ASTM E3302-23

Standard Guide for PFAS Analytical Methods Selection

SIGNIFICANCE AND USE
4.1 This guide provides an overview of analytical methods, techniques, and procedures that may be used in determination of PFAS in environmental media.  
4.2 This guide provides considerations relevant to the selection and application of PFAS analytical methods, techniques, and procedures, including the limitations of published analytical methods and the potential benefits and challenges of non-standard analytical approaches.  
4.3 This guide presents comparisons of published analytical methods and approaches, including tabular comparison of target analyte lists and method features, to aid users in the selection and application of analytical methods and techniques for project-specific applications.  
4.4 This guide describes qualitative techniques available to determine total PFAS, including explanation of terms, discussion of preparation and analytical techniques and limitations, conceptual overview schematic, and summary comparison table.  
4.5 This guide provides current information on research trends in PFAS determination techniques applied to environmental media.  
4.6 This guide provides an integrated framework that results in efficient, cost-effective decision-making for timely, appropriate response actions for PFAS-impacted environmental media.  
4.7 This guide is not intended to replace or supersede federal, state, local, or international regulatory requirements. Instead, this guide may be used to complement and support such requirements.  
4.8 This guide may be used by various parties involved in response actions for PFAS-impacted environmental media, including regulatory agencies, project sponsors, environmental consultants and contractors, site remediation professionals, analytical testing laboratories, data reviewers, data users, academic institutions, research institutes, and other stakeholders.  
4.9 The users of this guide should consider assembling a team of experienced professionals with appropriate expertise to scope, plan, and execute PFA...
SCOPE
1.1 This guide discusses the selection and application of analytical methods and techniques used to identify and quantitate per- and polyfluoroalkyl substances (PFAS) in environmental media. This guide provides a flexible, defensible framework applicable to a wide range of environmental programs. It is structured to support a tiered approach with analytical methods, procedures, and techniques of increasing complexity as the user proceeds through the evaluation process. This guide addresses key decision criteria and best practices to aid users in achieving project objectives. There are numerous technical decisions that must be made in the selection and application of analytical methods and techniques used during environmental data acquisition programs. It is not the intent of this guide to define appropriate technical decisions, but rather to provide technical support within existing decision frameworks.  
1.2 This guide informs practitioners on the considerations relevant to the selection and application of analytical methods and techniques for the quantitative and qualitative determination of PFAS in a variety of environmental sample media. This guide encourages user-led collaboration with stakeholders, including analytical laboratories, data evaluation practitioners, and regulators, in the selection and application of analytical methods and techniques used to support project-specific decision criteria and objectives as applied within a particular environmental regulatory program. This guide recognizes the complexity and diversity of environmental programs and project objectives and provides technical guidance for a range of project applications.  
1.3 This guide is intended to complement, not replace, existing regulatory requirements or guidance. ASTM International (ASTM) guides are not regulations; they are consensus-based standards that may be followed as needed.  
1.4 This guide recognizes that PFAS can be catego...

General Information

• Status: Published
• Publication Date: 14-Dec-2023
• ICS: 13.060.50 - Examination of water for chemical substances
• ICS: 13.080.10 - Chemical characteristics of soils
• Technical Committee: E50 - Environmental Assessment, Risk Management and Corrective Action
• Drafting Committee: E50.04 - Corrective Action

Relations

• Replaces: ASTM E3302-22 - Standard Guide for PFAS Analytical Methods Selection
• Effective Date: 15-Dec-2023
• Referred By: ASTM E3358-23a - Standard Guide for Per- and Polyfluoroalkyl Substances Site Screening and Initial Characterization
• Effective Date: 15-Dec-2023

Overview

ASTM E3302-23: Standard Guide for PFAS Analytical Methods Selection is an essential reference for professionals involved in the assessment and remediation of per- and polyfluoroalkyl substances (PFAS) in environmental media. Developed by ASTM International, this guide provides a flexible, defensible framework for selecting and applying analytical methods to identify and quantify PFAS in various matrices such as water, soil, and biological samples. With a focus on best practices and project-specific decision-making, ASTM E3302-23 supports practitioners in achieving high-quality, regulatory-compliant results throughout environmental programs.

Key Topics

• Analytical Methods for PFAS Detection: The guide outlines published and non-standard methods for both quantitative and qualitative determination of PFAS. This includes an overview and comparison of method features, target analyte lists, and analytical challenges.
• Project Planning and Data Quality Objectives (DQOs): Guidance is provided on integrating PFAS analytical method selection within systematic planning frameworks, such as Quality Assurance Project Plans (QAPPs) and data management strategies.
• Limitations and Challenges: The standard highlights the limitations of current PFAS analytical methods, acknowledges the complexity of the PFAS family (over 4,700 compounds), and discusses the benefits and limitations of both standard and emerging techniques.
• Interdisciplinary Collaboration: Emphasizes the importance of collaboration with regulatory agencies, laboratories, and other stakeholders throughout the selection and application of PFAS analytical methods.
• Qualitative Total PFAS Techniques: The guide presents qualitative assessment strategies for total PFAS determination, including conceptual schematics and summary comparison tables.
• Regulatory Compliance Support: While not a replacement for regulatory requirements, ASTM E3302-23 serves as a complementary resource for meeting federal, state, local, and international guidelines.

Applications

• Environmental Investigations: Used in the identification and quantitation of PFAS compounds during site assessments, groundwater monitoring, surface water analysis, and soil investigations.
• Remediation Projects: Supports analytical method selection for PFAS-impacted site remediation and verification of cleanup effectiveness.
• Risk Assessment: Guides the collection of defensible PFAS data for evaluating ecological or human health risks associated with contaminated media.
• Regulatory Reporting: Assists laboratories and consultants in delivering analytically robust data packages for compliance with regulatory oversight, including the preparation of electronic data deliverables (EDD).
• Research and Development: Provides an overview of current research trends in PFAS analysis, supporting further development and validation of new environmental analytical techniques.
• Quality Assurance and Data Review: Recommends best practices for field sampling, laboratory quality control, performance evaluation samples, and robust data review protocols.

Related Standards

Professionals referring to ASTM E3302-23 may also consider these key related standards and methods:

• ASTM D7968 – Determination of Polyfluorinated Compounds in Soil by LC/MS/MS
• ASTM D7979 – Determination of PFAS in Water, Sludge, and Wastewater by LC/MS/MS
• ASTM D8421 – Determination of PFAS in Aqueous Matrices by Co-solvation and LC/MS/MS
• USEPA Method 537 / 537.1 – PFAS Determination in Drinking Water
• USEPA Method 533 – PFAS Analysis in Drinking Water using Isotope Dilution
• USEPA Draft Methods 1633 and 1621 – PFAS Analysis in Various Matrices
• ISO 25101 and ISO 21675 – PFAS Determination in Water by Solid Phase Extraction and LC-MS/MS

These standards, alongside ASTM E3302-23, provide a robust toolkit for environmental professionals tasked with addressing the growing challenge of PFAS contamination.

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Keywords: PFAS analytical methods, PFAS detection, per- and polyfluoroalkyl substances, ASTM E3302-23, environmental media, PFAS remediation, PFAS compliance, PFAS analysis, PFAS in water and soil, PFAS regulations, environmental standards.

