1、Designation: D2036 09Standard Test Methods forCyanides in Water1This standard is issued under the fixed designation D2036; the 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
2、 the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the Department of Defense.1. Scope1.1 These test methods cover the determination of cyanidesin water. The following test me
3、thods are included:SectionsTest Method ATotal Cyanides afterDistillation12 to 18Test Method BCyanides Amenableto Chlorination2by Difference19 to 25Test Method CWeak Acid Disso-ciable Cyanides26 to 32Test Method DCyanides Amenableto Chlorination without Distillation(Short-Cut Method)33 to 391.2 Cyano
4、gen halides may be determined separately.NOTE 1Cyanogen chloride is the most common of the cyanogenhalide complexes as it is a reaction product and is usually present whenchlorinating cyanide-containing industrial waste water. For the presenceor absence of CNCl, the spot test method given in Annex A
5、1 can be used.1.3 These test methods do not distinguish between cyanideions and metallocyanide compounds and complexes. Further-more, they do not detect the cyanates. Cyanates can bedetermined using ion chromatography without digestion.NOTE 2The cyanate complexes are decomposed when the sample isaci
6、dified in the distillation procedure.1.4 The cyanide in cyanocomplexes of gold, platinum,cobalt and some other transition metals is not completelyrecovered by these test methods. Refer to Test Method D6994for the determination of cyanometal complexes.1.5 Cyanide from only a few organic cyanides are
7、recov-ered, and those only to a minor extent.1.6 Part or all of these test methods have been usedsuccessfully with reagent water and various waste waters. It isthe users responsibility to assure the validity of the testmethod for the water matrix being tested.1.7 This standard does not purport to ad
8、dress 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. Specific hazardstatements are given in sections 5.1, 8
9、.8, 8.18, 9, 11.3, and16.1.9.2. Referenced Documents2.1 ASTM Standards:3D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Closed Con
10、duitsD5788 Guide for Spiking Organics into Aqueous SamplesD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water AnalysisD6696 Guide for Understanding Cyanide SpeciesD6888 Test Method for Available Cyanide with LigandDisplacement and Flow Injection Analysis (FIA
11、) UtilizingGas Diffusion Separation and Amperometric DetectionD6994 Test Method for Determination of Metal CyanideComplexes in Wastewater, Surface Water, Groundwaterand Drinking Water Using Anion Exchange Chromatogra-phy with UV DetectionD7284 Test Method for Total Cyanide in Water by MicroDistillat
12、ion followed by Flow Injection Analysis with GasDiffusion Separation and Amperometric DetectionD7365 Practice for Sampling, Preservation and MitigatingInterferences in Water Samples for Analysis of CyanideD7511 Test Method for Total Cyanide by Segmented FlowInjection Analysis, In-Line Ultraviolet Di
13、gestion and Am-perometric DetectionE60 Practice for Analysis of Metals, Ores, and RelatedMaterials by Molecular Absorption SpectrometryE275 Practice for Describing and Measuring Performanceof Ultraviolet and Visible Spectrophotometers1These test methods are under the jurisdiction of ASTM Committee D
14、19 onWater and are the direct responsibility of Subcommittee D19.06 on Methods forAnalysis for Organic Substances in Water.Current edition approved Oct. 1, 2009. Published October 2009. Originallyapproved in 1964. Last previous edition approved in 2006 as D2036 06. DOI:10.1520/D2036-09.2For an expla
15、nation of the term cyanides amenable to alkaline chlorination, seeLancy, L. E. and Zabban, W., “Analytical Methods and Instrumentation forDetermining Cyanogen Compounds,” Papers on Industrial Water and IndustrialWaste Water, ASTM STP 337, 1962, pp. 3245.3For referenced ASTM standards, visit the ASTM
16、 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 C700, West Conshohocken, PA 19428-2959, United
17、 States.3. Terminology3.1 Definitions: For definitions of terms used in these testmethods, refer to Terminology D1129 and Guide D6696.3.2 Acronyms:3.2.1 HPLC, nhigh performance liquid chromatography3.2.2 IC, nion chromatography3.2.3 PAD, npulsed amperometric detection3.2.4 FIA, nflow injection analy
