1、Designation: C1432 15Standard Test Method forDetermination of Impurities in Plutonium: Acid Dissolution,Ion Exchange Matrix Separation, and Inductively CoupledPlasma-Atomic Emission Spectroscopic (ICP/AES) Analysis1This standard is issued under the fixed designation C1432; the number immediately fol
2、lowing the designation indicates the year oforiginal 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 metho
3、d covers the determination of 25 ele-ments in plutonium (Pu) materials. The Pu is dissolved in acid,the Pu matrix is separated from the target impurities by an ionexchange separation, and the concentrations of the impuritiesare determined by inductively coupled plasma-atomic emissionspectroscopy (IC
4、P-AES).1.2 This test method is specific for the determination ofimpurities in8MHNO3solutions. Impurities in other pluto-nium materials, including plutonium oxide samples, may bedetermined if they are appropriately dissolved (see PracticeC1168) and converted to8MHNO3solutions.1.3 The values stated in
5、 SI units are to be regarded asstandard. The values given in parentheses are mathematicalconversions that are provided for information only and are notconsidered standard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility
6、 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 Documents2.1 ASTM Standards:2C757 Specification for Nuclear-Grade Plutonium DioxidePowder, SinterableC758 Test Methods for Chemica
7、l, Mass Spectrometric,Spectrochemical, Nuclear, and Radiochemical Analysis ofNuclear-Grade Plutonium MetalC759 Test Methods for Chemical, Mass Spectrometric,Spectrochemical, Nuclear, and Radiochemical Analysis ofNuclear-Grade Plutonium Nitrate SolutionsC859 Terminology Relating to Nuclear MaterialsC
8、1168 Practice for Preparation and Dissolution of PlutoniumMaterials for AnalysisD1193 Specification for Reagent Water3. Terminology3.1 Except as otherwise defined herein, definitions of termsare as given in Terminology C859.4. Summary of Test Method4.1 A sample of plutonium metal is dissolved in a s
9、mallvolume of 6 M hydrochloric acid (HCl). Then, 10 M (HNO3)/0.03 M hydrofluoric acid (HF) is added to the dissolvedplutonium to oxidize the plutonium to the Pu (IV) state. Thesample solution is loaded onto a nitrate anion exchange resinand eluted with8MHNO3/0.006 M HF. The rinses contain thetarget
10、metallic impurities and less than 15 g/mL Pu. Theplutonium is stripped from the anion exchange resin with 0.1M HCl. The rinses containing the metallic impurities areanalyzed by ICP-AES.5. Significance and Use5.1 This test method can be used on plutonium matrices innitrate solutions.5.2 This test met
11、hod has been validated for all elementslisted in Test Methods C757 except sulfur (S) and tantalum(Ta).5.3 This test method has been validated for all of the cationelements measured in Table 1. Phosphorus (P) requires avacuum or an inert gas purged optical path instrument.6. Interferences6.1 Plutoniu
12、m concentrations of less than 50 g/mL in thefinal aqueous phase do not significantly affect the analyticalresults for most elements. Interference studies should be madeto determine the degree of Pu and other elemental interferenceson the target analytes; background and interelement correctionsmay be
13、 required.1This test method is under the jurisdiction of ASTM Committee C26 on NuclearFuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods ofTest.Current edition approved June 1, 2015. Published July 2015. Originally approvedin 1999. Last previous edition approved in 2008 as
14、 C1432 03 (2008). DOI:10.1520/C1432-15.2For 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.Copyright ASTM Interna
15、tional, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States17. Apparatus7.1 An ICP-AES equipped with a Charge Injection Device(CID) detector or an ICP-AES with a spectral bandpass of 0.05nm or less is required to provide the necessary spectralresolution. The spectrome
16、ter may be either a simultaneousmultielement or a sequential spectrometer. The spectrometermay be either an inert gas-path or vacuum instrument; theappropriate spectral lines should be selected for each specificinstrument. Either an analog or digital readout system may beused.7.2 The ICP-AES is inte
