ASTM D7363-13A(2021)e1

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.  
1.4 The test method may also be applied to the determination of additional PAH compounds (for example, 5- and 6-ring PAHs as described in Hawthorne et al.).4 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.  
1.5 The values stated in ...

General Information

• Status: Published
• Publication Date: 31-Oct-2021
• ICS: 13.080.10 - Chemical characteristics of soils
• Technical Committee: D19 - Water
• Drafting Committee: D19.06 - Methods for Analysis for Organic Substances in Water

Relations

• Refers: ASTM E178-16 - Standard Practice for Dealing With Outlying Observations
• Effective Date: 01-Jun-2016
• Refers: ASTM D2777-12 - Standard Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
• Effective Date: 15-Jun-2012
• Refers: ASTM D3370-10 - Standard Practices for Sampling Water from Closed Conduits
• Effective Date: 01-Dec-2010
• Refers: ASTM D3370-08 - Standard Practices for Sampling Water from Closed Conduits
• Effective Date: 01-Oct-2008
• Refers: ASTM E178-08 - Standard Practice for Dealing With Outlying Observations
• Effective Date: 01-Oct-2008
• Refers: ASTM D2777-08 - Standard Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
• Effective Date: 15-Jan-2008
• Refers: ASTM D3370-07 - Standard Practices for Sampling Water from Closed Conduits
• Effective Date: 01-Dec-2007
• Refers: ASTM D2777-06 - Standard Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
• Effective Date: 15-Aug-2006
• Refers: ASTM D1193-06 - Standard Specification for Reagent Water
• Effective Date: 01-Mar-2006
• Refers: ASTM D2777-03 - Standard Practice for Determination of Precision and Bias of Applicable Methods of Committee D-19 on Water
• Effective Date: 10-Aug-2003
• Refers: ASTM E178-02 - Standard Practice for Dealing With Outlying Observations
• Effective Date: 10-May-2002
• Refers: ASTM D3370-95a(1999)e1 - Standard Practices for Sampling Water from Closed Conduits
• Effective Date: 10-Jun-1999
• Refers: ASTM D1193-99e1 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999
• Refers: ASTM D1193-99 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999
• Refers: ASTM D1192-98 - Standard Guide for Equipment for Sampling Water and Steam in Closed Conduits (Withdrawn 2003)
• Effective Date: 10-Jul-1998

