ASTM D8535-23

• Abstract:

  SIGNIFICANCE AND USE; 5.1 PFAS are widely used in various industrial and commercial products; they are persistent, bio-accumulative, and ubiquitous in the environment. PFAS have been reported to exhibit developmental toxicity, hepatotoxicity, immunotoxicity, and hormone disturbance. PFAS have been detected in soils, sludges, surface, and drinking waters. This is a quick, easy, and robust method to quantitatively determine these compounds at trace levels in soil/biosolid matrices. ; 5.2 This test method has been validated using four ASTM reference soils (CH-1, ML-1, CL-1, and SP-1). ASTM reference soil CH-1 is Fat Clay (CH)—Vicksburg Buckshot Clay; ASTM reference soil ML-1 is silt (ML)—Vicksburg silt; ASTM reference soil CL-1 is lean clay (CL)—Annapolis clay; and ASTM reference soil SP-1 is sand (SP)—Frederick sand and four biosolids (Missouri, California, Idaho, and Georgia). Refer to the Precision and Bias (Section 17).; SCOPE; 1.1 This test method covers the determination of per- and polyfluoroalkyl substances (PFAS) in soil/biosolid matrices by solvent extraction, filtering, separation using liquid chromatography (LC), and detection with tandem mass spectrometry (MS/MS). These analytes are extracted from soil/biosolids with basic water and methanol then qualitatively and quantitatively determined by this test method. Quantitation is by selected reaction monitoring (SRM), sometimes referred to as multiple reaction monitoring (MRM). ; 1.2 The reporting limit (RL) and reporting range (see Note 2) for the target analytes are listed in Table 1. The reporting limit is calculated from the concentration of the Level 1 calibration standard as shown in Table 5 for the PFAS after taking into account a 2 g sample weight and a final extract volume of 10 mL, 50 % water/50 % MeOH with 0.1 % acetic acid. The final extract volume is assumed to be 10 mL because 10 mL of 50 % water/50 % MeOH with 0.1 % acetic acid was added to each soil sample and only the liquid layer after extraction is filtered, leaving the solid and any residual solvent behind. Sporadic PFAS hits due to PFAS contamination in consumables/collection tools used during sample collection and preparation is possible while executing this standard and must be monitored. All samples should be taken at a minimum as duplicates in order to compare the precision between the two prepared samples to help ensure the concentration/positive result is reliable. ; Note 1: This standard only includes the determination of the analytes listed in Table 1 and is only applicable to soil and biosolid matrices; any added compost or soil additives may contain PFAS that may be bound and not able to be determined by this method. Analysis of packaging materials and polymeric PFAS moieties are not amenable to this standard. ; Note 2: Injection volume variations and sensitivity of the instrument used will change the reporting limit and ranges. ; 1.2.1 Recognizing continual advancements in the sensitivity of instrumentation, advancements in column chromatography, and other processes not recognized here, the reporting limit may be lowered assuming the minimum performance requirements of this test method at the lower concentrations are met. ; 1.2.2 Depending on data usage, you may modify this test method but limit to modifications that improve performance while still meeting or exceeding the method quality acceptance criteria. Modifications to the solvents, ratio of solvent to sample, or shortening the chromatographic run simply to save time are not allowed. Use Practice E2935 or similar statistical tests to confirm that modifications produce equivalent results on non-interfering samples. In addition, use Guide E2857 or equivalent statistics to revalidate the modified test. ; 1.2.3 Analyte detections under the reporting limit are estimated concentrations. If results are to be reported below the RL using this standard and following the method detection limit procedure in 40 CFR Part 136 Appen...

• Status: Published
• Publication Date: 31-Oct-2023
• Technical Committee: D34 - Waste Management
• Drafting Committee: D34.01.06 - Analytical Methods

• Refers: ASTM E694-18(2024) - Standard Specification for Laboratory Glass Volumetric Apparatus
• Effective Date: 01-Feb-2024
• Refers: ASTM D1129-13(2020)e2 - Standard Terminology Relating to Water
• Effective Date: 01-May-2020
• Refers: ASTM D1129-13(2020)e1 - Standard Terminology Relating to Water
• Effective Date: 01-May-2020
• Refers: ASTM E694-18 - Standard Specification for Laboratory Glass Volumetric Apparatus
• Effective Date: 01-Jan-2018
• Refers: ASTM D3856-11(2015) - Standard Guide for Management Systems in Laboratories Engaged in Analysis of Water (Withdrawn 2024)
• Effective Date: 15-Dec-2015

Overview

ASTM D8535-23 is the recognized international standard for the determination of Per- and Polyfluoroalkyl Substances (PFAS) in soil and biosolid matrices. Developed by ASTM International, this robust method utilizes solvent extraction, filtration, and quantitative analysis through Liquid Chromatography Tandem Mass Spectrometry (LC/MS/MS). Given the persistent, bioaccumulative, and ubiquitous nature of PFAS in the environment, accurate and rapid detection at trace levels is vital for environmental monitoring, regulatory compliance, and scientific research.

PFAS are a class of synthetic chemicals found in a variety of industrial and consumer products, including firefighting foams, coatings, textiles, and cleaning agents. Their toxicity and environmental persistence have led to increased scrutiny and regulatory concern worldwide. ASTM D8535-23 provides laboratories and environmental professionals with a validated procedure to detect a comprehensive range of PFAS compounds in complex solid matrices.

Key Topics

• Detection of PFAS in Soils and Biosolids: The method targets both perfluoroalkyl and polyfluoroalkyl substances across various sample types.
• Solvent Extraction & Filtration: Samples undergo extraction with a water-methanol mixture, followed by filtration to isolate PFAS from solids.
• Quantitation by LC/MS/MS: Utilizes advanced tandem mass spectrometry, specifically selected reaction monitoring (SRM) or multiple reaction monitoring (MRM), to ensure sensitivity and specificity for PFAS detection.
• Precision & Validation: The method has been validated using ASTM reference soils (CH-1, ML-1, CL-1, SP-1) and biosolids from multiple US states, ensuring broad applicability and reliability.
• Reporting Limits & Quality Control: Recommends duplicate sampling to monitor precision; includes specific guidance for reporting limits, estimated concentrations below RL, and contamination control in labware and consumables.
• Modification Allowance: Flexibility to enhance method performance under conditions that meet or exceed quality criteria, with requirements for statistical validation of any changes.

Applications

ASTM D8535-23 is essential for:

• Environmental Site Assessment: Identifying and quantifying PFAS contamination in soils at manufacturing sites, landfills, military installations, and agricultural settings.
• Regulatory Compliance: Supporting efforts to meet local, national, or international regulations regarding PFAS limits in soils and biosolids.
• Wastewater and Sludge Monitoring: Providing reliable data for biosolid application programs and sludge treatment facilities.
• Remediation Projects: Informing cleanup strategies by providing accurate PFAS profiles and concentration measurements.
• Research and Development: Facilitating studies on PFAS fate, transport, and transformation in terrestrial environments.
• Public Health and Risk Assessment: Supplying critical data used in evaluating human exposure potential and ecological risks associated with PFAS in the environment.

