1、Designation: D4128 06 (Reapproved 2012)D4128 18Standard Guide forIdentification and Quantitation of Organic Compounds inWater by Combined Gas Chromatography and ElectronImpact Mass Spectrometry1This standard is issued under the fixed designation D4128; the number immediately following the designatio
2、n 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 This guide covers the identification
3、 and quantitation of organic compounds by gas chromatography/mass spectrometry(GC-MS) (electron impact) that are present or extracted from water and are capable of passing through a gas chromatographwithout alteration. The guide is intended primarily for solutions for which 1 ng or more of any compo
4、nent of interest can beintroduced onto a gas chromatographic column. This guide has the advantage of providingThis guide can be used to providetentative identifications of volatile and semi-volatile organics, but is restricted to (a) compounds for which reference spectra canbe obtained and (b) compo
5、unds that can be separated by gas chromatography (GC). These restrictions are imposed on the guide,but are not a limitation of the technique. The guide is written for, but not restricted to, for analysis using automated data acquisitionand handling.1.2 Guidelines have been included for quantitation
6、using ASTM Test Methods D3871, D3973, and other GC-MS volatile/semivolatile procedures used for environmental analysis2. A detection amount of 1 ng can only be considered approximate. Theactual detection limits for each component must be determined in each laboratory. Actual detection amounts will v
7、ary with thecomplexity of the matrix, the kind and condition of the GC-MS system, the sample preparation technique chosen, and theapplication of cleanup techniques to the sample extract, if any. Lower levels of detection can be achieved using modern sensitiveinstruments or with selected ion monitori
8、ng (SIM). To determine the interlaboratory detection estimate (IDE) and theinterlaboratory quantitation estimate (IQE), follow Practices D6091 and D6512.1.3 The guide is applicable to the identification of many organic constituents of natural and treated waters. It includes all modesof sample introd
9、uction, including injection of organic extracts, direct aqueous injection, and purge and trap techniques.1.4 The guide is applicable to either packed or capillary column gas chromatography, including wide-bore capillary columns.Because of their greatly enhanced resolution, capillary columns are stro
10、ngly recommended.chromatography.1.5 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, associated with its use. It is the responsibilityof the user
11、 of this standard to establish appropriate safety, health, and environmental practices and determine the applicability ofregulatory limitations prior to use.1.7 This international standard was developed in accordance with internationally recognized principles on standardizationestablished in the Dec
12、ision on Principles for the Development of International Standards, Guides and Recommendations issuedby the World Trade Organization Technical Barriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:3D1066 Practice for Sampling SteamD1129 Terminology Relating to Water1 This guide
13、 is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for OrganicSubstances in WaterCurrent edition approved June 15, 2012Dec. 15, 2018. Published August 2012January 2019. Originally published in 1982. Last previous
14、edition approved in 20062012as D4128 06.D4128 06 (2012). DOI: 10.1520/D4128-06R12.10.1520/D4128-18.2 U.S. EPA Methods 624 and 82608260C (volatiles) and U.S. EPA Methods 625 and 82708270D (semivolatiles) are suitable for quantitation.3 For referencedASTM standards, visit theASTM website, www.astm.org
15、 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.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes
16、 have been made to the previous version. 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
17、 document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1D1192 Guide for Equipment for Sampling Water and Steam in Closed Conduits (Withdrawn 2003)4D1193 Specification for Reagent WaterD2908 Practice for Measuring Volatile Organic Ma
18、tter in Water by Aqueous-Injection Gas ChromatographyD3370 Practices for Sampling Water from Flowing Process StreamsD3694 Practices for Preparation of Sample Containers and for Preservation of Organic ConstituentsD3871 Test Method for Purgeable Organic Compounds in Water Using Headspace SamplingD397
19、3 Test Method for Low-Molecular Weight Halogenated Hydrocarbons in WaterD5175 Test Method for Organohalide Pesticides and Polychlorinated Biphenyls in Water by Microextraction and GasChromatographyD5316 Test Method for 1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane in Water by Microextraction and
