction x Section 2.0: Analyte Lists and Laboratory Analytical Methods x Section 3.0: Reporting Requirements x Section 4.0: General Field Investigation and PFAS Sampling Guidelines x Section 5.0: QA/QC Sampling and Data Validation x Section 6.0: References

2.0 ANALYTE LISTS AND LABORATORY ANALYTICAL METHODS

The following sections summarize the identification of certified laboratories, potential analyte lists required by a site’s state/regional governing authority, as well as laboratory analytical methods to be used.

2.1 Laboratory Analytical Methods and Certified Labs The oversight of the field investigation, including the preparation of documents, should be completed by a licensed Professional Geologist (P.G.) or Professional Engineer (P.E.). Field personnel, under the direction of the certified P.G. or P.E., will be responsible for collecting the liquid, soil, subsurface soil, and/or groundwater samples, in accordance with the site-specific work plans for each site. Samples collected by the field personnel should be shipped to a commercial PFAS Testing and Analysis laboratory according to shipping instructions provided by the laboratory. Various analytical methods exist for PFAS analysis in different environmental matrices. As a result, there are tendencies for measurement uncertainties during PFAS analysis. Therefore, appropriate selection of the certified P.E./P.G., commercial laboratory, the analytical method, and compound-specific reporting limits should be used to obtain accurate and reliable PFAS quantification.

Hired certified P.E.’s and P.G.’s, along with field personnel, should have prior experience in collecting PFAS environmental samples and selecting appropriate commercial analytical labs. For high-quality data, the selected analytical laboratory should be accredited and certified to perform a method compliant with the Department of Defense (DoD) Table B-15 of Quality Systems Manual (QSM), dated 2017, version 5.1 or later.

2.2 Analyte Lists and Detection Limits Analyte lists for PFAS compounds for soil and water samples, as well as field parameters and general chemistry analytes for groundwater samples, are summarized below.

2.2.1 PFAS Compounds Due to the large number of PFAS compounds and current limitations in analytical capabilities, careful selection of analytes is necessary based on state, regional, or site-specific requirements. Table 1A presents analytes that are likely to be required to be tested at a site, while Table 1B



presents additional analytes that may help understand the fate and transport of PFAS at a site. Note that some laboratories may have additional analyte capabilities that are not included in the lists below and may need to be addressed on a case-by-case basis. Method detection limits (DL) and reporting limit (RL) requirements, or the lowest concentration that can be detected by a laboratory, should be included for both water and soil samples and should be verified prior to laboratory selection.



Table 1A: PFAS Compounds Likely to be Required for Analysis

Chemical Name Abbreviation

Chemical Abstracts Service

(CAS) No.

Drinking Water (ng/L)

Groundwater, Stormwater,

Wastewater (ng/L) Soil

(ng/kg) DL2 LCMRL3 DL4 DL5

Perfluoroalkyl Carboxylic Acids (PFCAs) Perfluorobutanoic acid PFBA 375-22-4 - 13 13.85 22.01 Perfluoropentanoic acid PFPeA 2706-90-3 - 3.9 11.59 20.93 Perfluorohexanoic acid PFHxA 307-24-4 1.0 5.3 1.31 15.44 Perfluoroheptanoic acid PFHpA 375-85-9 0.71 2.6 2.32 5.80 Perfluorooctanoic acid PFOA 335-67-1 0.53 3.4 3.04 6.24 Perfluorononanoic acid PFNA 375-95-1 0.70 4.8 1.76 2.82 Perfluorodecanoic acid PFDA 335-76-2 1.6 2.3 3.03 5.54 Perfluoroundecanoic acid PFUnA 2058-94-8 1.6 2.7 1.08 2.45 Perfluorododecanoic acid PFDoA 307-55-1 1.2 2.2 2.42 3.56 Perfluorotridecanoic acid PFTrdA 72629-94-8 0.72 0.532 - - Perfluorotetradecanoic acid PFTeDA 376-06-7 - - - - Perfluorinated Sulfonic Acids (PFSAs) Perfluorobutane sulfonic acid PFBS 375-73-5 1.8 3.5 7.60 6.49 Perfluoropentane sulfonic acid PFPeS 2706-90-3 - 6.3 - - Perfluorohexane sulfonic acid PFHxS 355-46-4 1.4 3.7 2.51 7.75 Perfluoroheptane sulfonic acid PFHpS 357-92-8 - 5.1 - - Perfluorooctane sulfonic acid PFOS 1763-23-1 1.1 4.4 4.19 18.83 Perfluorodecane sulfonic acid PFDS 335-77-3 - - - - Perfluoroocane Sulfonamide and Derivatives (PFOSA, FOSEs, FOSAs, and FOSAAs) Perfluoroocanesulfonamide PFOSA 754-91-6 - - N-Methyl perfluorooctane sulfonamidoacetic acid NMeFOSAA 2355-31-9 2.4 4.32 - - N-Ethyl perfluorooctane sulfonamidoacetic acid NEtFOSAA 2991-50-6 2.8 4.82 - - Fluorotelomer sulfonates (FTS) 4:2 Fluorotelomer sulfonic acid 4:2 FTS 757124-72-4 - 4.7 - - 6:2 Fluorotelomer sulfonic acid 6:2 FTS 27619-97-2 - 14 - - 8:2 Fluorotelomer sulfonic acid 8:2 FTS 39108-34-4 - 9.1 - - Chlorinated Polyfluoroalkyl Ether Sulfonic Acids (Cl-PFESAs) 9-Chlorohexadecafluoro-3-oxononane-1-sulfonic acid 9-Cl-PF3ONS 756426-58-1 1.4 1.4 - - 11-Chloroeicosafluoro-3-oxaundecane-1-sulfonic acid 11-Cl-PF3OUdS 763051-92-9 1.5 1.6 - -

Notes: 1. ng/L = nanograms per liter; ng/kg = nanograms per kilogram; DL = detection limit; RL = Reporting limit

2. Detection Limit based on EPA Method 537.1

3. LCMRL = Lowest concentration minimum reporting level based on EPA Method 533. 4. Detection Limit based on ASTM D7979 – 19 5. Detection Limit based on ASTM D7968 - 17a



Table 1B: Analytes that may help evaluate PFAS Transport

Chemical Name Abbreviation

Chemical Abstracts

Service (CAS) No.