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.
´1
Designation: D7363 − 13a (Reapproved 2021)
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.
ε NOTE—Reapproved with editorial changes in November 2021.
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
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
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
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
weight PAHs. 1.5 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
standard.
This test method is under the jurisdiction ofASTM Committee D19 on Water 1.6 This standard does not purport to address all of the
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
safety concerns, if any, associated with its use. It is the
Organic Substances in Water.
Current edition approved Nov. 1, 2021. Published December 2021. Originally
approved in 2007. Last previous edition approved in 2013 as D7363 – 13a. DOI:
10.1520/D7363-13AR21E01. Hawthorne, S. B., Grabanski, C. B., and Miller, D. J., “Measured Partitioning
Standard methods under the jurisdiction of ASTM Committee D19 may be Coefficients for Parent and Algae 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.
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 current technology accessible to Hydrocarbons in Milliliter Sediment Pore Water Samples and Determination of
users of standards, and to solicit additional input from the user community. K Values,” Environmental Science Technology, Vol 39, 2005, pp. 2795–2803.
DOC
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
´1
D7363 − 13a (2021)
A
TABLE 1 Target PAHs, Toxic Unit Factors and Performance Limits
Added d-PAH d-PAH Internal Conc. for One Basis for
Performance Limit
Analyte Internal Std. for Toxic Unit, Performance
(ng/mL)
B
Standard Calculation C , (ng/mL) Limit
tu
Naphthalene A A 193.47 5.69 B
2-Methylnaphthalene B 81.69 2.40 B
1-Methylnaphthalene B B 81.69 2.40 B
C2-Naphthalenes A 30.24 0.89 B
C3-Naphthalenes A 11.10 0.33 B
C4-Naphthalenes A 4.05 0.12 C
Acenaphthylene C 308.85 9.03 B
Acenaphthene C C 55.85 1.64 B
Fluorene D D 39.30 1.16 B
C1-Fluorenes D 13.99 0.41 B
C2-Fluorenes D 5.30 0.16 B
C3-Fluorenes D 1.92 0.06 S
Phenanthrene E E 19.13 0.56 B
Anthracene E 20.72 0.61 B
C1-Phenanthrenes/Anthracenes E 7.44 0.22 B
C2-Phenanthrenes/Anthracenes E 3.20 0.09 B
C3-Phenanthrenes/Anthracenes E 1.26 0.04 B
C4-Phenanthrenes/Anthracenes E 0.56 0.02 S
Fluoranthene F 7.11 0.21 B
Pyrene F F 10.11 0.30 B
C1-Fluoranthenes/Pyrenes F 4.89 0.14 C
Benz[a]anthracene G 2.23 0.066 B
Chrysene G G 2.04 0.060 B
C1-Chrysenes/Benz[a]anthracenes G 0.86 0.025 C
A
From Hawthorne, S. B., Grabanski, C. B., Miller, D. J., and Kreitinger, J. P., “Solid Phase Microextraction Measurement of Parent and Alkyl Polycyclic Aromatic
Hydrocarbons in Milliliter Sediment Pore Water Samples and Determination of K Values,” Environmental Science Technology, Vol 39, 2005, pp. 2795–2803.
DOC
B
Performance limits were determined as 3 times the background concentrations from the SPME fiber based on the analysis of water blanks (“B”), the lowest calibration
standard which consistently yielded a signal to noise ratio of at least 3:1 (“C”), or (for when no calibration standard was available) for the lowest concentrations consistently
found in pore water samples with a signal to noise ratio of at least 3:1 (“S”). Detection limits for alkyl PAHs are based on a single isomer.
responsibility of the user of this standard to establish appro- 3. Terminology
priate safety, health, and environmental practices and deter-
3.1 Definitions:
mine the applicability of regulatory limitations prior to use.
3.1.1 calibration standard, n—a solution prepared from a
For specific hazard statements, refer to Section 9.
secondary standard, stock solution, or both, and used to
1.7 This international standard was developed in accor-
calibrate the response of the instrument with respect to analyte
dance with internationally recognized principles on standard-
concentration.
ization established in the Decision on Principles for the
3.1.2 calibration verification standard (VER), n—the mid-
Development of International Standards, Guides and Recom-
pointcalibrationstandard(CS3)thatisanalyzeddailytoverify
mendations issued by the World Trade Organization Technical
the initial calibration.
Barriers to Trade (TBT) Committee.
3.1.3 CS1, CS2, CS3, CS4, n—shorthand notation for cali-
2. Referenced Documents
bration standards.
2.1 ASTM Standards:
3.1.4 data acquisition parameters, n—parameters affecting
D1192Guide for Equipment for Sampling Water and Steam
the scanning operation and conversion of the analytical signal
in Closed Conduits (Withdrawn 2003)
to digitized data files.
D1193Specification for Reagent Water
3.1.4.1 Discussion—These include the configuration of the
D2777Practice for Determination of Precision and Bias of
ADC circuitry, the ion dwell time, the MID cycle time, and
Applicable Test Methods of Committee D19 on Water
acquisition modes set up for the method. Examples of acqui-
D3370Practices for Sampling Water from Flowing Process
sition modes for the HP5973 include SIM mode, and Low
Streams
Mass Resolution Mode
E178Practice for Dealing With Outlying Observations
3.1.5 performance limit, n—performance limit for an indi-
vidual PAH is defined as the concentration of an individual
PAH that would yield ⁄34 of a toxic unit.
3.1.5.1 Discussion—For a performance limit of an indi-