20、 GasChromatographyD5317 Test Method for Determination of Chlorinated Organic Acid Compounds in Water by Gas Chromatography with anElectron Capture DetectorD5789 Practice for Writing Quality Control Specifications for Standard Test Methods for Organic Constituents (Withdrawn2002)4D6091 Practice for 9
21、9 %/95 % Interlaboratory Detection Estimate (IDE) for Analytical Methods with Negligible CalibrationErrorD6512 Practice for Interlaboratory Quantitation EstimateE260 Practice for Packed Column Gas ChromatographyE355 Practice for Gas Chromatography Terms and Relationships2.2 U.S. Environmental Protec
22、tion Agency:EPA Documents:EPAMethod 524.21995 Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry5EPA Method 6241984 Purgeables5EPA Method 6251984 Base/Neutrals and Acids5SW-846 Method 8270c8270D Semivolatile Organic Compounds by Gas Chromatog
23、raphy (GC-MS)6,7SW-846 Method 8260b8260C Volatile Organic Compounds by Gas Chromatography (GC-MS)6,7Methods for the Determination of Organic Compounds in Drinking Water-Supplement I, EPA/600/4-90/020, July 19905Methods for the Determination of Organic Compounds in Drinking Water-Supplement II, EPA/6
24、00/R-92/129, August 199053. Terminology3.1 Definitions:3.1.1 For definitions of terms relating to water used in this standard, refer to Terminology D1129. For definitions of termsrelating to gas chromatography used in this standard, refer to Practice E355.3.2 Definitions of Terms Specific to This St
25、andard:3.2.1 characteristic ion, nusually the primary ion in the mass spectrum used to measure response for quantitation purposes.When there are interferences in the mass chromatogram of a primary ion, a secondary characteristic ion must be used forquantitation.3.2.2 volatile organicconfirmed identi
26、fication, compoundnan organic compound that can be readily separated from water byinert gas sparging and thermally desorbed onto a GC column or is readily amenable to direct aqueous injection GC. Thecompounds must elute from the column within its temperature range without alteration of the structure
27、 of the in order to confirma tentative identification, both the GC retention time and the mass spectrum of a compound shall uniquely match those of areference compound as demonstrated by co-injection of the authentic standard with the tentatively identified compound.3.2.3 semi-volatile organicmass c
28、hromatogram, compoundnan organic(see Discussion) compound that can be separatedfrom water by extraction, either liquid/liquid or solid phase, undergo volume adjustment, and be injected onto a GC. Thecompounds must elute from the column within its temperature range without alteration of the structure
29、 of the compound.alimited mass RGC, or mass chromatogram, represents the intensities of ion currents for only those ions having particular mass tocharge ratios. It is a means of quickly scanning a complex RGC plot to locate peaks which could be specific compounds or typesof compounds. However, a com
30、plete mass spectrum is required for tentative identification.3.2.3.1 Discussion4 The last approved version of this historical standard is referenced on www.astm.org.5 Available from United States Environmental Protection Agency (EPA), William Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Wash
31、ington, DC 20460,http:/www.epa.gov.6 Available from National Technical Information Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161.5301 Shawnee Rd., Alexandria, VA 22312,http:/www.ntis.gov.7 SW 846 can be found online at http:/www.epa.gov/epaoswer/hazwaste/test/main.htm. https:/www.epa.g
32、ov/hw-sw846.D4128 182There are several synonyms in current use for mass chromatogram. These include: mass fragmentogram, extracted ion currentprofile, and limited mass reconstructed gas chromatogram.3.1.3 tentative identificationall identifications are considered tentative until confirmed by co-inje
33、ction of an authenticreference compound showing identical retention time and similar mass spectra. (Tentative identification based on library matchesonly are subjected to false positives.)3.2.4 matchmatch, ntwo criteria must be satisfied to verify a comparison of a sample component to a standard mat
34、ch: (1)elution of the sample component at the same retention time as the standard component as shown by co-injection or standardaddition, and (2) correspondence of the sample component and the standard component mass spectrum. If co-elution of interferingcomponents prohibits accurate assignment of t
