1、Designation: D 3373 03 (Reapproved 2007)e1Standard Test Method forVanadium in Water1This standard is issued under the fixed designation D 3373; 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
2、parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the Department of Defense.e1NOTESections 7.5 and 13.5 were updated editorially in September 20071. Sc
3、ope1.1 This test method covers the determination of dissolvedand total recoverable vanadium in most waters and wastewaterby graphite furnace atomic absorption spectrophotometry.1.2 The optimum range of this test method is 10 to 200 g/Lof vanadium based on a 20-L sample size. Concentrationshigher tha
4、n 200 g/L may be determined by proper dilution ofsample. A detection level as low as 4 g/L of vanadium hasbeen reported.1.3 This test method has been used successfully withreagent water, lake water, tap water, river water, condensatefrom a medium Btu coal gasification process, and well water.It is t
5、he users responsibility to ensure the validity of this testmethod for waters of untested matrices.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
6、 practices and determine the applica-bility or regulatory limitations prior to use.1.5 Former Test Method A (Catalytic) was discontinued.Refer to Appendix X1 for historical information.2. Referenced Documents2.1 ASTM Standards:2D 1066 Practice for Sampling SteamD 1129 Terminology Relating to WaterD
7、1192 Guide for Equipment for Sampling Water andSteam in Closed Conduits3D 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 3919 Practice for Measuri
8、ng Trace Elements in Water byGraphite Furnace Atomic Absorption SpectrophotometryD 4841 Practice for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic ConstituentsD 5810 Guide for Spiking into Aqueous SamplesD 5847 Practice for Writing Quality Control Specificationsfor Sta
9、ndard Test Methods for Water Analysis3. Terminology3.1 Definitions: For definitions of terms used in this testmethod refer to Terminology D 1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 total recoverable vanadiumdissolved vanadiumplus that solubilized by acid digestion of particulate
10、s andorganics in the sample.4. Summary of Test Method4.1 Vanadium is determined by an atomic absorption spec-trophotometer utilizing a graphite furnace for sample atomiza-tion.4.2 Asample volume of several microlitres, depending uponthe concentration of the analyte, is transferred to a graphitetube
11、housed within an electrical furnace and the system isheated in an inert or reducing atmosphere. The sample isevaporated to dryness, charred (pyrolyzed or ashed) andatomized.4.3 Ground state atoms, produced in atomization, absorb thelight of their spectrum emanating from a source and passingthrough t
12、he sample vapor. The amount of light absorbed isproportional to the concentration of the analyte in the sample.4.4 Since the graphite furnace uses the sample much moreefficiently than does flame atomization, the detection of lowconcentrations of the elements of interest in small volumes ispossible.4
13、.5 Finally, the absorption signal produced during atomiza-tion is recorded and compared to those of standards, takenthrough the same process, by means of an analytical curve.1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19
14、.05 on Inorganic Constituentsin Water.Current edition approved Aug. 1, 2007. Published September 2007. Originallyapproved in 1975. Last previous edition approved in 2003 as D 3373 03.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.
15、org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4.6 A general guide for graphite furnace application
16、s isgiven in Practice D 3919.4.7 Dissolved vanadium is determined after filtration andaddition of HNO3toapHof# 2.4.8 Total recoverable vanadium is determined followingacid digestion and filtration.5. Significance and Use5.1 Vanadium can be found in waste that result fromchemical cleaning of componen
17、ts in which the metal is alloyed.5.2 National Pollutant Discharge Elimination Systems per-mits or other standards, or both, require monitoring pollutantsin waste discharged onto the water shed of, or into, navigablewaters, and those disposed of in such a manner that eventualcontamination of undergro
18、und water could result.5.3 This test method affords an accurate and sensitive meansof determining compliance or noncompliance, or both, withthose permits.6. Interferences6.1 For a complete discussion on general interferences withfurnace procedures, the analyst is referred to Practice D 3919.7. Appar
19、atus7.1 Atomic Absorption Spectrophotometer, for use at 318.4nm with background correction.NOTE 1The manufacturers instructions should be followed for allinstrumental parameters.7.2 Vanadium Hollow Cathode Lamp.7.3 Graphite Furnace capable of reaching temperature suf-ficient to atomize the element o
20、f interest.7.4 Graphite Tubes, pyrolytically coated, compatible withfurnace device are recommended.7.5 Pipettes, microlitre with disposable tips, ranging in sizefrom 1 to 100 L.7.6 Strip Chart RecorderA recorder is strongly recom-mended. The tracings can be used as permanent records and areof diagno
21、stic value in the identification and analysis ofinstrument problems (such as drift, incomplete atomization,change in sensitivity, etc.). A fast response recorder (0.2 s orless for full-scale deflection) is recommended to ensure accu-racy. Electronic peak-measuring devices have also been founduseful.