Drinking Water (ng/L)

Groundwater, Stormwater,

Wastewater (ng/L) Soil

(ng/kg)

DL2 LCMRL3 DL 4 DL5 Perfluoroalkylcarboxylic Acids (PFCAs) Perfluorohexadecanoic acid PFHxDA 67905-19-5 - - Perfluorooctadecanoic acid PFODA 16517-11-6 - - Perfluorinated Sulfonic Acids (PFSAs) Perfluorononane sulfonic acid PFNS 68259-12-1 - Perfluoroocane Sulfonamide and Derivatives (PFOSA, FOSEs, FOSAs, and FOSAAs) N-Ethyl perfluorooctane sulfonamide ethanol EtFOSE 1691-99-2 - - - N-Methyl perfluorooctane sulfonamide ethanol

MeFOSE 24448-09-7 - - -

N-Ethyl perluorooctane sulfonamide EtFOSA 4151-50-2 - - - N-Methyl perfluorooctane sulfonamide MeFOSA 31506-32-8 - - - Fluorotelomer sulfonates (FTS) 10:2 Fluorotelomer sulfonic acid 10:2 FTS 120226-60-0 - Fluorotelomer Carboxylic Acids (FTCA) 2H, 2H, 3H, 3H-Perfluorohexanoic acid 3:3 FTCA 356-02-5 - - - 2H, 2H, 3H, 3H-Perfluorooctanoic acid 5:3 FTCA 914637-49-3 - - - 2H, 2H, 3H, 3H-Perfluorodecanoic acid 7:3 FTCA 812-70-4 - - - Perfluoroalkyl Ether Carboxylic Acids (PFECA) Hexafluoropropylene oxide dimer acid HFPO-DA 13252-13-6 1.9 3.7 - 4, 8-Dioxa-3H-perfluorononanoic acid ADONA 919005-14-4 0.88 3.4 -

Notes: 1. ng/L = nanograms per liter; ng/kg = nanograms per kilogram; DL = detection limit; RL = Reporting limit 2. Detection Limit based on EPA Method 537.1 3. LCMRL = Lowest concentration minimum reporting level based on EPA Method 533. 4. Detection Limit based on ASTM D7979 - 19 5. Detection Limit based on ASTM D7968 - 17a



2.2.2 Field Parameters and General Chemistry Analytes for Groundwater During groundwater sample collection, additional field parameters need to be collected and reported, as these parameters affect the distribution and detection of PFAS in environmental media. Tables 2 and 3 below summarize the field parameter and general chemistry analyses for these samples.

Field parameters can be obtained during sample collection using the following equipment:

x Electronic water level indicator (for measuring depth to groundwater). x Flow-through cell (for measuring pH, dissolved oxygen, temperature, oxidation-reduction

potential, and electrical conductivity). x Turbidity meter (for measuring turbidity).

Table 2: List of Field Parameters for Groundwater Samples

Field Parameter Units Depth to Groundwater Feet, bgs Temperature Degrees C Electrical Conductivity µmhos/cm pH Units Turbidity NTU Notes: 1. bgs – below ground surface 2. C – Celsius 3. µmhos/cm – micromhos per centimeter 4. NTU – nephelometric turbidity units 5. mg/L – milligrams per liter

The following general chemistry parameters (Table 3) are to be analyzed by the commercial laboratory and included on the analyte list for all groundwater samples.

Table 3: List of General Chemistry Parameters Required for Groundwater Samples General Chemistry Units Total Dissolved Solids mg/L Chloride mg/L Carbonate mg/L Bicarbonate mg/L Nitrate-Nitrogen mg/L Sulfate mg/L Calcium mg/L Magnesium mg/L Potassium mg/L Sodium mg/L Notes: 1. mg/L – milligrams per liter



2.3 Analytical Method Modification and Attention to Matrix Interferences Analytical methods for matrices other than drinking water often must be “modified” by analytical laboratories because of matrix effects. These “modifications” or changes are sometimes made during sample preparation procedures to resolve potential interferences that are present in the matrix. They can include, but are not limited to, use of solvents, acid/base extraction, and repeated washing. In the event that any sample has matrix interferences during sample preparation and analysis, the reporting lab will describe what “modifications” were made to the analytical method (including how the interference was addressed), and state the reasons for the “modifications”.

3.0 REPORTING REQUIREMENTS

After sample analysis, the laboratory should provide the data results in concentrations of the analyte per media sample in an electronic data deliverable (EDD) and laboratory report format. Additionally, sites are required to submit the results of the site investigation in a final report to the applicable state or regional authority, or Remedial Project Manager (RPM).

Reporting requirements generally include but not limited to the following, and may vary on a site-by-site basis:

x Submission of a site investigation work plan x Perform the site investigation x Submission of the results of the site investigation in a final report to the applicable authority

or RPM

Specifics of each reporting requirement are provided in the following sections.

3.1 Site Investigation Work Plan A Site Investigation Work Plan may be required and should be reviewed by the RPM prior to the start of the investigation. The RPM may provide comments on the submitted work plan to assure that the plan is complete and to verify that the proposed sample locations in relation to the potential source areas are appropriate.

As noted above, the oversight of the field investigation, including the preparation of the site-specific work plan, should be completed by a licensed P.G. or P.E.

The following information may be included in the Work Plan:

a) Text describing how, when, and where the potential PFAS-containing material was stored, used, and/or released. Also, a site map showing PFAS material storage and use areas, including other potential release locations to land, drains, sewers, surface water, air, and/or groundwater, should be provided in the text.

b) Text describing previous investigations, if any, conducted at the site to identify and evaluate the presence of PFAS in soil, groundwater, stormwater, air, or effluent wastewater.

c) Text and a map identifying municipal supply wells, domestic wells, and/or surface water bodies within a one-mile radius of any suspected release area.

d) Text describing the sampling rationale and a site map showing the following:

x Proposed surface and subsurface soil sample locations.



x Proposed representative groundwater sample locations. Existing monitoring wells may be used if functioning properly so that representative groundwater samples can be collected.

e) Sampling and Analysis Plan (this general SAP). This SAP includes the appropriate sampling procedures:

x sampling equipment x sampling containers x the quality of water used for blank preparation and equipment decontamination; iv) sample

holding times x quantities for sampling PFAS compounds

Finally, quality assurance/quality control (QA/QC) procedures are necessary to ensure that valid and representative data is obtained and reported.

