1、Designation: D 3694 96 (Reapproved 2004)Standard Practices forPreparation of Sample Containers and for Preservation ofOrganic Constituents1This standard is issued under the fixed designation D 3694; the number immediately following the designation indicates the year oforiginal adoption or, in the ca
2、se 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. Scope1.1 These practices cover the various means of (1) preparingsample containers used for collec
3、tion of waters to be analyzedfor organic constituents and (2) preservation of such samplesfrom the time of sample collection until the time of analysis.1.2 The sample preservation practice is dependent upon thespecific analysis to be conducted. See Section 9 for preserva-tion practices listed with t
4、he corresponding applicable generaland specific constituent test method. The preservation methodfor waterborne oils is given in Practice D 3325. Use of theinformation given herein will make it possible to choose theminimum number of sample preservation practices necessaryto ensure the integrity of a
5、 sample designated for multipleanalysis. For further considerations of sample preservation, seethe Manual on Water.21.3 This 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
6、 safety and health practices and determine the applica-bility of regulatory limitations prior to use. For specific hazardstatements, see 6.7, 6.24, and 8.1.3.2. Referenced Documents2.1 ASTM Standards:3D 1129 Terminology Relating to WaterD 1193 Specification for Reagent WaterD 1252 Test Methods for C
7、hemical Oxygen Demand(Dichromate Oxygen Demand) of WaterD 1783 Test Methods for Phenolic Compounds in WaterD 2036 Test Methods for Cyanides in WaterD 2330 Test Method for Methylene Blue Active Sub-stances4D 2579 Test Method for Total Organic Carbon in Water4D 2580 Test Method for Phenols in Water by
8、 Gas-LiquidChromatographyD 2908 Practice for Measuring Volatile Organic Matter inWater by Aqueous-Injection Gas ChromatographyD3113 Test Methods for Sodium Salts of EDTA in WaterD 3325 Practice for Preservation of Waterborne OilSamplesD 3371 Test Method for Nitriles in Aqueous Solution byGas-Liquid
9、Chromatography4D 3534 Test Method for Polychlorinated Biphenyls (PCBs)in WaterD 3590 Test Methods for Total Kjeldahl Nitrogen in Water4D 3695 Test Method for Volatile Alcohols in Water byDirect Aqueous-Injection Gas ChromatographyD 3856 Test Method for Organochlorine Pesticides in Wa-ter4D 3871 Test
10、 Method for Purgeable Organic Compounds inWater Using Headspace SamplingD 3921 Test Method for Oil and Grease and PetroleumHydrocarbons in WaterD 3973 Test Method for Low-Molecular Weight Haloge-nated Hydrocarbons in WaterD 4129 Test Method for Total and Organic Carbon in Waterby High-Temperature Ox
11、idation and Coulometric Detec-tionD 4165 Test Method for Cyanogen Chloride in WaterD 4193 Test Method for Thiocyanate in WaterD 4281 Test Method for Oil and Grease (FluorocarbonExtractable Substances) by Gravimetric DeterminationD 4282 Test Method for Determination of Free Cyanide inWater and Wastew
12、ater by MicrodiffusionD 4374 Test Methods for Cyanide in WaterAutomatedMethods for Total Cyanide,Acid Dissociable Cyanide, andThiocyanateD 4515 Practice for Estimation of Holding Time for WaterSamples Containing Organic ConstituentsD 4657 Test Method for Polynuclear Aromatic Hydrocar-bons in WaterD
13、4744 Test Method for Organic Halides in Water byCarbon Adsorption Microcoulometric Detection41These practices are under the jurisdiction of ASTM Committee D19 on Waterand are the direct responsibilities of Subcommittee D19.06 on Methods forAnalysisfor Organic Substances in Water.Current edition appr
14、oved June 1, 2004. Published June 2004. Originallyapproved in 1978. Last previous edition approved in 1996 as D 3694 96.2Manual on Water, ASTM STP 442, ASTM, 1969.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book
15、 of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4Withdrawn.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.D 4763 Practice for Identification of Chemicals in Water byFluorescence
16、SpectroscopyD 4779 Test Method for Total, Organic, and InorganicCarbon in High Purity Water by Ultraviolet (UV) orPersulfate Oxidation, or Both, and Infrared Detection4D 4839 Test Method for Total Carbon and Organic Carbonin Water by Ultraviolet, or Persulfate Oxidation, or Both,and Infrared Detecti
17、onD 4841 Practice for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic ConstituentsD 4983 Test Method for Cyclohexylamine, Morpholine,and Diethylaminoethanol in Water and Condensed Steamby Direct Aqueous Injection Gas Chromatography4D 5175 Test Method for Organohalide Pes
18、ticides and Poly-chlorinated Biphenyls in Water by Microextraction andGas ChromatographyD 5176 Test Method for Total Chemically Bound Nitrogenin Water by Pyrolysis and Chemiluminescence DetectionD 5315 Test Method for N-Methyl-Carbamoyloximes andN-Methylcarbamates in Water by DirectAqueous Injection
19、HPLC with Post-Column DerivatizationD 5316 Test Method for 1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane in Water by Microextractionand Gas ChromatographyD 5317 Test Method for the Determination of ChlorinatedOrganic Acid Compounds in Water by Gas Chromatogra-phy with an Electron Capture Detecto
20、rD 5412 Test Method for Quantification of Complex Poly-cyclic Aromatic Hydrocarbon Mixtures or Petroleum Oilsin WaterD 5475 Test Method for Nitrogen and Phosphorus Contain-ing Pesticides in Water by Gas Chromatography with aNitrogen-Phosphorus DetectorD 5790 Test Method for Measurement of Purgeable
21、OrganicCompounds in Water by Capillary Column GasChromatography/Mass SpectrometryD 5812 Test Method for Determination of OrganochlorinePesticides in Water by Capillary Column Gas Chromatog-raphy3. Terminology3.1 DefinitionsFor definitions of terms used in this prac-tice, refer to Terminology D 1129.