18、sis4. Summary of Test Methods4.1 The cyanide as hydrocyanic acid (HCN) is releasedfrom compounds by means of reflux distillation and absorbedin sodium hydroxide solution. The conditions used for thedistillation distinguish the type of cyanide. The sodium cyanidein the absorbing solution can be deter
19、mined colorimetrically,by ion chromatography, titration, by selective ion electrode, oras described in Test Method D6888 using flow injection withamperometric detection.4.2 Test Method A, Total Cyanides, is based on the decom-position of nearly all cyanides in the presence of strong acid,magnesium c
20、hloride catalyst, and heat during a 1-h refluxdistillation.4.3 Test Method B, Cyanide Amenable to Chlorination, isbased on chlorinating a portion of the sample under controlledconditions followed by the determination of total cyanide inboth the original and chlorinated samples. Cyanides amenableto c
21、hlorination are calculated by difference.4.3.1 This test method can be affected by compounds thatare converted during chlorination to color-producing com-pounds or react with the reagents used, and cause interferencein the procedure employed to determine cyanide in the absorp-tion solution.4.4 Test
22、Method C, Weak Acid Dissociable Cyanides, isbased on the decomposition of cyanides in the presence ofweak acid, zinc acetate and heat during a 1-h reflux distillation.4.5 Test Method D, Cyanide Amenable to Chlorinationwithout Distillation, is a direct colorimetric procedure.4.6 In the absence of int
23、erference, the minimum concentra-tion of cyanide in the absorption solution that can be accuratelydetermined colorimetrically is 0.005 mg/L, ion chromatogra-phy and Test Method D6888 are 0.002 mg/L, titration is 0.4mg/L and by selective ion electrode is 0.05 mg/L. Pretreatmentincluding distillation
24、tends to increase these concentrations toa degree determined by the amount of manipulation requiredand the type of sample.4.7 Round-robin data indicate the following minimum con-centrations: colorimetric 0.03 mg/L; titration 1.0 mg/L; andselective ion electrode 0.03 mg/L. Ion chromatography andTest
25、Method D6888 have a minimum levels equal to approxi-mately 0.002 mg/L.5. Significance and Use5.1 Cyanide is highly toxic. Regulations have been estab-lished to require the monitoring of cyanide in industrial anddomestic wastes and in surface waters (Appendix X1).5.2 Test Method D is applicable for n
26、atural water and cleanmetal finishing or heat treatment effluents. It may be used forprocess control in wastewater treatment facilities providing itsapplicability has been validated by Test Method B or C.5.3 The spot test outlined inAnnexA1 can be used to detectcyanide and thiocyanate in water or wa
27、stewater, and toapproximate its concentration.6. Interferences6.1 Common interferences in the analysis for cyanide in-clude oxidizing agents, sulfides, aldehydes, glucose and othersugars, high concentration of carbonate, fatty acids, thiocyan-ate, and other sulfur containing compounds.6.2 It is beyo
28、nd the scope of these test methods to describeprocedures for overcoming all of the possible interferences thatmay be encountered. Refer to Practice D7365 for potentialinterferences for the analysis of cyanide in water.7. Apparatus7.1 Distillation ApparatusThe reaction vessel shall be a1-L round bott
29、om flask, with provision for an inlet tube and acondenser. The inlet tube shall be a funnel with an 8-mmdiameter stem that extends to within 6 mm of the bottom of theflask. The condenser, which is recommended, shall be areflux-type, cold finger, or Allihn. The condenser shall beconnected to a vacuum
30、-type absorber which shall be in turnconnected to a vacuum line which has provision for finecontrol. The flask shall be heated with an electric heater.Examples of the apparatus are shown in Fig. 1. Equivalentapparatus is acceptable provided cyanide recoveries of 100 64 % are documented.7.1.1 Smaller
31、 distillation tubes such as 50-mL MIDI tubesor 6-mL MicroDist (trademarked) tubes described in TestMethod D7284 can be used if the quality control requirementsin Section 40 are satisfied. The reagents should be addedproportionately to those specified in this test method forsmaller sample sizes. Whil
32、e the use of smaller distillation tubesis generally accepted, the interlaboratory study was conductedwith 500-mL samples; therefore, the user is responsible toFIG. 1 Cyanide Distillation ApparatusD2036 092determine the actual precision and bias when using a differenttype of distillation apparatus.7.