3.2 Investigation and Final Report The site investigation should be performed based on the details described in the approved site investigation work plan. The final report summarizing the results of the site investigation should be submitted to the appropriate governing authority or RPM.

The following information should be included in the final report:

x Description of the sampling activities performed. x Summary table of the analytical results (including QA/QC samples). x Copy of the Chain of Custody forms. x Copy of the field sampling logs and field notes. x Copy of boring logs and any temporary/permanent monitoring well construction details. x Copy of the site map showing the sampling/monitoring locations. x Copy of the laboratory standard operating procedure for the analytical methods. x Copy of the laboratory-certified analytical results.

4.0 GENERAL FIELD INVESTIGATION AND PFAS SAMPLING GUIDELINES

4.1 Precautions for Minimizing Contamination from External Materials The unique physio-chemical properties of PFAS and their potential presence in consumer goods renders the sampling of PFAS susceptible to cross-contamination issues during field sampling activities. To obviate the possibility of cross-contamination, sampling necessitates careful attention to the following sampling procedures.

Cross-contamination sources are hypothesized to include the following:

x water used during drilling or decontamination x field clothing and personal protective equipment (PPE) x sun and biological protection products x personal care products, clothing, and laundry products x food packaging x the environment itself (CA SWQCB, 2019)



However, in a recent study by Rodowa et al., (2020), 66 materials were analyzed for 52 PFAS, of which only 22 materials had the potential to come into direct contact with samples during sampling. Of these 22 materials, none had quantifiable concentrations of routinely measured PFAS. Additionally, 10 materials did have measurable PFAS concentrations but had no plausible pathway for contaminating samples.

As such, material limitations should focus on those items that could potentially come into direct contact with environmental samples and impact PFAS concentrations to a level of concern. Implementing standard sampling practices and general standards of care (used for other contaminants) should prevent sample interferences of PFAS.

It is important to note however that state and regional boards may require specific sampling measures to avoid potential cross-contamination. These requirements may include adherence to sampling guidance published by federal and civilian organizations or private sector trade groups. As such, these measures need to be followed on a site-specific basis.

Table 4 summarizes materials that some authorities may suggest avoiding during field sampling.

Table 4: Sampling Equipment and Sample Collection Materials (CA SWQCB, 2019)

Allowable Materials Materials to Avoid Sampling Equipment x High-density polyethylene (HDPE) x Polypropylene x Silicone x Stainless steel x Nylon x PVC x Acetate x Cotton

x Polytetrafluoroethylene (PTFE), including Teflon and Hostaflon

x Polyvinylidene fluoride (PVDF), including Neoflon x Ethylene-tetrafluoro-ethylene (ETFE), including

Tefzel x Fluorinated ethylene propylene (FEP) including

Teflon FEP and Hostaflon FEP x Low density polyethylene (LDPE) x Aluminum foil (NGWA, 2018)

Sampling Collection and Storage x Ballpoint pens for labeling sample

containers x HDPE or polypropylene sample

bottles with Teflon-free caps, provided by the laboratory

x Regular/thick size markers (Sharpie) x Sticky Notes x Chemical or blue ice x Rite-in-the-rain paper, binders and plastic

clipboards (NGWA, 2018) x Sticky notes (NGWA, 2018) x Waterproof pens (NGWA, 2018)

While Table 5 lists other materials such as personal protective equipment (PPE), field supplies, clothing, and sunscreens that are sometimes included in state-specific guidance (e.g., California).



Table 5: Personal Protective Equipment, Clothing, Insect Repellants, and Sunscreens (CA SWQCB, 2019)

Allowable Materials Prohibited Materials Personal Protective Equipment and Clothing x Well-laundered synthetic or 100% cotton

clothing x Powderless nitrile gloves x Waterproof clothing made of or with

polyurethane, PVC, was-coated fabrics, rubber, neoprene

x Boots made of polyurethane and/or PVC

x Water/stain/dirt-resistant treated clothes (including but not limited to Gore-Tex, Scotchguard, RUCO, etc.)

x New, unwashed clothing x Clothes recently washed with fabric

softeners x Clothes chemically treated for insect

resistance and ultraviolet protection x Coated Tyvek x Latex gloves

Insect Repellants* OFF Deep Woods; Sawyer Pemethrin; Jason Natural Quit Bugging Me; Repel Lemon Eucalyptus Insect repellant; Herbal Armor, California Baby Natural Bug Spray

--

Sunscreens* Banana Boat Sport Performance Sunscreen Lotion Broad Spectrum SPF 30; Meijer Sunscreen Lotion Broad Spectrum SPF 30; Neutrogena Ultra-Sheer Dry-Touch Sunscreen Broad Spectrum SPF 30; Banana Boat for Men Triple Defense Continuous Spray Sunscreen SPF 30; Banana Boat Sport Performance Coolzone Broad Spectrum SPF 30; Banana Boat Sport Performance Sunscreen Lotion Broad Spectrum SPF 30; Banana Boat Sport Performance Sunscreen Stick SPF 50; Coppertone Sunscreen Lotion Ultra Guard Broad Spectrum SPF 50; Coppertone Sport High-Performance AccuSpray Sunscreen SPF 30; Coppertone Sunscreen Stick Kids SPF 55; L’Oréal Silky Sheer Face Lotion 50+; Meijer Clear Zinc Sunscreen Lotion Broad Spectrum SPF 15, 30 and 50; Meijer Wet Skin Kids Sunscreen Continuous Spray Broad Spectrum SPF 70; Neutrogena Beach Defense Water + Sun Barrier Lotion SPF 70; Neutrogena Beach Defense Water + Sun Barrier Spray Broad Spectrum SPF 30; Neutrogena Pure & Free Baby Sunscreen Broad Spectrum SPF 60+

--

Note: (*) This is not a comprehensive list of allowable insect repellants or sunscreens. If none of the listed products are available, an

equipment blank sample must be collected to verify that it is PFAS-free (CA SWQCB, 2019).