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: E3302 − 23
Standard Guide for
PFAS Analytical Methods Selection
This standard is issued under the fixed designation E3302; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope than 4 700 Chemical Abstracts Service (CAS)-registered sub-
stances. Environmental concerns pertaining to PFAS are cen-
1.1 This guide discusses the selection and application of
tered primarily on the perfluoroalkyl acids (PFAA), a subclass
analytical methods and techniques used to identify and quan-
of PFAS, which display extreme persistence in the environ-
titate per- and polyfluoroalkyl substances (PFAS) in environ-
ment and chain-length-dependent bioaccumulation and adverse
mental media. This guide provides a flexible, defensible
effects in biota.
framework applicable to a wide range of environmental pro-
grams. It is structured to support a tiered approach with
1.5 This guide recognizes that published analytical methods
analytical methods, procedures, and techniques of increasing
performed by commercial laboratories are limited to determi-
complexity as the user proceeds through the evaluation pro-
nation of a small subset of the more than 4 700 CAS-registered
cess. This guide addresses key decision criteria and best
PFAS.
practices to aid users in achieving project objectives. There are
1.6 The goal of this guide is to provide a technical frame-
numerous technical decisions that must be made in the selec-
work for informed selection and application of analytical
tion and application of analytical methods and techniques used
methods and techniques for the determination of target and
during environmental data acquisition programs. It is not the
non-target PFAS in environmental sample media.
intent of this guide to define appropriate technical decisions,
but rather to provide technical support within existing decision
1.7 This guide aids users in selecting PFAS analytical
frameworks.
methods for various environmental applications.
1.2 This guide informs practitioners on the considerations
1.8 This guide discusses existing published analytical meth-
relevant to the selection and application of analytical methods
ods for quantitative determination of method-specific lists of
and techniques for the quantitative and qualitative determina-
target analytes, as well as non-standard analytical approaches
tion of PFAS in a variety of environmental sample media. This
developed to qualitatively determine a broader range of PFAS,
guide encourages user-led collaboration with stakeholders,
for a variety of environmental applications. This guide also
including analytical laboratories, data evaluation practitioners,
provides an overview of research trends in this rapidly devel-
and regulators, in the selection and application of analytical
oping field.
methods and techniques used to support project-specific deci-
sion criteria and objectives as applied within a particular 1.9 This guide discusses the challenges and limitations of
environmental regulatory program. This guide recognizes the analytical methods and techniques in the detection and quan-
complexity and diversity of environmental programs and titation of the large, complex set of PFAS.
project objectives and provides technical guidance for a range
1.10 This guide describes widely accepted considerations
of project applications.
and best practices used in the selection and application of
1.3 This guide is intended to complement, not replace,
analytical procedures used during PFAS environmental pro-
existing regulatory requirements or guidance. ASTM Interna-
grams. This guide complements but does not replace existing
tional (ASTM) guides are not regulations; they are consensus-
technical guidance and regulatory requirements.
based standards that may be followed as needed.
1.11 Units—The values stated in SI units are to be regarded
1.4 This guide recognizes that PFAS can be categorized as
as the standard.
polymeric or nonpolymeric, collectively amounting to more
1.11.1 Other units, such as fractional units of parts per
billion and parts per trillion, are also included in this guide.
1.12 This standard does not purport to address all of the
This guide is under the jurisdiction of ASTM Committee E50 on Environmental
Assessment, Risk Management and Corrective Action and is the direct responsibil-
safety concerns, if any, associated with its use. It is the
ity of Subcommittee E50.04 on Corrective Action.
responsibility of the user of this standard to establish appro-
Current edition approved Dec. 15, 2023. Published January 2024. Originally
priate safety, health, and environmental practices and deter-
published in 2021. Last previous edition approved in 2021 as E3302–21. DOI:
10.1520/E3302–23 mine the applicability of regulatory limitations prior to use.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E3302 − 23
1.13 This international standard was developed in accor- roalkyl Substances (PFAS) in Aqueous, Solid, Biosolids,
dance with internationally recognized principles on standard- and Tissue Samples by LC-MS/MS, First Draft, EPA
ization established in the Decision on Principles for the 821-D-21-001, August 20211;Second Draft, EPA 821-D-
Development of International Standards, Guides and Recom- 22-001, June 2022; Third Draft, EPA 821-D-22-003,
mendations issued by the World Trade Organization Technical December 2022; Fourth Draft, EPA 821-D-23-001, July
Barriers to Trade (TBT) Committee. 2023.
USEPA Draft Method 1621, Screening Method for the De-
2. Referenced Documents
termination of Adsorbable Organic Fluorine (AOF) in
Aqueous Matrices by Combustion Ion Chromatography
2.1 ASTM Standards:
(CIC), EPA 821-D-22-002, April 2022.
D7968 Test Method for Determination of Polyfluorinated
U.S. Environmental Protection Agency PFAS Master List of
Compounds in Soil by Liquid Chromatography Tandem
PFAS Substances. CompTox Chemistry Dashboard, Ver-
Mass Spectrometry (LC/MS/MS)
sion 2.2.1, May 2023, Available Online at: https://
D7979 Test Method for Determination of Per- and Polyfluo-
comptox.epa.gov/dashboard/
roalkyl Substances in Water, Sludge, Influent, Effluent,
U.S. Environmental Protection Agency Drinking Water
and Wastewater by Liquid Chromatography Tandem Mass
Health Advisories for Perfluorooctanoate (PFOA) and
Spectrometry (LC/MS/MS)
Perfluorooctane Sulfonate (PFOS), 822-R-16-004, 2016
D8421 Test Method for Determination of Per- and Polyfluo-
U.S. Environmental Protection Agency Lifetime Health Ad-
roalkyl Substances (PFAS) in Aqueous Matrices by Co-
visories and Health Effects Support Documents for Per-
solvation followed by Liquid Chromatography Tandem
fluorooctanoic Acid (PFOA) and Perfluorooctane
Mass Spectrometry (LC/MS/MS)
Sulfonate (PFOS), Federal Register, Vol 81, No. 101, May
2.2 USEPA Documents:
25, 2016
EPA QA/G-4 Guidance on Systematic Planning Using the
U.S. Environmental Protection Agency , Lifetime Drinking
Data Quality Objectives Process, February 2006
Water Health Advisories for Four Perfluoroalkyl Sub-
EPA/600/F-17/022e PFAS Methods and Guidance for Sam-
stances (PFOA, PFOS, GenX, and PFBS), Federal Regis-
pling and Analyzing Water and Other Environmental
ter Vol. 87, No. 118, June 21, 2022.
Media – Technical Brief, February 2019, EPA/600/F-17/
U.S. Environmental Protection Agency , PFAS National
022h, updated January 2020
Primary Drinking Water Regulation Rule Proposal (for
USEPA 815-B-16-021 Technical Advisory – Laboratory
PFOA, PFOS, PFNA, HFPO-DA or GenX Chemicals,
Analysis of Drinking Water Samples for Perfluorooctano-
PFHxS, and PFBS), Federal Register Vol. 88, No. 60,
ate (PFOA) Using EPA 537 Rev. 1.1, September 2016
March 29, 2023.
USEPA Method 537 Version 1.1 Determination of Selected
2.3 ISO Documents:
Perfluorinated Alkyl Acids (PFAAs) in Drinking Water by
ISO 25101 Determination of Perfluorooctane Sulfonate
Solid Phase Extraction and Liquid Chromatography/
(PFOS) and Perfluorooctanoate (PFOA) in Water –
Tandem Mass Spectrometry (LC/MS/MS)EPA/600/R-08/
Method for Unfiltered Samples Using Solid Phase Extrac-
092, 2008, revised 2009.
tion and Liquid Chromatography / Tandem Mass Spec-
USEPA Method 537.1 Version 2.0 Determination of Selected
trometry (LC-MS/MS), 2009.
Per- and Polyfluorinated Alkyl Substances (PFAS) in
ISO 21675 Determination of Polyfluorinated Alkyl Sub-
Drinking Water by Solid Phase Extraction and Liquid
stances (PFAS) in Water – Method Using Solid Phase
Chromatography/Tandem Mass Spectrometry (LC/MS/
Extraction and Liquid Chromatography / Tandem Mass
MS)EPA/600/R-20/006, March 2020.
Spectrometry (LC-MS/MS), 2019.
USEPA Method 533 Determination of Per-and Polyfluoroal-
kyl Substances (PFAS) in Drinking Water by Isotope
3. Terminology
Dilution Anion Exchange Solid Phase Extraction and
3.1 Definitions:
Liquid Chromatography/Tandem Mass Spectrometry (LC/
3.1.1 adsorbable organofluorine (AOF), n—a fraction of
MS/MS), 815-B19-020, December 2019.
organofluorine that will sorb to a particular media, for example
USEPA Test Method 8327 Per-and Polyfluoroalkyl Sub-
carbon, and that remains sorbed to the media after removal
stances (PFAS) Using External Standard Calibration and
(washing) of the inorganic fluoride.
Multiple Reaction Monitoring (MRM) Liquid
3.1.2 combustion ion chromatography (CIC), n—a tech-
Chromatography/Tandem Mass Spectrometry (LC/MS/
MS), Revision 0, July 2021 nique that combines pyrolysis of a sample and analysis of the
combustion products using ion chromatography.
USEPA Draft Method 1633 Analysis of Per- and Polyfluo-
3.1.3 extractable organofluorine (EOF), n—the fraction of
organic fluorine that is first extracted and then analyzed.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
−
3.1.4 fluoride ion, n—the inorganic anion of fluorine (F );
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
that is, fluoride.
the ASTM website.
Available from United States Environmental Protection Agency (EPA), William
Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460, Available from American National Standards Institute (ANSI), 25 W. 43rd St.,
http://www.epa.gov. 4th Floor, New York, NY 10036, http://www.ansi.org.
E3302 − 23
3.1.5 fluorides, n—any compound containing fluorine are 3.1.16 total oxidizable precursor (TOP), n—a measure of
categorically deemed fluorides. oxidizable precursors determined by method-defined assays. In
this context, the precursors are limited to PFAA precursors.
3.1.6 fluorine (F), n—a chemical element, diatomic form
The analytical method that quantifies the precursors is widely
(F2); it is a highly toxic gas, reactive, and yellow-green in
known as TOP Assay.
color.
3.1.17 total PFAS, n—a surrogate estimate based on various
3.1.7 liquid chromatography mass spectrometry / mass
analytical techniques of the summation or total value of TOP
spectrometry (LC/MS/MS; also known as triple quadrupole or
assay or total organic fluorine.
triple quad LC/MS), n—an analytical instrument that labora-
tory methods use to separate, identify, and quantitate specific
4. Significance and Use
targeted organic compounds.
4.1 This guide provides an overview of analytical methods,
3.1.8 per- and polyfluoroalkyl substances (PFAS), n—a
techniques, and procedures that may be used in determination
group of manufactured chemicals consisting of polymeric
of PFAS in environmental media.
chains of carbon bonded to fluorine atoms, usually with a polar
4.2 This guide provides considerations relevant to the se-
functional group at the head.
lection and application of PFAS analytical methods,
3.1.8.1 Discussion—PFAS are fluorinated substances with a
techniques, and procedures, including the limitations of pub-
carbon chain structure. In perfluoroalkyl acids (PFAAs), each
lished analytical methods and the potential benefits and chal-
carbon atom in the chain is fully saturated with fluorine
lenges of non-standard analytical approaches.
(carbon-fluorine bonds only), whereas the carbon chain in
polyfluoroalkyl substances is mostly saturated with fluorine
4.3 This guide presents comparisons of published analytical
(carbon-fluorine bonds), but also contains carbon-hydrogen
methods and approaches, including tabular comparison of
bonds.
target analyte lists and method features, to aid users in the
selection and application of analytical methods and techniques
3.1.9 perfluoroalkyl acids (PFAA), n—a subclass of PFAS
for project-specific applications.
including sulfonic and carboxylic acids that display extreme
