1、Designation: D 7363 07Standard 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 D 7363; the numbe
2、r immediately 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope1
3、.1 The 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
4、of pore 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)
5、 followed 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
6、higher 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 milligram per litre
7、concentrations 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 (STUc) calculated forall “34 PAHs” measured in a pore water sample is greater thanor equal
8、to 1. For this reason, the performance limit requiredfor the individual PAH measurements were defined as theconcentration of an individual PAH that would yield 1/34 of atoxic unit (TU). However, the focus of this method is the 10parent PAHs and 14 groups of alkylated PAHs (Table 1) thatcontribute 95
9、 % of the toxic units based on the analysis of 120background and impacted sediment pore water samples.3Theprimary reasons for eliminating the rest of the 5-6 ring parentPAHs are: (1) these PAHs contribute insignificantly to the porewater TU, and (2) these PAHs exhibit extremely low saturationsolubil
10、ities that will make the detection of these compoundsdifficult in pore water. This method can achieve the requireddetection limits, which range from approximately 0.01 g/L,for high molecular weight PAHs, to approximately 3 g/L forhigh molecular weight PAHs.1.4 The test method may also be applied to
11、the determina-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 T
12、his standard 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 hazard
13、statements, refer to Section 9.2. Referenced Documents2.1 ASTM Standards:5D 1192 Guide for Equipment for Sampling Water and1This 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
14、 Water.Current edition approved Aug. 1, 2007. Published August 2007.2Standard 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 qualifyingreq
15、uirements 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 user
16、 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, 25, 2006, pp. 2901-2911.4Hawthorne, S. B
17、., Grabanski, C.B., Miller, D .J., and Kreitinger, J. P., “SolidPhase Microextraction Measurement of Parent and Alkyl Polycyclic AromaticHydrocarbons in Milliliter Sediment Pore Water Samples and Determination ofKDOCValues,” Environmental Science Technology, 39, 2005, pp. 2795-2803.5For referenced A
18、STM standards, visit 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.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Consho
19、hocken, PA 19428-2959, United States.Steam in Closed Conduits6D 1193 Specification for Reagent WaterD 2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD 3370 Practices for Sampling Water from Closed ConduitsD 5847 Practice for Writing Quality C
20、ontrol Specificationsfor Standard Test Methods for Water AnalysisE 178 Practice for Dealing With Outlying Observations3. Terminology3.1 Definitions:3.1.1 calibration standarda solution prepared from asecondary standard, stock solution, or both, and used tocalibrate the response of the instrument wit
21、h respect to analyteconcentration.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 calibra-tion standards.3.1.4 data acquisition parametersparameters affectingt
22、he scanning operation and conversion of the analytical signalto digitized data files. These include the configuration of theADC circuitry, the ion dwell time, the MID cycle time, andacquisition modes set up for the method. Examples of acqui-sition modes for the HP5973 include SIM mode, and LowMass R
23、esolution Mode.3.1.5 performance limitperformance limit for individualPAH is defined as the concentration of an individual PAH thatwould yield 1/34 of a toxic unit. For performance limit ofindividual PAH, refer to Table 2 (see 4.6).3.1.6 deuterated PAH (d-PAH)polycyclic aromatic hydro-carbons in whi
24、ch 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 resolution MS.3.1.10 internal standardsisotopically labeled analogs (d-PAHs) o
25、f 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 wateraliquot to the autosampler vial, and immediately after addingthe calibrat