Finally, hands should be thoroughly washed before sampling any environmental media. Clean and powderless nitrile gloves must be worn before collecting samples, handling sample containers, or equipment. Gloves should always be replaced in between sample collection locations.

4.2 Sample Containers and Holding Times The selected PFAS testing and analysis laboratory will ship empty sample containers specific to the media (i.e., soil and water) and analyte list to be collected. These sample containers should meet volume and preservative requirements from the laboratory to ensure data quality objectives are met.

Laboratory-specific volume requirements and sample container sizes may vary but usually consist of two 250-milliliter HDPE bottles per sample. No preservative is added to sample bottles. Holding times for PFAS samples are 14 days from the day of sample collection to the day of sample extraction. Note that for non-drinking water and soil matrices, holding time may vary depending on the analytical laboratory and test method.

For general chemistry analysis (Table 3), the required sample containers will vary, and will also be provided by the laboratory, along with method-specific requirements for holding times.

For field blanks, equipment blanks, and decontamination, the laboratory will provide deionized/distilled water that has been confirmed to be PFAS-free.

4.3 Effluent Wastewater and Influent Water The following sections describe the recommended sampling procedures for taking effluent wastewater samples, where applicable.

4.3.1 Locations The site-specific work plan shall describe the exact sample locations and rationale for the selected locations. Additionally, a sample of process rinse water or influent water (municipal tap water or other influent water to the facility) should be taken to determine current site-specific background PFAS concentrations.

4.3.2 Process Effluent Wastewater Sampling Samples can be obtained from the same sampling location(s) used for compliance sampling, where there is no other discharge. The sampling location should be representative of the actual discharge from the site (USEPA, 2017). The field personnel should collect grab samples from the center of the flow where the flow is turbulent and well mixed (USEPA, 2017).

Field water quality parameters can be measured using a multi-parameter probe with the ability to measure turbidity, electrical conductivity (EC), pH, and temperature. Samples should be collected from the rinse tank using a plastic container to minimize electromagnetic interference. The probe for the meter can be submerged into the sample within the plastic container and gently stirred and tapped to remove air bubbles that may be trapped inside the probe. This will help the meter reach equilibrium prior to logging the water quality parameter measurements.

4.4 Stormwater Runoff The following sections describe the recommended sampling procedures for collecting stormwater runoff samples.



4.4.1 Locations The site-specific work plan shall describe the exact sample locations and rationale.

4.4.2 Qualified Storm Event As described in CASQA, 2014, stormwater sampling needs to be conducted during Qualified Storm Events (QSEs). Where:

“A QSE is defined as any precipitation event that produces a discharge for at least one drainage area and is preceded by 48 hours with no discharge from any drainage area. Weather and precipitation forecasts will be tracked to identify potential QSEs. When targeting a QSE for stormwater sampling, the appropriate team member will weekly consult the National Oceanographic and Atmospheric Administration (NOAA) for weather forecasts. These forecasts can be obtained at http://www.srh.noaa.gov/. If weekly forecasts indicate potential for significant precipitation, the weather forecast will be closely monitored during the 48 hours preceding the event.”

4.4.3 Sample Collection Grab sampling is performed to collect a sample that represents the entire runoff stream. Samples are usually collected by dipping the collection container in the runoff flow paths and streams, as noted below (CASQA, 2014).

x For small streams and flow paths, simply dip the bottle facing upstream until full. x For larger streams that can be safely accessed, collect a sample in the middle of the flow

stream by directly dipping the mouth of the bottle. Face the opening of the bottle upstream to avoid contamination by the sampler.

x For larger streams that cannot be safely waded, pole samplers may be needed to access the representative flow safely.

x For outlet pipes discharging from a control structure, samples should be collected from the flow discharging from the outlet.

x For sheet flow samples that are not easily captured within sample containers, temporary berms/sandbags can be placed in a “V” formation to channelize and concentrate flow single collection point.

x Avoid collecting samples from ponded, sluggish, or stagnant water. x Avoid scraping the ground surface when collecting the sample. x Avoid collecting samples directly downstream from a bridge as the samples can be

affected by the bridge structure or runoff from the road surface. x Avoid touching the bottom of channels or pipes to avoid disturbing / stirring up solid

particles. x Do not stand upstream of the sampling point within the flow path.

To maintain sample integrity and prevent cross-contamination, sample collection personnel will follow the protocols below (CASQA, 2014).

x Wear clean, powder-free nitrile gloves when collecting samples. Change gloves whenever something not known to be clean, and PFAS-free has been touched.

x Change gloves between sampling locations. x Do not sample near a running vehicle. x Do not park vehicles in the immediate sample collection area, including non-running

vehicles.



If a site has any discharges to a sanitary sewer, the effluent wastewater treatment sampling procedures should be followed (see Section 4.3.2).

4.5 Soil Sampling The following sections describe the recommended sampling procedures for collecting surface soil and subsurface soil samples.

4.5.1 Locations The site-specific work plan shall describe the exact sample locations and rationale. If thick gravel or matted root zone is present at or near the surface, it should be removed prior to sample collection. Note that the depth measurement for the sample begins at the top of the soil horizon, below any removed materials (SESD, 2014).

4.5.2 Surface Soil Sampling Surface soils generally consist of soils between the ground surface and 6 to 12 inches below ground surface (SESD, 2014).

Stainless steel spoons or hand tools may be used for surface soil sampling for depths up to approximately 6 inches below ground surface. Here, the ground surface conditions need to be soft, with no vegetative layer to penetrate (SESD, 2014).

4.5.3 Subsurface Soil Sampling For samples requiring deeper depths, hand augers or direct push soil sampling may be used, as follows. Note that underground utilities should be located and marked prior to the start of any subsurface investigations. Subsurface geology should be recorded in field forms per depth interval (i.e., boring logs).

4.5.3.1 Hand Augers

Hand augers can be used to obtain disturbed soil samples for boring to depths where soil samples are to be collected, as follows:

x Auger to the depth required for soil sampling, and place cuttings on plastic sheeting. Record the geologic features of the soil.

x Remove the auger from the hole and set aside for subsequent decontamination. x Obtain the subsurface soil sample by driving the sample sleeve through the sample

interval with a slide hammer. Remove the liner from the slide hammer and screen the sleeve.

x Place the sample volume in laboratory-appropriate bottles for PFAS analysis. x Decontaminate auger bucket, and sample tube and shoe between each sample.