persistence and chain-length-dependent bioaccumulation and
4.4 This guide describes qualitative techniques available to
adverse effects in biota.
determine total PFAS, including explanation of terms, discus-
sion of preparation and analytical techniques and limitations,
3.1.10 precursor, n—a category of PFAS that includes all
conceptual overview schematic, and summary comparison
polyfluorinated alkyl substances and a subset of polymer PFAS
table.
known as side-chain fluorinated polymers, collectively known
as “precursors” because of their ability to transform into
4.5 This guide provides current information on research
terminal defluorinated alkyl substances.
trends in PFAS determination techniques applied to environ-
mental media.
3.1.11 proton-induced gamma-ray emission (PIGE), n—a
rapid screening technique that provides a qualitative and
4.6 This guide provides an integrated framework that results
quantitative measure of total fluorine.
in efficient, cost-effective decision-making for timely, appro-
priate response actions for PFAS-impacted environmental me-
3.1.12 quadrupole time of flight (Q-TOF), n—an accurate
dia.
MS/MS instrument that replaces the final quadrupole with a
time-of-flight (TOF) high-resolution mass spectrometer.
4.7 This guide is not intended to replace or supersede
federal, state, local, or international regulatory requirements.
3.1.13 solid phase extraction (SPE), n—a type of sample
Instead, this guide may be used to complement and support
preparation that extracts targeted analytes from an aqueous
such requirements.
matrix onto a solid medium, allowing the analytes to be
separated from the matrix and subsequently eluted and con-
4.8 This guide may be used by various parties involved in
centrated in an organic solvent.
response actions for PFAS-impacted environmental media,
including regulatory agencies, project sponsors, environmental
3.1.14 total fluorine (TF), n—a measure that includes or-
consultants and contractors, site remediation professionals,
ganic and inorganic fractions of fluorine.
analytical testing laboratories, data reviewers, data users,
3.1.15 total organic fluorine, n—a measure of the total
academic institutions, research institutes, and other stakehold-
organic fraction of fluorine in a sample.
ers.
3.1.15.1 Discussion— Total Organic Fluorine is the descrip-
4.9 The users of this guide should consider assembling a
tion of the category and measurement, but not all CIC-
team of experienced professionals with appropriate expertise to
dependent approaches can report a result that truly represents
scope, plan, and execute PFAS environmental data acquisition
total organic fluorine. The reason being when a sample is
activities.
extracted, adsorbed, or otherwise manipulated prior to
combustion, the percentage of the total that is amenable to the 4.10 The users of this guide should review the overall
structure and components of this guide before proceeding with
extraction, adsorption, or manipulation (and thus quantified) is
directly dependent on the approach used. Each approach has use, including the following sections:
4.10.1 Section 1: Scope
documented limitations. See guide Section 8 for more infor-
mation. 4.10.2 Section 2: Referenced Documents
E3302 − 23
4.10.3 Section 3: Terminology 5.2.4.1 This study will determine whether our groundwater
4.10.4 Section 4: Significance and Use has PFAS. If PFAS target analytes are not detected above the
4.10.5 Section 5: Project Planning Considerations state’s new action limit, we have met our goal. If PFAS target
4.10.6 Section 6: Analytical Method Selection Consider- analytes are detected above the state’s new action limit, then
ations additional sampling and source identification/control will
4.10.7 Section 7: Analytical Methods Comparison likely occur.
4.10.8 Section 8: Qualitative Techniques to Determine Total 5.2.5 Step 3: Identify Information Inputs. Identify data
PFAS and information needed to answer study questions.
4.10.9 Section 9: Research Trends 5.2.5.1 Groundwater levels and contour maps will be re-
4.10.10 Section 10: Keywords viewed to select the proper number and locations of the wells
4.10.11 Appendix X1: PFAS Analytical Interferences – A to be sampled.
Summary of Considerations 5.2.5.2 The special precautions associated with PFAS
sampling, method requirements and associated sample volume
5. Project Planning Considerations
requirements, the QC samples, and the specific list of PFAS
5.1 This guide complements applicable existing guidance
target analytes the state is requiring need to be reviewed with
used to develop a Quality Assurance Project Plan (QAPP) and
the planning team.
to establish data quality objectives (DQOs) necessary to meet
5.2.6 Step 4: Define the Boundaries of the Study. Specify
project goals and to evaluate data quality. This process encour-
the target population and characteristics of interest and define
ages planners to identify and focus on the key issues and
the scope and limitations of the study (that is, the study will not
elements necessary for successful, cost-effective, and defen-
consider potential non-targeted analytes).
sible project outcomes.
5.2.6.1 The state’s requirements are limited to the sampling
and analysis of on-site monitoring wells.
5.2 Data Quality Objective Process:
5.2.6.2 We need to propose a reasonable number and
5.2.1 An important functional aspect of project planning is
locations of the wells to be sampled to the state. One or two
the DQO process. It is necessary to formalize these planning
upgradient wells will be considered.
steps to ensure the type, quantity, and quality of PFAS data
5.2.7 Step 5: Develop the Analytic Approach. Define the
used in decision-making. Thoughtfully derived DQOs provide
analytical parameters of interest; specify the type of inference
the qualitative and quantitative framework by which data
and develop logic for drawing conclusions from the findings.
collection activities are successful in terms of achieving project
5.2.7.1 The list of specific PFAS target analytes needs to be
objectives. The qualitative aspect of DQOs seeks to encourage
reviewed with the state agency and our contract laboratory.
good planning for field investigations. The quantitative aspect
The method reference and any modifications need to be
of DQOs involves designing an efficient field investigation that
reviewed and approved. Reporting limits capable of ruling out
reduces the possibility of incorrect decision-making.
the state’s new action limits and the inclusion/omission of
5.2.2 The DQO process is defined in Guidance on System-
branched isomers need to be finalized with the contract
atic Planning Using the Data Quality Objectives Process
laboratory.
(USEPA 2006). The DQO process consists of seven steps as
5.2.7.2 At this stage in the process, consider augmenting the
presented in 5.2.3 through 5.2.9, and each step is followed by
study to include analysis of non-targeted PFAS (that is, “total”
specific examples (presented in italics). Included in the step
PFAS).
descriptions are simplistic (not intended to be complete)
5.2.8 Step 6: Specify Performance or Acceptance Crite-
example project circumstances involving the collection of
ria. Develop performance criteria for new data being collected
PFAS groundwater data. Note that every project is different,
and acceptance criteria for data already collected.
and the DQO process should yield project-specific objectives.
5.2.3 Step 1: State the Problem. Define the problem that 5.2.8.1 Through this sampling and analytical event, if PFAS
target analytes are not detected above state action limits, then
motivates the study; identify the planning team; and examine
the budget and schedule. we will not have to include PFAS target analytes in future
monitoring. If PFAS target analytes are detected above state
5.2.3.1 The state agency has required that the groundwater
action limits, then additional characterization, source
wells at our facility include a round of PFAS sampling and
analysis. identification/minimization and/or remediation could be future
activities.
5.2.3.2 Our environmental manager is working directly with
our consultant and laboratory project managers. 5.2.9 Step 7: Develop the Detailed Plan for Obtaining
5.2.3.3 Our consultant and laboratory have quoted $46,000, Data. Select the most resource-effective work plan or Sam-
which includes final reporting to the state agency. pling and Analysis Plan (SAP) that satisfies the performance or
5.2.3.4 We are required to issue a final report before the end acceptance criteria.
of this calendar year. 5.2.9.1 After preliminary discussions with the state agency,
5.2.4 Step 2: Identify the Goal of the Study. State how the we will meet with our consultant and contract laboratory, and
PFAS data will be used to meet objectives and solve the our consultant will draft a SAP with input from the planning
problem, identify study questions, and define alternative out- team members. The SAP will be reviewed and approved by the
comes. state before sampling activities proceed.
E3302 − 23
5.3 Project Data Quality Objectives: (10) Sample processing issues (such as concentrations of
5.3.1 One of the decisions to be made when developing target and non-target analytes, sample matrix interference,
DQOs for a PFAS project is determining if the resulting sensitivity, levels of detection and quantitation, dilutions,
analytical data need to meet performance or acceptance crite- re-runs, and QC excursions) (See Appendix X1).
ria. If PFAS data are to be used for screening-level analyses or (11) Turnaround time (for example, project schedule
pilot studies, for example, the level of data quality and the level expectations, sample preservation and handling, sample hold
of data evaluation conducted on the analytical data set may not times, analytical sequence, laboratory capacity, and sample
need to be as rigorous as the PFAS data quality needed to meet re-runs)
legally enforceable standards and regulatory compliance appli- (12) Data deliverable formats
cations. 5.5.2 This is not meant to be an exhaustive list, but a typical
set of project planning considerations that inform decisions that
5.4 Regulatory Considerations:
enhance successful project outcomes.
5.4.1 Regulatory stakeholders at the federal and state levels
have used various mechanisms to establish PFAS limits for 5.6 Data Acquisition Considerations:
environmental media, from non-enforceable health advisory
5.6.1 Communication within the project team, including the
levels (HAL), guidance levels, and screening values to legally
laboratory, is key to planning and executing a successful PFAS
enforceable regulatory compliance criteria such as drinking
sampling event. Increased risk of cross-contamination requires
water maximum contaminant levels (MCLs). Many regulatory
PFAS-specific sampling procedures and a series of field QC
agencies have developed PFAS regulatory limits for individual
samples. This is due to the persistence and surface-sorbing
compounds, and some regulatory agencies have designed
tendency of certain PFAS, as well as their ubiquitous presence
guidance and limits based on the summation of select PFAS.
in many products and materials.
5.4.2 Regulatory agencies implement accreditation and cer-
5.6.2 The selection and handling of sampling equipment
tification programs that govern laboratory sample processing
and materials (provided by the practitioner) and sample con-
and data reporting activities. Experienced laboratories have
tainers and blank water (provided by the laboratory) should be
secured these accreditations and certifications using sophisti-
carefully considered during the planning and execution of
cated sample extraction and analysis protocols to report spe-
PFAS field sampling programs. These items should not contain
cific PFAS target analytes in select sample media using both
PFAS at concentrations that will interfere with the proposed
published analytical methods and laboratory proprietary ana-
analysis.
lytical approaches. Project planners are encouraged to consider
5.6.3 Field QC samples should be included in the design and
the regulatory accreditations and certifications available (by
execution of a PFAS sampling program. Field QC samples
analyte, by method, and by sample matrix) and, when
typically include equipment blanks (EB), field reagent blanks
necessary, to engage the laboratory to consider analytical