Related Standards

Several related ASTM and regulatory standards support or complement ASTM D8535-23, including:

• ASTM D1129 – Terminology Relating to Water
• ASTM D1193 – Specification for Reagent Water
• ASTM D2777 – Practice for Determination of Precision and Bias of Applicable Test Methods
• ASTM D8272 – Guide for Developing and Optimizing Analytical Methods
• ASTM E2857 – Guide for Validating Analytical Methods
• ASTM E2935 – Practice for Evaluating Equivalence of Two Testing Processes
• EPA SW-846 – Test Methods for Evaluating Solid Waste, Physical/Chemical Methods
• 40 CFR Part 136, Appendix B – Regulatory method detection limits

Practical Value

This standard delivers a proven methodology for the sensitive, accurate, and reproducible determination of PFAS in challenging matrices. Laboratories implementing ASTM D8535-23 benefit from reduced false positives, clear guidance on contamination control, comprehensive compound lists, and compatibility with evolving regulatory frameworks. Its adoption facilitates consistency in PFAS data reporting, essential for environmental stewardship and protection of public health.

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: D8535 − 23
Standard Test Method for
Determination of Per- and Polyfluoroalkyl Substances
(PFAS) in Soil/Biosolid Matrices by Solvent Extraction,
Filtering, and Followed by Liquid Chromatography Tandem
Mass Spectrometry (LC/MS/MS)
This standard is issued under the fixed designation D8535; 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.
and polymeric PFAS moieties are not amenable to this standard.
1. Scope
NOTE 2—Injection volume variations and sensitivity of the instrument
1.1 This test method covers the determination of per- and
used will change the reporting limit and ranges.
polyfluoroalkyl substances (PFAS) in soil/biosolid matrices by
solvent extraction, filtering, separation using liquid chromatog- 1.2.1 Recognizing continual advancements in the sensitivity
raphy (LC), and detection with tandem mass spectrometry of instrumentation, advancements in column chromatography,
(MS/MS). These analytes are extracted from soil/biosolids
and other processes not recognized here, the reporting limit
with basic water and methanol then qualitatively and quanti-
may be lowered assuming the minimum performance require-
tatively determined by this test method. Quantitation is by
ments of this test method at the lower concentrations are met.
selected reaction monitoring (SRM), sometimes referred to as
1.2.2 Depending on data usage, you may modify this test
multiple reaction monitoring (MRM).
method but limit to modifications that improve performance
1.2 The reporting limit (RL) and reporting range (see Note
while still meeting or exceeding the method quality acceptance
2) for the target analytes are listed in Table 1. The reporting
criteria. Modifications to the solvents, ratio of solvent to
limit is calculated from the concentration of the Level 1
sample, or shortening the chromatographic run simply to save
calibration standard as shown in Table 5 for the PFAS after
time are not allowed. Use Practice E2935 or similar statistical
taking into account a 2 g sample weight and a final extract
tests to confirm that modifications produce equivalent results
volume of 10 mL, 50 % water/50 % MeOH with 0.1 % acetic
on non-interfering samples. In addition, use Guide E2857 or
acid. The final extract volume is assumed to be 10 mL because
equivalent statistics to revalidate the modified test.
10 mL of 50 % water/50 % MeOH with 0.1 % acetic acid was
1.2.3 Analyte detections under the reporting limit are esti-
added to each soil sample and only the liquid layer after
mated concentrations. If results are to be reported below the
extraction is filtered, leaving the solid and any residual solvent
RL using this standard and following the method detection
behind. Sporadic PFAS hits due to PFAS contamination in
limit procedure in 40 CFR Part 136 Appendix B, data shall be
consumables/collection tools used during sample collection
qualified estimated and extra caution must be taken to evaluate
and preparation is possible while executing this standard and
and identify false positives.
must be monitored. All samples should be taken at a minimum
as duplicates in order to compare the precision between the two
1.3 The values stated in SI units are to be regarded as
prepared samples to help ensure the concentration/positive
standard. No other units of measurement are included in this
result is reliable.
standard.
NOTE 1—This standard only includes the determination of the analytes
1.4 This standard does not purport to address all of the
listed in Table 1 and is only applicable to soil and biosolid matrices; any
safety concerns, if any, associated with its use. It is the
added compost or soil additives may contain PFAS that may be bound and
not able to be determined by this method. Analysis of packaging materials
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
This test method is under the jurisdiction of ASTM Committee D34 on Waste
Management and is the direct responsibility of Subcommittee D34.01.06 on
1.5 This international standard was developed in accor-
Analytical Methods.
dance with internationally recognized principles on standard-
Current edition approved Nov. 1, 2023. Published November 2023. DOI:
10.1520/D8535-23. ization established in the Decision on Principles for the
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8535 − 23
Development of International Standards, Guides and Recom- mass spectrometry in space) or in trap instruments (tandem
mendations issued by the World Trade Organization Technical mass spectrometry in time).
Barriers to Trade (TBT) Committee.
3.2.4 multiple reaction monitoring (MRM), n—application
of selected reaction monitoring to multiple product ions from
2. Referenced Documents
one or more precursor ions.
2.1 ASTM Standards:
3.2.5 precursor ion, n—ion that reacts to form product ions
D1129 Terminology Relating to Water
or undergoes specified neutral losses.
D1193 Specification for Reagent Water
3.2.6 product ion, n—ion formed as the product of a reaction
D2777 Practice for Determination of Precision and Bias of
involving a precursor ion.
Applicable Test Methods of Committee D19 on Water
3.2.7 single (or selected) reaction monitoring (SRM),
D3856 Guide for Management Systems in Laboratories