35、he sample component retention time from the total ion chromatogram, the retentiontime should be assigned by using extracted ion current profiles for ions unique to the component of interest. To meet the secondcriteria, all ions present in the authentic mass spectra at a relative intensity greater th
36、an 10 % (whereas the most abundant ion inthe spectrum equals 100 %) must be present in the sample spectrum; the relative intensities of these ions must agree within620 %within 620 % between the standard and sample spectra. (As an example, for an ion with an abundance of 50 % in the standardspectra,
37、the corresponding sample abundance must be between 30 % and 70 %.) However, there may be additional peaks in thesample mass spectrum caused by co-eluting interfering components that are not present in the reference mass spectrum.3.1.5 confirmed identificationin order to confirm a tentative identific
38、ation, both the GC retention time and the mass spectrumof a compound shall uniquely match those of a reference compound as demonstrated by co-injection of the authentic standard withthe tentatively identified compound.3.2.5 reconstructed gas chromatogram (see(RGC), Note n1) (RGC)an (see Discussion)a
39、n RGC is the computer outputrepresenting either the summed intensities of all scanned ion intensities or a sample of the total current in the ion beam for eachspectrum scan plotted against the corresponding spectrum number. Generally, it can be correlated with a flame ionization detectorgas chromato
40、gram.NOTE 1There are many synonyms in common use for RGC. These include: total ionization plot, total ionization current trace, reconstructed ionchromatogram, total ion current profile, and total ion chromatogram.3.2.5.1 DiscussionThere are many synonyms in common use for RGC. These include: total i
41、onization plot, total ionization current trace,reconstructed ion chromatogram, total ion current profile, and total ion chromatogram.3.2.6 reference compoundscompounds, nthese are authentic materials used to obtain mass spectra, gas chromatographicretention data, and response factors. The operator c
42、an prepare the standards or they can be prepared commercially. Quality controlsolutions should be prepared independently from the calibration solutions. Quantitation methods may also require surrogate spikingsolutions to determine extraction efficiency.3.2.7 mass chromatogram (seesemi-volatile organ
43、ic compound, Note n2)a limited mass RGC, or mass chromatogram,represents the intensities of ion currents for only those ions having particular mass to charge ratios. It is a means of quicklyscanning a complex RGC plot to locate peaks which could be specific compounds or types of compounds. However,
44、a completemass spectrum is required for tentative identification.an organic compound that can be separated from water by extraction, eitherliquid/liquid or solid phase, undergo volume adjustment, and be injected onto a GC. The compounds must elute from the columnwithin its temperature range without
45、alteration of the structure of the compound.NOTE 2There are several synonyms in current use for mass chromatogram. These include: mass fragmentogram, extracted ion current profile, andlimited mass reconstructed gas chromatogram.3.2.8 tentative identification, nall identifications are considered tent
46、ative until confirmed by co-injection of an authenticreference compound showing identical retention time and similar mass spectra. (Tentative identification based on library matchesonly are subjected to false positives.)3.2.9 characteristic ionvolatile organic compound, nusually the primary ion in t
47、he mass spectrum used to measure responsefor quantitation purposes. When there are interferences in the mass chromatogram of a primary ion, a secondary characteristic ionmust be used for quantitation. an organic compound that can be readily separated from water by inert gas sparging and thermallydes
48、orbed onto a GC column or is readily amenable to direct aqueous injection GC. The compounds must elute from the columnwithin its temperature range without alteration of the structure of the compound.D4128 1833.2 Definitions:3.2.1 For definitions of terms relating to water used in this guide, refer t
49、o definitions in D1129. For definitions of terms relatingto gas chromatography used in this guide, refer to Practice E355.4. Summary of Practice4.1 The guide consists of the introduction of organic compounds from water into a GC-MS for mass spectral identification andguidelines to determine concentration. Volatile organic compounds are typically introduced through a purge-and-trap sampleintroduction device, although volatile compounds can also be introduced by direct aqueous injection. Semi-volatile compounds aretypically introduced as organic ex