4.5.3.2 Direct Push Soil Sampling

A Direct Push Technology (DPT) probe will be driven in the subsurface to obtain continuous soil cores (approximately 5 ft each) to the total desired depths. Soil geology will be logged using the USCS Classification system for each soil core. Samples can then be collected using hand tools at the specific depths and put in laboratory-specified containers.

To the extent practical, tools should be cleaned and decontaminated between sampling depths and locations, as indicated in Section 4.7. At a minimum, field personnel should change gloves between cores, and DPT rods should be decontaminated between each sample location.



4.6 Groundwater Sampling 4.6.1 Locations The site-specific work plan shall describe the exact sample locations and rationale.

4.6.2 Existing Groundwater Monitoring Wells The following procedures can be followed to measure water levels and collect groundwater samples.

4.6.2.1 Depth to Water Measurements x Check the condition of the monitoring well for damage and record any observations in field

notes. x Unlock wellhead, and remove inner casing cap. x Measure the depth to water with an electronic water level indicator, and record on

sampling log (to nearest 0.01 ft). x Decontaminate the water level indicator per the procedures summarized in Section 4.7.

4.6.2.2 Sampling Procedures

See Section 4.6.3 (Low-Flow Sampling Procedures)

4.6.3 Low-Flow Sampling Procedures Low-flow sampling can be conducted using a peristaltic pump, or for deeper aquifers, pumps with the allowable materials summarized in Table 5 may be used.

4.6.3.1 Purging

x Position a new set of tubing (Silicone, vinyl, or HDPE tubing; no Teflon) until the location of the pump intake is approximately at the mid-point of the monitoring well-screened interval.

x Connect the discharge line from the pump to a flow-through cell and position the discharge line from the flow-through cell to be above a container/bucket to contain purge water during the purging and sampling of the well.

x Start pumping the well at a flow rate of < 0.1 to 0.5 L/min and check the water level. Maintain a steady flow rate and maintain a drawdown of less than 1 ft. If drawdown is greater than 1 ft, decrease the flow rate. Maintain flow rate throughout the purging, though certain site-specific geologic heterogeneities may require reductions in flow rate.

x Measure the discharge rate of the pump with a stopwatch and graduated cylinder and record on the sampling log.

x Monitor and record the following water quality field parameters via the flow-through cell every 3 to 5 minutes: pH, dissolved oxygen, temperature, oxidation-reduction potential, and specific conductance. Take subsequent turbidity readings using a stand-alone turbidity meter.

x Stabilization of groundwater conditions will be achieved when three (3) sets of consecutive readings have been obtained for pH (+/- 0.2 S.U.), temperature (+/- 10%), dissolved oxygen (+/- 0.2 mg/L) and specific conductance (+/- 3%). Once these criteria have been met, a sample can be taken at the monitoring well.



4.6.3.2 Sampling

x If the pumping rate is >250 mL/min, decrease the rate to approximately 250 mL/min. To collect the groundwater samples, disconnect the pump’s tubing from the flow-through cell, and collect the samples directly from the pump’s discharge tubing.

x Note that the laboratory-approved container must be filled directly from the pump discharge tubing and not through the flow-through cell.

x Remove and discard existing tubing.

4.6.4 Grab Samples Using Direct Push Technology (DPT) Drilling Rig If there are no existing groundwater monitoring wells, groundwater samples can be collected using a DPT drilling rig. The drilling rig must be operated by a drilling company.

At predetermined locations and depths, samples can be collected by advancing the DPT rods, as follows:

x A sealed-screen consisting of a short screen (e.g., 6 inches to 3 feet) is nested within a sealed, water-tight tool body.

x The DPT rod should be advanced by the drill rig operator to the desired depth interval. x The operator will then pull up on the DPT rods, allowing for the sampling screen to be

exposed. x Polyethylene tubing should be lowered into the open sampling screen, and a pump can

be used to extract water for sampling purposes. Applicable pumps include:

� Peristaltic pump (if depth to groundwater is <20 ft below ground surface); or � Waterra foot valve pump (if depth to groundwater is >20 ft below ground surface).

x Pumps and polyethylene tubing may be provided by the drillers. x A small volume of groundwater (< 100 mL) should be purged prior to sample collection. x Groundwater samples will be collected as grab samples and transferred to method-

specified containers and immediately placed in coolers with ice. x A YSI flow-through cell and turbidity meter should be used to collect data on field

parameters in all samples. These field parameters include: DO, pH, specific conductivity, temperature, oxidation-reduction potential, and turbidity (Section 2.2.2).

x The DPT rods will be extracted after each sample is collected, and new rods advanced for each sample. New polyethylene tubing should be used to collect each sample at various depths.

x Drilling rods should be decontaminated between locations using procedures indicated in Section 4.7 below. For members of the sampling crew, gloves should be changed between sampling depths to minimize the potential for cross-contamination.

4.7 Decontamination For non-dedicated sampling equipment, decontamination should be conducted before and between use at each sampling location. Decontamination procedures should also include triple rinsing with PFAS-free water. Specifically, the acceptable materials and procedures are as follows (CA SWQCB, 2019):

x Acceptable water and cleaning agents to be used:

� Laboratory supplied PFAS-free deionized water



� Alconox, Liquinox, and Citranox for equipment decontamination � Commercially available deionized water in an HDPE container if the water is verified

to be PFAS-free � Municipal drinking water if it is known to be PFAS-free.

x Acceptable materials to be used:

� Polyethylene or Polyvinyl chloride (PVC) brushes for scrubbing sampling equipment

x Do not use:

� Deacon 90

4.8 Investigation Derived Waste Investigation Derived Waste (IDW) will consist of wastewater from the decontamination of field equipment, purge water from groundwater monitoring wells, and soil cuttings from soil sampling locations. Each waste stream is to be addressed separately. IDW should be managed and disposed of in accordance with existing site-specific protocols for monitoring program procedures. If there are no pre-existing protocols for management of IDW, material/waste characterization should follow standard state hazardous waste determination protocols. In consultation with the state or regional governing authority and the site’s landfill of choice, the site will need to determine local requirements for PFAS.

