ASTM D7968-17a
(Test Method)Standard Test Method for Determination of Polyfluorinated Compounds in Soil by Liquid Chromatography Tandem Mass Spectrometry (LC/MS/MS)
Standard Test Method for Determination of Polyfluorinated Compounds in Soil by Liquid Chromatography Tandem Mass Spectrometry (LC/MS/MS)
SIGNIFICANCE AND USE
5.1 This test method has been developed by the U.S. EPA Region 5 Chicago Regional Laboratory (CRL).
5.2 PFCs are widely used in various industrial and commercial products; they are persistent, bio-accumulative, and ubiquitous in the environment. PFCs have been reported to exhibit developmental toxicity, hepatotoxicity, immunotoxicity, and hormone disturbance. A draft Toxicological Profile for Perfluoroalkyls from the U.S. Department of Health and Human Services is available.7 PFCs have been detected in soils, sludges, and surface and drinking waters. Hence, there is a need for a quick, easy, and robust method to determine these compounds at trace levels in various soil matrices for understanding of the sources and pathways of exposure.
5.3 This method has been used to determine selected polyfluorinated compounds in sand (Table 4) and four ASTM reference soils (Table 5).
TABLE 4 Single-Laboratory Recovery Data in Ottawa Sand
Sample
Measured ng/kg from Ottawa Sand P&A Data (400 ng/kg spike for all PFCs except 2000 ng/kg for PFBA and PFPeA and 8000 ng/kg spike for FHEA, FDEA, and FOEA)
PFTreA
PFTriA
PFDoA
PFUnA
PFDA
PFNA
PFOA
PFHpA
PFHxA
PFPeA
PFBA
Unspiked 1
Unspiked 2
P&A 1
389.6
394.3
384.7
376.7
362.1
347.6
345.8
232.9
222.2
1614.9
1344.5
P&A 2
462.1
424.6
397.2
379.1
378.4
376.9
365.9
247.9
229.8
1710.1
1388
P&A 3
402.7
387.7
383.1
365.9
374.7
363.3
347.1
242.4
222.9
1658.9
1376
P&A 4
403.9
397.1
395.4
381.5
379
359.4
342.7
246.8
225.8
1693.6
1401.9
P&A 5
467.2
445.8
412.6
388.5
376.8
370.3
369.7
249.3
231.4
1716.5
1433.4
P&A 6
392.1
385.3
374.2
370.9
353.2
351.7
340.3
236.7
220.5
1659
1366.4
Mean R...
SCOPE
1.1 This procedure covers the determination of selected polyfluorinated compounds (PFCs) in a soil matrix using solvent extraction, filtration, followed by liquid chromatography (LC) and detection with tandem mass spectrometry (MS/MS). These analytes are qualitatively and quantitatively determined by this method. This method adheres to multiple reaction monitoring (MRM) mass spectrometry. This procedure utilizes a quick extraction and is not intended to generate an exhaustive accounting of the content of PFCs in difficult soil matrices. An exhaustive extraction procedure for polyfluoralkyl substances, such as published by Washington et al.,2 for difficult matrices should be considered when analyzing PFCs.
1.2 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 The Method of Detection Limit3 and Reporting Range4 for the target analytes are listed in Table 1.
TABLE 1 Method Detection Limit and Reporting RangeA
Analyte
MDL
(ng/kg)
Reporting Limit
(ng/kg)
PFTreA
6.76
25–1000
PFTriA
5.26
25–1000
PFDoA
3.56
25–1000
PFUnA
2.45
25–1000
PFDA
5.54
25–1000
PFOS
18.83
50–1000
PFNA
2.82
25–1000
PFecHS
2.41
25–1000
PFOA
6.24
25–1000
PFHxS
7.75
25–1000
PFHpA
5.80
25–1000
PFHxA
15.44
50–1000
PFBS
6.49
25–1000
PFPeA
20.93
125–5000
PFBA
22.01
125–5000
FHEA
199.04
600–20 000
FOEA
258.37
750–20 000
FDEA
137.46
500–20 000
FOUEA
4.85
25–1000
FhpPa
5.09
25–1000
FHUEA
3.50
25–1000(A) Abbreviations are defined in 3.2.
