1、Designation: D3694 96 (Reapproved 2011)Standard Practices forPreparation of Sample Containers and for Preservation ofOrganic Constituents1This standard is issued under the fixed designation D3694; the number immediately following the designation indicates the year oforiginal adoption or, in the case
2、 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 These practices cover the various means of (1) preparingsample containers used for collectio
3、n 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 the
4、corresponding applicable generaland specific constituent test method. The preservation methodfor waterborne oils is given in Practice D3325. Use of theinformation given herein will make it possible to choose theminimum number of sample preservation practices necessaryto ensure the integrity of a sam
5、ple designated for multipleanalysis. For further considerations of sample preservation, seethe Manual on Water.21.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of thesafety c
6、oncerns, 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 hazardstatements, see 6.7, 6.24, and 8.1.3.2. Referenced Document
7、s2.1 ASTM Standards:3D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD1252 Test Methods for Chemical Oxygen Demand (Di-chromate Oxygen Demand) of WaterD1783 Test Methods for Phenolic Compounds in WaterD2036 Test Methods for Cyanides in WaterD2330 Test Method for Methylene Blu
8、eActive Substances4D2579 Test Method for Total Organic Carbon in Water4D2580 Test Method for Phenols in Water by Gas-LiquidChromatographyD2908 Practice for Measuring Volatile Organic Matter inWater by Aqueous-Injection Gas ChromatographyD3113 Test Methods for Sodium Salts of EDTA in Water4D3325 Prac
9、tice for Preservation of Waterborne Oil SamplesD3371 Test Method for Nitriles in Aqueous Solution byGas-Liquid Chromatography4D3534 Test Method for Polychlorinated Biphenyls (PCBs)in Water4D3590 Test Methods for Total Kjeldahl Nitrogen in WaterD3695 Test Method for VolatileAlcohols in Water by Direc
10、tAqueous-Injection Gas ChromatographyD3856 Guide for Good Laboratory Practices in Laborato-ries Engaged in Sampling and Analysis of WaterD3871 Test Method for Purgeable Organic Compounds inWater Using Headspace SamplingD3921 Test Method for Oil and Grease and PetroleumHydrocarbons in WaterD3973 Test
11、 Method for Low-Molecular Weight Haloge-nated Hydrocarbons in WaterD4129 Test Method for Total and Organic Carbon in Waterby High Temperature Oxidation and by Coulometric De-tectionD4165 Test Method for Cyanogen Chloride in WaterD4193 Test Method for Thiocyanate in WaterD4281 Test Method for Oil and
12、 Grease (FluorocarbonExtractable Substances) by Gravimetric DeterminationD4282 Test Method for Determination of Free Cyanide inWater and Wastewater by MicrodiffusionD4374 Test Methods for Cyanides in WaterAutomatedMethods for Total Cyanide, Weak Acid Dissociable Cya-nide, and ThiocyanateD4515 Practi
13、ce for Estimation of Holding Time for Water1These 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 approved May 1, 2011. Published June 2011. Originallya
14、pproved in 1978. Last previous edition approved in 2004 as D3694 96 (2004).DOI: 10.1520/D3694-96R11.2Manual 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 of ASTMStandards vo
15、lume information, refer to the standards Document Summary page onthe ASTM website.4Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.Samples
16、Containing Organic Constituents4D4657 Test Method for Polynuclear Aromatic Hydrocar-bons in Water4D4744 Test Method for Organic Halides in Water by Car-bon AdsorptionMicrocoulometric Detection4D4763 Practice for Identification of Chemicals in Water byFluorescence SpectroscopyD4779 Test Method for To
17、tal, Organic, and Inorganic Car-bon in High Purity Water by Ultraviolet (UV) or PersulfateOxidation, or Both, and Infrared Detection4D4839 Test Method for Total Carbon and Organic Carbonin Water by Ultraviolet, or Persulfate Oxidation, or Both,and Infrared DetectionD4841 Practice for Estimation of H
18、olding Time for WaterSamples Containing Organic and Inorganic ConstituentsD4983 Test Method for Cyclohexylamine, Morpholine, andDiethylaminoethanol in Water and Condensed Steam byDirect Aqueous Injection Gas Chromatography4D5175 Test Method for Organohalide Pesticides and Poly-chlorinated Biphenyls
19、in Water by Microextraction andGas ChromatographyD5176 Test Method for Total Chemically Bound Nitrogenin Water by Pyrolysis and Chemiluminescence DetectionD5315 Test Method for Determination of N-Methyl-Carbamoyloximes and N-Methylcarbamates in Water byDirect Aqueous Injection HPLC with Post-Column
20、De-rivatizationD5316 Test Method for 1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane in Water by Microextractionand Gas ChromatographyD5317 Test Method for Determination of Chlorinated Or-ganic Acid Compounds in Water by Gas Chromatographywith an Electron Capture DetectorD5412 Test Method for Quan
21、tification of Complex Polycy-clic Aromatic Hydrocarbon Mixtures or Petroleum Oils inWaterD5475 Test Method for Nitrogen- and Phosphorus-Containing Pesticides in Water by Gas Chromatographywith a Nitrogen-Phosphorus Detector4D5790 Test Method for Measurement of Purgeable OrganicCompounds in Water by
22、Capillary Column GasChromatography/Mass SpectrometryD5812 Test Method for Determination of OrganochlorinePesticides in Water by Capillary Column Gas Chromatog-raphy43. Terminology3.1 DefinitionsFor definitions of terms used in this prac-tice, refer to Terminology D1129.4. Significance and Use4.1 The
23、re 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. Although the significance ofpreser
24、vation 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, borosilicate or flint glass.NOTE 1
25、High 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 Cap, TFE-fluorocarbon or aluminu
26、mfoil-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 foil after each use.5.4 Sampl
27、e 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 specifications of the Commit-tee o
28、nAnalytical 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 indicated, referenceto water shall
29、be understood to mean reagent water conformingto Specification D1193, 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 aceticacid, with stirring.6.4 A
30、cetone.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 saturated sodium dichromate soluti
31、on 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.)6.8 Detergent, formulated for
32、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.5Reagent Chemicals, American Chemical Society Specifications, AmericanChemi
33、cal Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rock
34、ville,MD.D3694 96 (2011)26.11 Ice, crushed wet.6.12 Lead Acetate Test Paper.6.13 Lead Acetate SolutionDissolve 50 g of lead acetatein water and dilute to 1 L.6.14 Lead Carbonate, powdered.6.15 Lime, Hydrated, powdered.6.16 Mercuric Chloride.6.17 Monochloroacetic Acid Buffer (pH 3)Prepare bymixing 15
35、6 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.6.20 Phosphate SolutionDissolve 33
36、.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 Test Paper.6.25 Sodium Bisulfate.
37、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 approxi-mately 10.3 g of sodium
38、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 sulfuric acid (see 6.27) to 1 v
39、ol 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-Lsample bottles; therefore, use
40、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 oracetone. For some residues, a few alte
41、rnative 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 the chromic acid to its original
42、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 SO2fumes.)8.1.4 Rinse the contai
43、ner 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 removed,wash with three additio
44、nal 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. Upon cooling, fit the bottles
45、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 notyield acceptable results.8.2
46、.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 detergent and 90C water.8.2.3 Re
47、move 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 with septa (see Note 3).9. Sample
48、 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 reactions, such as hydrolysis, are to
49、be 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 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