22、4. Significance and Use4.1 There are four basic steps necessary to obtain meaning-ful analytical data: preparation of the sample container, sam-pling, sample preservation, and analysis. In fact these fourbasic steps comprise the analytical method and for this reasonno step should be overlooked. Alth
23、ough the significance ofpreservation is dependent upon the time between sampling andthe analysis, unless the analysis is accomplished within 2 hafter sampling, preservation is preferred and usually required.5. Apparatus5.1 Forced Draft Oven, capable of operating at 275 to325C.5.2 Sample Bottle, boro
24、silicate or flint glass.NOTE 1High density polyethylene (HDPE) bottles and caps havebeen demonstrated to be of sufficient quality to be compatible for all testsexcept pesticides, herbicides, polychlorinated biphenyls, and volatileorganics. However, this bottle cannot be recycled.5.3 Sample Bottle Ca
25、p, TFE-fluorocarbon or aluminumfoil-lined.NOTE 2Even these liners have some disadvantages. TFE is known tocollect some organic constituents, for example, PCBs. Aluminum foil willreact with samples that are strongly acid or alkaline. Clean TFE liners asdescribed in 7.1. Replace aluminum foil with new
26、 foil after each use.5.4 Sample Vial, glass.5.5 Septa, PTFE-faced with screw cap lid and matchingaluminum foil disks.6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the spec
27、ifications of the Commit-tee onAnalytical Reagents of theAmerican Chemical Society.5Other grades may be used, provided it is first ascertained thatthe reagent is of sufficiently high purity to permit its usewithout lessening the accuracy of the determination.6.2 Purity of WaterUnless otherwise indic
28、ated, referenceto water shall be understood to mean reagent water conformingto Specification D 1193, Type II and demonstrated to be free ofspecific interference for the test being performed.6.3 Acetic Acid Buffer Solution (pH 4)Dissolve 6.0 g ofsodium acetate in 75 mL of water. Add 30 mL of glacial
29、aceticacid, with stirring.6.4 Acetone.6.5 Acid Buffer Solution (pH 3.75)Dissolve 125 g ofpotassium chloride and 70 g of sodium acetate trihydrate in 500mL of water. Add 300 mL of glacial acetic acid and dilute to 1L.6.6 Ascorbic Acid.6.7 Chromic Acid Cleaning SolutionTo a 2-L beaker, add35 mL of sat
30、urated sodium dichromate solution followed by 1L of sulfuric acid (sp gr 1.84) with stirring. (WarningUserubber gloves, safety goggles, and protective clothing whenpreparing and handling this corrosive cleaning agent that is apowerful oxidant. Store the reagent in a glass bottle with aglass stopper.
31、)6.8 Detergent, formulated for cleaning laboratory glass-ware.6.9 Hydrochloric AcidConcentrated HCl (sp gr 1.19).6.10 Hydrochloric Acid (1 + 2)To 200 mL of water,carefully add 100 mL of hydrochloric acid (see 6.9). Store in aglass-stoppered reagent bottle.6.11 Ice, crushed wet.6.12 Lead Acetate Test
32、 Paper.6.13 Lead Acetate SolutionDissolve 50 g of lead acetatein water and dilute to 1 L.5Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards
33、 for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.D 3694 96 (2004)26.14 Lead Carbonate, powdered.6.15 Lime, Hydrated, powdered.6.16 Mercuric Chloride.6.17 Monochloroacetic Acid
34、Buffer (pH 3)Prepare bymixing 156 mL of chloroacetic acid solution (236.2 g/L) and100 mL of potassium acetate solution (245.4 g/L).6.18 Nitric AcidConcentrated HNO3(sp gr 1.42).6.19 Phosphate BufferDissolve 138 g of sodium dihydro-gen phosphate in water and dilute to 1 L. Refrigerate thissolution.6.
