1、Designation: D7363 13Standard Test Method forDetermination of Parent and Alkyl Polycyclic Aromatics inSediment Pore Water Using Solid-Phase Microextractionand Gas Chromatography/Mass Spectrometry in SelectedIon Monitoring Mode1,2This standard is issued under the fixed designation D7363; the number i
2、mmediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 T
3、he U.S. Environmental Protection Agency (USEPA)narcosis model for benthic organisms in sediments contami-nated with polycyclic aromatic hydrocarbons (PAHs) is basedon the concentrations of dissolved PAHs in the interstitialwater or “pore water” in sediment. This test method covers theseparation of p
4、ore water from PAH-impacted sedimentsamples, the removal of colloids, and the subsequent measure-ment of dissolved concentrations of the required 10 parentPAHs and 14 groups of alkylated daughter PAHs in the porewater samples. The “24 PAHs” are determined using solid-phase microextraction (SPME) fol
5、lowed by GasChromatography/Mass Spectrometry (GC/MS) analysis in se-lected ion monitoring (SIM) mode. Isotopically labeled ana-logs of the target compounds are introduced prior to theextraction, and are used as quantification references.1.2 Lower molecular weight PAHs are more water solublethan high
6、er molecular weight PAHs. Therefore, USEPA-regulated PAH concentrations in pore water samples varywidely due to differing saturation water solubilities that rangefrom 0.2 g/L for indeno1,2,3-cdpyrene to 31 000 g/L fornaphthalene. This method can accommodate the measurementof microgram per litre conc
7、entrations for low molecular weightPAHs and nanogram per litre concentrations for high molecularweight PAHs.1.3 The USEPA narcosis model predicts toxicity to benthicorganisms if the sum of the toxic units (TUc) calculated for all“34 PAHs” measured in a pore water sample is greater than orequal to 1.
8、 For this reason, the performance limit required forthe individual PAH measurements was defined as the concen-tration of an individual PAH that would yield134 of a toxic unit(TU). However, the focus of this method is the 10 parent PAHsand 14 groups of alkylated PAHs (Table 1) that contribute 95 %of
9、the toxic units based on the analysis of 120 background andimpacted sediment pore water samples.3The primary reasonsfor 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
10、that will make the detection of these compounds difficult inpore water. This method can achieve the required detectionlimits, which range from approximately 0.01 g/L, for highmolecular weight PAHs, to approximately 3 g/L for lowmolecular weight PAHs.1.4 The test method may also be applied to the det
11、ermina-tion of additional PAH compounds (for example, 5- and 6-ringPAHs as described in Hawthorne et al.).4However, it is theresponsibility of the user of this standard to establish thevalidity of the test method for the determination of PAHs otherthan those referenced in 1.1 and Table 1.1.5 This st
12、andard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. For specific hazardstatem
13、ents, refer to Section 9.1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved March 15, 2013. Published May 2013. Originallyapproved in 2007. La
14、st previous edition approved in 2011 as D7363 11. DOI:10.1520/D7363-13.2Standard methods under the jurisdiction of ASTM Committee D19 may bepublished for a limited time preliminary to the completion of full collaborative studyvalidation. Such standards are deemed to have met all other D19 qualifying
15、requirements but have not completed the required validation studies to fullycharacterize the performance of the test method across multiple laboratories andmatrices. Preliminary publication is done to make current technology accessible tousers of standards, and to solicit additional input from the u
16、ser community.3Hawthorne, S. B., Grabanski, C. B., and Miller, D. J., “Measured PartitioningCoefficients for Parent and Akyl Polycyclic Aromatic Hydrocarbons in 114Historically Contaminated Sediments: Part I, Koc Values,” Environmental Toxicol-ogy and Chemistry, Vol 25, 2006, pp. 29012911.4Hawthorne
17、, S. B., Grabanski, C. B., Miller, D. J., and Kreitinger, J. P., “SolidPhase Microextraction Measurement of Parent and Akyl Polycyclic AromaticHydrocarbons in Milliliter Sediment Pore Water Samples and Determination ofKDOCValues,” Environmental Science Technology, Vol 39, 2005, pp. 27952803.Copyrigh
18、t ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States12. Referenced Documents2.1 ASTM Standards:5D1192 Guide for Equipment for Sampling Water and Steamin Closed Conduits (Withdrawn 2003)6D1193 Specification for Reagent WaterD2777 Practice for Deter
