1、Designation: D7284 13Standard Test Method forTotal Cyanide in Water by Micro Distillation followed byFlow Injection Analysis with Gas Diffusion Separation andAmperometric Detection1This standard is issued under the fixed designation D7284; the number immediately following the designation indicates t
2、he 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 test method is used to determine the concent
3、rationof total cyanide in an aqueous wastewater or effluent. Themethod detects the cyanides that are free (HCN and CN-) andstrong-metal-cyanide complexes that dissociate and releasefree cyanide when refluxed under strongly acidic conditions.1.2 This method may not be applicable to process solutionsf
4、rom precious metals mining operations.1.3 This procedure is applicable over a range of approxi-mately 2 to 500 g/L (parts per billion) total cyanide. Higherconcentrations can be measured with sample dilution or lowerinjection volume.1.4 The determinative step of this method utilizes flowinjection wi
5、th amperometric detection based on Test MethodD6888. Prior to analysis, samples must be distilled with amicro-distillation apparatus described in this test method orwith a suitable cyanide distillation apparatus specified in TestMethods D2036.1.5 The values stated in SI units are to be regarded asst
6、andard. No other units of measurement are included in thisstandard.1.6 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 safety and health practices and determine the ap
7、plica-bility of regulatory limitations prior to use. Specific hazardstatements are given in 8.6 and Section 9.2. Referenced Documents2.1 ASTM Standards:2D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2036 Test Methods for Cyanides in WaterD2777 Practice for Determination of
8、 Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3856 Guide for Management Systems in LaboratoriesEngaged in Analysis of WaterD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water AnalysisD6696 Guide for Understanding Cyanide SpeciesD6888
9、 Test Method for Available Cyanide with LigandDisplacement and Flow InjectionAnalysis (FIA) UtilizingGas Diffusion Separation and Amperometric DetectionD7365 Practice for Sampling, Preservation and MitigatingInterferences in Water Samples for Analysis of CyanideE691 Practice for Conducting an Interl
10、aboratory Study toDetermine the Precision of a Test Method3. Terminology3.1 Definitions:3.1.1 For definitions of terms used in this test method, referto Terminology D1129 and Guide D6696.3.2 Definitions of Terms Specific to This Standard:3.2.1 total cyanideTotal cyanide is an analytically definedter
11、m that refers to the sum total of all of the inorganic chemicalforms of cyanide that dissociate and release free cyanide whenrefluxed under strongly acidic conditions. Total cyanide isdetermined analytically through strong acid distillation or UVradiation followed by analysis of liberated free cyani
12、de onaqueous samples preserved with NaOH (pH12). In water,total cyanide includes the following dissolved species: freecyanide, weak acid dissociable metal cyanide complexes andstrong metal cyanide complexes. Also, some of the strongmetal cyanide complexes, such as those of gold, cobalt andplatinum,
13、might not be fully recovered during the total cyanideanalytical procedure. Additionally, total cyanide may alsoinclude some organic forms of cyanide such as nitriles thatrelease free cyanide under the conditions of the analysis.1This test method is under the jurisdiction of ASTM Committee D19 on Wat
14、erand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved June 15, 2013. Published July 2013. Originallyapproved in 2008. Last previous edition approved in 2008 as D7284 081. DOI:10.1520/D7284-13.2For referenced ASTM stan
15、dards, visit the ASTM 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.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, P
16、A 19428-2959. United States14. Summary of Test Method4.1 The samples are distilled with a strong acid in thepresence of magnesium chloride catalyst and captured insodium hydroxide absorber solution.4.2 The absorber solution is introduced into a flow injectionanalysis (FIA) system where it is acidifi
17、ed to form hydrogencyanide (HCN). The hydrogen cyanide gas diffuses through ahydrophobic gas diffusion membrane, from the acidic donorstream into an alkaline acceptor stream.4.3 The captured cyanide is sent to an amperometric flow-cell detector with a silver-working electrode. In the presence ofcyan