vidual PAH, refer to Table 1 (see 4.6).
3.1.6 deuterated PAH (d-PAH), n—polycyclic aromatic hy-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
drocarbons in which deuterium atoms are substituted for all
Standards volume information, refer to the standard’s Document Summary page on
hydrogens (that is, perdeuterated).
the ASTM website.
3.1.6.1 Discussion—In this method, d-PAHs are used as
The last approved version of this historical standard is referenced on
www.astm.org. internal standards.
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D7363 − 13a (2021)
3.1.7 GC, n—gas chromatograph or gas chromatography. each ion. This results in greater instrument sensitivity for the
selectedions.Spectralscanningandlibrarysearching,usedfor
3.1.8 HRGC, n—high resolution GC.
tentatively identified compounds, are not supported in this
3.1.9 LRMS, n—low resolution MS.
mode.
3.1.10 internal standards, n—isotopically labeled analogs
3.1.20 signal-to-noise ratio, n—the ratio of the mass spec-
(d-PAHs) of the target analytes that are added to every sample,
trometerresponseofaGCpeaktothebackgroundnoisesignal.
blank, quality control spike sample, and calibration solution.
3.1.21 NIST, n—National Institute of Standards and Tech-
3.1.10.1 Discussion—They are added to the water samples
nology.
immediately after completing the flocculation step and trans-
3.1.22 SRM, n—Standard reference material obtained from
ferring the water aliquot to the autosampler vial, and immedi-
ately after adding the calibration PAH solution to water NIST.
calibrationstandards,butbeforeSPMEextraction.Theinternal
standards are used to calculate the concentration of the target 4. Summary of Test Method
analytes or estimated detection limits.
4.1 Either the use of an autosampler, or a manual approach
3.1.11 laboratory blank, n—see method blank.
can be used to perform the SPME extraction and the subse-
quent injection of collected analytes into the GC/MS. An
3.1.12 method blank, n—an aliquot of reagent water that is
autosampler (Leap Technologies Combi-Pal or equivalent) is
extracted and analyzed along with the samples to monitor for
much preferred over the manual method because: (1) the
laboratory contamination.
autosampleryieldslowerandmorereproducibleblanks, (2)the
3.1.12.1 Discussion—Blanks should consistently meet con-
manual method requires the use of a stir bar that can cause
centrations at or less than one-third of the performance limits
sample cross-contamination, (3) the manual method is highly
Table1.Alternatively,ifthePAH
forindividualPAHsstatedin
labor-intensive and requires multiple timed manipulations per
concentrations calculated from the water blank immediately
analysisleadingtooperatorfatigueandresultanterrors,and (4)
preceding the test samples are <20% of the test sample
theautosamplerreducesthetechniciantimerequiredtoprepare
concentrations, the blank is acceptable.
samples for a 24-h run sequence to approximately 3 h, while
3.1.13 low calibration level (LCL), n—thelevelatwhichthe
the manual method requires 24-h operator attendance.
entire analytical system must give a recognizable signal and
Therefore,themethodproceduresarewrittenassumingtheuse
acceptable calibration point for the analyte.
of an autosampler, with modifications to the autosampler
3.1.13.1 Discussion—Itisequivalenttotheconcentrationof
procedures listed for the manual method.
the lowest calibration standard assuming that all method-
specified sample weights, volumes, and cleanup procedures
AUTOSAMPLER METHOD
have been employed.
4.2 Pore Water Separation and Preparation—The pore
3.1.14 high or upper calibration level (UCL), n—the con-
water is separated from wet sediment samples by centrifuga-
centration or mass of analyte in the sample that corresponds to
tion and supernatant collection. Colloids are removed from the
the highest calibration level in the initial calibration.
separated pore water samples by flocculation with aluminum
3.1.14.1 Discussion—Itisequivalenttotheconcentrationof
potassiumsulfate(alum)andsodiumhydroxideasdescribedin
the highest calibration standard, assuming that all method-
Hawthorne et al. A second flocculation and centrifugation,
specified sample weights, volumes, and cleanup procedures
followed by supernatant collection completes the colloid re-
have been employed.
moval.The prepared pore water samples are then split into the
requirednumberofreplicatealiquots(1.5mLeach)andplaced
3.1.15 MS, n—mass spectrometer or mass spectrometry.
into silanized glass autosampler vials. The 7 perdeuterated
3.1.16 PAH, n—polycyclic aromatic hydrocarbon, or
PAH internal standards (d-PAHs) are then added immediately.
alternately, polynuclear aromatic hydrocarbon.
All of the water preparation steps beginning with the centrifu-
3.1.17 percent difference (%D), n—the difference between
gation and ending with the addition of d-PAH internal stan-
the analyzed concentration and expected concentration, ex-
dards should be conducted continuously and in the minimum
pressed as a percentage of the expected concentration.
amount of time possible.
4.2.1 TheSPMEfibershouldbecleanedatthebeginningof
3.1.18 relative response factor (RRF), n—the empirically
determined ratio between the area ratio (analyte to internal each sampling set (and after very contaminated samples) for 1
h by placing in the cleaning chamber under helium flow at
standard) and the unit mass of analyte in the calibration
standard (area ratio/ng)
...