1、Designation: D 3697 07Standard Test Method forAntimony in Water1This standard is issued under the fixed designation D 3697; 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 indicate
2、s the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of dissolvedand total recoverable antimony in water by atomic absorptionspectroscopy.21.2 This test method is applicable i
3、n the range from 1 to 15g/L of antimony. The range may be extended by less scaleexpansion or by dilution of the sample.1.3 The precision and bias data were obtained on reagentwater, tap water, salt water, and two untreated wastewaters.The information on precision and bias may not apply to otherwater
4、s.1.4 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 applica-bility of regulatory limitations prior to use.2. Referenced
5、 Documents2.1 ASTM Standards:3D 1129 Terminology Relating to WaterD 1193 Specification for Reagent WaterD 2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD 3370 Practices for Sampling Water from Closed ConduitsD 4691 Practice for Measuring Ele
6、ments in Water by FlameAtomic Absorption SpectrophotometryD 4841 Practice for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic ConstituentsD 5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water Analysis3. Terminology3.1 Definitions:
7、For definitions of terms used in this testmethod, refer to Terminology D 1129.3.2 Definition of Term Specific to This Standard:3.2.1 total recoverable antimonyan arbitrary analyticalterm relating to forms of antimony that are determinable by thedigestion method which is included in the procedure. So
8、meorganic compounds may not be completely recovered.3.2.2 laboratory control sample, na solution with a cer-tified concentration of the antimony.4. Summary of Test Method4.1 Organic antimony-containing compounds are decom-posed by adding sulfuric and nitric acids and repeatedlyevaporating the sample
9、 to fumes of sulfur trioxide. Theantimony so produced, together with inorganic antimonyoriginally present, is subsequently reacted with potassiumiodide and stannous chloride, and finally with sodium borohy-dride to form stibine. The stibine is removed from solution byaeration and swept by a flow of
10、nitrogen into a hydrogen flamewhere it is determined by atomic absorption at 217.6 nm.5. Significance and Use5.1 Because of the association with lead and arsenic inindustry, it is often difficult to assess the toxicity of antimonyand its compounds. In humans, complaints referable to thenervous syste
11、m have been reported. In assessing human cases,however, the possibility of lead or arsenic poisoning mustalways be borne in mind. Locally, antimony compounds areirritating to the skin and mucous membranes.6. Interference6.1 Since the stibine is freed from the original samplematrix, interferences in
12、the flame are minimized.6.2 Selenium and arsenic, which also form hydrides, do notinterfere at concentrations of 100 g/L. Higher concentrationswere not tested.7. Apparatus7.1 Atomic Absorption Spectrophotometer, for use at 217.6nm with a scale expansion of approximately 3. A general guidefor the use
13、 of flame atomic absorption applications is given inPractice D 4691.NOTE 1The manufacturers instructions should be followed for allinstrumental parameters.7.1.1 Antimony Electrodeless Discharge Lamp.1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsib
14、ility of Subcommittee D19.05 on Inorganic Constituentsin Water.Current edition approved Aug. 1, 2007. Published August 2007. Originallyapproved in 1978. Last previous edition approved in 2002 as D 3697 02.2Platte, J.A., and Marcy, V. M., “ANew Tool for the Water Chemist,” IndustrialWater Engineering
15、, IWEGA, May 1965.3For referenced ASTM standards, 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.1Copyright ASTM International, 100 Barr Har
16、bor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.7.2 Recorder or Digital Readout Any multirange variablespeed recorder or digital readout accessory, or both, that iscompatible with the atomic absorption spectrophotometer issuitable.7.3 Stibine Vapor Analyzer, assembled as show
17、n in Fig. 1.NOTE 2A static system, such as one using a balloon, has been foundto be satisfactory. See McFarren, E. F., “New, Simplified Method forMetal Analysis,” Journal of American Water Works Assoc., JAWWA, Vol64, 1972, p. 28.8. Reagents and Materials8.1 Purity of Reagents Reagent grade chemicals