n—data acquired from one or more specific product ions
Engaged in Analysis of Water
corresponding to m/z selected precursor ions recorded via two
D5847 Practice for Writing Quality Control Specifications
or more stages of mass spectrometry.
for Standard Test Methods for Water Analysis
D8272 Guide for Development and Optimization of D19 3.2.8 tandem mass spectrometer, n—mass spectrometer de-
Chemical Analysis Methods Intended for EPA Compli-
signed for mass spectrometry/mass spectrometry.
ance Reporting
3.2.9 triple quadrupole mass spectrometer (triple quad or
E694 Specification for Laboratory Glass Volumetric Appa-
QQQ), n—tandem mass spectrometer comprising two trans-
ratus
mission quadrupole mass spectrometers in series, with a
E2554 Practice for Estimating and Monitoring the Uncer-
(non-selecting) RF-only quadrupole (or other multipole) be-
tainty of Test Results of a Test Method Using Control
tween them to act as a collision cell.
Chart Techniques
E2857 Guide for Validating Analytical Methods
4. Summary of Test Method
E2935 Practice for Evaluating Equivalence of Two Testing
4.1 The operating conditions presented in this test method
Processes
have been validated for use in the determination of PFASs in
2.2 Other Standards:
solid samples. Alternative instrument operating conditions may
Code of Federal Regulations 40 Part 136, Appendix B Defi-
be used provided data quality objectives are met. Follow the
nition and Procedure for the Determination of the Method
manufacturer’s instructions. The preparation process as sum-
Detection Limit
marized in 4.2 and described in Section 14 may be automated,
EPA SW-846 Test Methods for Evaluating Solid Waste,
but cannot be modified.
Physical/Chemical Methods
4.2 For PFAS analysis, samples are shipped to the lab on ice
and analyzed within 28 days of collection. A sample (2 g) is
3. Terminology
transferred to a polypropylene tube, spiked with surrogates (all
3.1 Definitions:
samples) and target PFAS compounds (laboratory control and
3.1.1 For definitions of terms used in this standard, refer to
matrix spike samples). The analytes are tumbled for an hour
Terminology D1129.
with 10 mL of methanol:water (50:50) under basic condition
3.2 Definitions of Terms Specific to This Standard:
(pH ~9 to 10 adjusted with ~20 μL ammonium hydroxide). The
3.2.1 collision cell, n—chamber in the ion path between m/z
samples are centrifuged and the extract, leaving the solid
separation elements, or between ion source and the first
behind, is filtered through a polypropylene filter unit. Acetic
analyzer, in tandem mass spectrometry in space configurations.
acid (~50 μL) is added to all the filtered samples to adjust the
pH ~3 to 4 and then analyzed by LC/MS/MS.
3.2.2 continuing calibration verification (CCV), n—a mid-
range calibration standard which checks the continued validity
4.3 Most analytes are identified by comparing the SRM
of the initial calibration of the instrument.
transition and its confirmatory SRM transition correlated to the
3.2.3 mass spectrometry/mass spectrometry (MS/MS), known standard SRM transition (Table 3) and quantitated
utilizing an external calibration. The retention times and ion
n—acquisition and study of the spectra of the product ions or
precursor ions of m/z selected ions, or of precursor ions of a ratios are shown in Table 4 for each native analyte and isotope.
The surrogates and some analytes only have one SRM transi-
selected neutral mass loss.
3.2.3.1 Discussion—MS/MS can be accomplished using tion due to a less sensitive or non-existent secondary SRM
transition. As an additional quality control measure, isotopi-
instruments incorporating more than one analyzer (tandem
cally labeled surrogate (Table 1, 13.3) recoveries are moni-
tored. With external standard calibrations, there is no correc-
2 tion to the data based upon surrogate recoveries. Alternatively,
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
extract an isotopically labeled analog of each analyte (isotope
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
dilution), if available, and correct for recovery. Only exact
the ASTM website.
isotopes of the native analytes may be used for isotope dilution
Available from National Technical Information Service (NTIS), U.S. Depart-
correction. If a structurally different isotope is used to correct
ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http://
www.epa.gov/epawaste/hazard/testmethods/index.htm a native analyte, this is called surrogate correction and either
D8535 − 23
TABLE 1 Analyte List with Method Detection Limit and Reporting Range
RL Range
Analyte Name Acronym CAS Number
(ng/kg) (ng/kg)
Perfluorotetradecanoic acid PFTreA 376-06-7 25 25–1000
Perfluorotridecanoic acid PFTriA 72629-94-8 25 25–1000
Perfluorododecanoic acid PFDoA 307-55-1 25 25–1000
Perfluoroundecanoic acid PFUnA 2058-94-8 25 25–1000
Perfluorodecanoic acid PFDA 335-76-2 25 25–1000
Perfluorononanoic acid PFNA 375-95-1 25 25–1000
Perfluorooctanoic acid PFOA 335-67-1 25 25–1000
Perfluoroheptanoic acid PFHpA 375-85-9 25 25–1000
Perfluorohexanoic acid PFHxA 307-24-4 25 25–1000
Perfluoropentanoic acid PFPeA 2706-90-3 125 125–5000
Perfluorobutanoic acid PFBA 375-22-4 125 125–5000
Perfluorodecanesulfonic acid PFDS 335-77-3 25 25–1000
Perfluorononanesulfonic acid PFNS 68259-12-1 25 25–1000
Perfluorooctanesulfonic acid PFOS 1763-23-1 25 25–1000
Perfluoroheptanesulfonic acid PFHpS 375-92-8 25 25–1000
Perfluorohexanesulfonic acid PFHxS 355-46-4 25 25–1000
Perfluoropentanesulfonic acid PFPeS 2706-91-4 25 25–1000
Perfluorobutanesulfonic acid PFBS 375-73-5 25 25–1000
Perfluorooctanesulfonamide PFOSA 754-91-6 25 25–1000
8:2 Fluorotelomer sulfonic acid 8:2 FTS 39108-34-4 25 25–1000
6:2 Fluorotelomer sulfonic acid 6:2 FTS 27619-97-2 25 25–1000
4:2 Fluorotelomer sulfonic acid 4:2 FTS 757124-72-4 25 25–1000
N-Ethylperfluorooctanesulfonamidoacetic acid NEtFOSAA 2991-50-6 25 25–1000
N-Methylperfluorooctanesulfonamidoacetic acid NMeFOSAA 2355-31-9 25 25–1000
Perfluorododecanesulfonic acid PFDoS 79780-39-5 25 25–1000
N-Methylperfluorooctanesulfonamide NMeFOSA 31506-32-8 25 25–1000
N-Ethylperfluorooctanesulfonamide NEtFOSA 4151-50-2 25 25–1000
N-Methylperfluorooctanesulfonamidoethanol NMeFOSE 24448-09-7 25 25–1000
N-Ethylperfluorooctanesulfonamidoethanol NEtFOSE 1691-99-2 25 25–1000
