1、Designation: C 1432 03Standard 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 C 1432; the number immediately f
2、ollowing 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test me
3、thod 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
4、(ICP-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 PracticeC 1168) and converted to8MHNO3solutions.1.3 This standard do
5、es 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 practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Sta
6、ndards:C 757 Specification for Nuclear-Grade Plutonium DioxidePowder, Sinterable2C 758 Test Methods for Chemical, Mass Spectrometric,Spectrochemical, Nuclear, and Radiochemical Analysis ofNuclear-Grade Plutonium Metal2C 759 Test Methods for Chemical, Mass Spectrometric,Spectrochemical, Nuclear, and
7、Radiochemical Analysis ofNuclear-Grade Plutonium Nitrate Solutions2C 1168 Practice for Preparation and Dissolution of Pluto-nium Materials for Analysis2D 1193 Specification for Reagent Water33. Summary of Test Method3.1 A sample of plutonium metal is dissolved in a smallvolume of 6 M hydrochloric ac
8、id (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 metallic impurities and less than
9、 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.4. Significance and Use4.1 This test method can be used on plutonium matrices innitrate solutions.4.2 This test method has been validated for all el
10、ementslisted in Test Methods C 757 except sulfur (S) and tantalum(Ta).4.3 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.5. Interferences5.1 Plutonium concentrations of less than 50
11、 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 required.6. Apparatus6.1 An ICP
12、-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.4The spectrometer may be either a simultaneousmultielement or a sequential spectrometer. The spectrometermay be either an inert
13、gas-path or vacuum instrument; theappropriate spectral lines should be selected for each specificinstrument. Either an analog or digital readout system may beused.1This test method is under the jurisdiction of ASTM Committee C26 on NuclearFuel Cycle and is the direct responsibility of Subcommittee C
14、26.05 on Methods ofTest.Current edition approved Feb. 10, 2003. Published April 2003. Originallyapproved in 1999. Last previous edition approved in 1999 as C 1432 99.2Annual Book of ASTM Standards, Vol 12.01.3Annual Book of ASTM Standards, Vol 11.01.4A Thermo Jarrel Ash PolyScan Iris spectrometer (T
15、hermal Elemental, Franklin,MA), or an Applied Research Laboratories 3580 ICP-AES instrument (, Dearborn,MI) have been found to be acceptable.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.6.2 The ICP-AES is interfaced to a glovebox.
16、 The torch boxis glovebox enclosed, since plutonium containing materialscome in direct contact with the torch. This setup is described inASTM STP 951.56.3 Vacuum manifold set at approximately 23 cm Hg (9 in.Hg) is optional.6A gravity system is also acceptable.6.4 15 mL plastic disposable ion exchang
17、e columns.76.5 50 mL plastic vials.6.6 Plastic micro and macro pipettes.6.7 1000 mL plastic volumetric flasks.7. Reagents and Materials7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specificati
18、ons of the Commit-tee on Analytical Reagents of the American Chemical Society(ACS), where such specifications are available.8Other gradescould be used, provided it is first ascertained that the reagent isof sufficiently high purity to permit its use without lesseningthe accuracy of the determination
19、.7.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean laboratory accepteddemineralized or deionized water as describe by Type 1 ofSpecification D 1193.7.3 Ultra high purity acids shall be used for sample disso-lution and calibration standards preparation unle
20、ss 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 (PTFE) containers.7.4 Hydrochloric Acid (HCl, 11.3 M), concentrated ultrahigh purity9HCl.7.5 Hydrochl