19、mination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Closed ConduitsE178 Practice for Dealing With Outlying Observations3. Terminology3.1 Definitions:3.1.1 calibration standarda solution prepared from a sec-ondary standard, stock s
20、olution, or both, and used to calibratethe response of the instrument with respect to analyte concen-tration.3.1.2 calibration verification standard (VER)the mid-point calibration standard (CS3) that is analyzed daily to verifythe initial calibration.3.1.3 CS1, CS2, CS3, CS4shorthand notation for ca
21、libra-tion standards.3.1.4 data acquisition parametersparameters affecting thescanning operation and conversion of the analytical signal todigitized data files. These include the configuration of theADCcircuitry, the ion dwell time, the MID cycle time, and acqui-sition modes set up for the method. E
22、xamples of acquisitionmodes for the HP5973 include SIM mode, and Low MassResolution Mode.3.1.5 performance limitperformance limit for an indi-vidual PAH is defined as the concentration of an individualPAH that would yield134 of a toxic unit. For a performancelimit of an individual PAH, refer to Tabl
23、e 1.3.1.6 deuterated PAH (d-PAH)polycyclic aromatic hydro-carbons in which deuterium atoms are substituted for allhydrogens (that is, perdeuterated). In this method, d-PAHs areused as internal standards.3.1.7 GCgas chromatograph or gas chromatography.3.1.8 HRGChigh resolution GC.3.1.9 LRMSlow resolu
24、tion MS.3.1.10 internal standardsisotopically labeled analogs (d-PAHs) of the target analytes that are added to every sample,blank, quality control spike sample, and calibration solution.They are added to the water samples immediately aftercompleting the flocculation step and transferring the watera
25、liquot to the autosampler vial, and immediately after addingthe calibration PAH solution to water calibration standards, butbefore SPME extraction. The internal standards are used tocalculate the concentration of the target analytes or estimateddetection limits.5For referenced ASTM standards, visit
26、the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.6The last approved version of this historical standard is referenced onwww.astm.org.TABLE 1 Target
27、PAHs, Toxic Unit Factors and Performance LimitsAAnalyteAdded d-PAHInternalStandardd-PAH InternalStd. forCalculationConc. for OneToxic Unit,Ctu, (ng/mL)Performance Limit(ng/mL)Basis forPerformanceLimitBNaphthalene A A 193.47 5.69 B2-Methylnaphthalene B 81.69 2.40 B1-Methylnaphthalene B B 81.69 2.40 B
28、C2-Naphthalenes A 30.24 0.89 BC3-Naphthalenes A 11.10 0.33 BC4-Naphthalenes A 4.05 0.12 CAcenaphthylene C 308.85 9.03 BAcenaphthene C C 55.85 1.64 BFluorene D D 39.30 1.16 BC1-Fluorenes D 13.99 0.41 BC2-Fluorenes D 5.30 0.16 BC3-Fluorenes D 1.92 0.06 SPhenanthrene E E 19.13 0.56 BAnthracene E 20.72
29、0.61 BC1-Phenanthrenes/Anthracenes E 7.44 0.22 BC2-Phenanthrenes/Anthracenes E 3.20 0.09 BC3-Phenanthrenes/Anthracenes E 1.26 0.04 BC4-Phenanthrenes/Anthracenes E 0.56 0.02 SFluoranthene F 7.11 0.21 BPyrene F F 10.11 0.30 BC1-Fluoranthenes/Pyrenes F 4.89 0.14 CBenzaanthracene G 2.23 0.066 BChrysene
30、G G 2.04 0.060 BC1-Chrysenes/Benzaanthracenes G 0.86 0.025 CAFrom Hawthorne, S. B., Grabanski, C. B., Miller, D. J., and Kreitinger, J. P., “Solid Phase Microextraction Measurement of Parent and Alkyl Polycyclic AromaticHydrocarbons in Milliliter Sediment Pore Water Samples and Determination of KDOC
31、Values,” Environmental Science Technology, Vol 39, 2005, pp. 27952803.BPerformance limits were determined as 3 times the background concentrations from the SPME fiber based on the analysis of water blanks (“B”), the lowest calibrationstandard which consistently yielded a signal to noise ratio of at
32、least 3:1 (“C”), or (for when no calibration standard was available) for the lowest concentrations consistentlyfound 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.D7363 1323.1.11 laboratory blanksee method blank
33、.3.1.12 method blankan aliquot of reagent water that isextracted and analyzed along with the samples to monitor forlaboratory contamination. Blanks should consistently meetconcentrations at or less than one-third of the performancelimits for individual PAHs stated in Table 1. Alternatively, ifthe PA
34、H concentrations calculated from the water blankimmediately preceding the test samples are 0.99, and the area ratio per ng for each concentrationshould show a relative standard deviation of 0.99. The calibration curve must notbe forced through the origin; (3) The number of calibrationstandards may b