Hexafluoropropylene oxide dimer acid HFPO-DA 13252-13-6 25 25–1000
4,8-dioxa-3H-perfluorononanoic acid ADONA 919005-14-4 25 25–1000
9-chlorohexadecafluoro-3-oxanonane-1-sulfonic acid 9Cl-PF3ONS 756426-58-1 25 25–1000
11-chloroeicosafluoro-3-oxaundecane-1-sulfonic acid 11Cl-PF3OUdS 763051-92-9 25 25–1000
Pentafluorpropanoic acid PFPrA 422-64-0 125 125–5000
Perfluoro-3,6-dioxaheptanoic acid NFDHA 151772-58-6 25 25–1000
Perfluoro(2-ethoxyethane) sulfonic acid PFEESA 113507-82-7 25 25–1000
Perfluoro-3-methoxypropanoic acid PFMPA 377-73-1 25 25–1000
Perfluoro-4-methoxybutanoic acid PFMBA 863090-89-5 25 25–1000
2H,2H,3H,3H-Perfluorohexanoic Acid 3:3 FTCA 356-02-05 25 25–1000
2H,2H,3H,3H-Perfluorooctanoic Acid 5:3 FTCA 914637-49-3 25 25–1000
2H,2H,3H,3H-Perfluorodecanoic acid 7:3 FTCA 812-70-4 25 25–1000
2H-perfluoro-2-octenoic acid FHUEA 70887-88-6 25 25–1000
2H-perfluoro-2-decenoic acid FOUEA 70887-84-2 25 25–1000
A
Lithium Bis(trifluoromethane)sulfonimide HQ-115 90076-65-6 25 25–1000
Surrogates
Perfluoro-n-[13C4]butanoic acid MPFBA NA NA 25–1000
Perfluor0-n-[13C5]pentanoic acid M5PFPeA NA NA 25–1000
Perfluoro-n-[1,2,3,4,6-13C5]hexanoic acid M5PFHxA NA NA 25–1000
Perfluoro-n-[1,2,3,4-13C4]heptanoic acid M4PFHpA NA NA 25–1000
Perfluoro-n-[13C8]octanoic acid M8PFOA NA NA 25–1000
Perfluoro-n-[13C9]nonanoic acid M9PFNA NA NA 25–1000
Perfluoro-n-[1,2,3,4,5,6-13C6]decanoic acid M6PFDA NA NA 25–1000
Perfluoro-n-[1,2,3,4,5,6,7-13C7]undecanoic acid M7PFUnA NA NA 25–1000
Perfluoro-n-[1,2-13C2]dodecanoic acid MPFDoA NA NA 25–1000
Perfluoro-n-[1,2-13C2]tetradecanoic acid M2PFTreA NA NA 25–1000
Perfluoro-1-[13C8]octanesulfonamide M8FOSA NA NA 25–1000
N-methyl-d3-perfluoro-1-octanesulfonamidoacetic acid D3-N-MeFOSAA NA NA 25–1000
N-ethyl-d5-perfluoro-1-octanesulfonamidoacetic acid D5-N-EtFOSAA NA NA 25–1000
N-methyl-d3-perfluoro-1-octanesulfanamide d-N-MeFOSA NA NA 25–1000
N-ethyl-d5-perfluoro-1-octanesulfanamide d-N-EtFOSA NA NA 25–1000
2-(N-methyl-d3-perfluoro-1-octanesulfonamido)ethan-d4-ol d7-N-MeFOSE NA NA 25–1000
2-(N-ethyl-d5-perfluoro-1-octanesulfonamido)ethan-d4-ol D9-N-EtFOSE NA NA 25–1000
2,3,3,3-Tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy-13C3-propanoic acid MHFPO-DA NA NA 25–1000
1H,1H,2H,2H-perfluoro-1-[1,2-13C2]hexane sulfonate M4:2FTS NA NA 25–1000
1H,1H,2H,2H-perfluoro-1-[1,2-13C2]-octane sulfonate M6:2FTS NA NA 25–1000
1H,1H,2H,2H-perfluoro-1-[1,2-13C2]-decane sulfonate M8:2FTS NA NA 25–1000
Perfluoro-1-[13C8]octanesulfonate M8PFOS NA NA 25–1000
Perfluoro-1-[2,3,4-13C3]butanesulfonate MPFBS NA NA 25–1000
Perfluoro-1-[1,2,3-13C3]hexanesulfonate M3PFHxS NA NA 25–1000
A
The lithium is just the counter ion, report only Bis(trifluoromethane)sulfonimide.
D8535 − 23
must be clearly stated as performed in the accompanying data 6.4 Contaminants have been found in reagents, glassware,
report or not allowed. For isotope dilution, the analog and the tubing, glass disposable pipettes, filters, degassers, and other
native compound concentrations (areas) should be within 30 % apparatus and consumables that release PFAS. All these
of each other to obtain more accurate results. The final report materials and supplies must be routinely demonstrated to be
issued lists the concentration of PFAS, if detected, or as a free from interferences by analyzing laboratory reagent blanks
non-detect at the RL, if not detected, in ng/kg and the surrogate under the same conditions as the samples. If found, measures
recoveries. should be taken to remove the contamination or data should be
qualified; background subtraction of blank contamination is not
NOTE 3—For greater accuracy in the isotope dilution method, add the
allowed. It has become difficult to ensure consumables are
isotopes at the time of sampling or allow the sample and isotope to
PFAS free at the lower concentrations (approximately at less
equilibrate for at least 48 h prior to addition of methanol.
than 30 ng/L) for the entire lot by testing only a very small
5. Significance and Use
subsample. At a minimum, duplicates/triplicates should be
taken of each sample to evaluate precision between the set.
5.1 PFAS are widely used in various industrial and com-
mercial products; they are persistent, bio-accumulative, and
6.5 The LC system used should consist, as much as
ubiquitous in the environment. PFAS have been reported to
practical, of sample solution or eluent-contacting components
exhibit developmental toxicity, hepatotoxicity,
free of PFAS of interest.
immunotoxicity, and hormone disturbance. PFAS have been
6.6 Polyethylene LC vial caps or any other target analyte
detected in soils, sludges, surface, and drinking waters. This is
free vial caps should be used.
a quick, easy, and robust method to quantitatively determine
these compounds at trace levels in soil/biosolid matrices. 6.7 Polyethylene disposable pipettes or target analyte free
pipettes should be used. All disposable pipettes should be
5.2 This test method has been validated using four ASTM
checked for release of target analytes of interest.
reference soils (CH-1, ML-1, CL-1, and SP-1). ASTM refer-
ence soil CH-1 is Fat Clay (CH)—Vicksburg Buckshot Clay; 6.8 Degassers are important to continuous LC operation and
ASTM reference soil ML-1 is silt (ML)—Vicksburg silt; most commonly are made of fluorinated polymers. To enable
ASTM reference soil CL-1 is lean clay (CL)—Annapolis clay; use, an isolator column should be placed after the degasser and
and ASTM reference soil SP-1 is sand (SP)—Frederick sand prior to the sample injection valve to separate the PFAS in the
and four biosolids (Missouri, California, Idaho, and Georgia). sample from the PFAS in the LC system.
Refer to the Precision and Bias (Section 17).
6.9 Electro Spray Ionization (ESI)—ESI should be heated
and optimized for recovery of components analyzed by this test
6. Interferences
method. Using the suggested mobile phase, gradient, and
6.1 All glassware is washed in hot water (typically >45 °C)
adequate column separation minimizes or eliminates quench-
with detergent and rinsed in hot water followed by distilled
ing and enhancing of signal. This method was validated using
water. The glassware is then dried and heated in an oven
ESI, however, other modes of ionization may be used provided
(typically at 105 °C) for 15 to 30 min. All glassware is
the detection limits and quality control acceptance criteria of