26、ion PAH solution to water calibration standards, butbefore SPME extraction. The internal standards are used tocalculate the concentration of the target analytes or estimateddetection limits.3.1.11 laboratory blanksee method blank.3.1.12 method blankan aliquot of reagent water that isextracted and an
27、alyzed 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 2. Alternatively, ifthe PAH concentrations calculated from the water blankimmediately preceding t
28、he test samples are 0.99, and the relative response factor per ng for eachconcentration should show a relative standard deviation of0.99. The calibration curve must notbe forced through the origin; (3) The number of calibrationstandards may be reduced from four to three based on thecriteria in 12.3
29、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 nonconforming RSD if thesample results are less than the
30、PQL.16.2 Daily Duplicate Calibration Verifications:TABLE 8 HP-24 Low Concentration Quality ControlAnalyteTrue SpikedValue(ng/mL)Number ofRetainedValuesMeanRecovery(ng/mL)MeanRecovery(%)SingleStandardDeviation(So)RelativeStandardDeviation(%)2-Methylnaphthalene-d10 4.68 7 4.33 92.6 0.3161 7.3Benzaanth
31、racene-d12 0.0429 7 0.0352 81.9 0.0031 8.8TABLE 9 HP-3 Medium Concentration Quality ControlAnalyteTrue SpikedValue(ng/mL)Number ofRetainedValuesMeanRecovery(ng/mL)MeanRecovery(%)SingleStandardDeviation(So)RelativeStandardDeviation(%)2-Methylnaphthalene-d10 26.7 7 26.7 100.1 0.859 3.2Benzaanthracene-
32、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-Methylnaphthalene-d10 283.9 7 230.7 81.3 11.0 4.8Benzaanthracene-d12 2.61 7 2
33、.13 81.7 0.13 5.9FIG. 1 2-Methylnaphthalene-d10 Single Standard Deviation versus Spiked ConcentrationD7363071316.2.1 The following acceptance criteria will be used fordaily duplicate calibration verifications: (1) The S/N ratio forthe GC signals present in every SICP must be $10:1 for thelabeled int
34、ernal standards and the calibration compounds; (2)FIG. 2 Methylnaphthalene-d10 Mean Measured Value versus Spiked ConcentrationFIG. 3 Benzaanthracene-d12 Single Standard Deviation versus Spiked ConcentrationFIG. 4 Benzaanthracene-d12 Mean Measured Value versus Spiked ConcentrationD73630714The percent
35、 differences for the measured area ratio/ng of allanalytes must be within 625 % for high molecular 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 calib
36、ration verifications if the first acceptancecriterion is not satisfied: a new initial calibration 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 conta
37、mina-tion from flocculation reagents and handling. Target analytesmust not be detected above13 of 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 pr
38、oblem. Re-extract and reanalyze associatedsamples that are less than ten times the level of the contami-nants present in the method blank.16.4 Extraction and Analytical Blanks:16.4.1 The following acceptance criterion will be used forextraction and analytical blanks: Analyzed between everysample to
39、monitor the baseline. Target analytes must not bedetected above13 of the target detection limits or 20 % of theassociated sample result(s).16.4.2 The following corrective action will be adopted forextraction and analytical blanks: Locate the source of thecontamination; correct the problem. Re-extrac
40、t and reanalyzeassociated samples that are less than ten times the level of thecontaminants present in the method blank.16.5 Signal to Noise Ration: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 sele
41、cted 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 following corrective action will be adopted forsignal to noise ratio: Reanalyze the sample unless obviousmatrix interference is present.APPENDIX(Nonmandato
42、ry Information)X1. ION PLOTSX1.1 Selected ion chromatograms from a typical coal tarimpacted pore water of d-PAH internal standards (top chro-matogram 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
43、.”D73630715FIG. X1.1 NaphthalenesD73630716FIG. X1.2 Methylnaphthalenes(“s” is a spiked d10-methylnaphthalene surrogate)D73630717FIG. X1.3 Acenaphthylene/AcenaphtheneD73630718FIG. X1.4 FluorenesD73630719FIG. X1.5 Phenanthrenes/AnthracenesD73630720FIG. X1.6 Fluoranthenes/PyrenesD73630721FIG. X1.7 Benz
44、aanthracenes/Chrysenes(“s” is a spiked d12-benzaanthracene surrogate)D73630722ASTM 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 valid
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47、ot received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).D73630723