18、 shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications for the Com-mittee on Analytical Reagents of the American ChemicalSociety, where such specifications are available.4Other gradesmay be used, provided it is first ascertained th
19、at the reagent isof sufficiently high purity to permit its use without lesseningthe accuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Specification D 1193, Type I, II, or III water. Type I ispreferre
20、d and more commonly used. Other reagent water typesmay be used provided it is first ascertained that the water is ofsufficiently high purity to permit its use without adverselyaffecting the precision and bias of the test method. Type IIwater was specified at the time of round robin testing of theset
21、est methods.NOTE 3The user must ensure the type of reagent water chosen issufficiently free of interferences. The water should be analyzed using thetest method.8.3 Antimony Solution, Stock (1.00 mL = 100 g Sb)Dissolve 274.3 mg of antimony potassium tartrate,KSbOC4H4O61/2H2O, in water and dilute to 1
22、000 mL withwater. A purchased stock solution of adequate purity is alsoacceptable.8.4 Antimony Solution, Intermediate (1.00 mL = 10 gSb) Dilute 50.0 mL of antimony stock solution to 500.0 mLwith water.8.5 Antimony Solution, Standard (1.0 mL = 0.10 g Sb)Dilute 5.0 mL of antimony intermediate solution
23、 to 500.0 mLwith water. Prepare fresh before each use. This standard is usedto prepare working standards at the time of analysis.8.6 Hydrochloric Acid (sp gr 1.19) Concentrated hydro-chloric acid (HCl).8.7 Nitric Acid (sp gr 1.42) Concentrated nitric acid(HNO3).8.8 Nitric Acid (1 + 1)Add 250 mL of c
24、oncentrated nitricacid (sp gr 1.42) to 250 mL of water.8.9 Potassium Iodide Solution (15 g/100 mL) Dissolve 15g of potassium iodide (KI) in 100 mL of water. This solution isstable when stored in an amber bottle or in the dark.8.10 Sodium Borohydride Solution (4 g/100 mL) Dissolve4 g of sodium borohy
25、dride (NaBH4)and2gofsodiumhydroxide (NaOH) in 100 mL water. Prepare weekly.8.11 Stannous Chloride Solution (4.6 g/100 mL of concen-trated HCl)Dissolve5gofstannous chloride (SnCl2H2O) in100 mL of concentrated HCl (sp gr 1.19). This solution isstable if a few small pieces of mossy tin are added to pre
26、ventoxidation.8.12 Sulfuric Acid (1+1) Cautiously, and with constantstirring and cooling, add 250 mL of concentrated sulfuric acid(H2SO4, sp gr 1.84) to 250 mL of water.8.13 Hydrogen, commercially available. Set pressure onburner control box to 8 psig (55 KPa) and adjust flowmeter toapproximately 6
27、L/min.8.14 Nitrogen, commercially available. Set pressure onburner control box to 30 psig (206.8 KPa) and adjust flowmeterfor maximum sensitivity by volatilizing standards. A flow ofapproximately 9 L/min has been found satisfactory. This willvary depending on the burner used.9. Sampling9.1 Collect t
28、he sample in accordance with PracticesD 3370. The holding time for the samples may be calculated inaccordance with Practice D 4841.9.2 Immediately preserve samples with HNO3(sp gr 1.42)to a pH of 2 or less at the time of collection; normally about 2mL/L is required. If only dissolved antimony is to
29、be deter-mined, filter the sample through a (No. 325) 0.45-m mem-brane filter before acidification.10. Standardization10.1 Clean all glassware before use by rinsing first withHNO3(1 + 1) and then with water.10.2 Prepare, in 200 to 300-mL wide-mouth glass contain-ers, a blank and sufficient standards
30、 that contain from 0.0 to 1.5g of antimony by diluting 0.0 to 15.0-mL portions of theantimony standard solution to 100 mL with water.10.3 Proceed as directed in 11.3 to 11.8.10.4 Prepare an analytical curve by plotting recorder scalereadings versus micrograms of antimony on linear graph paperor calc
31、ulate a standard curve. Alternatively, read directly inconcentration if a concentration readout is provided with theinstrument.11. Procedure11.1 Clean all glassware before use by rinsing first withHNO3(1 + 1) and then with water.4Reagent Chemicals, American Chemical Society Specifications, AmericanC
32、hemical 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. Pharmacopeial Convention, Inc. (USPC), R
33、ockville,MD.FIG. 1 Stibine Vapor AnalyzerD 3697 07211.2 Pipet a volume of well-mixed acidified sample con-taining less than 1.5 g of antimony (100-mL max) into a 200to 300-mL wide-mouth glass container, and dilute to 100 mLwith water (see Fig. 1).NOTE 4If only dissolved antimony is to be determined,