subsequently rinsed with methanol or acetonitrile.
this method are met.
6.2 All reagents and solvents should be pesticide residue
purity or higher to minimize interference. Avoid the use of 7. Apparatus
PFAS-containing caps.
7.1 LC/MS/MS System:
6.3 Matrix interferences may be caused by contaminants in 7.1.1 Liquid Chromatography System—A complete LC sys-
the sample. The extent of matrix interferences varies consid- tem is required to analyze samples. This includes a sample
erably depending on variations of the sample matrices. Sepa- injection system, a solvent pumping system capable of mixing
ration of individual components by the LC is vital in minimi- solvents, a sample compartment capable of maintaining re-
zation of interferences. Shortening of run times simply to speed quired temperature, and a temperature-controlled column com-
analysis should be avoided, unless interferences are known to partment. This test method was developed using a ternary
be absent. (Table 2) pumping system. A binary LC system may be used by
TABLE 2 Gradient Conditions for a Ternary Pumping System
95 % Water:
Time Flow 95 % Water: 5 % Acetonitrile,
Acetonitrile %
(min) (mL/min) 5 % Acetonitrile % 400 mM Ammonium
Acetate %
0 0.3 95 0 5
1 0.3 75 20 5
6 0.3 50 45 5
13 0.3 15 80 5
14 0.4 0 95 5
17 0.4 0 95 5
18 0.4 95 0 5
21 0.4 95 0 5
D8535 − 23
adapting the ternary gradient to a binary system. An LC system 8.8 pH paper (pH range 1 to 14).
that can perform at the flow rates, pressures, controlled
8.9 Class A Volumetric Glassware.
temperatures, sample volumes, and requirements of the stan-
8.10 Pipette Tips—Polypropylene pipette tips free of release
dard shall be used.
agents or low retention coating of various sizes.
7.1.2 Analytical Column—UHPLC CSH Phenyl-Hexyl, 2.1
× 100 mm and 1.7 μm particle size column, or any column that 8.11 Polyethylene Disposable Pipettes.
achieves adequate resolution may be used. The retention times
8.12 Acetonitrile (CAS No. 75-05-8).
and order of elution may change depending on the column used
8.13 Methanol (CAS No. 67-56-1).
and needs to be monitored.
7.1.3 Isolator Column—A reverse-phase C18 AX column or
8.14 Ammonium acetate (CAS No. 631-61-8).
any column that achieves adequate separation of the target
8.15 Acetic acid (CAS No. 64-19-7).
analytes in the LC system and solvents from the target analytes
8.16 2-Propanol—(isopropyl alcohol, CAS No. 67-63-0).
in the analytical sample. Place the column between the solvent
mixing chamber and the injector sample loop.
8.17 Ammonium hydroxide (CAS No. 1336-21-6).
7.2 Tandem Mass Spectrometer System—An MS/MS system
8.18 PFAS Standards —Refer to Table 1 for the complete
capable of multiple reaction monitoring (MRM) analysis or
analyte list and CAS numbers. These may be purchased from
any system that is capable of performing at the requirements in
a commercial supplier individually or some as a mixture.
this test method.
9. Hazards
7.3 Filtration Device:
9.1 Precaution—The toxicity or carcinogenicity of chemi-
7.3.1 Hypodermic Syringe—A luer-lock tip glass syringe
cals used in this test method has not been precisely defined;
capable of holding a syringe-driven filter unit.
each chemical should be treated as a potential health hazard,
7.3.1.1 A 10 mL lock tip glass syringe size is recommended
and exposure to these chemicals should be minimized. Each
in this test method.
laboratory is responsible for maintaining awareness of OSHA
7.3.2 Filter Unit—Polypropylene syringe-driven filter units
regulations regarding safe handling of chemicals used in this
(0.2 μm) or equivalent, demonstrated contaminant free below
test method.
1/2 MRL.
9.2 Warning—The compound analytes in this test method
8. Reagents and Materials
have been classified as known or suspected human or mam-
8.1 Purity of Reagents—High performance liquid chroma-
malian carcinogens. Pure standards and stock solutions should
tography (HPLC) pesticide residue analysis and spectropho-
be handled in a hood or glovebox.
tometry grade chemicals shall be used in all tests. Unless
indicated otherwise, it is intended that all reagents shall 10. Sampling
conform to the Committee on Analytical Reagents of the
10.1 Sampling and Preservation—Avoid sample containers
American Chemical Society. Other reagent grades may be
and contact with surfaces of fluorinated polymers or PFAS-
used provided they are first determined to be of sufficiently
contaminated items. Collect field blanks that are exposed to the
high purity to permit their use without affecting the accuracy of
same field conditions as samples and analyze according to this
the measurements.
test method to assess the potential for field contamination. This
8.2 Purity of Water—Unless otherwise indicated, references test method is based on a 2 g sample size per analysis,
to water shall be understood to mean reagent water conforming generally 15 to 25 g in a polypropylene tube per sample
to Type I of Specification D1193. It shall be demonstrated that location is collected. Additional samples are collected for
this water does not contain contaminants at concentrations duplicates/triplicates, matrix spikes, and field blanks in poly-
sufficient to interfere with the analysis. propylene containers. Conventional sampling practices should
be followed with the caution that PFAS-containing products
8.3 Gases—Ultrapure nitrogen and argon.
may be present in sampling equipment. All sampling equip-
8.4 Vials—Greater than 1.0 mL amber glass or polypropyl-
ment and supplies shall be PFAS free to prevent contamination
ene autosampler vials.
of the samples. EPA Publication SW-846, Guide D3856, and
8.5 Polyethylene Autosampler Vial Caps, or equivalent. Specification E694 may be used as guides. Ship samples on ice
with a trip blank. The temperature of the samples upon receipt
8.6 Syringe—10 or 25 mL filter-adaptable glass syringe with
at the laboratory should be between freezing and 6 °C. If the
luer lock.
receiving temperature is greater than 6 °C, the sample tempera-
8.7 Polypropylene Tubes—15 and 50 mL conical with cali-
ture is noted in the case narrative accompanying the data.
bration lines.
Samples should be stored refrigerated between 0 °C and 6 °C
from the time of collection until analysis. Analyze the sample
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory PFAS standards may be difficult to find; some sources of PFAS standards that
