1、Designation: D 3645 08An American National StandardStandard Test Methods forBeryllium in Water1This standard is issued under the fixed designation D 3645; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A
2、 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 test methods cover the determination of dissolvedand total recoverable beryllium in most waters and wastewa-ters:ConcentrationRa
3、nge SectionsTest Method AAtomic Absorption,Direct10 to 500 g/L 7 to 16Test Method BAtomic Absorption,Graphite Furnace10 to 50 g/L 17 to 251.2 The analyst should direct attention to the precision andbias statements for each test method. It is the users responsi-bility to ensure the validity of these
4、test methods for waters ofuntested matrices.1.3 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 concerns, if any, associated with its use. It is theresponsibility of
5、 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 Section 12 and 23.4.2. Referenced Documents2.1 ASTM Standards:2D 858 Test Methods for Manganese in WaterD 1068
6、Test Methods for Iron in WaterD 1129 Terminology Relating to WaterD 1193 Specification for Reagent WaterD 1687 Test Methods for Chromium in WaterD 1688 Test Methods for Copper in WaterD 1691 Test Methods for Zinc in WaterD 1886 Test Methods for Nickel in WaterD 2777 Practice for Determination of Pre
7、cision and Bias ofApplicable Test Methods of Committee D19 on WaterD 3370 Practices for Sampling Water from Closed ConduitsD 3557 Test Methods for Cadmium in WaterD 3558 Test Methods for Cobalt in WaterD 3559 Test Methods for Lead in WaterD 3919 Practice for Measuring Trace Elements in Water byGraph
8、ite 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 Standard Test Methods for Water Analy
9、sis3. Terminology3.1 DefinitionsFor definitions of terms used in these testmethods, refer to Terminology D 1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 total recoverable berylliumtotal recoverable beryl-lium relates only to the recoverable forms of beryllium by thesetest methods.4.
10、Significance and Use4.1 These test methods are significant because the concen-tration of beryllium in water must be measured accurately inorder to evaluate potential health and environmental effects.5. Purity of Reagents5.1 Reagent grade chemicals shall be used in all tests.Unless otherwise indicate
11、d, it is intended that all reagents shallconform to the specifications of the Committee on AnalyticalReagents of the American Chemical Society, where suchspecifications are available.3Other grades may be used, pro-vided it is first ascertained that the reagent is sufficiently highin purity to permit
12、 its use without lessening the accuracy of thedetermination.5.2 Unless otherwise indicated, reference to water shall beunderstood to mean reagent water conforming to SpecificationD 1193, Type I. Other reagent water types may be used1These test methods are under the jurisdiction of ASTM Committee D19
13、 onWater and are the direct responsibility of Subcommittee D19.05 on InorganicConstituents in Water.Current edition approved Oct. 1, 2008. Published October 2008. Originallyapproved in 1978. Last previous edition approved in 2003 as D 3645 03.2For referenced ASTM standards, visit the ASTM website, w
14、ww.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.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestion
15、s on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.1Copyright ASTM International, 100
16、Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.provided it is first ascertained that the water is of sufficientlyhigh purity to permit its use without adversely affecting thebias and precision of the test method. Type II water wasspecified at the time of round robin
17、testing of this test method.6. Sampling6.1 Collect the samples in accordance with PracticesD 3370. The holding time for samples may be calculated inaccordance with Practice D 4841.6.2 Preserve samples with HNO3(sp gr 1.42), adding about2 mL/L, to a pH of 2 or less immediately at the time ofcollectio
18、n. If only dissolved beryllium is to be determined,filter the sample, before acidification, through a 0.45-mmembrane filter.TEST METHOD AATOMIC ABSORPTION, DIRECT7. Scope7.1 This test method is applicable in the range from 10 to500 g/L of beryllium. The range may be extended upward bydilution of the
19、 sample.7.2 The precision and bias data were obtained on reagentwater, tap water, salt water, river water, lake water, springwater, and untreated wastewater. The information on precisionand bias may not apply to other waters. It is the usersresponsibility to ensure the validity of this test method f