(FRB), field duplicates (FD), and project-specific matrix spike/
options where regulatory certification or accreditation may not
matrix spike duplicate samples. Each of these field QC samples
be offered. Project planners and data users should confirm that
requires sufficient sample volume to fill a separate container,
laboratory accreditation or certification meets project objec-
because these samples are individually processed and reported
tives and regulatory requirements.
as part of the project data set.
5.6.4 Laboratory subsampling should not be performed
5.5 Project Planning Considerations:
because it may cause a low bias for large PFAS (>C10
5.5.1 The project QAPP is used to document decisions made
perfluoroalkyl carboxylic acids, >C8 perfluoroalkyl sulfonic
in the consideration a range of elements considered in planning
acids). These considerations should be documented in the
a PFAS data acquisition project. Elements typically considered
project QAPP.
during project planning include the following:
5.6.5 Application of PFAS analytical methods designed for
(1) Regulatory program requirements
(2) Regulatory criteria and project action limits (such as a drinking water sample matrix to non-potable water samples
should be discussed with the laboratory in advance of sample
generic screening levels, site-specific criteria, and enforceable
regulatory compliance standards) collection. Consideration should be given to the intended
purpose of the preservative listed in method, which is to buffer
(3) Laboratory certification and accreditation requirements
(4) Project DQOs chlorine added to treated finished drinking water supplies. The
buffer is also essential to the SPE process by extraction of all
(5) Quality assurance (QA) and quality control (QC) re-
samples at the same pH. When a drinking water method is
quirements
applied to a non-drinking water sample matrix (such as
(6) QAPP and SAP development and regulatory approval
groundwater or surface water), the decision regarding the
(7) Data review, evaluation, validation, application, and
sample preservative should be documented in the project
uses
QAPP and SAP.
(8) Analytical chemistry approach (such as target analyte
list, sample preparation protocols, analytical instrumentation, 5.6.6 The laboratory may experience QC non-conformances
analytical method, data reporting, QC excursions, and data when processing untreated source water samples, which may
reporting format) contain elevated levels of suspended solids (turbidity), when
(9) Sample media (such as potable water, groundwater, applying an analytical method designed for treated finished
surface water, effluent, soil, sediment, biological tissue, and drinking water. This may result sample reprocessing (that is,
environmental waste) re-analysis of the sample extract or re-extraction of the original
E3302 − 23
sample) to confirm the initial result, which then results in 5.9 Quantitation of Branched and Linear Isomers:
extended turnaround time necessary to report final data.
5.9.1 Individual PFAS can exist as linear and branched
isomers. Ideally, the concentration of a given PFAS would
5.7 Performance Evaluation Samples—Single Blind and
include the linear isomer, which is usually but not always the
Double Blind:
case, together with any associated branched isomers to provide
5.7.1 The use of performance evaluation (PE) samples is an
a total concentration for that analyte. While the current practice
important QC component that environmental practitioners
is for laboratories to report a single total concentration, (if
should consider including in their environmental investiga-
qualitative and/or quantitative standards exist for the branched
tions. These known reference samples provide valuable infor-
isomer components.),there is growing interest in identifying
mation regarding the accuracy and comparability of laboratory
and reporting the linear and branched isomers separately
data when one or more laboratories are being used. When
although there are a number of technical challenges with this
possible, it is preferable to issue these samples double-blind to
reporting (such as the lack of chromatographic resolution
the project laboratories, meaning the receiving laboratories
criteria within the existing methods). However, at the time of
have no idea that they are analyzing a test sample. This can be
this writing, limited suitable quantitative standards containing
accomplished by simply having an accredited PE sample
both linear and branched standards exist for only four common
vendor prepare the sample(s) in ordinary sample bottles, such
PFAS: perfluorooctane sulfonate (PFOS), perfluorohexane
as those prepared for investigatory sampling. The practitioner
then labels (and separately documents) the sample with a sulfonic acid (PFHxS), N-ethyl perfluorooctane sulfonamido
acetic acid (NEtFOSAA), and N-methyl perfluorooctane sulfo-
fictious sample identification. It is critical when performing
these double-blind studies that the accredited PE sample namido acetic acid (NMeFOSAA). When USEPA Method 537
was promulgated in 2009, it specified that both linear and
vendor certify the PFAS values in their whole-volume PE
preparation. branched isomers be included in the calibration and quantifi-
cation of these compounds. A technical grade standard for
5.7.2 When using a single-blind PE sample, the receiving
perfluorooctanoate (PFOA), which included branched isomers
laboratories know they are receiving test samples (either whole
volume or ampulated), but they do not know the specific was available at the time leading to some laboratories including
PFOA branched isomers while others did not. To clarify this
analytes and the true (vendor-certified) concentrations.
requirement, USEPA issued a technical advisory (USEPA
5.7.3 Essentially, the purpose of PE studies is to determine
2016, EPA 815-B-16-021) for USEPA Method 537 that spe-
whether the laboratory can get the “right answer” on what
cifically identifies PFOS, PFHxS, NEtFOSAA, and NMe-
appears to be a routine investigatory sample. When available,
FOSAA as containing branched isomers and requires that
PFAS solid-matrix performance test (PT) samples, solid-matrix
quantitative standards be used to correctly identify and quan-
PFAS PE samples, and solid-matrix PFAS certified reference
titate all chromatographic peaks for these compounds (note that
materials (CRM) will provide a means to evaluate the solid
more recent data suggests that other PFAS may also include
extraction and analytical procedures for PFAS. These standard-
branched and linear isomers). The advisory further addressed
ized test materials could identify the ability of different
PFOA, stating that the technical grade standard should be used
laboratories to reproduce PFAS analytical results regardless of
to identify PFOA branched isomers and to include them with
their “accreditation” status. This is currently an issue because
the linear isomer to provide a total PFOA sample concentra-
laboratory PFAS procedures vary widely, and multi-laboratory-
tion.
validated analytical methods for PFAS in non-drinking water
sample matrices are limited.
NOTE 1—Draft Method 1633 adds qualitative branched isomer stan-
5.8 Calibration Standards—Primary Source and Secondary dards for 6 additional PFAS. That makes a total of 11 PFAS out of 40
target compounds that can be reported as total linear and branched - 4
Source:
using the quantitative standard and 7 using the qualitative standard for
5.8.1 For PFAS laboratory calibration and QC, the number
isomer identification. For the remaining target compounds, only the linear
of PFAS and the vendors who create these analytical standards
isomer is quantified. As other quantitative standards that include
and reference materials are limited. In 2020, there were two
the branched isomeric PFAS forms become available, they
should be incorporated into the applicable PFAS analytical
standard vendors who provide analytical reference material for
methodologies, which will allow for the total (and separately
analysis of PFAS in drinking water through USEPA Method
branched) PFAS concentration to be determined for these
537.1 and Method 533, as well as for analysis of PFAS in
analytes.
non-drinking water and solids through other methods with
5.10 Data Reporting Format:
extended PFAS target analyte lists. Due to the limited avail-
ability of standards, laboratories are not always able to use a 5.10.1 Laboratory data reporting formats should be consid-
true second-source standard to verify their calibration, which is ered during the project planning process and documented in the
why USEPA Method 533 does not currently require second- project QAPP. Data reporting format decisions should consider
source verification of initial calibration curves. When analyti- the range of data uses for the project application. Data uses
cal standards and reference materials are available, some may include site characterization, site remediation, source
laboratories may use a standard from a second vendor as a control, treatment of effluent, treatment of drinking water, risk
second-source verification. However, due to the limited avail- assessment, and regulatory compliance monitoring. Data man-
ability of PFAS standards, many will use different lots or agement decisions should consider the full range of intended
single-component standards from the same vendor to verify data uses and should be reviewed by the laboratory and
their initial calibration curves. documented in the project QAPP.
E3302 − 23
5.10.2 Laboratory data reports typically include a set of time the samples and residuals are retained by the laboratory
standardized elements as listed below: prior to disposal (or return) relative to the time needed by data
(1) Cover sheet users for data review and evaluation. Laboratories must be
(2) Table of contents notified regarding projects with Consent Orders and Legal
(3) Case narrative Hold requirements that stipulate indefinite storage of samples
(4) Chain-of-custody records and residuals. Effective communications must take place be-
(5) Sample receipt documentation tween practitioners and the laboratory to secure capacity and
(6) Data report (Form 1s) funding for long-term storage of unused samples, sample
(7) QC documentation (detail depends on reporting level) extracts, and residuals.
(8) Sample preparation logs (included in Level IV data
package)
6. Analytical Method Selection Considerations
(9) Raw data for each sample, blank, spike, duplicate, and
6.1 Overview:
standard (that is, quantitation reports, chromatograms, mass
6.1.1 The ongoing, expanding nature of PFAS environmen-
spectra, instrument printouts, and bench sheets) (included in
tal awareness and the need for more comprehensive investiga-
Level IV data package)
tions have caused increased demand for PFAS environmental
5.10.3 Data package deliverables produced by laboratories
sampling and analysis. There are limited analytical method
contain various levels of detail and are typically categorized
options available, particularly across the full spectrum of
into the levels listed below:
environmental media for a range of PFAS compounds. In many
(1) Level IV—Comprehensive validation-ready fully docu-
cases, the primary source in the search for available analytical
mented data package inclusive of raw data
methods for any environmental application is the USEPA. The
(2) Level III—Summary data with calibration and QC
USEPA has published analytical methods for the analysis of
forms, excludes raw data
select PFAS analytes in drinking water and non-potable water,
(3) Level II—Summary data with QC forms, excludes raw
and USEPA released a draft method for the analysis of select
data
PFAS analytes in nonpotable water, soil, sediment, biosolids,
(4) Level I—Results-only data report, excludes QC forms
and tissue. In addition to the USEPA, both the ASTM and the
and raw data
International Organization for Standardization (ISO) have also
5.10.4 Project planning should also consider the electronic
published PFAS analytical methods. These methods are dis-
data deliverables (EDD) format(s) needed to support project
cussed in Section 7.
data uses. EDD formats typically produced by environmental
6.2 Interplay of Sampling Objectives and Regulatory Re-
laboratories include CSV, Excel, and commercially available
quirements:
enterprise database file formats. These may be unformatted or