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia have been found suitable for use were from Aldrich Chemical Company, Wellington
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, Laboratories Inc., Accustandard, and Wako Laboratory. Standards from other
MD. vendors may be used.
D8535 − 23
within 28 days of collection. Holding time may vary depending the analysis time simply to speed the analysis. Refer to Fig. 1
on the matrix and individual laboratories should determine the as an example chromatogram of 24 surrogates showing reso-
holding time in their matrix. lution with limited coelution.
11.2 LC Sample Manager Conditions:
11. Preparation of LC/MS/MS
11.2.1 Needle Wash Solvent—60 % acetonitrile/40 %
11.1 LC Chromatograph Operating Conditions:
2-propanol. Eight second wash time before and after injection.
11.1.1 Injections of all standards and samples are made at a
Instrument manufacturer’s specifications should be followed in
10 to 30 μL volume. Other injection volumes may be used to
order to eliminate sample carryover.
optimize conditions. Calibration standards, reagent blanks,
11.2.2 Temperatures—Column, 35 °C; Sample
second source, and samples shall be in a 50:50 methanol:water
compartment, 15 °C.
solution containing 0.1 % acetic acid. In the case of extreme
11.2.3 Seal Wash—Solvent: 50 % water ⁄50 % methanol;
concentration differences among samples, it is wise to analyze
Time: 5 min.
a blank after a concentrated sample and before a dilute sample
11.3 Mass Spectrometer Parameters:
to eliminate carryover of analytes from sample injection to
sample injection. If a flow-through needle design is used, 11.3.1 To acquire the maximum number of data points per
carryover should not be a problem. The gradient conditions for SRM channel while maintaining adequate sensitivity, optimize
LC are shown in Table 2. To ensure chromatographic separa- the tune parameters according to instrument manufacturer
tion between the targeted analytes and any unknown non- instructions. Each peak requires a minimum of ten scans per
targeted potentially interfering compounds, avoid shortening
peak for adequate quantitation. This test method containing
FIG. 1 Example Chromatogram of 24 Surrogates, at the Level 1 Calibration Concentration, Overlayed Showing Resolution with Limited
Coelution
D8535 − 23
surrogates, which are select isotopically labeled PFAS, and the caps immediately after the injection may alleviate this
targeted PFAS may be split into multiple MRM acquisition problem, however, this should be verified in each laboratory.
functions to optimize sensitivity. Retention times and primary Calibration standards do not need to be filtered.
and confirmatory transitions are shown in Table 3. Retention
12.2.3 Incorporate a second source standard, if available.
times will vary between columns and gradient used. Each
The second source standard should be analyzed near the
manufacturer may have different terminology to represent
midpoint of the calibration range to verify that the standards
various mass spectrometer settings, and different set values
used are within 630 % of the expected concentration.
depending on the manufacturer and instrument model. Please
Currently, a second source from a different vendor may not be
refer to the manufacturer’s instructions in optimizing detector
readily available for all target analytes. In this case, a second
settings, including collision energies and cone voltages. Data
lot number from the same vendor may be used.
for this method was collected using electrospray ionization
12.2.4 Inject each standard and obtain its chromatogram.
(ESI) operated in negative mode. In recognition of the ad-
The instrument software collects the primary and confirmatory
vancement of LC/MS/MS instrumentation, other MS operating
SRM transitions of each analyte at the specified retention
conditions including ionization techniques may be used pro-
times. Calibration software conducts the quantitation of the
vided the quality control criteria of the method is met.
target analytes and surrogates using the primary SRM transi-
tion. The ratios of the primary/confirmatory MRM transition
12. Calibration and Standardization
area counts will vary depending on the individual tuning
12.1 The mass spectrometer is calibrated in accordance with
conditions. Refer to Table 4 for retention times and ion ratios.
manufacturer’s specifications prior to analysis. Prepare all
For confirmation of analyte identity, the primary/confirmatory
calibration solutions using Class A volumetric glassware
ratio shall be within 30 % of the individual ratios established
(Specification E694).
during the initial calibration. The average ion ratio is calculated
12.2 Calibration and Standardization—Analyze up to nine for each batch from the initial calibration levels.
calibration standards containing the PFAS and surrogates prior
12.2.5 Depending on sensitivity and sample-dependent ma-
to analysis as shown in Table 5. The calibration stock standard
trix interference, the confirmatory SRM transition may be used
solution is prepared from the target and surrogate spike
as the primary SRM transition for quantitation during analysis.
solutions. Stock standard Solution A containing the PFAS and
12.2.6 The calibration software manual or the instrument
surrogates is prepared at Calibration Level 9 concentration and
manufacturer should be consulted to ensure correct software
aliquots of that solution are diluted to prepare Calibration
use. The quantitation method is set using the peak areas in ppt
Levels 1 through 8. The following steps will produce standards
(ng/L) units. Concentrations may be calculated using the data
with the concentration values shown in Table 5. The analyst is
system software to generate linear regression or quadratic
responsible for recording initial component weights carefully
calibration curves. Forcing the calibration curve through the
when working with pure materials and correctly carrying the
origin (X = 0, Y = 0) is not recommended.
weights through the dilution calculations. At a minimum, five
12.2.7 Either of two procedures may be used to determine
calibration levels are required when using a linear calibration
calibration function acceptability for linear and nonlinear
and six calibration levels are required when using a quadratic
curves. These include refitting the calibration data back to the
calibration curve. An initial nine points may be used to enable
model. Both % Error and Relative Standard Error (RSE)
dropping the lower calibration points if the instrument cannot
evaluate the difference between the measured and the true
achieve low detection limits on certain PFAS. This will allow
amounts or concentrations used to create the model.
at least a five or six-point calibration curve per analyte to be
12.2.7.1 Calculation of % Error is shown as Eq 1. Percent
obtained.
error between the calculated and expected amounts should be
12.2.1 Calibration stock standard Solution A (Calibration
≤30 % for all standards.
Level 9, Table 5) is prepared from the target and surrogate
'
spike solutions. Transfer 500 μL of the surrogate spike x 2 x
i i
%Error 5 × 100 (1)
(20 μg ⁄L), 500 μL of PFAS Target Spike I, and 500 μL of PFAS
x
i
Target Spike II (refer to Table 7) to a 50 mL volumetric flask
where:
and dilute to 50 mL volume with 50:50 methanol:water
'
x = measured amount of analyte at calibration level i, in
i
containing 0.1 % acetic acid. Ensure that the analytes are
mass or concentration units, and
solubilized in the Level 9 standard.
x = true amount of analyte at calibration level i, in mass or
i
12.2.2 Aliquots of Solution A (Calibration Level 9) are then
concentration units.
diluted with 50:50 methanol:water containing 0.1 % acetic acid
to prepare the desired calibration levels (Table 5) in polypro-
12.2.7.2 Calculation of Relative Standard Error (RSE, ex-
pylene LC vials. For best results, use the calibration standards
pressed as %) is shown in Eq 2. The RSE acceptance limit
within 24 h of preparation. Prepare the end CCV at a mid-level
criterion for the calibration model is the same as the RSD limit.
concentration in a separate LC vial. All calibration standards
n
' 2
x 2 x
should be used only once because the analyte concentration in
i i
RSE 5 100 ׌ ⁄ ~n 2 p! (2)
F G
(
x
the vial may change after the vial cap is pierced. Changing the i51
i
D8535 − 23
TABLE 3 Transitions for Target Analytes and Surrogates
Analyte Name Acronym CAS Number Primary Ion Transition Confirmation Ion Trans.
Perfluorotetradecanoic acid PFTreA 376-06-7 712.9 → 668.9 712.9 → 168.9
Perfluorotridecanoic acid PFTriA 72629-94-8 662.9 → 618.9 662.9 → 168.9
Perfluorododecanoic acid PFDoA 307-55-1 612.9 → 568.9 612.9 → 168.9
Perfluoroundecanoic acid PFUnA 2058-94-8 562.9 → 519 562.9 → 269
Perfluorodecanoic acid PFDA 335-76-2 512.9 → 469 512.9 → 218.9
Perfluorononanoic acid PFNA 375-95-1 462.9 → 419 462.9 → 218.9
Perfluorooctanoic acid PFOA 335-67-1 412.9 → 369 412.9 → 168.9
Perfluoroheptanoic acid PFHpA 375-85-9 362.9 → 318.9 362.9 → 168.9
Perfluorohexanoic acid PFHxA 307-24-4 312.9 → 269 312.9 → 118.9
Perfluoropentanoic acid PFPeA 2706-90-3 262.9 → 218.9 NA
Perfluorobutanoic acid PFBA 375-22-4 212.9 →168.9 NA
Perfluorodecanesulfonic acid PFDS 335-77-3 598.9 → 79.9 598.9 → 98.9
Perfluorononanesulfonic acid PFNS 68259-12-1 548.9 → 79.9 548.9 → 98.9
Perfluorooctanesulfonic acid PFOS 1763-23-1 498.9 → 79.9 498.9 → 98.9
Perfluoroheptanesulfonic acid PFHpS 375-92-8 448.9 → 79.9 448.9 → 98.9
Perfluorohexanesulfonic acid PFHxS 355-46-4 398.9 → 79.9 398.9 → 98.9
Perfluoropentanesulfonic acid PFPeS 2706-91-4 348.9 → 79.9 348.9 → 98.9
Perfluorobutanesulfonic acid PFBS 375-73-5 298.9 → 79.9 298.9 → 98.9
Perfluorooctanesulfonamide PFOSA 754-91-6 497.9 → 77.9 NA
8:2 Fluorotelomer sulfonic acid 8:2 FTS 39108-34-4 526.9 → 506.9 526.9 → 80.9
6:2 Fluorotelomer sulfonic acid 6:2 FTS 27619-97-2 427 → 407 427 → 80.9
4:2 Fluorotelomer sulfonic acid 4:2 FTS 757124-72-4 326.9 → 306.9 326.9 → 80.9
N-Ethylperfluorooctanesulfonamidoacetic acid NEtFOSAA 2991-50-6 584 → 419 584 → 482.9
N-Methylperfluorooctanesulfonamidoacetic acid NMeFOSAA 2355-31-9 569.9 → 419 569.9 → 482.9
Perfluorododecanesulfonic acid PFDoS 79780-39-5 698.9 → 79.9 698.9 → 98.9
N-Methylperfluorooctanesulfonamide NMeFOSA 31506-32-8 511.9 → 168.9 511.9 → 218.9
N-Ethylperfluorooctanesulfonamide NEtFOSA 4151-50-2 525.9 → 168.9 525.9 → 218.9
N-Methylperfluorooctanesulfonamidoethanol NMeFOSE 24448-09-7 616 → 58.9 NA
N-Ethylperfluorooctanesulfonamidoethanol NEtFOSE 1691-99-2 630 → 58.9 NA
Hexafluoropropylene oxide dimer acid HFPO-DA 13252-13-6 285 → 168.9 285 → 184.9
4,8-dioxa-3H-perfluorononanoic acid ADONA 919005-14-4 376.9 → 251 376.9 → 84.9
9-chlorohexadecafluoro-3-oxanonane-1-sulfonic acid 9Cl-PF3ONS 756426-58-1 530.9 → 350.9 532.9 → 352.9
11-chloroeicosafluoro-3-oxaundecane-1-sulfonic acid 11Cl-PF3OUdS 763051-92-9 630.8 → 450.9 632.8 → 452.9
Pentafluorpropanoic acid PFPrA 422-64-0 162.9 → 118.9 NA
Perfluoro-3,6-dioxaheptanoic acid NFDHA 151772-58-6 295 → 200.9 295 → 84.9
Perfluoro(2-ethoxyethane)sulfonic acid PFEESA 113507-82-7 314.9 → 134.9 314.9→ 82.9
Perfluoro-3-methoxypropanoic acid PFMPA 377-73-1 228.9 → 84.9 NA
Perfluoro-4-methoxybutanoic acid PFMBA 863090-89-5 278.9 → 84.9 NA
2H,2H,3H,3H-Perfluorohexanoic Acid 3:3 FTCA 356-02-05 241 → 176.9 241→ 116.9
2H,2H,3H,3H-Perfluorooctanoic Acid 5:3 FTCA 914637-49-3 340.9 → 216.9 340.9 →237
2H,2H,3H,3H-Perfluorodecanoic acid 7:3 FTCA 812-70-4 440.9 → 337 440.9 → 316.9
2H-perfluoro-2-octenoic acid FHUEA 70887-88-6 356.9 → 292.9 NA
2H-perfluoro-2-decenoic acid FOUEA 70887-70-4 456.9 → 393 NA
Lithium Bis(trifluoromethane)sulfonimide HQ-115 90076-65-6 279.9 →146.9 279.9 →210.9
Surrogates
Perfluoro-n-[ C ]butanoic acid MPFBA NA 216.9 → 171.9 NA
Perfluoro-n-[ C ]pentanoic acid M5PFPeA NA 267.9 → 222.9 NA
Perfluoro-n-[1,2,3,4,6- C ]hexanoic acid M5PFHxA NA 317.9 → 272.9 NA
Perfluoro-n-[1,2,3,4- C ]heptanoic acid M4PFHpA NA 366.9 → 321.9 NA
Perfluoro-n-[ C ]octanoic acid M8PFOA NA 421 → 376 NA
Perfluoro-n-[ C ]nonanoic acid M9PFNA NA 471.9 → 426.9 NA
Perfluoro-n-[1,2,3,4,5,6- C ]decanoic acid M6PFDA NA 518.9 → 473.9 NA
Perfluoro-n-[1,2,3,4,5,6,7- C ]undecanoic acid M7PFUnA NA 569.9 → 524.9 NA
Perfluoro-n-[1,2- C ]dodecanoic acid MPFDoA NA 614.9 → 569.9 NA
Perfluoro-n-[1,2- C ]tetradecanoic acid M2PFTreA NA 714.9 → 669.9 NA
Perfluoro-1-[ C ]octanesulfonamide M8FOSA NA 505.9 → 77.9 NA
N-methyl-d -perfluoro-1-octanesulfonamidoacetic acid D3-N-MeFOSAA NA 572.9 → 418.9 NA
N-ethyl-d -perfluoro-1-octanesulfonamidoacetic acid D5-N-EtFOSAA NA 589 → 418.9 NA
N-methyl-d -perfluoro-1-octanesulfanamide d-N-MeFOSA NA 514.9 → 168.9 NA
N-ethyl-d -perfluoro-1-octanesulfanamide d-N-EtFOSA NA 531 →168.9 NA
