ASTM D7363-13
(Test Method)Standard Test Method for Determination of Parent and Alkyl Polycyclic Aromatics in Sediment Pore Water Using Solid-Phase Microextraction and Gas Chromatography/Mass Spectrometry in Selected Ion Monitoring Mode
Standard Test Method for Determination of Parent and Alkyl Polycyclic Aromatics in Sediment Pore Water Using Solid-Phase Microextraction and Gas Chromatography/Mass Spectrometry in Selected Ion Monitoring Mode
SIGNIFICANCE AND USE
5.1 This method directly determines the concentrations of dissolved PAH concentrations in environmental sediment pore water samples. The method is important from an environmental regulatory perspective because it can achieve the analytical sensitivities to meet the goals of the USEPA narcosis model for protecting benthic organisms in PAH contaminated sediments. Regulatory methods using solvent extraction have not achieved the wide calibration ranges from nanograms to milligrams per litre and the required levels of detection in the nanogram-per-litre range. In addition, conventional solvent extraction methods require large aliquot volumes (litre or larger), use of large volumes of organic solvents, and filtration to generate the pore water. This approach entails the storage and processing of large volumes of sediment samples and loss of low molecular weight PAHs in the filtration and solvent evaporation steps.
5.2 This method can be used to determine nanogram to milligram per litre PAH concentrations in pore water. Small volumes of pore water are required for SPME extraction, only 1.5 mL per determination and virtually no solvent extraction waste is generated.
SCOPE
1.1 The U.S. Environmental Protection Agency (USEPA) narcosis model for benthic organisms in sediments contaminated with polycyclic aromatic hydrocarbons (PAHs) is based on the concentrations of dissolved PAHs in the interstitial water or “pore water” in sediment. This test method covers the separation of pore water from PAH-impacted sediment samples, the removal of colloids, and the subsequent measurement of dissolved concentrations of the required 10 parent PAHs and 14 groups of alkylated daughter PAHs in the pore water samples. The “24 PAHs” are determined using solid-phase microextraction (SPME) followed by Gas Chromatography/Mass Spectrometry (GC/MS) analysis in selected ion monitoring (SIM) mode. Isotopically labeled analogs of the target compounds are introduced prior to the extraction, and are used as quantification references.
1.2 Lower molecular weight PAHs are more water soluble than higher molecular weight PAHs. Therefore, USEPA-regulated PAH concentrations in pore water samples vary widely due to differing saturation water solubilities that range from 0.2 µg/L for indeno[1,2,3-cd]pyrene to 31 000 µg/L for naphthalene. This method can accommodate the measurement of microgram per litre concentrations for low molecular weight PAHs and nanogram per litre concentrations for high molecular weight PAHs.
1.3 The USEPA narcosis model predicts toxicity to benthic organisms if the sum of the toxic units (ΣTUc) calculated for all “34 PAHs” measured in a pore water sample is greater than or equal to 1. For this reason, the performance limit required for the individual PAH measurements was defined as the concentration of an individual PAH that would yield 1/34 of a toxic unit (TU). However, the focus of this method is the 10 parent PAHs and 14 groups of alkylated PAHs (Table 1) that contribute 95 % of the toxic units based on the analysis of 120 background and impacted sediment pore water samples.3 The primary reasons for eliminating the rest of the 5-6 ring parent PAHs are: (1) these PAHs contribute insignificantly to the pore water TU, and (2) these PAHs exhibit extremely low saturation solubilities that will make the detection of these compounds difficult in pore water. This method can achieve the required detection limits, which range from approximately 0.01 µg/L, for high molecular weight PAHs, to approximately 3 µg/L for low molecular weight PAHs.TABLE 1 Target PAHs, Toxic Unit Factors and Performance LimitsA
Analyte
Added d-PAH
Internal
Standard
d-PAH Internal
Std. for Calculation
Conc. for One
Toxic Unit,
Ctu, (ng/mL)
Performance Limit
(ng/mL)
Basis for
Performance
LimitB
Naphthalene
A
A
193.47
5.69
B
2-Methylnaphthalene
B
81.69
2.40
B
...