TABLE 2 Concentrations of Calibration Standards (ng/L)
Analyte/Surrogate
LV1
LV2
LV3
LV4
LV5
LV6
LV7
LV8
LV9
PFPeA, PFBA
25
50
100
200
300
400
500
750
1000 ...
General Information
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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:D7968 −17a
Standard Test Method for
Determination of Polyfluorinated Compounds in Soil by
Liquid Chromatography Tandem Mass Spectrometry (LC/
1
MS/MS)
This standard is issued under the fixed designation D7968; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope calibrationstandardasshowninTable2forthepolyfluorinated
compounds after taking into account a 2-g sample weight and
1.1 This procedure covers the determination of selected
afinalextractvolumeof10mL,50%water/50%MeOHwith
polyfluorinated compounds (PFCs) in a soil matrix using
0.1% acetic acid. The final extract volume is assumed to be
solvent extraction, filtration, followed by liquid chromatogra-
10mLbecause 10 mLof 50% water/50% MeOH with 0.1%
phy (LC) and detection with tandem mass spectrometry (MS/
acetic acid was added to each soil sample and only the liquid
MS). These analytes are qualitatively and quantitatively deter-
layer after extraction is filtered, leaving the solid and any
mined by this method. This method adheres to multiple
residual solvent behind. It is raised above the Level 1 calibra-
reaction monitoring (MRM) mass spectrometry. This proce-
tionconcentrationforPFOS,PFHxA,FHEA,andFOEA;these
dure utilizes a quick extraction and is not intended to generate
compounds can be identified at the Level 1 concentration but
anexhaustiveaccountingofthecontentofPFCsindifficultsoil
the standard deviation among replicates at this lower spike
matrices. An exhaustive extraction procedure for polyfluo-
2
level resulted in a higher reporting limit.
ralkyl substances, such as published by Washington et al., for
difficult matrices should be considered when analyzing PFCs.
1.4 This standard does not purport to address all of the
1.2 Units—The values stated in SI units are to be regarded
safety concerns, if any, associated with its use. It is the
asstandard.Nootherunitsofmeasurementareincludedinthis responsibility of the user of this standard to establish appro-
standard.
priate safety, health and environmental practices and deter-
3 4
mine the applicability of regulatory limitations prior to use.
1.3 The Method of Detection Limit and Reporting Range
1.5 This international standard was developed in accor-
for the target analytes are listed in Table 1.
1.3.1 Thereportinglimitinthistestmethodistheminimum dance with internationally recognized principles on standard-
value below which data are documented as non-detects. Ana- ization established in the Decision on Principles for the
lyte detections between the method detection limit and the Development of International Standards, Guides and Recom-
reporting limit are estimated concentrations and are not re- mendations issued by the World Trade Organization Technical
ported following this test method. In most cases, the reporting
Barriers to Trade (TBT) Committee.
limit is calculated from the concentration of the Level 1
2. Referenced Documents
5
2.1 ASTM Standards:
1
This test method is under the jurisdiction ofASTM Committee D34 on Waste
D1193Specification for Reagent Water
Management and is the direct responsibility of Subcommittee D34.01.06 on
D2777Practice for Determination of Precision and Bias of
Analytical Methods.
Current edition approved Sept. 1, 2017. Published September 2017. Originally
Applicable Test Methods of Committee D19 on Water
approved in 2014. Last previous edition approved in 2017 as D7968–17. DOI:
D5847Practice for Writing Quality Control Specifications
10.1520/D7968-17A.
2 for Standard Test Methods for Water Analysis
Washington, J. W., Naile, J. E., Jenkins, T. M., and Lynch, D. G., “Character-
izing Fluorotelomer and Polyfluoroalkyl Substances in New and Aged
E2554Practice for Estimating and Monitoring the Uncer-
Fluorotelomer-Based Polymers for Degradation Studies with GC/MS and LC/MS/
tainty of Test Results of a Test Method Using Control
MS,” Environmental Science and Technology, Vol 48, 2014, pp. 5762–5769.