18、ide, silver in the working electrode is oxidized at theapplied potential. The anodic current measured is proportionalto the concentration of cyanide.4.4 Calibrations and data are processed with the instru-ments data acquisition software.5. Significance and Use5.1 Cyanide and hydrogen cyanide are hig
19、hly toxic. Regu-lations have been established to require the monitoring ofcyanide in industrial and domestic wastes and surface waters.35.2 This test method is applicable for natural waters, indus-trial wastewaters and effluents.6. Interferences6.1 Improper sample collection or pretreatment can resu
20、lt insignificant positive or negative bias, therefore it is imperativethat samples be collected and mitigated for interferences asdescribed in Practice D7365.6.1.1 Sulfide captured in the absorber solution above 50-mg/L S2-will diffuse through the gas diffusion membraneduring flow injection analysis
21、 and can be detected in theamperometric flowcell as a positive response. Refer to Section11.2 for sulfide abatement.6.1.2 Thiocyanate in the presence of oxidants (for example,nitrates, hydrogen peroxide, chlorine or chloramine, Carosacid), can decompose to form cyanide during the distillationresulti
22、ng in positive interference regardless of the determina-tive step (amperometry, colorimetry, etc.). During acidicdistillation, decomposition of thiocyanate in the absence ofoxidants produces elemental sulfur, sulfur(IV) oxide, as well ascarbonyl sulfide which eventually leads to the formation ofsulf
23、ite ion (SO32-) in the NaOH absorbing solution. The sulfiteion slowly oxidizes cyanide to cyanate resulting in a negativeinterference. Therefore, samples that are known to containsignificant amounts of thiocyanate may need to be analyzedwith a method that does not require distillation, for example,a
24、vailable cyanide by Test Method D6888.6.1.2.1 During the validation study, synthetic samples con-taining up to 15 mg/LSCN-and 25 mg/LNO3as N yielded lessthan 0.5 % of the SCN-to be measurable CN-. For example, asolution that did not contain any known amount of cyanide, butdid contain 15-mg/L SCN-and
25、 25 mg/L NO3as N, wasmeasured as 53.1 g/L CN-.7. Apparatus and Instrumentation7.1 The instrument should be equipped with a precisesample introduction system, a gas diffusion manifold withhydrophobic membrane, and an amperometric detection sys-tem to include a silver working electrode, a Ag/AgCl refe
26、renceelectrode, and a Pt or stainless steel counter electrode. Theapparatus schematic is shown in Fig. 1, and example instru-ment settings are shown in Table 1.4NOTE 1The instrument settings in Table 1 are only examples. The340 CFR Part 136.4Both the OI Analytical CN Solution and Lachat Instruments
27、QuikChemAutomated Ion Analyzer have been found to be suitable for this analysis.FIG. 1 Flow Injection Analysis ApparatusD7284 132analyst may modify the settings as long as performance of the method hasnot been degraded. Contact the instrument manufacturer for recommendedinstrument parameters.7.1.1 A
28、n autosampler is recommended but not required toautomate sample injections and increase throughput. Autosam-plers are usually available as an option from the instrumentsmanufacturer.7.1.2 Data Acquisition SystemUse the computer hardwareand software recommended by the instrument manufacturer tocontro
29、l the apparatus and to collect data from the detector.7.1.3 Pump TubingUse tubing recommended by instru-ment manufacturer. Replace pump tubing when worn, or whenprecision is no longer acceptable.7.1.4 Gas Diffusion MembranesAhydrophobic membranewhich allows gaseous hydrogen cyanide to diffuse from t
30、hedonor to the acceptor stream at a sufficient rate to allowdetection. The gas diffusion membrane should be replacedwhen the baseline becomes noisy or every 1 to 2 weeks.57.1.5 Use parts and accessories as directed by instrumentmanufacturer.7.2 Distillation ApparatusThe Micro-Distillation Systemdesc
31、ribed below was utilized during the laboratory study todemonstrate precision and bias for this test method. A largerdistillation apparatus such as the MIDI distillation described insection 7 of Test Methods D2036 can also be used to preparesamples prior to flow injection analysis, but the user isres
32、ponsible to determine the precision and bias.7.2.1 Micro-Distillation Apparatus consisting of a distilla-tion sample tube, hydrophobic membrane, and collector tubecontaining 1.5 mL of 1.0 M sodium hydroxide with a break-away top section, guard membrane, and cap as shown in Fig.2.67.2.2 Heater block
33、assembly, temperature controlled, ca-pable of heating the micro-distillation tubes to 120C.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of theAmericanC