34、 use a filteredand acidified sample (9.2).11.3 To each container, add 7 mL of H2SO4(1 + 1) and 5mL of concentrated HNO3. Add a small boiling chip andcarefully evaporate to fumes of SO3. Maintain an excess ofHNO3until all organic matter is destroyed. This preventsdarkening of the solution and possibl
35、e reduction and loss ofantimony. Cool, add 25 mL of water, and again evaporate tofumes of SO3to expel oxides to nitrogen.11.4 Cool, and adjust the volume of each container toapproximately 100 mL with water.11.5 To each container, add successively, with thoroughmixing after each addition, 8 mL of con
36、centrated HCl, 1 mL ofKI solution, and 0.5 mL of SnCl2solution. Allow about 15 minfor reaction.11.6 Attach one container at a time to the rubber stoppercontaining the gas dispersion tube.11.7 Fill the medicine dropper or syringe with 1 mL ofNaBH4solution and insert into the hole in the rubber stoppe
37、r.11.8 Add the NaBH4solution to the sample solution. Afterthe recorder reading (scale reading) has reached a maximumand has returned to the baseline, remove the container. Rinsethe gas dispersion tube in water before proceeding to the nextsample. Treat each succeeding sample, blank, and standard ina
38、 like manner.12. Calculation12.1 Determine the weight or concentration of antimony ineach sample by referring to 10.4. If the weight is determinedfrom the analytical curve, calculate the concentration ofantimony in the sample in micrograms per litre, as follows:Antimony, g/L 5 1000 3 W/Vwhere:V = vo
39、lume of sample, mL, andW = weight of antimony in sample, g.13. Precision and Bias13.1 The single operator and overall precision of this testmethod for four laboratories, which included a total of sixoperators analyzing each sample on three different days, withinits designated range varies with the q
40、uantity being tested.13.2 Recoveries of known amounts of antimony (fromantimony potassium tartrate) in a series of prepared standardfor the same laboratories and operators are given in Table 1.13.3 The precision and bias data were obtained on reagentwater, tap water, salt water, and two untreated wa
41、stewaters.The information on precision and bias may not apply to otherwaters.13.4 Precision and bias for this test method conforms toPractice D 2777-77, which was in place at the time ofcollaborative testing. Under the allowances made in 1.4 of D2777-06, these precision and bias data do meet existin
42、grequirements for interlaboratory studies of Committee D19 testmethods.14. Quality Control (QC)14.1 The following quality control information is recom-mended for the determination of antimony in water.14.2 The instrument shall be calibrated using a minimum offour calibration standards and a calibrat
43、ion blank. The calibra-tion correlation coefficient shall be equal to or greater than0.990. In addition to the initial calibration blank, a calibrationblank should be analyzed at the end of the batch run to ensurecontamination was not a problem during the batch analysis.14.3 An instrument check stan
44、dard shall be analyzed at aminimum frequency of 10 % throughout the batch analysis.The value of the instrument check standard shall fall between80 % and 120 % of the true value.14.4 Two method blanks shall be prepared ensuring that anadequate method blank volume is present for a minimum ofseven repe
45、titive analysis. The standard deviation of the methodblank is used to determine the minimum detectable concentra-tion of each sample and control in the batch.14.5 A Laboratory Control Sample shall be analyzed witheach batch of sample at a minimum frequency of 10 %.14.6 If the QC for the sample batch
46、 is not within theestablished control limits, reanalyze the samples or qualify theresults with the appropriate flags, or both.14.7 Blind control samples should be submitted by anoutside agency in order to determine the laboratory perfor-mance capabilities.15. Keywords15.1 antimony; atomic absorption
47、; vapor hydride genera-tion; waterTABLE 1 Recovery and Precision DataMethodTestSolutionNumberofLabsTrueValue,g/LMeanValue,g/LST,g/LSo,g/LBias,%StatedRange,g/LR2Precision RegressionEquationsHydride/ Flame RGW 4 3.0 3.15 0.92 0.70 + 5.0 115 0.80 ST=0.451+0.104xAAS 7.012.06.4211.160.881.710.781.548.3y7
48、.00.89 So=0.255+0.109xWOC 4 3.07.012.02.746.0010.730.661.221.730.660.951.438.714.3y10.6y0.981.00STSo=0.346+0.132x= 0.386 + 0.0967 xD 3697 073ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this
49、 standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful cons