Chart Techniques
3
The MDL is determined following the Code of Federal Regulations, 40 CFR
Part 136, Appendix B utilizing solvent extraction of soil. Two-gram sample of
Ottawa sand was utilized.Adetailed process determining the MDL is explained in
the reference and is beyond the scope of this standard to be explained here.
4 5
Reporting range concentration is calculated from Table 2 concentrations For referenced ASTM standards, visit the ASTM website, www.astm.org, or
assuminga30-µLinjectionoftheLevel1calibrationsta
...
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: D7968 − 17 D7968 − 17a
Standard Test Method for
Determination of Polyfluorinated Compounds in Soil by
Liquid Chromatography Tandem Mass Spectrometry (LC/
1
MS/MS)
This standard is issued under the fixed designation D7968; 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 procedure covers the determination of selected polyfluorinated compounds (PFCs) in a soil matrix using solvent
extraction, filtration, followed by liquid chromatography (LC) and detection with tandem mass spectrometry (MS/MS). These
analytes are qualitatively and quantitatively determined by this method. This method adheres to multiple reaction monitoring
(MRM) mass spectrometry. This procedure utilizes a quick extraction and is not intended to generate an exhaustive accounting of
the content of PFCs in difficult soil matrices. An exhaustive extraction procedure for polyfluoralkyl substances, such as published
2
by Washington et al., for difficult matrices should be considered when analyzing PFCs.
1.2 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this
standard.
3 4
1.3 The Method of Detection Limit and Reporting Range for the target analytes are listed in Table 1.
1.3.1 The reporting limit in this test method is the minimum value below which data are documented as non-detects. Analyte
detections between the method detection limit and the reporting limit are estimated concentrations and are not reported following
this test method. In most cases, the reporting limit is calculated from the concentration of the Level 1 calibration standard as shown
in Table 2 for the polyfluorinated compounds 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. It is raised above the Level 1 calibration concentration for PFOS, PFHxA, FHEA,
and FOEA; these compounds can be identified at the Level 1 concentration but the standard deviation among replicates at this
lower spike level resulted in a higher reporting limit.
1.4 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 safety, health and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use.
1.5 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
5
2.1 ASTM Standards:
D653 Terminology Relating to Soil, Rock, and Contained Fluids
D1193 Specification for Reagent Water
1
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 Analytical
Methods.
Current edition approved May 1, 2017Sept. 1, 2017. Published May 2017September 2017. Originally approved in 2014. Last previous edition approved in 20142017 as
D7968 – 14.D7968 – 17. DOI: 10.1520/D7968-17.10.1520/D7968-17A.
2
Washington, J. W., Naile, J. E., Jenkins, T. M., and Lynch, D. G., “Characterizing Fluorotelomer and Polyfluoroalkyl Substances in New and Aged Fluorotelomer-Based
Polymers for Degradation Studies with GC/MS and LC/MS/MS,” Environmental Science and Technology, Vol 48, 2014, pp. 5762–5769.
3
The MDL is determined following the Code of Federal Regulations, 40 CFR Part 136, Appendix B utilizing solvent extraction of soil. Two-gram sample of Ottawa sand
was utilized. A detailed process determining the MDL is explained in the reference and is beyond the scope of this standard to be explained here.
4
Reporting range concentration is calculated from Table 2 concentrations assuming a 30-μL injection of the Level 1 calibration standard for the PFCs, and the highest
level calibration standard with a 10-mL final extract vol
...