35、20 Phosphate SolutionDissolve 33.8 g of potassiumdihydrogen phosphate in 250 mL of water.6.21 Phosphoric AcidConcentrated H3PO4(sp gr 1.83).6.22 Phosphoric Acid Solution (1 + 1)Dilute 1 vol ofphosphoric acid (sp gr 1.83).6.23 pH Paper, narrow range for pH 12, and pH5to7.6.24 Potassium IodideStarch T
36、est Paper.6.25 Sodium Bisulfate.6.26 Sodium Bisulfite SolutionDissolve2gofsodiumbisulfite in 1 L of water and adjust to pH 2 by the slow additionof H2SO4(1 + 1). (WarningPrepare and use this reagent in awell ventilated hood to avoid exposure to SO2fumes.)6.27 Sodium Sulfite Solution (0.1 M)Transfer
37、approxi-mately 10.3 g of sodium sulfite to a 1-L volumetric flask.Dilute to volume with water.6.28 Sodium Thiosulfate.6.29 Sodium Hydroxide Pellets.6.30 Mercuric Chloride (10 mg/mL)Dissolve 100 mg ofHgCl2in reagent water and dilute to 10 mL.6.31 Sulfuric Acid (1 + 1) Slowly and carefully add 1vol of
38、 sulfuric acid (see 6.27) to 1 vol of water, stirring andcooling the solution during addition.7. Preparation of HDPE Sample Bottles7.1 Wash the bottles with two 100-mL portions of HCl(1 + 2) and rinse with three 100-mL portions of water. Thesevolumes of wash and rinse portions are recommended for 1-
39、Lsample bottles; therefore, use proportionate volumes for wash-ing and rinsing sample bottles of a different volume.8. Preparation of Glass Sample Bottles and Vials8.1 Solvent-Detergent/Chromic Acid Preparation of GlassSample Bottles:8.1.1 Rinse the container with 100 mL of dilute detergent oraceton
40、e. For some residues, a few alternative detergent andacetone rinses may be more satisfactory. Then rinse at leastthree times with tap water followed by a reagent water rinse toremove the residual detergent or acetone, or both.8.1.2 Rinse the container with 100 mL of chromic acidsolution, returning t
41、he chromic acid to its original containerafter use. Then rinse with at least three 100-mL portions of tapwater followed by a reagent water rinse.8.1.3 Rinse the container with 100 mL of NaHSO3solutionto remove residual hexavalent chromium. (WarningCarryout this step in a hood to prevent exposure to
42、SO2fumes.)8.1.4 Rinse the container with water until sulfurous acid andits vapors have been removed. Test rinsings for acid with a pHmeter or an appropriate narrow range pH paper. Rinsingsshould have a pH approximately the same as the water used forrinsing.8.1.5 When the last trace of NaHSO3has been
43、 removed,wash with three additional 100-mL portions of water. Allow todrain. This procedure is for 1-L sample containers, therefore,use proportionate volumes for washing and rinsing samplecontainers of a different volume.8.1.6 Heat for a minimum of 4 h (mouth up) in a forced draftoven at 275 to 325C
44、. Upon cooling, fit the bottles with capsand the vials with septa.NOTE 3For some tests, heating may not be required. Refer to theindividual method to determine the necessity for this treatment.8.2 Machine Washing Glass Sample Bottles and Vials:NOTE 4Machine washing of narrow mouth sample bottles may
45、 notyield acceptable results.8.2.1 Rinse the container with 100 mL of chromic acidsolution, returning the chromic acid to its original containerafter use. Then rinse with at least three 100-mL portions of tapwater.8.2.2 Machine wash in accordance with the machine manu-facturers instructions using a
46、detergent and 90C water.8.2.3 Remove the bottles from the machine and rinse themwith two 100-mL portions of HCl (1 + 2), followed with three100-mL portions of water.8.2.4 Heat for a minimum of 4 h (mouth up) in a forced draftoven at 275 to 325C. Upon cooling, fit the bottles with capsand the vials w
47、ith septa (see Note 3).9. Sample Preservation9.1 Depending upon the type of analysis required, use anyone or a combination of the following methods of samplepreservation (see Tables 1-3, Annex A1, and Annex A2).9.1.1 Adjust the pH. An adjustment to neutral pH is usuallyprescribed when chemical react
48、ions, such as hydrolysis, are tobe avoided. Adjustment to an extreme pH, for example, 2, isusually prescribed to inhibit biological activity for biodegrad-able organic chemicals.NOTE 5To confirm the adjustment of the pH of samples to the propervalue, place a drop of sample on an appropriate pH test
49、paper or measurewith a pH meter.9.1.1.1 Sulfuric AcidTo the sample bottle partially filledwith sample, slowly add 2 mL of H2SO4(sp gr 1.84) and mixthoroughly. Confirm that the pH is less than 2. If the pH isgreater than 2, add additional acid until the pH is less than 2.This procedure is based on a 1-L sample bottle; therefore, useproportionate volumes for sample bottles with a differentvolume.9.1.1.2 Hydrochloric AcidTo a sample bottle partiallyfilled with sample, add 6 mL of HCl (sp gr 1.19) while swirlingthe bottle. After the acid addition, con