4.9 Sample Documentation, Handling, and Shipping This section outlines sample documentation, handling, and shipping procedures to ensure proper documentation, handling, and shipping from the field to the laboratory for PFAS analyses.

4.9.1 Labeling For labeling samples, laboratory pre-printed labels may be used, or labels can be filled out by field personnel using a ballpoint pen. Labels should include the following information:

x Sample identifier. x Sampling date and time in 24-hour format. x Sampler’s initials. x Method of sample preservation, if applicable. x Project name and Analytical method.

Field duplicates should be labeled such that they are blind duplicates, and all QC samples should be labeled and included on the chain of custody record.

4.9.2 Daily Field Notes Daily records of observations, measurements, and significant events, including sampling activities during field investigations, are to be recorded on appropriate data sheets or on field records. Field personnel are responsible for monitoring the collection and reporting of field data. Upon completion of the field investigation, the pertinent data should be entered into a spreadsheet and tabulated for evaluation and presentation in the report. The following items may be recorded in the field notes:

x Sampling date and time in 24-hour format x Sample’s initials x Number and volume of samples taken at each sample location



x Description of sampling and drilling procedure, and problems encountered if any x Details of sampling location x Names of any site visitors x Field measurements (e.g., temperature, pH, ORP, DO and conductivity) x Sample collection method

4.9.3 Sample Handling and Packaging Samples for laboratory analysis should be handled as follows:

x Cap sample containers with the laboratory-provided container lids. Check that the caps on all containers are tightened.

x Complete sample container labels for each container (ensure labels are intact, legible, and that sample identifier exactly matches the chain of custody).

x Place containers in a resealable storage bag (e.g., zip-loc bag). x Place sample containers into an ice-chilled cooler (cooler should be partially filled with

double-bagged wet ice; chemical blue ice should not be used). x Seal the entire cooler with duct tape to prevent leaks. x Complete the Chain of Custody (CoC) Record.

Samples for laboratory analysis must be maintained cool (between 0 6 °C) during delivery to the laboratory and should be shipped promptly. Holding times are measured from the time the sample is collected to the time the sample is extracted. The analytical laboratory should receive samples with sufficient time to complete the analysis within the method holding time. Details of laboratory receipt of shipped samples and planned extraction and analytical schedule should be discussed with the laboratory project manager prior to shipment of samples.

4.9.4 Chain of Custody When generating defensible analytical data, sample custody procedures should be implemented for handling environmental samples and associated records during sample collection, shipment, transfer, and storage. These procedures will support the authenticity of sampling data by tracing samples from the time of collection, through analysis, data generation, and report preparation.

A sample is considered to be within custody if the item is:

x in one’s physical possession; x in one’s view after being in one’s physical possession; x in a locked receptacle after being in one’s physical possession; or x in a designated secure area.

Procedures described below address custody during field sample collection and laboratory analysis.

When completing written records to document sample custody, errors should be corrected by drawing a single line through the error, re-entering the correct information, and initialing and dating the correction.

4.9.4.1 Field Custody Procedures

Sample containers provided by the laboratory should be shipped by a common carrier. The laboratory will include a shipping form/laboratory chain-of-custody listing containers shipped and



the purpose of each container. Containers should be considered in the custody of the laboratory until received by a designated representative. Upon receipt, the shipment should be checked to verify that all containers are intact and are suitable for the required test method. The containers should be maintained in the custody of the receiver in a clean, secure area until used for sample collection.

Procedures described below address custody during field sample collection, laboratory analysis, and file storage for the data collected in the study.

x Field sampling personnel will be personally responsible for the care and custody of the samples until transferred or duly dispatched.

x Sample bottles and vessels should be labeled with sample numbers and locations at the time of sample collection.

x Sample labels should be completed with ink.

After collection, field sampling personnel should maintain sample custody in accordance with the following procedure:

x The sample label affixed to the container should be inspected to confirm that all of the required information has been provided.

x If appropriate (e.g., for water samples), the sample container should be sealed in a zip-lock plastic bag, wrapped in bubble pack, and packed in a wet-ice cooler in a manner to minimize shifting or movement.

x For each set of samples sent to the laboratory, a triplicate chain-of-custody form will be completed. Information on the chain-of-custody form and the sample container labels will be checked against the field logbook entries, and the samples will be recounted. The information contained on the chain-of-custody form should include the following:

x Site name and address or location. x Project number. x Date of sample collection. x Name of sampler responsible for sample submittal. x Identification of samples that accompany the form including: x Field ID number. x Number of samples. x Date/time collected. x Sample container type, volume, preservative. x Parameters/methods of interest. x Data level requirement (e.g., Level III). x Comments about sample conditions. x Signature of person relinquishing custody and signature of person accepting custody, plus

date and time. x Identification of common carrier. x If a commercial courier service (e.g., Federal Express) transports the samples to the

laboratory, the chain-of-custody form should be signed by a member of the field team, and a copy retained by the field team. The remaining two copies of the form should be included in the package sent to the laboratory. If appropriate (e.g., for water samples), the remaining two copies of the form should be sealed in a zip-type plastic bag and placed in the cooler with the samples. The package/cooler should be sealed with packaging.



Package routing documentation maintained by the courier service will serve as chain-of-custody documentation during shipment because commercial couriers do not sign chain-of-custody forms.

x If samples are picked up by a laboratory representative, a member of the field team will sign the chain-of-custody record indicating that the samples have been transferred to the lab courier. The lab courier will also sign the form, indicating that the samples have been transferred to his or her custody. One copy of the chain-of-custody form should be retained by the field team, and the remaining two copies should be sealed in the package with the samples as described above.

4.9.4.2 Laboratory Custody Procedures

Standard laboratory custody procedures should be implemented. Samples received and logged into the laboratory will remain in the custody of the laboratory personnel at the laboratory until disposal.

5.0 QA/QC SAMPLING AND DATA VALIDATION

QA/QC sampling and data validation requirements may vary by state and should be consulted during the development of the Site Investigation Work Plan. The procedures below summarize a typical field program and QA/QC requirements.

