1、Designation: D7363 11D7363 13aStandard 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
2、 number 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.Note
3、Balloted information was included and the year date changed on May 17, 2013.1. Scope1.1 The U.S. Environmental ProtectionAgency (USEPA) narcosis model for benthic organisms in sediments contaminated withpolycyclic aromatic hydrocarbons (PAHs) is based on the concentrations of dissolved PAHs in the i
4、nterstitial 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 daughterPAHs in the pore
5、 water samples. The “24 PAHs” are determined using solid-phase microextraction (SPME) followed by GasChromatography/Mass Spectrometry (GC/MS) analysis in selected ion monitoring (SIM) mode. Isotopically labeled analogs of thetarget compounds are introduced prior to the extraction, and are used as qu
6、antification references.1.2 Lower molecular weight PAHs are more water soluble than higher molecular weight PAHs. Therefore, USEPA-regulatedPAH concentrations in pore water samples vary widely due to differing saturation water solubilities that range from 0.2 g/L forindeno1,2,3-cdpyrene to 31 000 g/
7、L for naphthalene. This method can accommodate the measurement of milligrammicrogramper litre concentrations for low molecular weight PAHs and nanogram per litre concentrations for high molecular weight PAHs.1.3 The USEPAnarcosis model predicts toxicity to benthic organisms if the sum of the toxic u
8、nits (TUc) calculated for all “34PAHs” measured in a pore water sample is greater than or equal to 1. For this reason, the performance limit required for theindividual PAH measurements was defined as the concentration of an individual PAH that would yield 1/34134 of a toxic unit (TU).However, the fo
9、cus of this method is the 10 parent PAHs and 14 groups of alkylated PAHs (Table 1) that contribute 95 % of thetoxic units based on the analysis of 120 background and impacted sediment pore water samples.3 The primary reasons foreliminating the rest of the 5-6 ring parent PAHs are: (1) these PAHs con
10、tribute insignificantly to the pore water TU, and (2) thesePAHs exhibit extremely low saturation solubilities that will make the detection of these compounds difficult in pore water. Thismethod can achieve the required detection limits, which range from approximately 0.01 g/L, for high molecular wei
11、ght PAHs,to approximately 3 g/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 PAHsas described in Hawthorne et al).al.).4 However, it is the responsibility of the user of this standard to establish t
12、he validity of thetest 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 forOrganic Substances in Water.Curren
13、t edition approved Dec. 1, 2011May 17, 2013. Published December 2011November 2013. Originally approved in 2007. Last previous edition published 2007approved in 2013 as D736311. DOI: 10.1520/D7363-11. 13. DOI: 10.1520/D7363-13A.2 Standard methods under the jurisdiction of ASTM Committee D19 may be pu
14、blished for a limited time preliminary to the completion of full collaborative studyvalidation. Such standards are deemed to have met all other D19 qualifying requirements but have not completed the required validation studies to fully characterize theperformance of the test method across multiple l
15、aboratories and matrices. Preliminary publication is done to make current technology accessible to users ofStandards,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 Pol
16、ycyclic Aromatic Hydrocarbons in 114 HistoricallyContaminated Sediments: Part I, Koc Values,” Environmental Toxicology and Chemistry, 25, 2006, pp. 2901-2911. Hawthorne, S. B., Grabanski, C. B., and Miller, D. J.,“Measured Partitioning Coefficients for Parent andAlgae PolycyclicAromatic Hydrocarbons
17、 in 114 Historically Contaminated Sediments: Part I, Koc Values,” EnvironmentalToxicology and Chemistry, Vol 25, 2006, pp. 29012911.4 Hawthorne, S. B., Grabanski, C.B., Miller, D .J., and Kreitinger, J. P., “Solid Phase Microextraction Measurement of Parent andAkyl PolycyclicAromatic Hydrocarbonsin
18、Milliliter Sediment Pore Water Samples and Determination of KDOC Values,” Environmental Science Technology, 39, 2005, pp. 2795-2803.Hawthorne, S. B., Grabanski,C. B., Miller, D. J., and Kreitinger, J. P., “Solid Phase Microextraction Measurement of Parent andAkyl PolycyclicAromatic Hydrocarbons in M
19、illiliter Sediment Pore WaterSamples and Determination of KDOC Values,” Environmental Science Technology, Vol 39, 2005, pp. 27952803.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
20、. Becauseit 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 versionof the standard as published by ASTM is to be considered the official document.Copyright ASTM International,
21、 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States11.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.6 This standard does not purport to address all of the safety concerns, if any, associa
22、ted with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use. For specific hazard statements, refer to Section 9.2. Referenced Documents2.1 ASTM Standards:5D1192 Guide
23、 for Equipment for Sampling Water and Steam in Closed Conduits (Withdrawn 2003)6D1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Closed ConduitsD5847 Practice for Wr
24、iting Quality Control Specifications for Standard Test Methods for Water AnalysisE178 Practice for Dealing With Outlying Observations3. Terminology3.1 Definitions:3.1.1 calibration standarda solution prepared from a secondary standard, stock solution, or both, and used to calibrate theresponse of th
25、e instrument with respect to analyte concentration.5 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.6 The last
26、 approved version of this historical standard is referenced on www.astm.org.TABLE 1 Target PAHs, Toxic Unit Factors and Performance LimitsAcolwidth=“43.42*“/COLSPECcolwidth=“8.89*“/COLSPECcolwidth=“10.33*“/COLSPECcolwidth=“12.75*“/COLSPECcolwidth=“11.60*“/COLSPECcolwidth=“13.04*“/COLSPECAnalyte Adde
27、d d-PAHInternalStandardd-PAH InternalStd. for CalculationConc. for OneToxic Unit,Ctu, (ng/mL)Performance LimiLimitt (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 BC2-Naphthalenes A 30.24 0.89 BC3-Naphthalenes A 11.1
28、0 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 0.61 BC1-Phenanthrenes/Anthracenes E 7.44 0.22 BC2-P
29、henanthrenes/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 G G 2.04 0.060 BC1-Chrysenes/Benzaanthracenes G 0.86
30、 0.025 CA From Hawthorne, S. B., Grabanski, C.B., Miller, D .J.,C. B., Miller, D. J., and Kreitinger, J. P., “Solid Phase Microextraction Measurement of Parent and Alkyl PolycyclicAromatic Hydrocarbons in Milliliter Sediment Pore Water Samples and Determination of KDOC Values,” Environmental Science
31、 Technology, Vol 39, 2005, pp.2795-2803.27952803.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 calibrationstandard which consistently yielded a signal to noise ratio of at least 3:1 (“C”), or
32、(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.C Alkyl PAHs used to determine the SPME-GC/MS relative response fact
33、ors including alkyl naphthalenes (1-methyl-, 2-methyl-, 1,2-dimethyl-, 1,3-dimethyl- 1,8-dimethyl-,2,7-dimethyl-, 1-ethyl, 2-ethyl, 1,4,5-trimethyl-, 2,3,5-trimethyl-, and 2-isopropyl-), 1-methylfluorene, 2-methyl- and 9-methylanthracene, 1-methyl-, 2-methyl-, and3-methylphenanthrene, 9,10-dimethyla
34、nthracene, 2-ethylanthracene, 2-tertbutylanthracene, 1-methyl-7-isopropylphenanthrene, 1-methylpyrene,7-methylbenzaanthracene, and 7,12-dimethylbenzaanthracene.D All relative response factors are based on the SPME-GC/MS peak area per ng of the alkyl PAH in a water standard compared to that of its pa
35、rent PAH as determinedby SPME followed by GC/MS.When several isomers were available, (for example, C2-naphthalenes), the mean relative response factor is reported. The relative responsefactors of alkyl PAHs for which no standards were available were estimated based on the closest analogous alkyl PAH
36、 as described in reference 2.1.E From 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 Values,” Environmental Scien
37、ce Technology, 39, 2005, pp. 2795-2803.D7363 13a23.1.2 calibration verification standard (VER)the mid-point calibration standard (CS3) that is analyzed daily to verify theinitial calibration.3.1.3 CS1, CS2, CS3, CS4shorthand notation for calibration standards.3.1.4 data acquisition parametersparamet
38、ers affecting the scanning operation and conversion of the analytical signal todigitized data files. These include the configuration of the ADC circuitry, the ion dwell time, the MID cycle time, and acquisitionmodes set up for the method. Examples of acquisition modes for the HP5973 include SIM mode
39、, and Low Mass Resolution Mode.3.1.5 performance limitperformance limit for an individual PAH is defined as the concentration of an individual PAH thatwould yield 1/34134 of a toxic unit. For a performance limit of an individual PAH, refer to Table 1 (see 4.84.6).3.1.6 deuterated PAH (d-PAH)polycycl
40、ic aromatic hydrocarbons in which deuterium atoms are substituted for all hydrogens(that is, perdeuterated). In this method, d-PAHs are used 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 standardsisotopi
41、cally 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 after completing theflocculation step and transferring the water aliquot to the autosampler vial, and im
42、mediately after adding the calibration PAHsolution to water calibration standards, but before SPME extraction. The internal standards are used to calculate the concentrationof the target analytes or estimated detection limits.3.1.11 laboratory blanksee method blank.3.1.12 method blankan aliquot of r
43、eagent water that is extracted and analyzed along with the samples to monitor for laboratorycontamination. Blanks should consistently meet concentrations at or less than one-third of the performance limits for individualPAHs stated in Table 1. Alternatively, if the PAH concentrations calculated from
44、 the water blank immediately preceding the testsamples are 0.99, and the area ratio per ng for each concentration should show a relative standard deviation of 0.99. The calibration curve must not be forced through the origin; (3) The number of calibration standards may be reducedfrom four to three b
45、ased on the criteria in 12.3 of this test method.16.1.2 The following corrective action will be adopted for initial calibration: (1) Initial calibration must be re-established if theRSD(s) exceed the limit(s); (2) The calibration will not be re-established in response to a nonconforming RSD if the s
46、ample resultsare less than the PQL.Performance Limit.16.2 Daily Duplicate Calibration Verifications:16.2.1 The following acceptance criteria will be used for daily duplicate calibration verifications: (1) The S/N ratio for the GCsignals present in every SICP must be 10:1 for the labeled internal sta
47、ndards and the calibration compounds; (2) The percentdifferences for the measured area ratio/ng of all analytes must be within 625 % for high molecular weight PAHs and less than620 % for low molecular weight PAHs of the mean values established during the initial calibration.16.2.2 The following corr
48、ective action will be adopted for daily duplicate calibration verifications if the first acceptancecriterion is not satisfied: a new initial calibration curve must be established before sample extracts can be analyzed.16.3 Flocculation Blanks:16.3.1 The following acceptance criterion will be used fo
49、r flocculation blanks: Prepared as needed to assess contamination fromflocculation reagents and handling. Target analytes must not be detected above 13 of the target detection limits or 20 % of theassociated sample result(s).16.3.2 The following corrective action will be adopted for flocculation blanks: Locate the source of the contamination; correctthe problem. Re-extract and reanalyze associated samples that are less than ten times the level of the contaminants present in themethod blank.16.4 Extraction and Analytical Blanks:16.4.1 The followi
