1、Designation: C1637 13Standard Test Method forthe Determination of Impurities in Plutonium Metal: AcidDigestion and Inductively Coupled Plasma-MassSpectroscopy (ICP-MS) Analysis1This standard is issued under the fixed designation C1637; the number immediately following the designation indicates the y
2、ear 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 Method covers the determination of 58 trace
3、elements in plutonium (Pu) metal. The Pu sample is dissolvedin acid, and the concentration of the trace impurities aredetermined by Inductively Coupled Plasma-Mass Spectros-copy (ICP-MS).1.2 This Test Method is specific for the determination oftrace impurities in Pu metal. It may be applied to other
4、 types ofPu materials, such as Pu oxides, if the samples are dissolvedand oxidized to the Pu(IV) state. However, it is the responsi-bility of the user to evaluate the performance of other matrices.1.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are incl
5、uded in thisstandard.1.4 This standard does not purport to address all of thesafety concerns associated with its use. It is the responsibilityof the user of this method to establish appropriate safety andhealth practices and to determine the applicability of regula-tory limitations prior to use of t
6、his standard.2. Referenced Documents2.1 ASTM Standards:2C757 Specification for Nuclear-Grade Plutonium DioxidePowder, SinterableC758 Test Methods for Chemical, Mass Spectrometric,Spectrochemical, Nuclear, and Radiochemical Analysis ofNuclear-Grade Plutonium MetalC759 Test Methods for Chemical, Mass
7、Spectrometric,Spectrochemical, Nuclear, and Radiochemical Analysis ofNuclear-Grade Plutonium Nitrate SolutionsC1168 Practice for Preparation and Dissolution of PlutoniumMaterials for AnalysisC1432 Test Method for Determination of Impurities inPlutonium: Acid Dissolution, Ion Exchange MatrixSeparatio
8、n, and Inductively Coupled Plasma-AtomicEmission Spectroscopic (ICP/AES) AnalysisD1193 Specification for Reagent Water3. Summary of Test Method3.1 A sample of Pu metal is dissolved in a small volume of6 M hydrochloric acid (HCl). Then, 10 M nitric acid (HNO3)/0.03 M hydrofluoric acid (HF) is added t
9、o the dissolved Pu tooxidize the Pu to the Pu(IV) state. An aliquot of the originalsample is taken and diluted with 1 % HNO3by volume to aprescribed volume. Aliquots from a second dilution of theoriginal sample are used to prepare run batch dilutions that areanalyzed for trace impurities by ICP-MS.3
10、4. Significance and Use4.1 This test method may be run together with Test MethodC1432 to analyze for trace impurities in Pu metal. Using thetechnique described in this test method and the techniquedescribed in Test Method C1432 will provide the analyst witha more thorough verification of the impurit
11、y concentrationscontained in the Pu metal sample. In addition, Test MethodC1432 can be used to determine impurity concentrations foranalytes such as Ca, Fe, Na, and Si, which have not beendetermined using this test method.4.2 This test method can be used on Pu matrices in nitratesolutions.4.3 This t
12、est method has been validated for use on materialsthat meet the specifications described in Specification C757and Test Methods C758 and C759.4.4 This test method has been validated for all elementslisted in Table 1.1This test method is under the jurisdiction of ASTM Committee C26 on NuclearFuel Cycl
13、e and is the direct responsibility of Subcommittee C26.05 on Methods ofTest.Current edition approved Jan. 1, 2013. Published January 2013. Originallyapproved in 2006. Last previous edition approve in 2006 as D1637 06. DOI:10.1520/C1637-06.2For referenced ASTM standards, visit the ASTM website, www.a
14、stm.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.3“Inductively Coupled Plasma Mass Spectrometry Using the VG ElementalPlasma Quad,” Actinide Analytical Chemistry Procedure
