1、Designation: C1287 10Standard Test Method forDetermination of Impurities in Nuclear Grade UraniumCompounds by Inductively Coupled Plasma MassSpectrometry1This standard is issued under the fixed designation C1287; the number immediately following the designation indicates the year oforiginal adoption
2、 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 covers the determination of 67 ele-ments in uranium dioxide
3、 samples and nuclear grade uraniumcompounds and solutions without matrix separation by induc-tively coupled plasma mass spectrometry (ICP-MS). Theelements are listed in Table 1. These elements can also bedetermined in uranyl nitrate hexahydrate (UNH), uraniumhexafluoride (UF6), triuranium octoxide (
4、U3O8) and uraniumtrioxide (UO3) if these compounds are treated and converted tothe same uranium concentration solution.1.2 The elements boron, sodium, silicon, phosphorus, po-tassium, calcium and iron can be determined using differenttechniques. The analysts instrumentation will determinewhich proce
5、dure is chosen for the analysis.1.3 The test method for technetium-99 is given in AnnexA1.1.4 The values stated in SI units are to be regarded asstandard.1.5 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of t
6、his standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. WarningTheICP-MS is a source of intense ultra-violet radiation from theradio frequency induced plasma. Protection from radio fre-quency radiation and UV radiati
7、on is provided by the instru-ment under normal operation.2. Referenced Documents2.1 ASTM Standards:2C753 Specification for Nuclear-Grade, Sinterable UraniumDioxide PowderC776 Specification for Sintered Uranium Dioxide PelletsC787 Specification for Uranium Hexafluoride for Enrich-mentC788 Specificati
8、on for Nuclear-Grade Uranyl Nitrate Solu-tion or CrystalsC967 Specification for Uranium Ore ConcentrateC996 Specification for Uranium Hexafluoride Enriched toLess Than 5 %235UC1346 Practice for Dissolution of UF6from P-10 TubesC1347 Practice for Preparation and Dissolution of UraniumMaterials for An
9、alysisD1193 Specification for Reagent Water3. Summary of Test Method3.1 The sample is dissolved in acid if it is not already asolution. A fixed quantity of internal standard is added tomonitor and correct for signal instability. The level of impuri-ties in the solution is measured by ICP-MS. Customi
10、zedsoftware calculates the concentration of each element.3.2 Uranium-concentration-matched standard solutions areused to calibrate the ICP-MS instrument. The calibration islinear up to at least 0.2 g/ml (100 g/g U) for each analyte.3,43.3 Microwave dissolution may be used as an alternatedissolution
11、method.4. Significance and Use4.1 This test method is capable of measuring the elementslisted in Table 1, some of which are required by SpecificationsC753, C776, C787, C788, C967 and C996.1This test method is under the jurisdiction ofASTM Committee C26 on NuclearFuel Cycle and is the direct responsi
12、bility of Subcommittee C26.05 on Methods ofTest.Current edition approved June 1, 2010. Published July 2010. Originally approvedin 1994. Last previous edition approved in 2003 as C1287 03. DOI: 10.1520/C1287-10.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Custo
13、mer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3“ICP-MS Versus Conventional Methods for theAnalysis of Trace Impurities inNuclear Fuel,” by Allenby, P., Clarkson, A. S., Makinson, P. R., presented a
14、t 2ndSurrey Conference on Plasma Source Mass Spectrometry, Guildford, UK, July1987.4“Trace Metals in NBL Uranium Standard CRM 124 Using ICP-MS,” byAldridge, A. J., Clarkson, A. S., Makinson, P. R., Dawson, K. W., presented at 1stDurham International Conference on Plasma Source Mass Spectrometry, Dur