34、hemical Society, where such specifications are available.7Other 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.8.2 Purity of WaterUnless otherwise indicated, referencesto water s
35、hall be understood to mean reagent water that meetsthe purity specifications of Type I or Type II water, presentedin Specification D1193.8.3 Sodium Hydroxide Solution (1.00 M)Dissolve 40 gNaOH in laboratory water and dilute to 1 L.8.4 Absorber Solution for MIDI Distillations (0.25 MNaOH)Dissolve 10
36、g NaOH in laboratory water and dilute to1L.8.5 Acceptor Solution (0.10 M NaOH) Dissolve 4.0 gNaOH in laboratory water and dilute to 1 L.5The sole source of supply of the apparatus known to the committee at this timeis PALL Life Sciences Part Number M5PU025, OI Analytical Part NumberA0015200, and Lac
37、hat Instruments Part Number 50398. If you are aware ofalternative suppliers, please provide this information to ASTM InternationalHeadquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee,1which you may attend.6The sole source of supply of the
38、apparatus known to the committee at this timeis Lachat Instruments, PNA17001 (subject to US Reg. Patent No. 5,022,967). If youare aware of alternative suppliers, please provide this information to ASTMInternational Headquarters. Your comments will receive careful consideration at ameeting of the res
39、ponsible technical committee,1which you may attend.7Reagent 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 for LaboratoryChemicals, BDH Ltd., P
40、oole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.TABLE 1 Flow Injection Analysis ParametersFIA Instrument Parameter Recommended Method SettingPump Flow Rates 0.5 to 2 mL/minCycle period (total) Approximately 120 se
41、condsSample load period At least enough timeto completely fill thesample loop priorto injectionInjection valve rinse timebetween samplesAt least enough timeto rinse the sample loopPeak Evaluation Peak height or areaWorking Potential 0.0 V vs Ag/AgClFIG. 2 Micro Distillation Sample TubeD7284 1338.6 S
42、tock Cyanide Solution (1000 g/mL CN-)Dissolve2.51 g of KCN and 2.0 g of NaOH in 1 L of water. Standardizewith silver nitrate solution as described in Test MethodsD2036, section 16.2. Store the solution under refrigeration andcheck concentration approximately every 6 months and correctif necessary. (
43、WarningBecause KCN is highly toxic, avoidcontact or inhalation.)88.7 Intermediate Cyanide Standards:8.7.1 Intermediate Standard 1 (100 g/mL CN-)Pipette10.0 mL of stock cyanide solution (see 8.6) into a 100 mLvolumetric flask containing 1 mL of 1.0 M NaOH (see 8.3).Dilute to volume with laboratory wa
44、ter. Store under refrigera-tion. The standard should be stable for at least 2 weeks.8.7.2 Intermediate Cyanide Solution 2 (10 g/mL CN-)Pipette 10.0 mL of Intermediate Cyanide Solution 1 (see 8.7.1)into a 100 mL volumetric flask containing 1.0 mL of 1.00 MNaOH (see 8.3). Dilute to volume with laborat
45、ory water. Thestandard should be stable for at least 2 weeks.8.8 Working Cyanide Calibration StandardsPrepare freshdaily as described in 8.8.1 and 8.8.2 ranging in concentrationfrom 2 to 500 g/L CN-.8.8.1 Calibration Standards (50, 100, 200, and 500 g/LCN-)Pipette 50, 100, 200, and 500 L of Intermed
46、iateStandard 1 (see 8.7.1) into separate 100 mL volumetric flaskscontaining 1.0 mL of 1.00 M NaOH (see 8.3). Dilute to volumewith laboratory water.8.8.2 Calibration Standards (2, 5, and 10 g/L CN-)Pipette 20, 50, and 100 L of Intermediate Cyanide Solution 2(see 8.7.2) into separate 100 mL volumetric
47、 flasks containing1.0 mL of 1.00 M NaOH (see 8.3). Dilute to volume withlaboratory water.8.9 Potassium Ferricyanide Stock Solution (1000 g/mL asCN-)Weigh 0.2109 g K3Fe(CN)6into a 100-mL volumetricflask containing 1 mL 1 M NaOH, then dilute to volume withlaboratory water.8.9.1 Potassium Ferricyanide
48、Spiking Solution (100 g/mLCN-)Pipette 10.0 mL of potassium ferricyanide stock solu-tion into a 100 mL volumetric flask containing 1.0 mL of 1.00M NaOH, then dilute to volume with laboratory water.8.10 Cyanide Electrode Stabilization Solution (Approxi-mately 2 ppm as CN-)Pipette 200 L of Stock Cyanid
49、e (see8.6) into a 100 mL volumetric flask containing 1.0 mL of 1.00M NaOH (see 8.3). Dilute to volume with laboratory water.The solution should be stored under refrigeration.8.11 CarrierWater as indicated in Section 8.2.8.12 Acidification and Sulfide Abatement SolutionWeigh1.00 g bismuth nitrate pentahydrate, Bi(NO3)35H2O, into a 1L volumetric flask. Add 55 mL of water then carefully add 55mL of concentrated sulfuric acid to the flask. Gently swirl theflask until the bismuth nitrate pentahydrate has dissolved in theacid solution. Carefull
