1、Designation: C1287 10C1287 18Standard 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
2、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 covers the determination of 67 elements in uranium
3、dioxide samples and nuclear grade uraniumcompounds and solutions without matrix separation by inductively coupled plasma mass spectrometry (ICP-MS). The elements arelisted in Table 1. These elements can also be determined in uranyl nitrate hexahydrate (UNH), uranium hexafluoride (UF6),triuranium oct
4、oxide (U3O8) and uranium trioxide (UO3) if these compounds are treated and converted to the same uraniumconcentration solution.1.2 The elements boron, sodium, silicon, phosphorus, potassium, calcium and iron can be determined using different techniques.The analysts instrumentation will determine whi
5、ch procedure is chosen for the analysis.1.3 The test method for technetium-99 is given in Annex A1.1.4 The values stated in SI units are to be regarded as standard.1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof th
6、e user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine theapplicability of regulatory limitations prior to use. WarningThe ICP-MS is a source of intense ultra-violet radiation from theradio frequency induced plasma. Protection from rad
7、io frequency radiation and UV radiation is provided by the instrument undernormal operation.1.6 This international standard was developed in accordance with internationally recognized principles on standardizationestablished in the Decision on Principles for the Development of International Standard
8、s, Guides and Recommendations issuedby the World Trade Organization Technical Barriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2C753 Specification for Nuclear-Grade, Sinterable Uranium Dioxide PowderC776 Specification for Sintered Uranium Dioxide Pellets for Light Water Re
9、actorsC787 Specification for Uranium Hexafluoride for EnrichmentC788 Specification for Nuclear-Grade Uranyl Nitrate Solution or CrystalsC859 Terminology Relating to Nuclear MaterialsC967 Specification for Uranium Ore ConcentrateC996 Specification for Uranium Hexafluoride Enriched to Less Than 5 % 23
10、5UC1346 Practice for Dissolution of UF6 from P-10 TubesC1347 Practice for Preparation and Dissolution of Uranium Materials for AnalysisD1193 Specification for Reagent Water3. Terminology3.1 Definitions:3.1.1 For definitions of terms relating to the nuclear fuel cycle, refer to Terminology C859.1 Thi
11、s test method is under the jurisdiction of ASTM Committee C26 on Nuclear Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of Test.Current edition approved June 1, 2010Jan. 1, 2018. Published July 2010January 2018. Originally approved in 1994. Last previous edition approv
12、ed in 20032010 asC1287 03.C1287 10. DOI: 10.1520/C1287-10.10.1520/C1287-18.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the
13、 ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users con
14、sult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States14. Summary of Test Method4.1 The s
15、ample is dissolved in acid if it is not already a solution. A fixed quantity of internal standard is added to monitor andcorrect for signal instability. The level of impurities in the solution is measured by ICP-MS. Customized software calculates theconcentration of each element.4.2 Uranium-concentr
16、ation-matched standard solutions are used to calibrate the ICP-MS instrument. The calibration is linear upto at least 0.2 g/mlg/mL (100 g/g U) for each analyte.3,44.3 Microwave dissolution may be used as an alternate dissolution method.5. Significance and Use5.1 This test method is capable of measur
17、ing the elements listed in Table 1, some of which are required by Specifications C753,C776, C787, C788, C967 and C996.6. Apparatus6.1 ICP-MS, controlled by computer and fitted with the associated software and peripherals. May be fitted with cold plasmaoption. Current instrumentation is available wit
18、h dynamic reaction cell or collision cell options.6.2 Autosampler, with tube racks and disposable plastic sample tubes compatible with 5.16.1 (optional).6.3 Variable Micropipettes:6.3.1 10 L to 100 L capacity.6.3.2 100 L to 1000 L capacity.6.3.3 1000 L to 10.00 mL capacity.6.4 Volumetric Flasks:6.4.