17、rfaced to an enclosure. The torchbox is contained with an enclosure, since plutonium containingmaterials may come in direct contact with the torch despite thesubstantial removal by ion exchange in 10.3. A possible setupis described in ASTM STP 951.37.3 Vacuum manifold set at approximately 23 cm Hg (
18、9 in.Hg) is optional. A gravity system is also acceptable.7.4 15 mL plastic disposable ion exchange columns.7.5 50 mL plastic vials.7.6 Plastic micro and macro pipettes.7.7 1000 mL plastic volumetric flasks.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all te
19、sts. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society(ACS), where such specifications are available.4Other gradescould be used, provided it is first ascertained that the reagent i
20、sof 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 laboratory accepteddemineralized or deionized water as described by Type 1 ofSpecification D1193.8.3 Ultra h
21、igh purity acids shall be used for sample disso-lution and calibration standards preparation unless otherwisenoted.NOTE 1The molarity of ultra high purity acids may vary fromstandard ACS specifications for concentrated acids.NOTE 2All reagents are prepared and stored in polytetrafluoroethyl-ene (PTF
22、E) containers.8.4 Hydrochloric Acid (HCl, 11.3 M), concentrated ultrahigh purity HCl.8.5 Hydrochloric Acid (HCl, 6 M)Add 531 mL of con-centrated ultra high purity HCl (11.3 M) to less than 450 mL ofwater and dilute to 1 L with water.8.6 Hydrochloric Acid (HCl, 0.1 M)Add 8.8 mL ofconcentrated ultra h
23、igh purity HCl (11.3 M) to water, whilestirring, and dilute to 1 L with water. (Reagent grade HCl canbe used in preparing this reagent.)8.7 Hydrofluoric Acid (HF, 28.3 M), concentrated ultra highpurity HF.3Edellson, M. C., and Daniel, J. Leland, “Plasma Spectroscopy of the Analysisof Hazardous Mater
24、ials: Design and Application of Enclosed Plasma Sources,”Conference Proceedings, ASTM STP 951, ASTM, 1986.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see
25、 Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.TABLE 1 Percent Recovery and Repeatability Standard Deviation for Sixteen Spiked SamplesElementWavelength/Order
26、(nm)Actual Conc(g/mL)Mean Conc(g/mL)Average(%R)R.S.D.(%)Aluminum Al 396.152 67 2.5 2.4 95 6Barium Ba 455.403 58 2.5 2.4 95 5Beryllium Be 313.042 84 2.5 2.3 94 6Boron B 249.773 106 2.5 2.5 100 7Cadmium Cd 226.502 116 2.5 2.5 101 12Calcium Ca 396.847 66 2.5 2.6 104 20Chromium Cr 283.563 93 2.5 2.3 92
27、8Cobalt Co 228.616 115 2.5 2.5 101 6Copper Cu 324.754 81 2.5 2.4 97 6Iron Fe 259.940 101 2.5 2.5 101 12Lead Pb 220.353 120 2.5 3.1 122 12Lithium Li 670.784 39 2.5 2.2 87 6Magnesium Mg 280.270 94 2.5 2.4 95 6Manganese Mn 257.610 102 2.5 2.5 98 5Molybdenum Mo 202.030 130 2.5 2.6 103 10Nickel Ni 231.60
28、4 114 2.5 2.5 100 11Silicon Si 251.612 104 2.5 2.3 92 16Sodium Na 588.995 45 25.0 24.7 97 16Strontium Sr 421.552 62 2.5 2.4 95 5Tin Sn 189.989 139 2.5 2.7 109 19Titanium Ti 334.941 79 2.5 2.5 102 8Tungsten W 207.911 127 2.5 2.5 99 11Vanadium V 292.402 90 2.5 2.0 82 7Zinc Zn 213.856 123 2.5 2.5 100 8
29、Zirconium Zr 339.198 78 2.5 2.5 101 10C1432 1528.8 Nitric Acid (HNO3, 15.8 M), concentrated ultra highpurity nitric acid.8.9 Nitric Acid-Hydrofluoric Acid Mixture, 10 M HNO3/0.03 M HFAdd 1 mL of concentrated ultra high purity HF(28.3 M) to water; using a plastic pipette, while stirring, add633 mL co
30、ncentrated ultra high purity HNO3(15.8 M) anddilute to 1 L with water.8.10 Nitric Acid-Hydrofluoric Acid Mixture, 8 M HNO3/0.006 M HFAdd 0.21 mL of concentrated ultra high purityHF (28.3 M) to water; using a plastic pipette, while stirring,add 506 mL of concentrated ultra high purity HNO3(15.8 M)and
31、 dilute to 1 L with water.8.11 Nitric Acid (HNO3,4M)Add 253 mL of concen-trated ultra high purity nitric acid (15.8 M) to water, whilestirring, and dilute to 1 L with water.8.12 Anion Exchange Resin, macroporous-1 (MP-1), 200-400 mesh, either nitrate form or chloride form, high purity.58.13 Stock So
32、lutions, traceable to a national standard, ofmultielement spike solutions are available from a commercialvendor. The stock solutions of multielement spike solutionscan also be prepared in-house.8.13.1 Spike Solution 1 (SS-1), contains 500 g/mL of Al,Ba, Be, Ca, Li, Mg, Sr, and Na in 0.8 M HNO3.8.13.