20、orwaters of untested matrices.8. Summary of Test Method8.1 Beryllium is determined by atomic absorption spectro-photometry. Dissolved beryllium is determined by aspirating afiltered sample directly with no pretreatment. Total recoverableberyllium in the sample is determined in a portion of the filtr
21、ateobtained after a hydrochloric-nitric acid digestion of thesample. The same digestion procedure is used to determinetotal recoverable cadmium (Test Methods D 3557), chromium(Test Methods D 1687), cobalt (Test Methods D 3558), copper(Test Methods D 1688), iron (Test Methods D 1068), lead (TestMetho
22、ds D 3559), manganese (Test Methods D 858), nickel(Test Methods D 1886), and zinc (Test Methods D 1691).9. Interferences9.1 Aluminum at concentrations greater than 500 g/L hasbeen reported to depress the beryllium absorbance.9.2 Sodium and silicon at concentrations in excess of 1000mg/L have been re
23、ported to severely depress the berylliumabsorbance.9.3 Beryllium is slightly ionized in the nitrous oxide-acetylene flame. This ionization is suppressed by addingcalcium chloride to give a final concentration of 900 mg/Lcalcium in all standard and sample solutions.10. Apparatus10.1 Atomic Absorption
24、 Spectrophotometer, for use at 234.9nm.NOTE 1The manufacturers instructions should be followed for allinstrument parameters.10.2 Beryllium Hollow Cathode Lamp.10.3 Pressure RegulatorsThe supplies of oxidants andfuel shall be maintained at pressures somewhat higher than thecontrolled operating pressu
25、re of the instrument by suitableregulators.11. Reagents and Materials11.1 Beryllium Solution, Stock (1.00 mL = 1000 g Be)Dissolve 1.000 g of beryllium metal in a minimum volume ofHCl (1 + 1) and dilute to 1 L. (Beryllium is toxic and thesolution should be prepared in a well-ventilated hood.)NOTE 2Ce
26、rtified beryllium stock solutions are commercially avail-able through chemical supply vendors.11.2 Beryllium Solution, Intermediate (1.00 mL = 100 gBe)Dilute 10.0 mL of the beryllium stock solution to 100.0mL with nitric acid (HNO3, 1 + 499).11.3 Beryllium Solution, Standard (1.00 mL = 1.00 gBe)Dilu
27、te 5.00 mL of the beryllium intermediate solution to500.0 mL with nitric acid (HNO3, 1 + 499).11.4 Calcium Solution (10 g/L)Dissolve 25 g of calciumcarbonate in a minimum volume of HCl (1 + 1) and dilute to 1L with water.11.5 Hydrochloric Acid (sp gr 1.19)Concentrated hydro-chloric acid (HCl).NOTE 3
28、If a high reagent blank is obtained, distill the HCl or usespectrograde acid. (When HCl is distilled, an azeotropic mixture isobtained (approximately 6 N HCl). Therefore, whenever concentrated HClis specified in the preparation of a reagent or in the procedure, use doublethe amount if distilled acid
29、 is used.)11.6 Hydrochloric Acid (1 + 1)Mix 1 volume of HCl (spgr 1.19) with 1 volume of water. Always add acid to water.11.7 Nitric Acid (sp gr 1.42)Concentrated nitric acid(HNO3).NOTE 4If a high reagent blank is obtained, distill the HNO3or usespectrograde acid.11.8 Nitric Acid (1 + 499)Add 1 volu
30、me of HNO3(sp gr1.42) to 499 volumes of water.11.9 Oxidant:11.9.1 Air, which has been passed through a suitable filter toremove oil, water, and other foreign substances, is the oxidantused prior to switching to nitrous oxide.11.9.2 Nitrous Oxide is the required oxidant.11.10 Fuel:11.10.1 AcetyleneSt
31、andard commercially available acety-lene is the required fuel. Acetone, always present in acetylenecylinders, can affect analytical results. The cylinder should bereplaced at a gage pressure of 75 psi (517 kPa). (“Prepurified”grade acetylene containing a special proprietary solvent otherthan acetone
32、 should not be used with poly (vinyl chloride)tubing as weakening of the walls can cause a potentiallyhazardous situation.)12. Hazards12.1 Due to the high toxicity of beryllium, all samplepreparation and digestion steps should be carried out in awell-ventilated hood. Also, the atomic absorption unit
33、 shouldbe vented as recommended by the manufacturer.D364508213. Standardization13.1 Prepare a blank and at least four standard solutions tobracket the expected beryllium concentration range of thesamples to be analyzed by diluting the beryllium standardsolution (11.3) with HNO3(1 + 499). Prepare the
34、 standards(100 mL) each time the test is to be performed.13.2 For total recoverable beryllium, add 0.5 mL ofHNO3(sp gr 1.42) and proceed as directed in 14.2-14.6. Fordissolved beryllium, proceed with 13.3.13.3 Add 1.0 mL of calcium solution to a 10.0-mL aliquotof each standard and blank solution. Mi