22、7.7 Automatic Sampling Accessory is recommended, ifavailable.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 Committeeon Analytical Reagents of the Ame
23、rican Chemical Society,where such specifications are available.4Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, referencesto wa
24、ter shall be understood to mean reagent water conformingto Specification D 1193, Type I. Other reagent water types maybe 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.8.3 Nitri
25、c Acid (sp gr 1.42)Concentrated nitric acid(HNO3).8.4 Vanadium Solution, Stock (1.0 mL = 100 g vanadium).Dissolve 0.2296 g of ammonium metavanadate (NH4VO3)inwater and dilute to 1000 mL.8.5 Vanadium Solution, Intermediate (1.0 mL = 1.0 gvanadium)Dilute 5 mL of vanadium stock solution to 500mL with w
26、ater.8.6 Vanadium Solution, Standard (1.0 mL = 0.100 gvanadium)Dilute 10.0 mLof vanadium intermediate solutionto 100 mL with water.8.7 Nitrogen Gasstandard, welders grade, commerciallyavailable.NOTE 2It is probable that argon or some other inert gas can be usedin place of nitrogen. It is the analyst
27、s responsibility to verify suitability.9. Sampling9.1 Collect the sample in accordance with Practice D 1066,Specification D 1192, and Practices D 3370, as applicable. Theholding time for the sample may be calculated in accordancewith Practice D 4841.9.2 Preserve samples with nitric acid (HNO3, sp gr
28、 1.42) toa pH of 2 or less immediately at the time of collection,normally about 2 mL/L. If only dissolved vanadium is to bedetermined, filter the sample through a 0.45-m (No. 325)membrane filter before acidification.10. Standardization10.1 Initially, set the instrument in accordance with themanufact
29、urers specifications. Follow the general instructionsas provided in Practice D 3919.11. Procedure11.1 Clean all glassware to be used for preparation ofstandard solutions or in the digestion step, or both, by rinsingfirst with HNO3(1 + 1) and then with water. Alternatively,soaking the glassware overn
30、ight in HNO3(1 + 1) is useful forlow levels.11.2 Measure 100.0 mL of each standard and well-mixedsample into a 125-mL beaker or flask. For total recoverablevanadium, add 5 mL of HNO3(sp gr 1.42) to each sample andproceed as directed in 11.4 through 11.6.4Reagent Chemicals, American Chemical Society
31、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., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial C
32、onvention, Inc. (USPC), Rockville,MD.D 3373 03 (2007)e1211.3 If only dissolved vanadium is to be determined, pro-ceed to 11.6.11.4 Heat the samples at 95C on a steam bath or hotplate ina well-ventilated fume hood until the volume has been reducedto 15 to 20 mL making certain that the samples do not
33、boil.NOTE 3When analyzing samples of brines or samples containingappreciable amounts of suspended matter or dissolved solids, the amountof reduction in volume is left to the discretion of the analyst.11.5 Cool and filter the sample through a suitable filter (suchas fine-textured, acid washed, ashles
34、s paper) into a 100-mLvolumetric flask. Wash the filter paper 2 or 3 times with waterand bring to volume. See Note 4. The acid concentration at thispoint should be 5 % HNO3.NOTE 4If suspended material is not present, this filtration may beomitted, however, digested sample must still be diluted to 10
35、0 mL.11.6 Inject a measured aliquot of sample into the furnacedevice following the directions as provided by the particularinstrument manufacturer. Refer to Practice D 3919.12. Calculation12.1 Determine the concentration of vanadium in eachsample in accordance with the Samples Analysis ProcedureSect
36、ion of Practice D 3919.13. Precision and Bias513.1 Based on data from twelve participating laboratories,the overall precision of this test method and recoveries from aseries of standards containing known amounts of vanadium,were as given in Table 1.13.2 Because of the large number of metals analyzed