5.1 Field Quality Control Samples Field quality control (QC) samples should be collected and analyzed to evaluate field precision and accuracy and to facilitate validation of sample results for soil, subsurface soil, stormwater, wastewater effluent, and/or groundwater samples, as appropriate. Field sampling precision and accuracy can be assessed through the collection and laboratory analysis of field replicates and field blanks.

Data from field QC samples should be evaluated to determine if any problems are evident for specific media or with laboratory procedures.

Table 6: Summary of QA/QC Sampling Program QA/QC Sample Category Sampling Frequency Equipment Rinsate Blanks New materials, new sample locations, and questionable

equipment Field Blanks One per field day Field Duplicates Approximately 1 for every 10 samples Matrix Spike/ Matrix Spike Duplicates

Approximately 1 for every 20 samples

Laboratory Control Samples One per method, batch, and matrix Laboratory Method Blank One per method, batch, and matrix Trip Blank One per each shipping cooler Temperature Blank One per each shipping cooler



5.1.1 Blank Samples

5.1.1.1 Equipment Rinsate Blanks

For wells sampled using a portable submersible pump or new materials, the pump/new materials should be decontaminated between wells in accordance with decontamination procedures outlined in Section 4.7. Following decontamination, an equipment rinsate blank will be collected to evaluate the effectiveness of the decontamination procedures and any potential cross-contamination from equipment materials. PFAS-free water should be used for equipment rinsate blanks.

As an additional measure, wells sampled using a submersible pump should be sampled sequentially from least contaminated to most contaminated based on recent historic monitoring results, if available.

5.1.1.2 Field Blanks

If water samples are collected, a field blank should be collected in order to evaluate the potential for contamination of a sample by site contaminants from a source not associated with the sample collected. The field blank sample is prepared in the field, where PFAS-free water is taken to the field in sealed containers. The water is then poured into the appropriate sample containers at pre-designated locations at the site.

Proper labeling and documentation should be completed for field blanks. Field blanks will be prepared and analyzed with other samples being analyzed for PFAS at a minimum frequency of one per day when water samples are transmitted to the laboratory.

5.1.1.3 Trip Blanks

A clean sample of the sampled matrix should be shipped by the laboratory alongside the sample containers to the sampling site and transported back to the laboratory without exposure to the sampling procedures. The trip blank is typically analyzed for volatile compounds and is used to evaluate the potential for contamination during shipping and field handling procedures

5.1.1.4 Temperature Blanks

Temperature blank typically constitutes of a sample container of at least 40-mL filled with clean or distilled water that is placed in each shipping coolers, clearly marked as a temperature blank. Temperature blanks are not analyzed for possible contamination; instead, they are used to evaluate if samples were properly cooled during shipping. That is, they provide a fair representation of sample temperature upon laboratory receipt.

5.1.2 Duplicates The precision of field sample collection techniques should be evaluated by collecting and analyzing field duplicates. Duplicate samples will be defined as those samples collected simultaneously from the same source under identical conditions into separate but identical containers preserved, stored, transported, and analyzed in the same manner. Thus, to prepare a duplicate, an aliquot will be collected from a particular sample source and divided equally into two separate but identical sample containers. Each duplicate will undergo the same sampling, handling, shipping, and laboratory analysis as the parent sample. Field duplicates should be given a different identification number to disguise the source of the sample from the laboratory.



Duplicates should be collected at a minimum frequency of one duplicate for every 10 samples for each matrix and analyzed for the same PFAS compounds list as standard samples.

5.2 Laboratory Quality Control Checks The site-specific work plan will identify the chosen commercial laboratory for analysis of liquid and soil samples, per requirements described above in Section 2.1. Each site and P.E. or P.G. should be aware of the laboratory’s quality assurance and QA/QC measures for PFAS. The laboratory will implement a QA/QC program to ensure the reliability and validity of analyses performed in the laboratory. Internal quality control checks differ slightly for specific procedures and laboratories, but in general, QC requirements should include the following:

x Method blanks. x Instrument blanks. x Matrix spikes/matrix spike duplicates. x Surrogate spikes. x Laboratory duplicates.

x Laboratory control standards. x Surrogate spikes. x Internal standard spikes. x Mass spectral tuning.

QC sample results should be properly recorded and included in the analytical data package. The data package should contain sufficient QC information to allow reconstruction and evaluation of the laboratory QC process by an independent data reviewer (i.e. the P.E./P.G. and lead agent for the site).

Data generated in the laboratory should be adequately recorded and compiled into a deliverable package containing sufficient QC information for comparison to relevant criteria. Samples analyzed in non-conformance with the QC criteria will be re-analyzed by the laboratory if sufficient volume is available.

The principal criteria for validating data quality will be the continuous monitoring of acceptable analytical accuracy, precision, and overall method performance, through systematic analyses of quality control samples. The laboratory will conduct both initial and continuous analytical method performance evaluations. This is to ensure that all generated analytical data meet applicable QC and method performance criteria. Each analytical method commonly used in the laboratory should utilize specific quality control procedures to monitor acceptable analytical method accuracy and precision continually.

5.3 Data Validation Data validation and review should be performed by the P.E./P.G. for the field data, and by the Laboratory QA Manager for laboratory operations to ensure that laboratory-generated data satisfy project objectives. Data generated by Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS) will be validated as described in the Department of Defense PFAS Module 3 Data Validation Guidelines (EDQW 2020). While non-LC/MS/MS generated data should be validated and reviewed as described below.

Note that laboratory data validation by the analytical laboratory is necessary to ensure the usability of the generated data to provide an accurate and representative picture of the current water/soil quality conditions at sampling locations.

5.3.1 Procedures Used to Validate Field Data The field data package, including field records and measurements acquired by the sampling team personnel, should be reviewed, as follows:



x Sampling records and chain-of-custody forms should be reviewed to verify that samples, field duplicates, and trip blanks were collected at the frequency specified in the site-specific work plan and were prepared correctly, preserved, and submitted to the laboratory.

x Chain-of-custody forms should be reviewed for proper completion, signatures of field personnel, and laboratory sample custodian, and dates.

x Per the PFAS Module 3 Data Validation Guidelines:

“When multiple blank type contaminations are present, the evaluation should not involve a ‘hierarchy’ of one blank type over another. Each blank is evaluated separately and independently. The final validated result should be assessed on the blank with the highest value (i.e., greatest effect on sample analyte concentration).”