35、x thoroughly.13.4 Aspirate the blank and standards and record the instru-ment readings. Aspirate HNO3(1 + 499) between each stan-dard. (The atomic absorption unit should be vented properly.)13.5 Prepare an analytical curve by plotting the absorbanceversus the standard concentration for each standard
36、 on lineargraph paper. Alternatively, use a direct concentration readout ifthe instrument is so equipped.14. Procedure14.1 Measure 100.0 mL of a well-mixed acidified sampleinto a 150-mL beaker.NOTE 5If only dissolved beryllium is to be determined, start with14.5.14.2 Add 5 mL of HCl (sp gr 1.19) to
37、each sample.14.3 Heat the samples on a steam bath or hot plate until thevolume has been reduced to 15 or 20 mL, making certain thatthe samples do not boil. (Perform in a well-ventilated hood.)NOTE 6For brines and samples with high levels of suspended matteror total dissolved solids, the amount of re
38、duction is left to the discretionof the analyst.14.4 Cool and filter the samples through a suitable filter(such as a fine-textured, acid-washed, ashless paper) into100-mL volumetric flasks. Wash the filter paper two or threetimes with water and adjust to volume.14.5 Add 1.0 mL of calcium solution to
39、 a 10.0-mL aliquotof each sample and mix thoroughly.14.6 Aspirate each sample and determine its absorbance orconcentration. Aspirate HNO3(1 + 499) between each sample.15. Calculation15.1 Calculate the concentration of beryllium in eachsample, in micrograms per litre, using the analytical curvedescri
40、bed in 13.5.16. Precision and Bias416.1 Based on the round-robin results from seven laborato-ries and ten operators, the following precision and biasstatements can be made:16.1.1 The overall and single-operator precision of this testmethod, within its designated range for reagent water andselected w
41、ater matrices, varies with the quantity tested asshown in Table 1.16.1.2 The bias of this test method is listed in Table 2.16.2 The precision and bias data were obtained on reagentwater, tap water, salt water, river water, lake water, springwater, and untreated wastewater. It is the users responsibi
42、lityto ensure the validity of this test method for waters of untestedmatrices.16.3 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 ofPractice D 2777 06, these precision and bias data do me
43、etexisting requirements for interlaboratory studies of CommitteeD19 test methods.TEST METHOD BATOMIC ABSORPTION,GRAPHITE FURNACE17. Scope17.1 This test method covers the determination of dissolvedand total recoverable beryllium in most waters and wastewa-ters.17.2 This test method is applicable in t
44、he range from 10 to50 g/L of beryllium using a 20-L injection. The range can beincreased or decreased by varying the volume of sampleinjected or the instrumental settings. High concentrations maybe diluted but preferably should be analyzed by direct-aspiration atomic-absorption spectrophotometry.17.
45、3 This test method has been used successfully withreagent water, lake water, river water, well water, filtered tapwater, and a condensate from a medium Btu coal gasificationprocess. It is the users responsibility to ensure validity of thistest method to waters of untested matrices.4Supporting data h
46、ave been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR: D19-1043.TABLE 1 Overall S(T) and Single-Operator (SO) InterlaboratoryPrecision for Beryllium by Flame AAS, Test Method AReagent WaterConcentration (X), g/L 15.4 211.0 444.8ST2.7 10.8 21.3SO1.2 4.4
47、 11.9Natural WaterConcentration (X), g/L 16.9 214.7 444.4ST2.9 7.7 19.2SO2.2 5.4 10.3TABLE 2 Precision and Bias, Atomic Absorption, DirectAmountAdded,g/LAmountFound,g/L% BiasStatisticallySignificant (95 %Confidence Level)Reagent Water, Type II16 15.4 3.75 no220 211.0 4.09 yes460 444.8 3.30 yesSelect
48、ed Water Matrices16 16.9 + 5.60 no220 214.7 2.41 yes460 444.4 3.39 yesD364508317.4 The analyst is encouraged to consult Practice D 3919for a general discussion of interferences and sample analysisprocedures for graphite furnace atomic absorption spectropho-tometry.18. Summary of Test Method18.1 Bery
49、llium is determined by an atomic-absorption spec-trophotometer used in conjunction with a graphite furnace. Asample is placed in a graphite tube, evaporated to dryness,charred (pyrolyzed or ashed), and atomized. Since the graphitefurnace uses the sample much more efficiently than flameatomization, the detection of low concentrations of elements insmall sample volumes is possible. Finally, the absorption signalgenerated during atomization is recorded and compared tostandards. A general guide for the application of the graphitefurnace