15、ham,UK, September 1988.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5. Apparatus5.1 ICP-MS, controlled by computer and fitted with theassociated software and peripherals. May be fitted with coldplasma option. Current instrumentati
16、on is available with dy-namic reaction cell or collision cell options.5.2 Autosampler, with tube racks and disposable plasticsample tubes compatible with 5.1 (optional).5.3 Variable Micropipettes:5.3.1 10 L to 100 L capacity.5.3.2 100 L to 1000 L capacity.5.3.3 1000 L to 10.00 mL capacity.5.4 Volume
17、tric Flasks:5.4.1 50 mL capacitypolypropylene.5.4.2 100 mL capacitypolypropylene.5.4.3 1 L capacityglass.5.5 Platinum Dish100 mL capacity.5.6 Silica Beaker250 mL capacity.5.7 Watch Glasses75 mm diameter.5.8 Polypropylene Tubes50 mL, with graduation marksand with caps.6. Reagents6.1 The sensitivity o
18、f the ICP-MS technique requires the useof ultra high purity reagents in order to be able to obtain thelow levels of detection. All the reagents below are ultra highpurity grade unless otherwise stated:6.1.1 Element stock standards at 1000 g/mL for all theelements in Table 1.6.1.2 Hydrofluoric Acid (
19、HF), (40 g/100 g), 23 molar.6.1.2.1 WarningHydrofluoric acid is highly corrosiveacid that can severely burn skin, eyes, and mucous membranes.TABLE 1 Reporting Limits of Impurity ElementsNOTE 1The impurity elements were determined in 0.2 % uraniumsolutions, prepared following Section 8.NOTE 2Acquisit
20、ion time = 10 s/isotope using peak jump mode.NOTE 3103 Rh was used as an internal standard. For the elementswhere the technique is identified as Perkin Elmer DRCII scandium wasused as internal standard for boron, sodium and phosphorus. Rhodium wasused as the internal standard for potassium, calcium
21、and iron in ReactionCell mode.NOTE 4The LRL is based on the within run standard deviation (Sb)of20 uranium-matched blank determinations for each analyte. This limitequals 4 3 Sb, rounded up to a preferred value in the series 1, 1.5, 2, 3, 4,6, multiplied or divided by the appropriate integer power o
22、f ten.NOTE 5The upper reporting limit can be increased by extending thecalibration to 10 g/mL(5000 g/g U) if the ICP-MS used has an extendeddynamic range (EDR) accessory.NOTE 6For the elements where the technique is listed as P-E DRCII,the instrumentation may be specific to those elements. Alternati
23、vely coldplasma technique may be used and it is up to the analyst to performtestwork using spikes and reference materials and to determine the lowerreporting levels. The impurity elements were determined in 0.16 %uranium solutions, prepared following Section 8. The dwell times arelisted in 8.4.1.1.N
24、OTE 7Some of the elements are not included in the materialspecifications and have been included only as a research record for thereaders interest.AnalyteMassUsedAnalyteGroupLowerReportingLimit (LRL),g/g UUpperReportingLimit (URL),g/g UTechniqueLithium 7 A 0.01 100 normal plasmaBeryllium 9 A 0.04 100
25、 normal plasmaBoron 11 E 0.3 100 DRCIISodium 23 E 0.3 100 DRCIIMagnesium 24 A 4 100 normal plasmaAluminum 27 D 2 1000 normal plasmaPhosphorus 31 E 1 100 DRCIIPotassium 39 E 2.0 100 DRCIICalcium 40 E 3 100 DRCIIScandium 45 A 4 100 normal plasmaTitanium 48 B 0.2 100 normal plasmaVanadium 51 B 0.04 100
26、 normal plasmaChromium 52 B 0.1 100 normal plasmaManganese 55 A 0.1 100 normal plasmaIron 56 A 0.2 100 DRCIICobalt 59 A 0.02 100 normal plasmaNickel 60 A 0.4 100 normal plasmaCopper 65 A 0.2 100 normal plasmaZinc 66 A 0.3 100 normal plasmaGallium 69 A 0.04 100 normal plasmaGermanium 74 A 0.2 100 nor