33、2 Spectrophotometer or Filter Photometer, suitable formeasurement in the region of 578 nm, using 1.0-, 2.0-, 5.0-,and 10.0-cm absorption cells. Filter photometers and photo-metric practices used in these test methods shall conform toPractice E60. Spectrophotometers shall conform to PracticeE275.7.3
34、Selective Ion Meter, or a pH meter with expandedmillivolt scale equipped with a cyanide activity electrode anda reference electrode.7.4 Mixer, magnetic, with a TFE-fluorocarbon-coated stir-ring bar.7.5 Buret, Koch, micro, 2- or 5-mL, calibrated in 0.01 mL.7.6 Ion Chromatograph, high performance ion
35、chromato-graph equipped with a 10-L sample injection device andpulsed-amperometric detector.7.7 Chromatography Column, Dionex IonPac AS7 anion-exchange, 4 3 250 mm and matching guard column or equiva-lent.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all test
36、s. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.4Other grades may beused, provided it is first ascertained that the reagent is ofsuffic
37、iently high purity to permit its use without lessening theaccuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water that meetsthe purity specifications of Type I or Type II water, presentedin D1193.8.3 Acetic Acid (1 + 9
38、)Mix 1 volume of glacial aceticacid with 9 volumes of water.8.4 Acetate BufferDissolve 410 g of sodium acetate tri-hydrate (NaC2H3O23H2O) in 500 mL of water. Add glacialacetic acid to yield a solution pH of 4.5, approximately 500mL.8.5 Barbituric Acid.8.6 Calcium Hypochlorite Solution (50 g/L)Dissol
39、ve 5 gof calcium hypochlorite (Ca(OCl)2) in 100 mL of water. Storethe solution in an amber glass bottle in the dark. Prepare freshmonthly.8.7 Chloramine-T Solution (10 g/L)Dissolve 1.0 g of thewhite-colored, water-soluble grade powder chloramine-T in100 mL of water. Prepare fresh weekly.8.8 Cyanide
40、Solution, Stock (1 mL = 250 g CN)Dissolve 0.6258 g of potassium cyanide (KCN) in 40 mL ofsodium hydroxide solution (40 g/L). Dilute to 1 L with water.Mix thoroughly. Standardize with standard silver nitrate solu-tion following the titration procedure (see 16.2). (WarningBecause KCN is highly toxic,
41、avoid contact or inhalation (see9). Commercial solutions may also be used if certified by themanufacturer and used within the recommended storage date.8.8.1 Cyanide I Solution, Standard (1 mL = 25 g CN)Dilute a calculated volume (approximately 100 mL) of KCNstock solution to 1 L with NaOH solution (
42、1.6 g/L).8.8.2 Cyanide II Solution, Standard (1 mL = 2.5 g CN)Dilute exactly 100 mL of KCN standard solution I to 1 L withNaOH solution (1.6 g/L).8.8.3 Cyanide III Solution, Standard (1 mL = 0.25 gCN) Dilute exactly 100 mL of KCN standard solution II to1 L with NaOH solution (1.6 g/L). Prepare fresh
43、 solution dailyand protect from light.8.8.4 Cyanide IV Solution, Standard (1 mL = 0.025 gCN) Dilute exactly 100 mL of KCN standard solution III to1 L with NaOH solution (1.6 g/L). Prepare fresh solution dailyand protect from light.8.9 Hydrogen Peroxide Solution, 3 %Dilute 10 mL of30 % hydrogen perox
44、ide (H2O2) to 100 mL. Prepare freshweekly.8.10 Isooctane, Hexane, Chloroform (solvent preference inthe order named).8.11 Lead Carbonate (PbCO3), Lead Acetate (Pb(C2H3O2)23H2O), or Lead Nitrate (Pb(NO3)2)Lead acetate andlead nitrate can be put in solution with water, if desired, at asuggested concent
45、ration of 50 g/L.8.12 Lime, hydrate (Ca(OH)2), powder.8.13 Magnesium Chloride SolutionDissolve 510 g ofmagnesium chloride (MgCl26H2O) in water and dilute to 1 L.8.14 Potassium Iodide-Starch Test Paper.8.15 Pyridine-Barbituric Acid ReagentPlace 15 g of bar-bituric acid in a 250-mL volumetric flask an
46、d add just enoughwater to wash the sides of the flask and wet the barbituric acid.Add 75 mL of pyridine and mix. Add 15 mL of hydrochloricacid (sp gr 1.19), mix, and cool to room temperature. Dilute tovolume with water and mix until all of the barbituric acid isdissolved. This solution is usable for
47、 about 6 months if storedin a cold dark place. Commercially prepared solutions may beavailable; follow the manufacturers expiration date.8.16 Rhodanine Indicator Solution (0.2 g/L)Dissolve 0.02g of (p-dimethylaminobenzylidene) in 100 mL of acetone.8.17 Silver Nitrate Solution, Standard (0.01 N)Disso
48、lve1.6987 g of silver nitrate (AgNO3) in water and dilute to 1 L.Mix thoroughly. Commerical solutions that are certified at thedesignated normality are suitable if used within the manufac-turers recommended storage date. Store in a dark container.8.18 Sodium Arsenite Solution (20 g/L)Dissolve2gofNaA
49、sO2in 100 mL of water. WarningThis material hasappeared on lists of suspected and known carcinogens. Avoidcontact with skin.8.19 Sodium Hydroxide Solution (40 g/L)Dissolve 40 g ofsodium hydroxide (NaOH) in water and dilute to 1 L withwater.8.20 Sodium Hydroxide Solution (1.6 g/L)Dilute 40 mLofNaOH solution (40 g/L) to 1 L.8.21 Sulfamic Acid Solution (133 g/L)Dissolve 133 g ofsulfamic acid in water and dilute to 1 L.4Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggesti