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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: D7363 − 13
Standard Test Method for
Determination of Parent and Alkyl Polycyclic Aromatics in
Sediment Pore Water Using Solid-Phase Microextraction
and Gas Chromatography/Mass Spectrometry in Selected
1,2
Ion Monitoring Mode
This standard is issued under the fixed designation D7363; 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 1.3 The USEPA narcosis model predicts toxicity to benthic
organismsifthesumofthetoxicunits(ΣTU )calculatedforall
c
1.1 The U.S. Environmental Protection Agency (USEPA)
“34 PAHs” measured in a pore water sample is greater than or
narcosis model for benthic organisms in sediments contami-
equal to 1. For this reason, the performance limit required for
nated with polycyclic aromatic hydrocarbons (PAHs) is based
the individual PAH measurements was defined as the concen-
on the concentrations of dissolved PAHs in the interstitial
1
trationofanindividualPAHthatwouldyield ⁄34ofatoxicunit
water or “pore water” in sediment.This test method covers the
(TU).However,thefocusofthismethodisthe10parentPAHs
separation of pore water from PAH-impacted sediment
and14groupsofalkylatedPAHs(Table1)thatcontribute95%
samples, the removal of colloids, and the subsequent measure-
of the toxic units based on the analysis of 120 background and
ment of dissolved concentrations of the required 10 parent
3
impacted sediment pore water samples. The primary reasons
PAHs and 14 groups of alkylated daughter PAHs in the pore
for eliminating the rest of the 5-6 ring parent PAHs are: (1)
water samples. The “24 PAHs” are determined using solid-
thesePAHscontributeinsignificantlytotheporewaterTU,and
phase microextraction (SPME) followed by Gas
(2) these PAHs exhibit extremely low saturation solubilities
Chromatography/Mass Spectrometry (GC/MS) analysis in se-
that will make the detection of these compounds difficult in
lected ion monitoring (SIM) mode. Isotopically labeled ana-
pore water. This method can achieve the required detection
logs of the target compounds are introduced prior to the
limits, which range from approximately 0.01 µg/L, for high
extraction, and are used as quantification references.
molecular weight PAHs, to approximately 3 µg/L for low
1.2 Lower molecular weight PAHs are more water soluble
molecular weight PAHs.
than higher molecular weight PAHs. Therefore, USEPA-
1.4 The test method may also be applied to the determina-
regulated PAH concentrations in pore water samples vary
tion of additional PAH compounds (for example, 5- and 6-ring
widely due to differing saturation water solubilities that range
4
PAHs as described in Hawthorne et al.). However, it is the
from 0.2 µg/L for indeno[1,2,3-cd]pyrene to 31000 µg/L for
responsibility of the user of this standard to establish the
naphthalene. This method can accommodate the measurement
validityofthetestmethodforthedeterminationofPAHsother
ofmicrogramperlitreconcentrationsforlowmolecularweight
than those referenced in 1.1 and Table 1.
PAHsandnanogramperlitreconcentrationsforhighmolecular
1.5 This standard does not purport to address all of the
weight PAHs.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
1
priate safety and health practices and determine the applica-
This test method is under the jurisdiction of ASTM Committee D19 on Water
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
bility of regulatory limitations prior to use. For specific hazard
Organic Substances in Water.
statements, refer to Section 9.
Current edition approved March 15, 2013. Published May 2013. Originally
approved in 2007. Last previous edition approved in 2011 as D7363 – 11. DOI:
3
10.1520/D7363-13. Hawthorne, S. B., Grabanski, C. B., and Miller, D. J., “Measured Partitioning
2
Standard methods under the jurisdiction of ASTM Committee D19 may be Coefficients for Parent and Akyl Polycyclic Aromatic Hydrocarbons in 114
publishedforalimitedtimepreliminarytothecompletionoffullcollaborativestudy Historically Contaminated Sediments: Part I, Koc Values,” Environmental Toxicol-
validation. Such standards are deemed to have met all other D19 qualifying ogy and Chemistry, Vol 25, 2006, pp. 2901–2911.