27、mal plasmaArsenic 75 A 0.2 100 normal plasmaSelenium 82 A 3 100 normal plasmaRubidium 85 A 0.06 100 normal plasmaStrontium 88 A 0.06 100 normal plasmaYttrium 89 A 0.04 100 normal plasmaZirconium 90 B 0.02 100 normal plasmaNiobium 93 B 0.01 100 normal plasmaMolybdenum 95 B 0.04 100 normal plasmaRuthe
28、nium 102 B 0.02 100 normal plasmaPalladium 106 B 0.2 100 normal plasmaSilver 107 A 0.1 100 normal plasmaCadmium 111 A 0.03 100 normal plasmaIndium 115 A 0.04 100 normal plasmaTin 116 B 0.04 100 normal plasmaAntimony 121 B 0.02 100 normal plasmaTellurium 130 B 0.4 100 normal plasmaCaesium 133 A 0.06
29、100 normal plasmaBarium 138 A 0.02 100 normal plasmaLanthanum 139 C 0.1 100 normal plasmaCerium 140 C 0.01 100 normal plasmaTABLE 1 ContinuedAnalyteMassUsedAnalyteGroupLowerReportingLimit (LRL),g/g UUpperReportingLimit (URL),g/g UTechniquePraseody-mium141 C 0.01 100 normal plasmaNeodymium 146 C 0.01
30、 100 normal plasmaSamarium 149 C 0.01 100 normal plasmaEuropium 151 C 0.01 100 normal plasmaGadolinium 158 C 0.01 100 normal plasmaTerbium 159 C 0.01 100 normal plasmaDysprosium 163 C 0.01 100 normal plasmaHolmium 165 C 0.01 100 normal plasmaErbium 166 C 0.01 100 normal plasmaThulium 169 C 0.01 100
31、normal plasmaYtterbium 174 C 0.01 100 normal plasmaLutetium 175 C 0.01 100 normal plasmaHafnium 178 B 0.01 100 normal plasmaTantalum 181 B 0.01 100 normal plasmaTungsten 184 B 0.01 100 normal plasmaRhenium 187 A 0.02 100 normal plasmaOsmium 190 B 0.2 100 normal plasmaIridium 193 B 0.2 100 normal pla
32、smaPlatinum 195 B 0.2 100 normal plasmaGold 197 B 0.06 100 normal plasmaMercury 202 A 0.4 100 normal plasmaThallium 205 A 0.02 100 normal plasmaLead 208 A 0.02 100 normal plasmaBismuth 209 A 0.03 100 normal plasmaThorium 232 B 0.01 100 normal plasmaC1287 102Hydrofluoric acid is similar to other acid
33、s in that the initialextent of a burn depends on the concentration, the temperature,and the duration of contact with the acid. Hydrofluoric aciddiffers from other acids because the fluoride ion readilypenetrates the skin, causing destruction of deep tissue layers.Unlike other acids that are rapidly
34、neutralized, hydrofluoricacid reactions with tissue may continue for days if leftuntreated. Due to the serious consequences of hydrofluoric acidburns, prevention of exposure or injury of personnel is theprimary goal. Utilization of appropriate laboratory controls(hoods) and wearing adequate personne
35、l protective equipmentto protect from skin and eye contact is essential. Acuteexposure to HF can cause painful and severe burns upon skincontact that require special medical attention. Chronic orprolonged exposure to low levels on the skin may causefluorosis.6.1.3 Nitric AcidConcentrated nitric acid
36、 (HNO3), 15molar.6.1.4 Rhodium Stock Solution (1000 g/mL Rh)Commercially available solution (see Note 1).NOTE 1Rhodium stock solution is commercially available suppliedwith a certificate of analysis for the element and a full range of traceimpurities. The solutions are prepared by the manufacturer u
37、sing a varietyof media designed to keep each element in solution for a minimum of oneyear.6.1.5 Sulfuric AcidConcentrated sulfuric acid (H2SO4),18 molar.6.1.6 Uranium Standard Base SolutionUranyl nitrate so-lution to Specification C788, of known uranium (100 g/L) andaluminum content (# 2 g/g U). The
38、 total metallic impurity(TMI) content must not exceed 50 g/g U and no individualanalyte must exceed 10 g/g U.6.1.7 Purity of WaterUnless otherwise indicated, refer-ences to water shall be understood to mean reagent waterconforming to Specification D1193, Type I.6.1.8 AmmoniaAnhydrous, NH3, 99.9995 %