6.2.1 PFAS sampling and analytical programs are no differ-
formatted to conform to a practitioner’s specific database. State
ent than other environmental sampling programs in that the
regulatory programs may require a formatted EDD for a
procedures used must comply with applicable regulatory re-
specific program application. Examples include, but are far
quirements. As discussed in 5.4, the PFAS regulatory frame-
from limited to, the New Jersey Hazsite EDD designed for
work is rapidly evolving. This, in combination with the limited
upload to the New Jersey Department of Environmental
availability of PFAS analytical methods, makes the develop-
Protection (NJDEP) Site Remediation Program database, and
ment of project SAPs for PFAS much more challenging
the New Jersey Electronic Environmental (E2) Reporting
relative to other environmental sampling programs. Practitio-
System EDD designed for upload to the database for the Safe
ners and data users must continually check for revisions to the
Drinking Water Act (SDWA) compliance monitoring program
applicable regulatory requirements between writing the plan
administered by the NJDEP Bureau of Safe Drinking Water.
and executing it.
Federal programs may require a formatted EDD for a program-
6.2.2 Another major consideration is that, given the limited
specific data application. Examples include the Environmental
number of standardized, published, multi-laboratory validated
Resources Program Information Management System (ER-
analytical methods to determine a wide range of PFAS in a
PIMS) EDD used by the U.S. Air Force Civil Engineer Center
wide range of sample matrices, practitioners may have no other
(AFCEC) for validation and management of data from envi-
option except to use a laboratory-specific, proprietary method.
ronmental projects at Air Force bases, and the Staged Elec-
This is commonly the case when there are specific PFAS that
tronic Data Deliverable (SEDD) used by the USEPA Superfund
need to be included and a published method for those com-
program with automated data review tools.
pounds is not available. More prevalent are cases where
5.11 Sample Disposition:
environmental media such as soil, sediment, or biologic tissue
5.11.1 Project planning should also consider the timeline for need to be analyzed for a specific list of PFAS target analytes
retention and disposal of samples by the receiving laboratory. using a robust analytical approach to accommodate sample
These may include unused sample material, sample extracts, matrix effects for which published analytical methods do not
sample containers, expired reagents, and related waste gener- exist. Proper planning is essential for any environmental data
ated in the processing of environmental samples. Laboratories acquisition program. For projects that include PFAS, compre-
typically follow waste management plans, use licensed waste hensive planning with the involvement of all data users and the
disposal contractors, and maintain records of waste manage- laboratory is paramount and quite literally can be the difference
ment. Project planning decisions should account for the total between success and failure.
E3302 − 23
6.2.3 PFAS environmental investigations should be con- 6.3 Source Identification, Site Characterization, and Reme-
ducted in compliance with applicable regulatory requirements. dial Design Applications:
Regulations at the national level, such as the SDWA, and
6.3.1 Many of the concepts and principals that apply to
protocols, such as the U.S. Department of Defense (DoD)
conducting routine environmental site assessments also apply
Quality Systems Manual (QSM) (1) , may differ from or
to PFAS sites. Generally speaking, the intent is to identify the
conflict with state, regional, or provincial regulatory require-
source(s) of contaminants as well as the nature and extent of
ments. In many cases, these jurisdictional regulatory conflicts
the contamination. A conceptual site model is developed, and a
add a confounding degree of complexity.
SAP is prepared to either confirm or further elucidate the
6.2.4 The analysis of public water supplies in the United
sources, pathways, and receptors addressed in the conceptual
States is regulated under the SDWA. The USEPA released
site model. SAPs can be application specific in that the targeted
Method 537 for PFAS in 2009, with revision in 2018 as
PFAS list could vary depending on whether the data collection
Method 537.1, revised in 2020. The USEPA also released
activity is strictly for regulatory compliance or the information
Method 533 for drinking water analysis in 2019.
is also being used for remedial design or source identification.
6.2.5 The DoD manages all environmental analysis in PFAS adds a degree of complexity due to the rapidly devel-
oping regulatory framework, the limited availability of stan-
accordance with their QSM. PFAS contamination has varying
degrees of concern at DoD sites, and that concern may not be dardized PFAS analytical methods, and the limited availability
limited to public water supplies. DoD environmental sampling of internal, isotopically labeled standards.
programs often include additional PFAS and other environ-
6.4 Non-Targeted Analysis—Tools for the Forensic Practi-
mental media that are not addressed by existing USEPA
tioner:
methods. Because of this, laboratory-specific, proprietary
6.4.1 When analyzing samples for environmental
PFAS analytical methods are often used. To manage the
contaminants, the usual quest is to accurately quantify a
application of these methods and to standardize wherever
relatively short list of targeted compounds and trace elements.
possible, the DoD QSM established method performance and
Mass spectrometry (MS) environmental methods focus on the
QA/QC requirements. The DoD QSM represents a logical first
USEPA Target Compound List or a project-specific list of
step toward the standardization of PFAS analytical methods,
contaminants of concern, capturing only those compounds with
particularly those that include additional compounds or address
established cleanup benchmarks. These analyses cover only
other environmental media until additional recognized standard
perhaps 200–300 of the 65 million chemicals identified in the
methods are promulgated.
CAS database.
6.2.6 The partnership between the USEPA and the DoD
6.4.2 PFAS include a wide variety of head groups, chain
Strategic Environmental Research and Development Program
lengths, and branching, so thousands of such chemicals may be
(SERDP) has produced draft Method 1633 (August 2021, rev.
present in the environment. However, because regulatory
June 20
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: E3302 − 22 E3302 − 23
Standard Guide for
PFAS Analytical Methods Selection
This standard is issued under the fixed designation E3302; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 This guide discusses the selection and application of analytical methods and techniques used to identify and quantitate per-
and polyfluoroalkyl substances (PFAS) in environmental media. This guide provides a flexible, defensible framework applicable
to a wide range of environmentenvironmental programs. It is structured to support a tiered approach with analytical methods,
procedures, and techniques of increasing complexity as the user proceeds through the evaluation process. This guide addresses key
decision criteria and best practices to aid users in achieving project objectives. There are numerous technical decisions that must
be made in the selection and application of analytical methods and techniques used during environmental data acquisition
programs. It is not the intent of this guide to define appropriate technical decisions, but rather to provide technical support within
existing decision frameworks.
1.2 This guide informs practitioners on the considerations relevant to the selection and application of analytical methods and
techniques for the quantitative and qualitative determination of PFAS in a variety of environmental sample media. This guide
encourages user-led collaboration with stakeholders, including analytical laboratories, data evaluation practitioners, and regulators,
in the selection and application of analytical methods and techniques used to support project-specific decision criteria and
objectives as applied within a particular environmental regulatory program. This guide recognizes the complexity and diversity of
environmental programs and project objectives and provides technical supportguidance for a range of project applications.
1.3 This guide is intended to complement, not replace, existing regulatory requirements or guidance. ASTM International (ASTM)
guides are not regulations; they are consensus-based standards that may be followed as needed.
1.4 This guide recognizes that PFAS can be categorized as polymeric or nonpolymeric, collectively amounting to more than 4 700
Chemical Abstracts Service (CAS)-registered substances. Environmental concerns pertaining to PFAS are centered primarily on
the perfluoroalkyl acids (PFAA), a subclass of PFAS, which display extreme persistence in the environment and chain-length-
dependent bioaccumulation and adverse effects in biota.
1.5 This guide recognizes that published analytical methods performed by commercial laboratories are limited to determination
of a small subset of the more than 4 700 CAS-registered PFAS.
1.6 The goal of this guide is to provide a technical framework for informed selection and application of analytical methods and
techniques for the determination of target and non-target PFAS in environmental sample media.
1.7 This guide aids users in selecting PFAS analytical methods for various environmental applications.
This guide is under the jurisdiction of ASTM Committee E50 on Environmental Assessment, Risk Management and Corrective Action and is the direct responsibility
of Subcommittee E50.04 on Corrective Action.
Current edition approved July 1, 2022Dec. 15, 2023. Published July 2022January 2024. Originally published in 2021. Last previous edition approved in 2021 as E3302–21.
DOI: 10.1520/E3302–2210.1520/E3302–23
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E3302 − 23
1.8 This guide discusses existing published analytical methods for quantitative determination of method-specific lists of target
analytes, as well as non-standard analytical approaches developed to qualitatively determine a broader range of PFAS, for a variety
of environmental applications. This guide also provides an overview of research trends in this rapidly developing field.
1.9 This guide discusses the challenges and limitations of analytical methods and techniques in the detection and quantitation of
the large, complex set of PFAS.
1.10 This guide describes widely accepted considerations and best practices used in the selection and application of analytical
procedures used during PFAS environmental programs. This guide complements but does not replace existing technical guidance
and regulatory requirements.
1.11 Units—The values stated in SI units are to be regarded as the standard.
1.11.1 Other units, such as fractional units of parts per billion and parts per trillion, are also included in this guide.
1.12 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of
regulatory limitations prior to use.
1.13 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D7968 Test Method for Determination of Polyfluorinated Compounds in Soil by Liquid Chromatography Tandem Mass
Spectrometry (LC/MS/MS)
D7979 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)
D8421 Test Method for Determination of Per- and Polyfluoroalkyl Substances (PFAS) in Aqueous Matrices by Co-solvation
followed by Liquid Chromatography Tandem Mass Spectrometry (LC/MS/MS)
2.2 USEPA Documents:
EPA QA/G-4 Guidance on Systematic Planning Using the Data Quality Objectives Process, February 2006
EPA/600/F-17/022e PFAS Methods and Guidance for Sampling and Analyzing Water and Other Environmental Media –
Technical Brief, February 2019, EPA/600/F-17/022h, updated January 2020
USEPA 815-B-16-021 Technical Advisory – Laboratory Analysis of Drinking Water Samples for Perfluorooctanoate (PFOA)
Using EPA 537 Rev. 1.1, September 2016
USEPA Method 537 Version 1.1 Determination of Selected Perfluorinated Alkyl Acids (PFAAs) in Drinking Water by Solid
Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)(LC/MS/MS)EPA/600/R-08/092,