4
requirements but have not completed the required validation studies to fully Hawthorne, S. B., Grabanski, C. B., Miller, D. J., and Kreitinger, J. P., “Solid
characterize the performance of the test method across multiple laboratories and Phase Microextraction Measurement of Parent and Akyl Polycyclic Aromatic
matrices. Preliminary publication is done to make curren
...
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: D7363 − 11 D7363 − 13
Standard Test Method for
Determination of Parent and Alkyl Polycyclic Aromatics in
Sediment Pore Water Using Solid-Phase Microextraction
and Gas Chromatography/Mass Spectrometry in Selected
1,2
Ion Monitoring Mode
This standard is issued under the fixed designation D7363; 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 The U.S. Environmental Protection Agency (USEPA) narcosis model for benthic organisms in sediments contaminated with
polycyclic aromatic hydrocarbons (PAHs) is based on the concentrations of dissolved PAHs in the interstitial water or “pore water”
in sediment. This test method covers the separation of pore water from PAH-impacted sediment samples, the removal of colloids,
and the subsequent measurement of dissolved concentrations of the required 10 parent PAHs and 14 groups of alkylated daughter
PAHs in the pore water samples. The “24 PAHs” are determined using solid-phase microextraction (SPME) followed by Gas
Chromatography/Mass Spectrometry (GC/MS) analysis in selected ion monitoring (SIM) mode. Isotopically labeled analogs of the
target compounds are introduced prior to the extraction, and are used as quantification references.
1.2 Lower molecular weight PAHs are more water soluble than higher molecular weight PAHs. Therefore, USEPA-regulated
PAH concentrations in pore water samples vary widely due to differing saturation water solubilities that range from 0.2 μg/L for
indeno[1,2,3-cd]pyrene to 31 000 μg/L for naphthalene. This method can accommodate the measurement of milligrammicrogram
per litre concentrations for low molecular weight PAHs and nanogram per litre concentrations for high molecular weight PAHs.
1.3 The USEPA narcosis model predicts toxicity to benthic organisms if the sum of the toxic units (ΣTU ) calculated for all “34
c
PAHs” measured in a pore water sample is greater than or equal to 1. For this reason, the performance limit required for the
1
individual PAH measurements was defined as the concentration of an individual PAH that would yield 1/34 ⁄34 of a toxic unit (TU).
However, the focus of this method is the 10 parent PAHs and 14 groups of alkylated PAHs (Table 1) that contribute 95 % of the
3
toxic units based on the analysis of 120 background and impacted sediment pore water samples. The primary reasons for
eliminating the rest of the 5-6 ring parent PAHs are: (1) these PAHs contribute insignificantly to the pore water TU, and (2) these
PAHs exhibit extremely low saturation solubilities that will make the detection of these compounds difficult in pore water. This
method can achieve the required detection limits, which range from approximately 0.01 μg/L, for high molecular weight PAHs,
to approximately 3 μg/L for low molecular weight PAHs.
1.4 The test method may also be applied to the determination of additional PAH compounds (for example, 5- and 6-ring PAHs
4
as described in Hawthorne et al).al.). However, it is the responsibility of the user of this standard to establish the validity of the
test method for the determination of PAHs other than those referenced in 1.1 and Table 1.
1
This test method is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved Dec. 1, 2011March 15, 2013. Published December 2011May 2013. Originally approved in 2007. Last previous edition published 2007 approved
in 2011 as D7363–11. DOI: 10.1520/D7363-11. – 11. DOI: 10.1520/D7363-13.
2
Standard methods under the jurisdiction of ASTM Committee D19 may be published for a limited time preliminary to the completion of full collaborative study
validation. Such standards are deemed to have met all other D19 qualifying requirements but have not completed the required validation studies to fully characterize the
performance of the test method across multiple laboratories and matrices. Preliminary publication is done to make current technology accessible to users of
Standards,standards, and to solicit additional input from the user community.
3
Hawthorne, S. B., Grabanski, C. B., and Miller, D. J., “Measured Partitioning Coefficients for Parent and Akyl Polycyclic Aromatic Hydrocarbons in 114 Historically
Contaminated Sediments: Part I
...
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