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D7968 − 17a
Standard Test Method for
Determination of Polyfluorinated Compounds in Soil by
Liquid Chromatography Tandem Mass Spectrometry (LC/
1
MS/MS)
This standard is issued under the fixed designation D7968; 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 calibration standard as shown in Table 2 for the polyfluorinated
compounds after taking into account a 2-g sample weight and
1.1 This procedure covers the determination of selected
a final extract volume of 10 mL, 50 % water/50 % MeOH with
polyfluorinated compounds (PFCs) in a soil matrix using
0.1 % acetic acid. The final extract volume is assumed to be
solvent extraction, filtration, followed by liquid chromatogra-
10 mL because 10 mL of 50 % water/50 % MeOH with 0.1 %
phy (LC) and detection with tandem mass spectrometry (MS/
acetic acid was added to each soil sample and only the liquid
MS). These analytes are qualitatively and quantitatively deter-
layer after extraction is filtered, leaving the solid and any
mined by this method. This method adheres to multiple
residual solvent behind. It is raised above the Level 1 calibra-
reaction monitoring (MRM) mass spectrometry. This proce-
tion concentration for PFOS, PFHxA, FHEA, and FOEA; these
dure utilizes a quick extraction and is not intended to generate
compounds can be identified at the Level 1 concentration but
an exhaustive accounting of the content of PFCs in difficult soil
the standard deviation among replicates at this lower spike
matrices. An exhaustive extraction procedure for polyfluoral-
2
level resulted in a higher reporting limit.
kyl substances, such as published by Washington et al., for
difficult matrices should be considered when analyzing PFCs.
1.4 This standard does not purport to address all of the
1.2 Units—The values stated in SI units are to be regarded safety concerns, if any, associated with its use. It is the
as standard. No other units of measurement are included in this
responsibility of the user of this standard to establish appro-
standard.
priate safety, health and environmental practices and deter-
3 4
mine the applicability of regulatory limitations prior to use.
1.3 The Method of Detection Limit and Reporting Range
1.5 This international standard was developed in accor-
for the target analytes are listed in Table 1.
1.3.1 The reporting limit in this test method is the minimum dance with internationally recognized principles on standard-
value below which data are documented as non-detects. Ana- ization established in the Decision on Principles for the
lyte detections between the method detection limit and the Development of International Standards, Guides and Recom-
reporting limit are estimated concentrations and are not re-
mendations issued by the World Trade Organization Technical
ported following this test method. In most cases, the reporting Barriers to Trade (TBT) Committee.
limit is calculated from the concentration of the Level 1
2. Referenced Documents
5
2.1 ASTM Standards:
1
This test method is under the jurisdiction of ASTM Committee D34 on Waste
D1193 Specification for Reagent Water
Management and is the direct responsibility of Subcommittee D34.01.06 on
D2777 Practice for Determination of Precision and Bias of
Analytical Methods.
Current edition approved Sept. 1, 2017. Published September 2017. Originally
Applicable Test Methods of Committee D19 on Water
approved in 2014. Last previous edition approved in 2017 as D7968 – 17. DOI:
D5847 Practice for Writing Quality Control Specifications
10.1520/D7968-17A.
2
for Standard Test Methods for Water Analysis
Washington, J. W., Naile, J. E., Jenkins, T. M., and Lynch, D. G., “Character-
izing Fluorotelomer and Polyfluoroalkyl Substances in New and Aged
E2554 Practice for Estimating and Monitoring the Uncer-
Fluorotelomer-Based Polymers for Degradation Studies with GC/MS and LC/MS/
tainty of Test Results of a Test Method Using Control
MS,” Environmental Science and Technology, Vol 48, 2014, pp. 5762–5769.
3 Chart Techniques
The MDL is determined following the Code of Federal Regulations, 40 CFR
Part 136, Appendix B utilizing solvent extraction of soil. Two-gram sample of
Ottawa sand was utilized. A detailed process determining the MDL is explained in
the reference and is beyond the scope of this standard to be explained here.
4 5
Reporting range concentration is calculated from Table 2 concentrations For referenced ASTM standards, visit the ASTM website, www.astm.org, or
assuming a 30-µL injection of the Level 1 calibration standard for the PFCs, and the contact ASTM Customer Servic
...
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