19、1 50 mL capacitypolypropylene.6.4.2 100 mL capacitypolypropylene.6.4.3 1 L capacityglass.6.5 Platinum Dish100 mL capacity.6.6 Silica Beaker250 mL capacity.6.7 Watch Glasses75 mm diameter.6.8 Polypropylene Tubes50 mL, with graduation marks and with caps.7. Reagents7.1 The sensitivity of the ICP-MS te
20、chnique requires the use of ultra high purity reagents in order to be able to obtain the lowlevels of detection. All the reagents below are ultra high purity grade unless otherwise stated:7.1.1 Element stock standards at 1000 g/mL for all the elements in Table 1.7.1.2 Hydrofluoric Acid (HF), (40 g/1
21、00 g), 23 molar.7.1.2.1 WarningHydrofluoric acid is a highly corrosive acid that can severely burn skin, eyes, and mucous membranes.Hydrofluoric acid is similar to other acids in that the initial extent of a burn depends on the concentration, the temperature, andthe duration of contact with the acid
22、. Hydrofluoric acid differs from other acids because the fluoride ion readily penetrates the skin,causing destruction of deep tissue layers. Unlike other acids that are rapidly neutralized, hydrofluoric acid reactions with tissue maycontinue for days if left untreated. Due to the serious consequence
23、s of hydrofluoric acid burns, prevention of exposure or injuryof personnel is the primary goal. Utilization of appropriate laboratory controls (hoods) and wearing adequate personnel protectiveequipment to protect from skin and eye contact is essential. Acute exposure to HF can cause painful and seve
24、re burns upon skincontact that require special medical attention. Chronic or prolonged exposure to low levels on the skin may causefluorosis.Familiarization and compliance with the Safety Data Sheet is essential.7.1.3 Nitric AcidConcentrated nitric acid (HNO3), 15 molar.7.1.4 Rhodium Stock Solution
25、(1000 g/mL Rh)Commercially available solution (see Note 1).NOTE 1Rhodium stock solution is commercially available supplied with a certificate of analysis for the element and a full range of trace impurities.The solutions are prepared by the manufacturer using a variety of media designed to keep each
26、 element in solution for a minimum of one year.7.1.5 Sulfuric AcidConcentrated sulfuric acid (H2SO4), 18 molar.3 “ICP-MS Versus Conventional Methods for the Analysis of Trace Impurities in Nuclear Fuel,” by Allenby, P., Clarkson, A. S., Makinson, P. R., presented at 2nd SurreyConference on Plasma So
27、urce Mass Spectrometry, Guildford, UK, July 1987.4 “Trace Metals in NBL Uranium Standard CRM 124 Using ICP-MS,” by Aldridge, A. J., Clarkson, A. S., Makinson, P. R., Dawson, K. W., presented at 1st DurhamInternational Conference on Plasma Source Mass Spectrometry, Durham, UK, September 1988.C1287 18
28、2TABLE 1 Reporting Limits of Impurity ElementsNOTE 1The impurity elements were determined in 0.2 % uraniumsolutions, prepared following Section 89.NOTE 2Acquisition time = 10 s/isotope using peak jump mode.NOTE 3103 Rh was used as an internal standard. For the elementswhere the technique is identifi
29、ed as Perkin Elmer DRCII scandium wasused as internal standard for boron, sodium and phosphorus. Rhodium wasused as the internal standard for potassium, calcium and iron in ReactionCell mode.NOTE 4The LRL is based on the within run standard deviation (Sb) of20 uranium-matched blank determinations fo
30、r each analyte. This limitequals 4 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 of 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 extended
31、dynamic range (EDR) accessory.NOTE 6For the elements where the technique is listed as P-E DRCII,the instrumentation may be specific to those elements. Alternatively coldplasma technique may be used and it is up to the analyst to performtestwork using spikes and reference materials and to determine t
32、he lowerreporting levels. The impurity elements were determined in 0.16 %uranium solutions, prepared following Section 89. The dwell times arelisted in 8.4.1.19.4.1.1.NOTE 7Some of the elements are not included in the materialspecifications and have been included only as a research record for therea
33、ders interest.Analyte MassUsed AnalyteGroupLowerReportingLimit (LRL),g/g UUpperReportingLimit (URL),g/g UTechniqueLithium 7 A 0.01 100 normal plasmaBeryllium 9 A 0.04 100 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 plasm
34、aPhosphorus 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 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 n
35、ormal 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 normal plasmaArsenic 75 A 0.2 100 normal plasmaSelenium 82 A 3 100 normal plasmaRubidium 85 A 0.06 100 normal plasmaStrontium 88 A 0.