2008, revised 2009.
USEPA Method 537.1 Version 2.0 Determination of Selected Per- and Polyfluorinated Alkyl Substances (PFAS) in Drinking
Water by Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)(LC/MS/MS)EPA/
600/R-20/006, March 2020.
USEPA Method 533 Determination of Per-and Polyfluoroalkyl Substances (PFAS) in Drinking Water by Isotope Dilution Anion
Exchange Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS), Revision July
2021815-B19-020, December 2019.
USEPA Test Method 8327 Per-and Polyfluoroalkyl Substances (PFAS) Using External Standard Calibration and Multiple
Reaction Monitoring (MRM) Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)(LC/MS/MS), Revision 0,
July 2021
USEPA Draft Method 1633 Analysis of Per- and Polyfluoroalkyl Substances (PFAS) in Aqueous, Solid, Biosolids, and Tissue
Samples by LC-MS/MS, First Draft, EPA 821-D-21-001, August 2021.20211;Second Draft, EPA 821-D-22-001, June 2022;
Third Draft, EPA 821-D-22-003, December 2022; Fourth Draft, EPA 821-D-23-001, July 2023.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Available from United States Environmental Protection Agency (EPA), William Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,
http://www.epa.gov.
E3302 − 23
USEPA Draft Method 1621, Screening Method for the Determination of Adsorbable Organic Fluorine (AOF) in Aqueous
Matrices by Combustion Ion Chromatography (CIC), EPA 821-D-22-002, April 2022.
U.S. Environmental Protection Agency PFAS Master List of PFAS Substances. CompTox Chemistry Dashboard, Last updated
September 16, 2020, Online, Available: https://comptox.epa.gov/dashboard/chemical_lists/PFASMASTERVersion 2.2.1, May
2023, Available Online at: https://comptox.epa.gov/dashboard/
U.S. Environmental Protection Agency Drinking Water Health Advisories for Perfluorooctanoate (PFOA) and Perfluorooctane
Sulfonate (PFOS), 822-R-16-004, 2016
U.S. Environmental Protection Agency Lifetime Health Advisories and Health Effects Support Documents for Perfluorooctanoic
Acid (PFOA) and Perfluorooctane Sulfonate (PFOS), Federal Register, Vol 81, No. 101, May 25, 2016
U.S. Environmental Protection Agency , Lifetime Drinking Water Health Advisories for Four Perfluoroalkyl Substances (PFOA,
PFOS, GenX, and PFBS), Federal Register Vol. 87, No. 118, June 21, 2022.
U.S. Environmental Protection Agency , PFAS National Primary Drinking Water Regulation Rule Proposal (for PFOA, PFOS,
PFNA, HFPO-DA or GenX Chemicals, PFHxS, and PFBS), Federal Register Vol. 88, No. 60, March 29, 2023.
2.3 ISO Documents:
ISO 25101 Determination of Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoate (PFOA) in Water – Method for
Unfiltered Samples Using Solid Phase Extraction and Liquid Chromatography / Tandem Mass Spectrometry (LC-MS/
MS)(LC-MS/MS), 2009.
ISO 21675 Determination of Polyfluorinated Alkyl Substances (PFAS) in Water – Method Using Solid Phase Extraction and
Liquid Chromatography / Tandem Mass Spectrometry (LC-MS/MS)(LC-MS/MS), 2019.
3. Terminology
3.1 Definitions:
3.1.1 adsorbable organofluorine (AOF), n—a fraction of organofluorine that will sorb to a particular media, for example carbon,
and that remains sorbed to the media after removal (washing) of the inorganic fluoride.
3.1.2 combustion ion chromatography (CIC), n—a technique that combines pyrolysis of a sample and analysis of the combustion
products using ion chromatography.
3.1.3 extractable organofluorine (EOF), n—the fraction of organic fluorine that is first extracted and then analyzed.
−
3.1.4 fluoride ion, n—the inorganic anion of fluorine (F ); that is, fluoride.
3.1.5 fluorides, n—any compound containing fluorine are categorically deemed fluorides.
3.1.6 fluorine (F), n—a chemical element, diatomic form (F2); it is a highly toxic gas, reactive, and yellow-green in color.
3.1.7 liquid chromatography mass spectrometry / mass spectrometry (LC/MS/MS; also known as triple quadrupole or triple quad
LC/MS), n—an analytical instrument that laboratory methods use to separate, identify, and quantitate specific targeted organic
compounds.
3.1.8 per- and polyfluoroalkyl substances (PFAS), n—a group of manufactured chemicals consisting of polymeric chains of carbon
bonded to fluorine atoms, usually with a polar functional group at the head.
3.1.8.1 Discussion—
PFAS are fluorinated substances with a carbon chain structure. In perfluoroalkyl substancesacids (PFAAs), each carbon atom in
the chain is fully saturated with fluorine (carbon-fluorine bonds only), whereas the carbon chain in polyfluoroalkyl substances is
mostly saturated with fluorine (carbon-fluorine bonds), but also contains carbon-hydrogen bonds.
3.1.9 perfluoroalkyl acids (PFAA), n—a subclass of PFAS including sulfonic and carboxylic acids that display extreme persistence
and chain-length-dependent bioaccumulation and adverse effects in biota.
3.1.10 precursor, n—a category of PFAS that includes all polyfluorinated alkyl substances and a subset of polymer PFAS known
as side-chain fluorinated polymers, collectively known as “precursors” because of their ability to degradetransform into terminal
defluorinated alkyl substances.
Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http://www.ansi.org.
E3302 − 23
3.1.11 proton-induced gamma-ray emission (PIGE), n—a rapid screening technique that provides a qualitative and quantitative
measure of total fluorine.
3.1.12 quadrupole time of flight (Q-TOF), n—an accurate MS/MS instrument that replaces the final quadrupole with a
time-of-flight (TOF) high-resolution mass spectrometer.
3.1.13 solid phase extraction (SPE), n—a type of sample preparation that extracts targeted analytes from an aqueous matrix onto
a solid medium, allowing the analytes to be separated from the matrix and subsequently eluted and concentrated in an organic
solvent.
3.1.14 total fluorine (TF), n—a measure that includes organic and inorganic fractions of fluorine.
3.1.15 total organic fluorine, n—a measure of the total organic fraction of fluorine in a sample.
3.1.15.1 Discussion—
Total Organic Fluorine is the description of the category and measurement, but not all CIC-dependent approaches can report a
result that truly represents total organic fluorine. The reason being when a sample is extracted, adsorbed, or otherwise manipulated
prior to combustion, the percentage of the total that is amenable to the extraction, adsorption, or manipulation (and thus quantified)
is directly dependent on the approach used. Each approach has documented limitations. See guide Section 8 for more information.
3.1.16 total oxidizable precursor (TOP), n—a measure of oxidizable precursors determined by method-defined assays. In this
context, the precursors are limited to PFAA precursors. The analytical method that quantifies the precursors is widely known as
TOP Assay.
3.1.17 total PFAS, n—a surrogate estimate based on various analytical techniques of the summation or total value of TOP assay
or total organic fluorine.
4. Significance and Use
4.1 This guide provides an overview of analytical methods, techniques, and procedures that may be used in determination of PFAS
in environmental media.
4.2 This guide provides considerations relevant to the selection and application of PFAS analytical methods, techniques, and
procedures, including the limitations of published analytical methods and the potential benefits and challenges of non-standard
analytical approaches.
4.3 This guide presents comparisons of published analytical methods and approaches, including tabular comparison of target
analyte lists and method features, to aid users in the selection and application of analytical methods and techniques for
project-specific applications.
4.4 This guide describes qualitative techniques available to determine total PFAS, including explanation of terms, discussion of
techniques, preparation and analytical techniques and limitations, conceptual overview schematic, and summary comparison table.
4.5 This guide provides current information on research trends in PFAS determination techniques applied to environmental media.
4.6 This guide provides an integrated framework that results in efficient, cost-effective decision-making for timely, appropriate
response actions for PFAS-impacted environmental media.
4.7 This guide is not intended to replace or supersede federal, state, local, or international regulatory requirements. Instead, this
guide may be used to complement and support such requirements.
4.8 This guide may be used by various parties involved in response actions for PFAS-impacted environmental media, including
regulatory agencies, project sponsors, environmental consultants and contractors, site remediation professionals, analytical testing
laboratories, data reviewers, data users, academic institutions, research institutes, and other stakeholders.
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4.9 The users of this guide should consider assembling a team of experienced professionals with appropriate expertise to scope,
plan, and execute PFAS environmental data acquisition activities.
4.10 The users of this guide should review the overall structure and components of this guide before proceeding with use,
including the following sections:
4.10.1 Section 1: Scope
4.10.2 Section 2: Referenced Documents
4.10.3 Section 3: Terminology
4.10.4 Section 4: Significance and Use
4.10.5 Section 5: Project Planning Considerations
4.10.6 Section 6: Analytical Method Selection Considerations
4.10.7 Section 7: Analytical Methods Comparison
4.10.8 Section 8: Qualitative Techniques to Determine Total PFAS
9: Research Trends
4.10.9 Section
4.10.10 Section 10: Keywords
4.10.11 Appendix X1: PFAS Analytical Interferences – A Summary of Considerations
5. Project Planning Considerations
5.1 This guide complements applicable existing guidance used to develop a Quality Assurance Project Plan (QAPP) and to
establish data quality objectives (DQOs) necessary to meet project goals and to evaluate data quality. This process encourages
planners to identify and focus on the key issues and elements necessary for successful, cost-effective, and defensible project
outcomes.
5.2 Data Quality Objective Process:
5.2.1 An important functional aspect of project planning is the DQO process. It is necessary to formalize these planning steps to
ensure that the type, quantity, and quality of PFAS data used in decision-making. Thoughtfully derived DQOs provide the
qualitative and quantitative framework by which data collection activities are successful in terms of achieving project objectives.
The qualitative aspect of DQOs seeks to encourage good planning for field investigations. The quantitative aspect of DQOs
involves designing an efficient field investigation that reduces the possibility of incorrect decision-making.
5.2.2 The DQO process is defined in Guidance on Systematic Planning Using the Data Quality Objectives Process (USEPA 2006).
The DQO process consists of seven steps as presented in 5.2.3 through 5.2.9, and each step is followed by specific examples
(presented in italics). Included in the step descriptions are simplistic (not intended to be complete) example project circumstances
involving the collection of PFAS groundwater data. Note that every project is different, and the DQO process should yield
project-specific objectives.
5.2.3 Step 1: State the Problem. Define the problem that motivates the study; identify the planning team; and examine the budget
and schedule.
5.2.3.1 The state agency has required that the groundwater wells at our facility include a round of PFAS sampling and analysis.
5.2.3.2 Our environmental manager is working directly with our consultant and laboratory project managers.
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5.2.3.3 Our consultant and laboratory have quoted $46,000, which includes final reporting to the state agency.
5.2.3.4 We are required to issue a final report before the end of this calendar year.
5.2.4 Step 2: Identify the Goal of the Study. State how the PFAS data will be used to meet objectives and solve the problem,
identify study questions, and define alternative outcomes.
5.2.4.1 This study will determine whether our groundwater has PFAS. If PFAS target analytes are not detected above the state’s
new action limit, we have met our goal. If PFAS target analytes are detected above the state’s new action limit, then additional
sampling and source identification/control will likely occur.
