1、Designation: D7363 11Standard 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
2、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 () indicates an editorial change since the last revision or reapproval.1. Scope1.1
3、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 of
4、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) fo
5、llowed 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 hig
6、her 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 con
7、centrations 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 to
8、1. For this reason, the performance limit requiredfor the individual PAH measurements was 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 % o
9、f 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 saturationsolubilitie
10、s 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 forlow molecular weight PAHs.1.4 The test method may also be applied to the d
11、etermina-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 s
12、tandard 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 hazardstate
13、ments, refer to Section 9.2. Referenced Documents2.1 ASTM Standards:51This 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 Dec. 1, 2011. Publishe
14、d December 2011. Last previousedition published 2007 as D736311. DOI: 10.1520/D7363-11.2Standard 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 othe
15、r D19 qualifyingrequirements 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
16、input from the user 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. 2901-29
17、11.4Hawthorne, 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, 39, 2005, pp. 2795-2803
18、.5For referenced ASTM 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
19、 C700, West Conshohocken, PA 19428-2959, United States.D1192 Guide for Equipment for Sampling Water and Steamin Closed Conduits6D1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling
20、Water from Closed ConduitsD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water AnalysisE178 Practice for Dealing With Outlying Observations3. Terminology3.1 Definitions:3.1.1 calibration standarda solution prepared from asecondary standard, stock solution, or
21、both, and used tocalibrate the response of the instrument with 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 sta
22、ndards.3.1.4 data acquisition parametersparameters affectingthe 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 acqu
23、i-sition modes for the HP5973 include SIM mode, and LowMass Resolution Mode.3.1.5 performance limitperformance limit for an indi-vidual PAH is defined as the concentration of an individualPAH that would yield 1/34 of a toxic unit. For a performancelimit of an individual PAH, refer to Table 1 (see 4.
24、8).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 resolut
25、ion 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 wateral
26、iquot 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.3.1.11 laboratory blanksee method blank
27、.6Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.TABLE 1 Target PAHs, Toxic Unit Factors and PerformanceLimitsAAnalyteAdded d-PAHInternalStandardd-PAH InternalStd. for CalculationConc. for OneToxic Unit,Ctu, (ng/mL)Performance Limit (ng/mL)Basis forPerf
28、ormanceLimitBNaphthalene A A 193.47 5.69 B2-Methylnaphthalene B 81.69 2.40 B1-Methylnaphthalene B B 81.69 2.40 BC2-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
29、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 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
30、 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 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
31、 and Alkyl Polycyclic Aro-matic Hydrocarbons in Milliliter Sediment Pore Water Samples and Determinationof KDOCValues,” Environmental Science Technology, 39, 2005, pp. 2795-2803.BPerformance limits were determined as 3 times the background concentra-tions from the SPME fiber based on the analysis of
32、 water blanks (“B”), the lowestcalibration 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 concen-trations consistently found in pore water samples with a signal to noise ratio of atleast 3:1 (“S”).
33、Detection limits for alkyl PAHs are based on a single isomer.D7363 1123.1.12 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 performance
34、limits for individual PAHs stated in Table 1. Alternatively, ifthe PAH 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 fo
35、rced through the origin; (3) The number of calibrationstandards may be 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 lim
36、it(s); (2) The calibration will notbe re-established in response to a nonconforming RSD if thesample results are less than the PQL.TABLE 9 HP-3 Medium Concentration Quality ControlAnalyteTrue SpikedValue(ng/mL)Number ofRetainedValuesMeanRecovery(ng/mL)MeanRecovery(%)SingleStandardDeviation(So)Relati
37、veStandardDeviation(%)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)RelativeStandardDe
38、viation(%)2-Methylnaphthalene-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 111416.2 Daily Duplicate Cal
39、ibration Verifications:16.2.1 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 internal standards and the calibration compounds; (2)The percent differences for the measu
40、red 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 calibration verifications if th
41、e 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 contamina-tion from flocculatio
42、n 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 problem. Re-extract and rean
43、alyze associatedsamples that are less than ten times the level of the contami-nants present in the method blank.16.4 Extraction and Analytical Blanks:FIG. 3 Benzaanthracene-d12 Single Standard Deviation versus Spiked ConcentrationFIG. 4 Benzaanthracene-d12 Mean Measured Value versus Spiked Concentra
44、tionFIG. 5 Total PAH24Standard Deviation and Mean Recovery versus Youden Pair ConcentrationD7363 111516.4.1 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 ta
45、rget 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-extract and reanalyzeassociated samples that are less than ten times the level of
46、 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 selected ion current profile (SICP)must be $3:1 for target compounds in environ
47、mental 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(Nonmandatory Information)X1. ION PLOTSX1.1 Selected ion chromatograms from a typical
48、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.”D7363 1116FIG. X1.1 NaphthalenesD7363 1117FIG. X1.2 Methylnaphthalenes(“s
49、” is a spiked d10-methylnaphthalene surrogate)D7363 1118FIG. X1.3 Acenaphthylene/AcenaphtheneD7363 1119FIG. X1.4 FluorenesD7363 1120FIG. X1.5 Phenanthrenes/AnthracenesD7363 1121FIG. X1.6 Fluoranthenes/PyrenesD7363 1122FIG. X1.7 Benzaanthracenes/Chrysenes(“s” is a spiked d12-benzaanthracene surrogate)D7363 1123ASTM 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 validi