21、oric 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.7.6 Hydrochloric Acid (HCl, 0.1 M)Add 8.8 mL ofconcentrated ultra high purity HCl (11.3 M) to water, whilestirring, and dilute to 1 L with water. (Reagent grade HCl
22、 canbe used in preparing this reagent.)7.7 Hydrofluoric Acid (HF, 28.3 M), concentrated ultra highpurity9HF.7.8 Nitric Acid (HNO3, 15.8 M), concentrated ultra highpurity9nitric acid.7.9 Nitric Acid-Hydrofluoric Acid Mixture,10MHNO3/0.03 M HFAdd 1 mL of concentrated ultra high purity HF(28.3 M) to wa
23、ter; using a plastic pipette, while stirring, add633 mL concentrated ultra high purity HNO3(15.8 M) anddilute to 1 L with water.7.10 Nitric Acid-Hydrofluoric Acid Mixture,8MHNO3/0.006 M HFAdd 0.21 mL of concentrated ultra high purityHF (28.3 M) to water; using a plastic pipette, while stirring,add 5
24、06 mL of concentrated ultra high purity HNO3(15.8 M)and dilute to 1 L with water.5Edellson, M. C., and Daniel, J. Leland, “Plasma Spectroscopy of the Analysisof Hazardous Materials: Design and Application of Enclosed Plasma Sources,”Conference Proceedings, ASTM STP 951, ASTM, 1986.6Eichrom Technolog
25、ies Vacuum Box System (Part # AC-24-BOX), EichromTechnologies Inc., Darien. IL, has been found to be acceptable.7Ion exchange columns from either Applied Separation or Bio-Rad Inc., havebeen found to be acceptable.8Reagent Chemicals, American Chemical Society Specification, Am. Chem.Soc., Washington
26、, DC. For suggestions on the testing of reagents not listed by theAmerican Chemical Society, see Reagents Chemicals and Standards, by JosephRosin, D. Van Nostrand Co., New York, NY and the United States Pharmacopeia.9The Ultrex (J. T. Baker, Inc.) and Seastar brands of ultra high purity acids havebe
27、en found to be acceptable.TABLE 1 Percent Recovery and Repeatability Standard Deviation for Sixteen Spiked SamplesElementWavelength/Order(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 6Bor
28、on 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 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
29、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 231.604 114 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 19Ti
30、tanium 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 8Zirconium Zr 339.198 78 2.5 2.5 101 10C14320327.11 Nitric Acid (HNO3, 4 M)Add 253 mL of concen-trated ultra high purity nitric acid (15.8 M) to water, whilestirrin
31、g, and dilute to 1 L with water.7.12 Anion Exchange Resin, macroporous-1 (MP-1), 200-400 mesh, either nitrate form or chloride form, high purity.107.13 Stock Solutions, traceable to a national standard, ofmultielement spike solutions are available from a commercialvendor. The stock solutions of mult
32、ielement spike solutionscan also be prepared in-house.7.13.1 Spike Solution 1 (SS-1), contains 500 g/mL of Al,Ba, Be, Ca, Li, Mg, Sr, and Na in 0.8 M HNO3.117.13.2 Spike Solution 2 (SS-2), contains 500 g/mL of B,Mo, Si, Sn Ti, W, and Zr in 0.8 M HNO3.117.13.3 Spike Solution 3 (SS-3), contains 500 g/
33、mL of Cd,Cr, Co, Cu, Fe, Pb, Mn, Ni, V, and Zn in 0.8 M HNO3.117.14 Stock Solutions, traceable to a national standard, ofmultielement impurity standards are available from a commer-cial vendor. The stock solutions of multielement standards canalso be prepared in-house.7.14.1 Calibration Stock Soluti
34、on-2 (CSS-2), contains 5000g/mL of Na in 0.8 M HNO3.127.14.2 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.127.14.3 Calibration Stock Solution-5 (CSS-5), contains 500g/mL of Al, Ba, and Sr in 0.8 M HNO3.127.14.4 Calibration Stock Solution-
35、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 HNO3.127.15 Prepare the multielement impurity standards andblanks as described in 7.15.1-7.15.5. All calibration standardsolutions are stored in PTFE containers.7.15.1 Calibration Standard One High (C