5.2.5 Step 3: Identify Information Inputs. Identify data and information needed to answer study questions.
5.2.5.1 Groundwater levels and contour maps will be reviewed to select the proper number and locations of the wells to be
sampled.
5.2.5.2 The special precautions associated with PFAS sampling, method requirements and associated sample volume
requirements, the QC samples, and the specific list of PFAS target analytes the state is requiring need to be reviewed with the
planning team.
5.2.6 Step 4: Define the Boundaries of the Study. Specify the target population and characteristics of interest and define the
scope and limitations of the study (that is, the study will not consider potential non-targeted analytes).
5.2.6.1 The state’s requirements are limited to the sampling and analysis of on-site monitoring wells.
5.2.6.2 We need to propose a reasonable number and locations of the wells to be sampled to the state. One or two upgradient wells
will be considered.
5.2.7 Step 5: Develop the Analytic Approach. Define the analytical parameters of interest; specify the type of inference and
develop logic for drawing conclusions from the findings.
5.2.7.1 The list of specific PFAS target analytes needs to be reviewed with the state agency and our contract laboratory. The
method reference and any modifications need to be reviewed and approved. Reporting limits capable of ruling out the state’s new
action limits and the inclusion/omission of branched isomers need to be finalized with the contract laboratory.
5.2.7.2 At this stage in the process, consider augmenting the study to include analysis of non-targeted PFAS (that is, total“total”
PFAS).
5.2.8 Step 6: Specify Performance or Acceptance Criteria. Develop performance criteria for new data being collected and
acceptance criteria for data already collected.
5.2.8.1 Through this sampling and analytical event, if PFAS target analytes are not detected above Statestate action limits, then
we will not have to include PFAS target analytes in future monitoring. If PFAS target analytes are detected above Statestate action
limits, then additional characterization, source identification/minimization and/or remediation could be future activities.
5.2.9 Step 7: Develop the Detailed Plan for Obtaining Data. Select the most resource-effective work plan or Sampling and
Analysis Plan (SAP) that satisfies the performance or acceptance criteria.
5.2.9.1 After preliminary discussions with the state agency, we will meet with our consultant and contract laboratory, and our
consultant will draft a SAP with input from the planning team members. The SAP will be reviewed and approved by the state before
sampling activities proceed.
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5.3 Project Data Quality Objectives:
5.3.1 One of the decisions to be made when developing DQOs for a PFAS project is determining if the resulting analytical data
need to meet performance or acceptance criteria. If PFAS data are to be used for screening-level analyses or pilot studies, for
example, the level of data quality and the level of data evaluation conducted on the analytical data set may not need to be as
rigorous as the PFAS data intended quality needed to meet legally enforceable standards.standards and regulatory compliance
applications.
5.4 Regulatory Considerations:
5.4.1 Regulatory stakeholders at the federal and state levels have used various mechanisms to establish PFAS limits for
environmental media, from non-enforceable health advisory levels (HAL), guidance levels, and screening values to legally
enforceable regulatory compliance criteria such as drinking water maximum contaminant levels (MCLs). Many regulatory
agencies have developed PFAS regulatory limits for individual compounds, and some regulatory agencies have designed guidance
and limits based on the summation of select PFAS.
5.4.2 Regulatory agencies implement accreditation and certification programs that govern for laboratory sample processing and
data reporting activities. Experienced laboratories have secured these accreditations and certifications using sophisticated sample
extraction and analysis protocols to report specific PFAS target analytes in select sample media using both published analytical
methods and laboratory proprietary analytical approaches. Project planners are encouraged to consider the regulatory accreditations
and certifications available (by analyte, by method, and by sample matrix) and, when necessary, to engage the laboratory to
consider analytical options where regulatory certification or accreditation may not be offered. Project planners and data users
should confirm that laboratory accreditation or certification meets project objectives and regulatory requirements.
5.5 Project Planning Considerations:
5.5.1 The project QAPP is used to document decisions made in the consideration a range of elements considered in planning a
PFAS data acquisition project. Elements typically considered during project planning include the following:
(1) Regulatory program requirements
(2) Regulatory criteria and project action limits (such as generic screening levels, site-specific criteria, and enforceable
regulatory compliance standards)
(3) Laboratory certification and accreditation requirements
(4) Project DQOs
(5) Quality assurance (QA) and quality control (QC) requirements
(6) QAPP and SAP development and regulatory approval
(7) Data review, evaluation, validation, application, and uses
(8) Analytical chemistry approach (such as target analyte list, sample preparation protocols, analytical instrumentation,
analytical method, accreditation or certification, data reporting, QC excursions, and data reporting format)
(9) Sample media (such as potable water, groundwater, surface water, effluent, soil, sediment, biological tissue, and
environmental waste)
(10) Sample processing issues (such as concentrations of target and non-target analytes, sample matrix interference, sensitivity,
levels of detection and quantitation, dilutions, re-runs, and QC excursions) (See Appendix X1).
(11) Turnaround time (for example, project schedule expectations, sample preservation and handling, sample hold times,
analytical sequence, laboratory capacity, and sample re-runs)
(12) Data deliverable formats
5.5.2 This is not meant to be an exhaustive list, but a typical set of project planning considerations that inform decisions that
enhance successful project outcomes.
5.6 Data Acquisition Considerations:
5.6.1 Communication within the project team, including the laboratory, is key to planning and executing a successful PFAS
sampling event. Increased risk of cross-contamination requires PFAS-specific sampling procedures and a series of field QC
samples. This is due to the persistence and surface-sorbing tendency of certain PFAS, as well as their ubiquitous presence in many
products and materials.
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5.6.2 The selection and handling of sampling equipment and materials (provided by the practitioner) and sample containers and
blank water (provided by the laboratory) should be carefully considered during the planning and execution of PFAS field sampling
programs. These items should not contain PFAS at concentrations that will interfere with the proposed analysis.
5.6.3 Field QC samples should be included in the design and execution of a PFAS sampling program. Field QC samples typically
include equipment blanks (EB), field reagent blanks (FRB), field duplicates (DUP),(FD), and project-specific matrix spike/matrix
spike duplicate samples. Each of these field QC samples requires sufficient sample volume to fill a separate container, because these
samples are individually processed and reported as part of the project data set.
5.6.4 Laboratory subsampling should not be performed because it may cause a low bias for large PFAS (>C10 perfluoroalkyl
carboxylic acids, >C8 perfluoroalkyl sulfonic acids). These considerations should be documented in the project QAPP.
5.6.5 Application of PFAS analytical methods designed for a drinking water sample matrix to non-potable water samples should
be discussed with the laboratory in advance of sample collection. Consideration should be given to the intended purpose of the
preservative listed in method, which is to buffer chlorine added to treated finished drinking water supplies. The buffer is also
essential to the SPE process by extraction of all samples at the same pH. When a drinking water method is applied to a
non-drinking water sample matrix (such as groundwater or surface water), the decision regarding the sample preservative should
be documented in the project QAPP and SAP.
5.6.6 The laboratory may experience QC non-conformances when processing untreated source water samples, which may contain
elevated levels of suspended solids (turbidity), when applying an analytical method designed for treated finished drinking water.
This may result sample reprocessing (that is, re-analysis of the sample extract or re-extraction of the original sample) to confirm
the initial result, which then results in extended turnaround time necessary to report final data.
5.7 Performance Evaluation Samples—Single Blind and Double Blind:
5.7.1 The use of performance evaluation (PE) samples is an important QC component that environmental practitioners should
consider including in their environmental investigations. These known reference samples provide valuable information regarding
the accuracy and comparability of laboratory data when one or more laboratories are being used. When possible, it is preferable
to issue these samples double-blind to the project laboratories, meaning the receiving laboratories have no idea that they are
analyzing a test sample. This can be accomplished by simply having an accredited PE sample vendor prepare the sample(s) in
ordinary sample bottles, such as those prepared for investigatory sampling. The practitioner then labels (and separately documents)
the sample with a fictious sample identification. It is critical when performing these double-blind studies that the accredited PE
sample vendor certify the PFAS values in their whole-volume PE preparation.
5.7.2 When using a single-blind PE sample, the receiving laboratories know they are receiving test samples (either whole volume
or ampulated), but they do not know the specific analytes and the true (vendor-certified) concentrations.
5.7.3 Essentially, the purpose of PE studies is to determine whether the laboratory can get the “right answer” on what appears to
be a routine investigatory sample. When available, PFAS solid-matrix performance test (PT) samples, solid-matrix PFAS PE
samples, and solid-matrix PFAS certified reference materials (CRM) will provide a means to evaluate the solid extraction and
analytical procedures for PFAS. These standardized test materials could identify the ability of different laboratories to reproduce
PFAS analytical results regardless of their “accreditation” status. This is currently an issue because laboratory PFAS procedures
vary widely, and multi-laboratory-validated analytical methods for PFAS in non-drinking water sample matrices are limited.
5.8 Calibration Standards—Primary Source and Secondary Source:
5.8.1 For PFAS laboratory calibration and QC, the number of PFAS and the vendors who create these analytical standards and
reference materials are limited. In 2020, there were two standard vendors who provide analytical reference material for analysis
of PFAS in drinking water through USEPA Method 537.1 and Method 533, as well as for analysis of PFAS in non-drinking water
and solids through other methods with extended PFAS target analyte lists. Due to the limited availability of standards, laboratories
are not always able to use a true second-source standard to verify their calibration, which is why USEPA Method 533 does not
currently require second-source verification of initial calibration curves. When analytical standards and reference materials are
available, some laboratories may use a standard from a second vendor as a second-source verification. However, due to the limited
availability of PFAS standards, many will use different lots or single-component standards from the same vendor to verify their
initial calibration curves.
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5.9 Quantitation of Branched and Linear Isomers:
5.9.1 Individual PFAS can exist as linear and branched isomers. Ideally, the concentration of a given PFAS would include the
linear isomer, which is usually but not always the case, together with any associated branched isomers to provide a total
concentration for that analyte. While the current practice is for laboratories withto report a single total concentration, there (if
qualitative and/or quantitative standards exist for the branched isomer components.),there is growing interest in identifying and
reporting the linear and branched isomers separately although there are a number of technical challenges with this reporting (such
as the lack of chromatographic resolution criteria within the existing methods). However, at the time of this writing, limited
suitable quantitative standards containing both linear and branched standards exist for only four common PFAS: perfluorooctane
sulfonate (PFOS), perfluorohexane sulfonic acid (PFHxS), N-ethyl perfluorooctane sulfonamido acetic acid (NEtFOSAA), and
N-methyl perfluorooctane sulfonamido acetic acid (NMeFOSAA). When USEPA Method 537 was promulgated in 2009, it
specified that both linear and branched isomers be included in the calibration and quantification of these compounds. A technical
grade standard for perfluorooctanoate (PFOA), which included branched isomers was available at the time leading to some
laboratories including PFOA branched isomers while others did not. To clarify this requirement, USEPA issued a technical advisory
(USEPA 2016, EPA 815-B-16-021) for USEPA Method 537 that specifically identifies PFOS, PFHxS, NEtFOSAA, and
NMeFOSAA as containing branched isomers and requires that quantitative standards be used to correctly identify and quantitate
all chromatographic peaks for these compounds (note that more recent data suggests that other PFAS may also include branched
and linear isomers). . The advisory further addressed PFOA, stating that the technical grade standard should be used to identify
PFOA branched isomers and to include them with the linear isomer to provide a total PFOA sample concentration.
NOTE 1—Draft Method 1633 adds qualitative branched isomer standards for 6 additional PFAS. That makes a total of 11 PFAS out of 40 target compounds
that can be reported as total linear and branched - 4 using the quantitative standard and 7 using the qualitative standard for isomer identification. For the
remaining target compounds, only the linear isomer is quantified. As other quantitative standards that include the branched isomeric PFAS
forms become available, they should be incorporated into the applicable PFAS analytical methodologies, which will allow for the
total (and separately branched) PFAS concentration to be determined for these analytes.
5.10 Data Reporting Format:
5.10.1 Laboratory data reporting formats should be considered during the project planning process and documented in the project
QAPP. Data reporting format decisions should consider the range of data uses for the project application. Data uses may include
site characterization, site remediation, source control, treatment of effluent, treatment of drinking water, risk assessment, and
regulatory compliance monitoring. Data management decisions should consider the full range of intended data uses and should be
reviewed by the laboratory and documented in the project QAPP.
5.10.2 Laboratory data reports typically include a set of standardized elements as listed below:
(1) Cover sheet
(2) Table of contents
(3) Case narrative
(4) Chain-of-custody records
(5) Sample receipt documentation
(6) Data report (Form 1s)
(7) QC documentation (detail depends on reporting level)
(8) Sample preparation logs (included in Level IV data package)
(9) Raw data for each sample, blank, spike, duplicate, and standard (that is, quantitation reports, chromatograms, mass spectra,
instrument printouts, and bench sheets) (included in Level IV data package)
5.10.3 Data package deliverables produced by laboratories contain various levels of detail and are typically categorized into
threethe levels listed below:
(1) Level IV—Comprehensive validation-ready fully documented data package inclusive of raw data
(2) Level III—Summary data with calibration and QC forms, excludes raw data
(3) Level II—Summary data with QC forms, excludes raw data
(4) Level II—Results-onlyI—Results-only data report, excludes QC forms and raw data
5.10.4 Project planning should also consider the electronic data deliverables (EDD) format(s) needed to support project data uses.
EDD formats typically produced by environmental laboratories include CSV, Excel, and commercially available enterprise
database file formats. These may be unformatted or formatted to conform to a practitioner’s specific database. State regulatory
programs may require a formatted EDD for a specific program application. Examples include, but are far from limited to, the New
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Jersey Hazsite EDD designed for upload to the New Jersey Department of Environmental Protection (NJDEP) Site Remediation
Program database, and the New Jersey Electronic Environmental (E2) Reporting System EDD designed for upload to the database
for the Safe Drinking Water Act (SDWA) compliance monitoring program administered by the NJDEP Bureau of Safe Drinking
Water. Federal programs may require a formatted EDD for a program-specific data application. Examples include the
Environmental Resources Program InfoInformation Management System (ERPIMS) EDD used by the U.S. Air Force Civil
Engineer Center (AFCEC) for validation and management of data from environmental projects at Air Force bases, and the Staged
Electronic Data Deliverable (SEDD) used by the USEPA Superfund program with automated data review tools.
5.11 Sample Disposition:
5.11.1 Project planning should also consider the timeline for retention and disposal of samples by the receiving laboratory. These
may include unused sample material, sample extracts, sample containers, expired reagents, and related waste generated in the
processing of environmental samples. Laboratories typically follow waste management plans, use licensed waste disposal
contractors, and maintain records of waste management. Project planning decisions should account for the total time the samples
and residuals are retained by the laboratory prior to disposal (or return) relative to the time needed by data users for data review
and evaluation. Laboratories must be notified regarding projects thatwith Consent Orders and Legal Hold requirements that
stipulate indefinite storage of samples and residuals. Effective communications must take place between practitioners and the
laboratory to secure capacity and funding for long-term storage of unused samples, sample extracts, and residuals.
6. Analytical Method Selection Considerations
6.1 Overview:
6.1.1 The ongoing, expanding nature of PFAS environmental awareness and the need for more comprehensive investigations have
caused increased demand for PFAS environmental sampling and analysis. There are limited analytical method options available,
particularly across the full spectrum of environmental media for a range of PFAS compounds. In many cases, the primary source
in the search for available analytical methods for any environmental application is the USEPA. The USEPA has published
analytical methods for the analysis of select PFAS analytes in drinking water and non-potable water, and USEPA released a draft
method for the analysis of select PFAS analytes in nonpotable water, soil, sediment, biosolids, and tissue. In addition to the USEPA,
both the ASTM and the International Organization for Standardization (ISO) have also published PFAS analytical methods. These
methods are discussed in Section 7.
6.2 Interplay of Sampling Objectives and Regulatory Requirements:
6.2.1 PFAS sampling and analytical programs are no different than other environmental sampling programs in that the procedures
used must comply with applicable regulatory requirements. As discussed in 5.4, the PFAS regulatory framework is rapidly
evolving. This, in combination with the limited availability of PFAS analytical methods, makes the development of project SAPs
for PFAS much more challenging relative to other environmental sampling programs. Practitioners and data users must continually
check for revisions to the applicable regulatory requirements between writing the plan and executing it.
6.2.2 Another major consideration is that, given the limited number of standardized, published, multi-laboratory validated
analytical methods to determine a wide range of PFAS in a wide range of sample matrices, practitioners may have no other option
except to use a laboratory-specific, proprietary method. This is commonly the case when there are specific PFAS that need to be
included and a published method for those compounds is not available. More prevalent are cases where environmental media such
as soil, sediment, or biologic tissue need to be analyzed for a specific list of PFAS target analytes using a robust analytical approach
to accommodate sample matrix effects for which published analytical methods do not exist. Proper planning is essential for any
environmental data acquisition program. For projects that include PFAS, comprehensive planning with the involvement of all data
users and the laboratory is paramount and quite literally can be the difference between success and failure.
6.2.3 PFAS environmental investigations should be conducted in compliance with applicable regulatory requirements. Regulations
at the national level, such as the SDWA, and protocols, such as the U.S. Department of Defense (DoD) Quality Systems Manual
(QSM) (1) , may differ from or conflict with state, regional, or provincial regulatory requirements. In many cases, these
jurisdictional regulatory conflicts add a confounding degree of complexity.
The boldface numbers in parentheses refer to the list of references at the end of this standard.
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6.2.4 The analysis of public water supplies in the United States is regulated under the SDWA. The USEPA released Method 537
for PFAS in 2009, with revision in 2018 as Method 537.1. 537.1, revised in 2020. The USEPA also released Method 533 for
drinking water analysis in 2019.
6.2.5 The DoD manages all environmental analysis in accordance with their QSM. PFAS contamination has varying degrees of
concern at DoD sites, and that concern may not be limited to public water supplies. DoD environmental sampling programs often
include additional PFAS and other environmental media that are not addressed by existing USEPA methods. Because of this,
laboratory-specific, proprietary PFAS analytical methods are often used. To manage the application of these methods and to
standardize wherever possible, the DoD QSM established method performance and QA/QC requirements. The DoD QSM
represents a logical first step toward the standardization of PFAS analytical methods, particularly those that include additional
compounds or address other environmental media until additional recognized standard methods are promulgated.
6.2.6 The partnership between the USEPA and the DoD Strategic Environmental Research and Development Program (SERDP)
has produced draft Method 1633 (August 2021) 2021, rev. June 2022, rev. Dec. 2022, rev. July 2023) for determination of 4140
PFAS target analytes in wastewater, surface water, groundwater, soil, biosolids, sediment, landfill leachate, and fish tissue. This
draft method can be used in various applications, including National Pollutant Discharge Elimination System (NPDES) permits.
The method will support NPDES implementation by providing a consistent PFAS method that has been tested in a wide variety
of wastewaters and contains all the required quality control procedures for a Clean Water Act (CWA) method. This method can
also be used for DoD applications. The DoD QSM Ver. 5.4 (released in October 2021) includesincluded in Appendix B Quality
Control Requirements, the Table B-24 for PFAS Draft Method 1633.
6.2.7 As a screening option, the USEPA released draft Method 1621 in April 2022 for the analysis of Adsorbable Organic Fluorine
(AOF). This method-defined parameter can be used for the measurement of organofluorines that adsorb onto carbon sorption media
for wastewater and surface water sample analysis applications. The method limitations
...