37、 in thisstudy the requirement for replicate tests have been waived;therefore, single-operator precision is not available.13.3 Each participating laboratory evaluated this testmethod in reagent water. Individual laboratories selected onewater of choice as an additional matrix of interest in which tot
38、est recovery. Listed among those choices were: lake water, tapwater, river water, well water, and condensate from a mediumBtu coal gasification process.13.4 These data may not apply to waters of other matrices.13.5 This section on precision and bias conforms to PracticeD 2777 77 which was in place a
39、t the time of collaborativetesting. Under the allowances made in 1.4 of D 2777 06,these precision and bias data do meet existing requirements ofinterlaboratory studies of Committee D19 test methods.14. Quality Control14.1 In order to be certain that analytical values obtainedusing these test methods
40、 are valid and accurate within theconfidence limits of the test, the following QC procedures mustbe followed when analyzing vanadium.14.2 Calibration and Calibration Verification14.2.1 Analyze at least three working standards containingconcentrations of vanadium that bracket the expected sampleconce
41、ntration, prior to analysis of samples, to calibrate theinstrument. The calibration correlation coefficient shall beequal to or greater than 0.990. In addition to the initialcalibration blank, a calibration blank shall be analyzed at theend of the batch run to ensure contamination was not a problemd
42、uring the batch analysis.14.2.2 Verify instrument calibration after standardization byanalyzing a standard at the concentration of one of thecalibration standards. The concentration of a mid-range stan-dard should fall within 615% of the known concentration.14.2.3 If calibration cannot be verified,
43、recalibrate theinstrument.14.3 Initial Demonstration of Laboratory Capability14.3.1 If a laboratory has not performed the test before, or ifthere has been a major change in the measurement system, forexample, new analyst, new instrument, and so forth, a precisionand bias study must be performed to d
44、emonstrate laboratorycapability.14.3.2 Analyze seven replicates of a standard solutionprepared from an Independent Reference Material containing amidrange concentration of vanadium. The matrix and chemis-try of the solution should be equivalent to the solution used inthe collaborative study. Each re
45、plicate must be taken throughthe complete analytical test method including any samplepreservation and pretreatment steps. The replicates may beinterspersed with samples.14.3.3 Calculate the mean and standard deviation of theseven values and compare to the acceptable ranges of bias inTable 1. This st
46、udy should be repeated until the recoveries arewithin the limits given in Table 1. If a concentration other thanthe recommended concentration is used, refer to PracticeD 5847 for information on applying the F test and t test inevaluating the acceptability of the mean and standard devia-tion.14.4 Lab
47、oratory Control Sample (LCS)14.4.1 To ensure that the test method is in control, analyzea LCS containing a known concentration of vanadium witheach batch or ten samples. If large numbers of samples areanalyzed in the batch, analyze the LCS after every ten samples.The laboratory control samples for a
48、 large batch should coverthe analytical range when possible. The LCS must be takenthrough all of the steps of the analytical method includingsample preservation and pretreatment. The result obtained fora mid-range LCS shall fall within 615 % of the knownconcentration.14.4.2 If the result is not with
49、in these limits, analysis ofsamples is halted until the problem is corrected, and either allthe samples in the batch must be reanalyzed, or the results must5Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR: D191114.TABLE 1 Determination of Precision and Bias for VanadiumAmountAdded,g V/LAAmountFound,g V/LAST,g/LBias,g/L% BiasStatisticallySignificantReagent Water Type II25 24 2.6 1.0 4.0 no70 73.4 4.8 + 3.4 4.9 no240 232.7 25.5 7.3 3.0 noWater of Choice25 25.9 3.6 + 0.9 3.6 no70