5.3.2 Procedures Used to Validate Laboratory Data Data production should begin with the generation of data results by the analyst and continue through a multi-level review and validation process. Each step in the review process should be performed to assure the integrity and validity of the data generated by the laboratories. Data will be sequentially passed on to the peer review analyst of the staff chemist, the department supervisor, and, finally, the data entry personnel. The laboratory report should be reviewed by the Laboratory QA Manager assigned to the project and then should be certified by the laboratory manager or designee. Each step in the review process should be performed to assure the integrity and validity of the data generated by the laboratories, as follows:

Quality control data (e.g., laboratory duplicates, surrogates, matrix spikes, and matrix spike duplicates) should be compared to method acceptance criteria. Data considered to be acceptable will be entered into the laboratory computer system. Data summaries should be sent to the Laboratory QA Manager for review. If approved, data should be logged into the project database. Unacceptable data should be appropriately qualified in the project report. Case narratives will be prepared to include information concerning data falling outside acceptance limits, and any other anomalous conditions encountered during sample analysis. Data should be issued after approval by the Laboratory QA Manager.

5.4 Procedures to Assess Data Quality Objectives 5.4.1 Accuracy Assessment When evaluating the accuracy of laboratory results, laboratory control samples (LCS) and matrix spike/matrix spike duplicates (MS/MSD) should be prepared at the frequency shown in Table 6 by spiking with analytes prior to analysis. For the LCS, the ratio between the measured concentration and the known concentration in the spiked sample converted to a percentage is equal to the percent recovery. For MS/MSDs, the difference between the measured concentration in the spike and the concentration in the native sample is divided by the known spike concentration to obtain the percent recovery, as follows:

Daily tabulations for each commonly analyzed compound will be maintained on instrument-specific, matrix-specific, and analyte-specific bases. Control charts of results obtained from LCS will be maintained for selected organic analytes to track the accuracy of laboratory data. Per the



PFAS Module 3 Data Validation Guidelines, laboratories should use in-house LCS limits project if limits are not specified.

If aqueous PFAS samples were prepared using serial dilution instead of solid-phase extraction (SPE) post spike QC sample should be used to evaluate the accuracy of laboratory results. The post spike percent recoveries should be within 70 – 130 % (EDQW, 2020).

Per the PFAS Module 3 Validation Guidelines, for initial calibration, the internal standard recovery for all “analytes must be within 70 - 130% of their true value for each calibration standard”. While WKH�UHODWLYH�VWDQGDUG�GHYLDWLRQ��56'��RI�WKH�UHVSRQVH�IDFWRU��5)��IRU�DOO�DQDO\WHV�PXVW�EH��or their linear or non- OLQHDU�FDOLEUDWLRQV�PXVW�KDYH�U��IRU�HDFK�DQDO\WH�

5.4.2 Precision Assessment Spiked samples should be prepared by selecting a sample at random from each sample shipment received at the laboratory, dividing the sample into equal aliquots, and then spiking each of the aliquots with a known amount of analyte. The duplicate samples should then be included in the analytical sample set. The splitting of the sample allows the analyst to determine the precision of the preparation and analytical techniques associated with the duplicate sample. The RPD between the spike and duplicate spike (or between MS and MSD) will be calculated as follows DQG�PXVW�EH��IRU�DOO�DQDO\WHV��('4:��

5.4.3 Completeness Assessment Completeness is the ratio of the number of valid sample results to the total number of samples analyzed with a specific matrix and/or analysis. After analytical testing, the percent completeness will be calculated as follows:



REFERENCES

ASTM D7968 -17a, 2017. Standard Test Method for Determination of Polyfluorinated Compounds in Soil by Liquid Chromatography Tandem Mass Spectrometry (LC/MS/MS), ASTM International, West Conshohocken, PA, 2017, www.astm.org

ASTM D7979-19, 2019. Standard Test Method for Determination of Per- and Polyfluoroalkyl Substances in Water, Sludge, Influent, Effluent, and Wastewater by Liquid Chromatography Tandem Mass Spectrometry (LC/MS/MS), ASTM International, West Conshohocken, PA, 2019, www.astm.org

CASQA SWPPP Template, 2014. Stormwater Pollution Prevention Plan Template, BMP Handbook Portal: Industrial and Commercial. California Stormwater Quality Association (CASQA). September 2014.

CA SWQCB, 2019. Per- and Polyfluoroalkyl Substances (PFAS) Sampling Guidelines. California State Water Quality Control Board, Division of Water Quality. March 2019.

NGWA, 2018. Groundwater and PFAS: State of Knowledge and Practice. National Groundwater Association. 2018.

EDQW Environmental Data Quality Workgroup, 2020. Data Validation Guidelines Module 3: Data Validation Procedure for Per- and Polyfluoroalkyl Substances Analysis by QSM Table B-15. May 1, 2020.

Rodowa, A. E., Emerson, C., Sedlak, J., Peaslee, G.F., Bogdan, D., DiGuiseppi B., Field, J.A., 2020. Field Sampling Materials Unlikely Source of Contamination for Perfluoroalkyl and Polyfluoroalkyl Substances in Field Samples. Environmental Science and Technology Letters. 7, 156-163.

SESD, 2014. Soil Sampling Operating Procedure. Region 4, U.S. Environmental Protection Agency Science and Ecosystem Support Division. August 21, 2014.

USEPA, 2017. Industrial User Inspection and Sampling Manual for POTWs. U.S. Environmental Protection Agency, Office of Compliance. January 2017.

USEPA, 2019. Method 533: Determination Of Per- And Polyfluoroalkyl Substances in Drinking Water By Isotope Dilution Anion Exchange Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry. December 2019.

USEPA, 2020. Method 537.1 Determination of Selected Per- and Polyflourinated Alkyl Substances in Drinking Water by Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS). April 8, 2020.

https://www.astm.org/

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SAMPLING AND ANALYSIS PLAN · Finally, quality assurance/quality control (QA/QC) procedures are necessary to ensure that valid and representative data is obtained and reported. 3.2