2-(N-ethyl-d -perfluoro-1-octanesulfonamido)ethan-d4-ol d7-N-MeFOSE NA 623 → 58.9 NA
2-(N-methyl-d -perfluoro-1-octanesulfonamido)ethan-d4-ol D9-N-EtFOSE NA 639 → 58.9 NA
2,3,3,3-Tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy- C - MHFPO-DA NA 287 → 168.9 NA
propanoic acid
1H,1H,2H,2H-perfluoro-1-[1,2- C ]hexane sulfonate M4:2FTS NA 328.9 → 308.9 NA
A
328.9 → 80.9
1H,1H,2H,2H-perfluoro-1-[1,2- C ]-octane sulfonate M6:2FTS NA 428.9 → 408.9 NA
A
428.9 → 80.9
1H,1H,2H,2H-perfluoro-1-[1,2- C ]-decane sulfonate M8:2FTS NA 528.9 → 508.9 NA
A
528.9 → 80.9
Perfluoro-1-[ C ]octanesulfonate M8PFOS NA 506.9 → 79.9 NA
Perfluoro-1-[2,3,4- C ]butanesulfonate M3PFBS NA 301.9 → 79.9 NA
Perfluoro-1-[1,2,3- C ]hexanesulfonate M3PFHxS NA 401.9 → 79.9 NA
A
If high concentrations of the native FTS interfere with the isotope of the FTS, this transition should be used. It is not as sensitive, but the interference/high bias is removed.
D8535 − 23
TABLE 4 Retention Times and Ion Ratios for Target Analytes and Surrogates
Primary/Confirmatory Ion
Analyte Name Acronym Retention Time
Ratio
Perfluorotetradecanoic acid PFTreA 10.40 4.7
Perfluorotridecanoic acid PFTriA 9.94 4.2
Perfluorododecanoic acid PFDoA 9.43 5.2
Perfluoroundecanoic acid PFUnA 8.90 5.0
Perfluorodecanoic acid PFDA 8.33 5.4
Perfluorononanoic acid PFNA 7.70 4.5
Perfluorooctanoic acid PFOA 7.03 2.4
Perfluoroheptanoic acid PFHpA 6.28 3.7
Perfluorohexanoic acid PFHxA 5.45 20
Perfluoropentanoic acid PFPeA 4.58 NA
Perfluorobutanoic acid PFBA 3.67 NA
Perfluorodecanesulfonic acid PFDS 9.76 1.0
Perfluorononanesulfonic acid PFNS 9.24 1.0
Perfluorooctanesulfonic acid PFOS 8.64 1.2
Perfluoroheptanesulfonic acid PFHpS 8.00 1.0
Perfluorohexanesulfonic acid PFHxS 7.29 1.1
Perfluoropentanesulfonic acid PFPeS 6.49 1.2
Perfluorobutanesulfonic acid PFBS 5.56 1.5
Perfluorooctanesulfonamide PFOSA 10.08 NA
8:2 Fluorotelomer sulfonic acid 8:2 FTS 8.06 3.1
6:2 Fluorotelomer sulfonic acid 6:2 FTS 6.76 3.1
4:2 Fluorotelomer sulfonic acid 4:2 FTS 5.22 3.3
N-Ethylperfluorooctanesulfonamidoacetic acid NEtFOSAA 8.73 1.8
N-Methylperfluorooctanesulfonamidoacetic acid NMeFOSAA 8.47 1.8
Perfluorododecanesulfonic acid PFDoS 10.74 1.0
N-Methylperfluorooctanesulfonamide NMeFOSA 12.10 1.6
N-Ethylperfluorooctanesulfonamide NEtFOSA 12.60 1.6
N-Methylperfluorooctanesulfonamidoethanol NMeFOSE 11.65 NA
N-Ethylperfluorooctanesulfonamidoethanol NEtFOSE 12.16 NA
Hexafluoropropylene oxide dimer acid HFPO-DA 5.75 2.0
4,8-dioxa-3H-perfluorononanoic acid ADONA 6.61 2.2
9-chlorohexadecafluoro-3-oxanonane-1-sulfonic acid 9Cl-PF3ONS 9.21 3.1
11-chloroeicosafluoro-3-oxaundecane-1-sulfonic acid 11Cl-PF3OUdS 10.29 3.1
Pentafluorpropanoic acid PFPrA 1.79 NA
Nonafluoro-3,6-dioxaheptanoic acid NFDHA 5.33 3.1
Perfluoro(2-ethoxyethane)sulfonic acid PFEESA 5.96 15.5
Perfluoro-3-methoxypropanoic acid PFMPA 4.05 NA
Perfluoro-4-methoxybutanoic acid PFMBA 4.84 NA
2H,2H,3H,3H-Perfluorohexanoic Acid 3:3 FTCA 4.27 3.9
2H,2H,3H,3H-Perfluorooctanoic Acid 5:3 FTCA 6.01 1.0
2H,2H,3H,3H-Perfluorodecanoic acid 7:3 FTCA 7.59 1.0
2H-perfluoro-2-octenoic acid FHUEA 6.00 NA
2H-perfluoro-2-decenoic acid FOUEA 7.45 NA
Lithium Bis(trifluoromethane)sulfonimide HQ-115 6.8 6.3
Surrogates
Perfluoro-n-[ C ]butanoic acid MPFBA 3.67 NA
Perfluor0-n-[ C ]pentanoic acid M5PFPeA 4.71 NA
Perfluoro-n-[1,2,3,4,6- C ]hexanoic acid M5PFHxA 5.45 NA
Perfluoro-n-[1,2,3,4- C ]heptanoic acid M4PFHpA 6.28 NA
Perfluoro-n-[ C ]octanoic acid M8PFOA 7.03 NA
Perfluoro-n-[ C ]nonanoic acid M9PFNA 7.70 NA
Perfluoro-n-[1,2,3,4,5,6- C ]decanoic acid M6PFDA 8.34 NA
Perfluoro-n-[1,2,3,4,5,6,7- C ]undecanoic acid M7PFUnA 8.9 NA
Perfluoro-n-[1,2- C ]dodecanoic acid MPFDoA 9.43 NA
Perfluoro-n-[1,2- C ]tetradecanoic acid M2PFTreA 10.4 NA
Perfluoro-1-[ C ]octanesulfonamide M8FOSA 10.09 NA
N-methyl-d -perfluoro-1-octanesulfonamidoacetic acid D3-N-MeFOSAA 8.47 NA
N-ethyl-d -perfluoro-1-octanesulfonamidoacetic acid D5-N-EtFOSAA 8.73 NA
N-methyl-d -perfluoro-1-octanesulfanamide d-N-MeFOSA 12.10 NA
N-ethyl-d -perfluoro-1-octanesulfanamide d-N-EtFOSA 12.60 NA
2-(N-ethyl-d -perfluoro-1-octanesulfonamido)ethan-d4-ol d7-N-MeFOSE 11.65 NA
2-(N-methyl-d -perfluoro-1-octanesulfonamido)ethan-d4-ol D9-N-EtFOSE 12.16 NA
2,3,3,3-Tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy- C -propanoic acid MHFPO-DA 5.75 NA
1H,1H,2H,2H-perfluoro-1-[1,2- C ]hexane sulfonate M4:2FTS 5.22 NA
1H,1H,2H,2H-perfluoro-1-[1,2- C ]-octane sulfonate M6:2FTS 6.76 NA
1H,1H,2H,2H-perfluoro-1-[1,2- C ]-decane sulfonate M8:2FTS 8.06 NA
Perfluoro-1-[ C ]octanesulfonate M8PFOS 8.64 NA
Perfluoro-1-[2,3,4- C ]butanesulfonate M3PFBS 5.56 NA
Perfluoro-1-[1,2,3- C ]hexanesulfonate M3PFHxS 7.29 NA
D8535 − 23
TABLE 5 Concentrations of Calibration Standards (ng/L)
Analyte/Surrogate Cal1 Cal2 Cal3 Cal4 Cal5 Cal6 Cal7 Cal8 Cal9
PFPeA, PFBA, PFPrA 25 50 100 200 300 400 500 750 1000
All Other PFAS and Surrogates 5 10 20 40 60 80 100 150 200
(Exclude PFPeA, PFBA and PFPrA)
where: glass beads, etc.) containing the analytes and surrogates at a
prepared sample concentration in the range of Calibration
x = true amount of analyte in calibration level i, in mass or
i
Levels 4 to 7. Calibration Level 6 was used to establish the QC
concentration units,
'
acceptance criteria in this test method. Take each replicate
x = measured amount of analyte in calibration level i, in
i
through the complete analytical test method, including any
mass or concentration units,
sample manipulation and pretreatment steps.
p = number of terms in the fitting equation (average = 1,
linear = 2, quadratic = 3, cubic = 4), and
13.2.2 Calculate the mean (average) percent recovery and
n = number of calibration points.
relative standard deviation (RSD) of the four values and
compare to the acceptable ranges of the QC acceptance criteria
12.2.8 The retention time window of an unknown shall be
for the initial demonstration of performance in Table 6.
within 5 % of the retention time of the analyte in a midpoint
13.2.3 Repeat until the single-operator precision and mean
calibration standard. If this is not the case, re-analyze the
recovery are within the limits in Table 6. If a concentration
calibration curve to determine if there was a shift in retention
other than the recommended concentration is used, refer to
time during the analysis. If the retention time of the known
Practice D5847 for informati
...