39、 minimumpurity. Used with instruments fitted with dynamic reaction celloption.7. Standards7.1 Four separate mixed standard solutions (A, B, C, and E)are prepared to prevent the precipitation of some elements (asinsoluble chlorides, fluorides etc; see Table 1 for details of theanalyte groups). Analyt
40、e group A contains element stocksolutions prepared in HNO3or HNO3/HF, analyte group Bcontains element stock solutions prepared in HCl or HCl/HF,analyte group C contains the rare earth element stock solutions,and analyte group E contains boron sodium silicon, phospho-rus, potassium and calcium. The m
41、ixed standard solutionsshould be prepared to contain only the analytes of interest.Other combinations of mixed standard solutions may beprepared to minimize the precipitation of the analytes.7.1.1 Mixed standard solution A is prepared from stocksolutions of each element from analyte groupA. Transfer
42、 1000L of the stock solution (1000 g/mL) of each element into a50 mL polypropylene volumetric flask and add 500 L ofconcentrated nitric acid. Dilute to 50 mL with water and mix.This multi-element standard contains 20 g/mLof each analytein 1 % nitric acid. This solution must be used on the day ofprep
43、aration.7.1.2 Mixed standard solution B is prepared from stocksolutions of each element from analyte group B. Transfer 1000L of the stock solution (1000 g/mL) of each element into a50 mL polypropylene volumetric flask and add 500 L ofconcentrated nitric acid. Dilute to 50 mL with water and mix.This
44、multi-element standard contains 20 g/mLof each analytein 1 % nitric acid. This solution must be used within one weekof preparation.7.1.3 Mixed standard solution C is prepared from stocksolutions of each element from analyte group C. Transfer 1000L of the stock solution (1000 g/mL) of each element in
45、to a50 mL polypropylene volumetric flask and add 500 L ofconcentrated nitric acid. Dilute to 50 mL with water and mix.This multi-element standard contains 20 g/mLof each analytein 1 % nitric acid. This solution must be used within one weekof preparation.7.2 Standard solution D is prepared from the s
46、tock solutionof aluminum from analyte group D. Transfer 1000 L of thestock solution (1000 g/mL Al) into a 50 mL polypropylenevolumetric flask and add 500 L of concentrated nitric acid.Dilute to 50 L with water and mix. This standard contains 20g/mL of aluminum in 1 % nitric acid. This solution must
47、beused within one week of preparation.7.3 Mixed standard solution E is prepared from stocksolutions of each element from analyte group E. Transfer 1000L of the stock solution (1000 g/mL) of each element into a50 mL polypropylene volumetric flask and add 500 L ofconcentrated nitric acid. Dilute to 50
48、 mL with water and mix.This multi-element standard contains 20 g/mLof each analytein 1 % nitric acid. This solution must be used within one weekof preparation.7.4 Rhodium internal standard solution is prepared from thestock solution. Transfer 1000 L of the stock solution (1000g/mL Rh) into a 100 mL
49、polypropylene volumetric flask andadd 1000 L of concentrated nitric acid. Dilute to 100 mL withwater and mix. This internal standard solution contains 10g/mLRh in a 1 % nitric acid solution. Other internal standardssuch as scandium may be used. With high mass elements theanalyst may choose internal standards such as iridium orterbium. Other elements may be applicable as well but it is upto the analyst to conduct the appropriate testwork.NOTE 2Throughout this standard, references to Rh internal standardsolution will