36、06 100 normal plasmaYttrium 89 A 0.04 100 normal plasmaZirconium 90 B 0.02 100 normal plasmaNiobium 93 B 0.01 100 normal plasmaMolybde-num95 B 0.04 100 normal plasmaRuthenium 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 nor
37、mal 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 0.06 100 normal plasmaC1287 1837.1.6 Uranium Standard Base SolutionUranyl nitrate solution to Specification C788, of known uranium (100
38、 g/L) andaluminum content ( 2 g/g U). The total metallic impurity (TMI) content must not exceed 50 g/g U and no individual analytemust exceed 10 g/g U.7.1.7 Purity of WaterUnless otherwise indicated, references to water shall be understood to mean reagent water conformingto Specification D1193, Type
39、 I.7.1.8 AmmoniaAnhydrous, NH3, 99.9995 % 99.9995 % minimum purity. Used with instruments fitted with dynamic reactioncell option.8. Standards8.1 Four separate mixed standard solutions (A, B, C, and E) are prepared to prevent the precipitation of some elements (asinsoluble chlorides, fluorides etc;
40、see Table 1 for details of the analyte groups). Analyte group A contains element stock solutionsprepared in HNO3 or HNO3/HF, analyte group B contains element stock solutions prepared in HCl or HCl/HF, analyte group Ccontains the rare earth element stock solutions, and analyte group E contains boron
41、sodium silicon, phosphorus, potassium andcalcium. The mixed standard solutions should be prepared to contain only the analytes of interest. Other combinations of mixedstandard solutions may be prepared to minimize the precipitation of the analytes.8.1.1 Mixed standard solution A is prepared from sto
42、ck solutions of each element from analyte group A. Transfer 1000 L ofthe stock solution (1000 g/mL) of each element into a 50 mLpolypropylene volumetric flask and add 500 Lof concentrated nitricacid. Dilute to 50 mL with water and mix. This multi-element standard contains 20 g/mL of each analyte in
43、1 % nitric acid. Thissolution must be used on the day of preparation.8.1.2 Mixed standard solution B is prepared from stock solutions of each element from analyte group B. Transfer 1000 L ofthe stock solution (1000 g/mL) of each element into a 50 mLpolypropylene volumetric flask and add 500 Lof conc
44、entrated nitricacid. Dilute to 50 mL with water and mix. This multi-element standard contains 20 g/mL of each analyte in 1 % nitric acid. Thissolution must be used within one week of preparation.8.1.3 Mixed standard solution C is prepared from stock solutions of each element from analyte group C. Tr
45、ansfer 1000 L ofthe stock solution (1000 g/mL) of each element into a 50 mLpolypropylene volumetric flask and add 500 Lof concentrated nitricacid. Dilute to 50 mL with water and mix. This multi-element standard contains 20 g/mL of each analyte in 1 % nitric acid. Thissolution must be used within one
46、 week of preparation.8.2 Standard solution D is prepared from the stock solution of aluminum from analyte group D. Transfer 1000 L of the stocksolution (1000 g/mL Al) into a 50 mL polypropylene volumetric flask and add 500 L of concentrated nitric acid. Dilute to 50L with water and mix. This standar
47、d contains 20 g/mL of aluminum in 1 % nitric acid. This solution must be used within oneweek of preparation.TABLE 1 ContinuedAnalyte MassUsed AnalyteGroupLowerReportingLimit (LRL),g/g UUpperReportingLimit (URL),g/g UTechniqueBarium 138 A 0.02 100 normal plasmaLanthanum 139 C 0.1 100 normal plasmaCer
48、ium 140 C 0.01 100 normal plasmaPraseo-dymium141 C 0.01 100 normal plasmaNeodymium 146 C 0.01 100 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 plasmaH
49、olmium 165 C 0.01 100 normal plasmaErbium 166 C 0.01 100 normal plasmaThulium 169 C 0.01 100 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 plasmaPlatinum 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