33、2 Spike Solution 2 (SS-2), contains 500 g/mL of B,Mo, Si, Sn, Ti, W, and Zr in 0.8 M HNO3.8.13.3 Spike Solution 3 (SS-3), contains 500 g/mL of Cd,Cr, Co, Cu, Fe, Pb, Mn, Ni, V, and Zn in 0.8 M HNO3.8.14 Stock Solutions, traceable to a national standard, ofmultielement impurity standards are availabl
34、e from a commer-cial vendor. The stock solutions of multielement standards canalso be prepared in-house.8.14.1 Calibration Stock Solution-2 (CSS-2), contains 5000g/mL of Na in 0.8 M HNO3.8.14.2 Calibration Stock Solution-3 (CSS-3), contains 500g/mL of Mo, Si, Sn, Ti, W, and Zr in 0.3 M HNO3/0.1 M HF
35、.8.14.3 Calibration Stock Solution-5 (CSS-5), contains 500g/mL of Al, Ba, and Sr in 0.8 M HNO3.8.14.4 Calibration Stock Solution-6 (CSS-6), contains 500g/mL of Be, B, Cd, Ca, Cr, Co, Cu, Fe, Li, Mg, Mn, Ni, Pb,V, and Zn in 0.8 M HNO3.8.15 Prepare the multielement impurity standards andblanks as desc
36、ribed in 8.15.1 8.15.5. All calibration standardsolutions are stored in PTFE containers.8.15.1 Calibration Standard One High (CAL 1 HI)Pipette20 mL each, of stock solutions CSS-3, and CSS-5 intoa1Lvolumetric flask. Dilute to 1 L with8MHNO3/0.006 M HF.This standard solution contains the target analyt
37、es at a concen-tration of 10 g/mL.8.15.2 Calibration Standard One Low (CAL 1 LO)Pipette10 mL each, of stock solutions CSS-3, and CSS-5 intoa1Lvolumetric flask. Dilute to 1 L with8MHNO3/0.006 M HF.This standard solution contains the target analytes at a concen-tration of 5 g/mL.8.15.3 Calibration Sta
38、ndard Two High (CAL 2 HI)Pipette20 mL each, of stock solutions CCS-2, and CSS-6 intoa1Lvolumetric flask. Dilute to 1 L with8MHNO3/0.006 M HF.This standard solution contains the target analytes at a concen-tration of 10 g/mL, except Na. Na is 100 g/mL.8.15.4 Calibration Standard Two Low (CAL 2 LO)Pip
39、ette10 mL each, of stock solutions CCS-2, and CCS-6 intoa1Lvolumetric flask. Dilute to 1 L with8MHNO3/0.006 M HF.This standard solution contains the target analytes at a concen-tration of 5 g/mL, except Na. Na is 50 g/mL.8.15.5 Calibration Standard Blank (CAL BL)This blank isan 8 M HNO3/0.006 M HF s
40、olution.9. Hazards9.1 Plutonium bearing materials are radioactive and toxic.Adequate laboratory facilities, gloveboxes and fume hoodsalong with safe techniques, must be used in handling samplescontaining these materials. A detailed discussion of all theprecautions necessary is beyond the scope of th
41、is test method;however, personnel who handle these materials should befamiliar with such safe handling practices.9.2 Hydrofluoric acid is a highly corrosive acid that canseverely burn skin, eyes, and mucous membranes. Hydroflu-oric acid differs from other acids because the fluoride ionreadily penetr
42、ates the skin, causing destruction of deep tissuelayers. Unlike other acids that are rapidly neutralized, hydro-fluoric acid reactions with tissue may continue for days if leftuntreated. Familiarization and compliance with the Safety DataSheet is essential.10. Procedure10.1 Preparation of Anion Exch
43、ange Resin Slurry:10.1.1 If the anion exchange resin was purchased in thenitrate form, prepare a 1:1 (volume:volume) slurry of the resinin 4 M HNO3and proceed to 10.2.10.1.2 If the anion resin was purchased in the chloride form,convert it to the nitrate form using4MHNO3as necessary tobe sure that ch
44、loride has been completely exchanged.10.2 Sample Dissolution and Preparation:10.2.1 Obtain an aliquot of plutonium metal of approxi-mately 0.5 g for every sample that will be analyzed. For one ofthe samples that will be analyzed, obtain a second aliquot to beanalyzed as a spiked sample. A spiked sam
45、ple should beanalyzed with each analytical batch of samples.10.2.1.1 Leach all sample dissolution vials, sample collec-tion vials, and ion exchange columns with 10 M HNO3/0.03 MHF for 48 h (use reagent grade acids to prepare the leachingacid). Rinse thoroughly with water and allow the vials to airdr
46、y before proceeding with sample dissolution.NOTE 3Pu samples of 0.25 g can be analyzed using this test method.The amount of acids and resin used for the 0.5 g sample should bedecreased by one half for the preparation of the 0.25 g Pu sample.10.2.2 Label (using the sample identification) a clean plas
47、ticvial for each sample to be analyzed. Label three additionalvials as follows: (1) spiked sample (include the identification of5The sole source of supply of the resin known to the committee at this time isAG MP-1 anion exchange resin, Bio-Rad, Hercules, CA. If you are aware ofalternative suppliers,
48、 please provide this information to ASTM InternationalHeadquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee,1which you may attend.C1432 153the Pu sample that will be used), (2) blank, and (3) spike. Thesevials will be used as dissolution vi
49、als. Weigh and record theweight of each of the plutonium metal aliquots to 60.0001 g.Place the weighed plutonium metal aliquot into the appropri-ately labeled plastic vial.10.2.3 Pipette 0.1 mL each of the SS-1, SS-2, and SS-3 intothe vials labeled Spike and Spiked Sample.10.2.4 Pipette 2 mL of 6 M HCl into the Blank and Spikevials.10.2.5 Add 2 mL of 6 M HCl to the vial labeled spikedsample and all vials containing samples.10.2.5.1 Addition of the dissolution acid (6 M HCl) to thesamples should be