36、AL 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 analytes at a concen-tration of 10 g/mL.7.15.2 Calibration Standard One Low (CAL 1 LO)Pipette10 mL each, of stock solutions CSS-3, an
37、d 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.7.15.3 Calibration Standard Two High (CAL 2 HI)Pipette20 mL each, of stock solutions CCS-2, and CSS-6 intoa1Lvolumetric flask. Dilute to 1 L with8MHN
38、O3/0.006 M HF.This standard solution contains the target analytes at a concen-tration of 10 g/mL, except Na. Na is 100 g/mL.7.15.4 Calibration Standard Two Low (CAL 2 LO)Pipette10 mL each, of stock solutions CCS-2, and CCS-6 intoa1Lvolumetric flask. Dilute to 1 L with8MHNO3/0.006 M HF.This standard
39、solution contains the target analytes at a concen-tration of 5 g/mL, except Na. Na is 50 g/mL.7.15.5 Calibration Standard Blank (CAL BL)This blankis an 8 M HNO3/0.006 M HF solution.8. Hazards8.1 Plutonium bearing materials are radioactive and toxic.Adequate laboratory facilities, glove boxes and fum
40、e hoodsalong with safe techniques, must be used in handling samplescontaining these materials. A detailed discussion of all theprecautions necessary is beyond the scope of this test method;however, personnel who handle these materials should befamiliar with such safe handling practices.9. Procedure9
41、.1 Preparation of Anion Exchange Resin Slurry:9.1.1 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 9.2.9.1.2 If the anion resin was purchased in the chloride form,convert it to the nitrate form.9.2 Sample Disso
42、lution and Preparation:9.2.1 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 sample should beanalyzed with each analytical batch of sam
43、ples.NOTE 3Leach all sample dissolution vials, sample collection vials,and ion exchange columns with 10 M HNO3/0.03 M HF for 48 h (usereagent grade acids to prepare the leaching acid). Rinse thoroughly withwater and allow the vials to air dry before proceeding with sampledissolution.NOTE 4Pu samples
44、 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.9.2.2 Label (using the sample identification) a clean plasticvial for each sample to be analyzed. Label three additiona
45、lvials as follows: (1) spiked sample (include the identification ofthe Pu sample that will be used), (2) blank, and (3) spike. Thesevials will be used as dissolution vials. Weigh and record theweight of each of the plutonium metal aliquots to 60.0001 g.Place the weighed plutonium metal aliquot into
46、the appropri-ately labeled plastic vial.9.2.3 Pipette 0.1 mL each of the SS-1, SS-2, and SS-3 intothe vials labeled Spike and Spiked Sample.9.2.4 Pipette 2 mL of 6 M HCl into the Blank and Spikevials.9.2.5 Add 2 mL of 6 M HCl to the vial labeled spikedsample and all vials containing samples.9.2.5.1
47、Addition of the dissolution acid (6 M HCl) to thesamples should be performed by slowly adding a few drops ata time and swirling the sample vial; if the reaction becomes tovigorous the solution may bubble out of the plastic vial. Do notcap and do not vigorously shake the vials containing samples.9.2.
48、6 Add 4 mL of 10 M HNO3/0.03 M HF to each vial.9.3 Ion Exchange:9.3.1 Label 15 mL plastic disposable ion exchange columnsfor each vial.9.3.2 Fill the ion exchange columns with ;15 mL of theresin slurry, MP-1, 200-400 mesh, wet resin, in the nitrateform. Compress the resin to ;8 mL with the PTFE frit
49、. Pour10AG MP-1 anion exchange resin, Bio-Rad, Richmond, CA, has been found tobe acceptable.11Multielement spike solutions, Inorganic Ventures, NJ, has been found to beacceptable.12Multielement impurity standards, High Purity, SC, has been found to beacceptable.C1432033off the 4 M HNO3solution, and rinse above the frit with waterso that no resin remains. Step 9.3.2 may be performed in afume hood; the columns can be introduced into a containmentbox after they are rinsed with water.9.3.3 Place each resin c