35、e reduced from four to three based on thecriteria in 12.3 of this test method.16.1.2 The following corrective action will be adopted forinitial calibration: (1) Initial calibration must be re-establishedif the RSD(s) exceed the limit(s); (2) The calibration will notbe re-established in response to a
36、 nonconforming RSD if thesample results are less than the PQL.16.2 Daily Duplicate Calibration Verifications:TABLE 9 HP-3 Medium Concentration Quality ControlAnalyteTrue SpikedValue(ng/mL)Number ofRetainedValuesMeanRecovery(ng/mL)MeanRecovery(%)SingleStandardDeviation(So)RelativeStandardDeviation(%)
37、2-Methylnaphthalene-d10 26.7 7 26.7 100.1 0.859 3.2Benzaanthracene-d12 0.25 7 0.199 81.0 0.015 7.5TABLE 10 HP-4 High Concentration Quality ControlAnalyteTrue SpikedValue(ng/mL)Number ofRetainedValuesMeanRecovery(ng/mL)MeanRecovery(%)SingleStandardDeviation(So)RelativeStandardDeviation(%)2-Methylnaph
38、thalene-d10 283.9 7 230.7 81.3 11.0 4.8Benzaanthracene-d12 2.61 7 2.13 81.7 0.13 5.9FIG. 1 2-Methylnaphthalene-d10 Single Standard Deviation versus Spiked ConcentrationFIG. 2 Methylnaphthalene-d10 Mean Measured Value versus Spiked ConcentrationD7363 131416.2.1 The following acceptance criteria will
39、be used fordaily duplicate calibration verifications: (1) The S/N ratio forthe GC signals present in every SICP must be 10:1 for thelabeled internal standards and the calibration compounds; (2)The percent differences for the measured area ratio/ng of allanalytes must be within 625 % for high molecul
40、ar weightPAHs and less than 620 % for low molecular weight PAHs ofthe mean values established during the initial calibration.16.2.2 The following corrective action will be adopted fordaily duplicate calibration verifications if the first acceptancecriterion is not satisfied: a new initial calibratio
41、n curve must beestablished before sample extracts can be analyzed.16.3 Flocculation Blanks:16.3.1 The following acceptance criterion will be used forflocculation blanks: Prepared as needed to assess contamina-tion from flocculation reagents and handling. Target analytesmust not be detected above13 o
42、f the target detection limits or20 % of the associated sample result(s).16.3.2 The following corrective action will be adopted forflocculation blanks: Locate the source of the contamination;correct the problem. Re-extract and reanalyze associatedsamples that are less than ten times the level of the
43、contami-nants present in the method blank.FIG. 3 Benzaanthracene-d12 Single Standard Deviation versus Spiked ConcentrationFIG. 4 Benzaanthracene-d12 Mean Measured Value versus Spiked ConcentrationFIG. 5 Total PAH24Standard Deviation and Mean Recovery versus Youden Pair ConcentrationD7363 131516.4 Ex
44、traction and Analytical Blanks:16.4.1 The following acceptance criterion will be used forextraction and analytical blanks: Analyzed between everysample to monitor the baseline. Target analytes must not bedetected above13 of the target detection limits or 20 % of theassociated sample result(s).16.4.2
45、 The following corrective action will be adopted forextraction and analytical blanks: Locate the source of thecontamination; correct the problem. Re-extract and reanalyzeassociated samples that are less than ten times the level of thecontaminants present in the method blank.16.5 Signal to Noise Rati
46、on:16.5.1 The following acceptance criterion will be used forsignal to noise ratio: The signal to noise (S/N) ratio for the GCsignals present in every selected ion current profile (SICP)must be 3:1 for target compounds in environmental samplesand 10:1 for the labeled internal standards.16.5.2 The fo
47、llowing corrective action will be adopted forsignal to noise ratio: Reanalyze the sample unless obviousmatrix interference is present.APPENDIX(Nonmandatory Information)X1. ION PLOTSX1.1 Selected ion chromatograms from a typical coal tarimpacted pore water of d-PAH internal standards (top chro-matogr
48、am of each page), and the related target parent and alkylPAHs. Target species are indicated with brackets, and interfer-ing species are marked with an “X.”D7363 1316FIG. X1.1 NaphthalenesD7363 1317FIG. X1.2 Methylnaphthalenes(“s” is a spiked d10-methylnaphthalene surrogate)D7363 1318FIG. X1.3 Acenap
49、hthylene/AcenaphtheneD7363 1319FIG. X1.4 FluorenesD7363 1320FIG. X1.5 Phenanthrenes/AnthracenesD7363 1321FIG. X1.6 Fluoranthenes/PyrenesD7363 1322FIG. X1.7 Benzaanthracenes/Chrysenes(“s” is a spiked d12-benzaanthracene surrogate)D7363 1323ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of s