15、s, Los Alamos NationalLaboratory, ANC102 R.1.2, LA-UR-05-7605, 2004.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States15. Interferences5.1 Ions from doubly charged (2+) species are formed in theICP-MS. The actinide related spectral inter
16、ferences are fromactinide 2+ and actinide-oxide 2+. The spectral interferencesare observed at 120.5 and 127.5 atomic mass unit (amu), whenanalyzing plutonium-239.5.2 Spectral interferences from the argon plasma and theacid used to transport the sample to the plasma. These spectralinterferences occur
17、 between 12 and 80 amu.5.3 Ions from plutonium cause a matrix related signalsuppression. Signal suppression increases as the Pu concentra-tion increases. In order to minimize signal suppression effectsfrom Pu, samples are diluted so that the concentration of Pu inthe analyzed aliquot is less than 50
18、0 g/mL. Three internalstandards are added to samples to correct for matrix relatedsignal suppression and signal drift. Scandium, rhodium andthulium are used as internal standards. Analytes at the low endof the mass range (below 75 amu) are referenced to scandium.Rhodium is a reference for analytes a
19、t the middle of the massrange (76-138) and all analytes at the high end of the massrange are referenced to thulium (139-238 amu).6. Apparatus6.1 An ICP-MS instrument with a quadrupole mass spec-trometer and a electron multiplier that operates at 1 amuresolution is used for this determination. The in
20、strument canalso be a magnetic sector instrument or a time of flightinstrument.6.2 The ICP-MS is interfaced to a glovebox. The torch box,and the analyzer region of the mass spectrometer are gloveboxenclosed, since Pu containing materials come in direct contactwith these sections of the instrument. M
21、ethods for enclosingplasma spectroscopic sources so that hazardous materials canbe analyzed safely are described in ASTM STP 951.46.3 Graduated 14 mL disposable plastic round bottom tubesand caps or similar.6.4 Electronic pipettes.7. Reagents and Materials7.1 Ultra high purity acids shall be used fo
22、r sample disso-lution and calibration standards preparation unless otherwisenoted.57.2 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the
23、American Chemical Society(ACS), where such specification are available.64Edellson, M. C., and Daniel, J. Leland, “Plasma Spectroscopy of the Analysisof Hazardous Materials: Design and Application of Enclosed Plasma Sources,”Conference Proceedings, ASTM 951, ASTM, 1986.5“The ULTREX II (J. T. Baker) a
24、nd INSTRUMENT QUALITY (SeastarChemicals) lines of ultra high purity acids have been found satisfactory for thispurpose.”6Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemica
25、l Society, see 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 Impurity Elements, Mean Percent Recoveries andPercent Relative Standard DeviationsElement
26、 N Mean R, % RSD, %Lithium 22 93.65 7.26Beryllium 22 96.46 8.14Boron 22 98.48 6.97Magnesium 22 98.30 7.58Aluminium 22 99.66 8.62Phosphorus 22 99.43 8.96Titanium 22 99.25 2.44Vanadium 22 94.44 7.38Chromium 22 97.29 3.90Manganese 22 95.48 3.46Cobalt 22 95.92 4.35Nickel 22 96.78 3.98Zinc 22 94.24 4.12C
27、opper 22 96.66 3.70Germanium 22 98.16 4.54Arsenic 22 101.38 8.67Selenium 22 101.15 8.00Rubidium 22 100.24 5.36Strontium 22 98.89 4.16Yttrium 22 98.07 3.81Zirconium 22 98.10 3.41Niobium 22 96.92 3.65Molybdenum 22 97.82 3.81MolybdenumA21 98.36 2.90Ruthenium 22 98.32 2.14Palladium 22 97.69 2.49Silver 2
28、2 105.14 7.88SilverA21 106.56 4.26Cadmium 22 96.03 3.72Indium 22 98.01 3.57Tin 22 97.25 3.94Antimony 22 95.05 6.21Tellurium 22 100.10 6.86Caesium 22 101.81 6.93Barium 22 97.99 3.68Lanthanum 22 98.31 3.84Cerium 22 97.57 3.72Praeseodymium 22 97.32 3.00Neodymium 22 97.22 3.56Samarium 22 98.39 3.34Europ
29、ium 22 97.43 3.02Gadolinium 22 100.04 2.78Terbium 22 97.62 2.72Dysprosium 22 98.18 2.20Holmium 22 98.61 2.21Erbium 22 98.05 2.29Ytterbium 22 99.59 2.43Lutetium 22 97.06 5.00LutetiumA21 97.79 3.72Hafnium 22 100.32 3.95Tantalum 22 93.42 3.21TantalumA21 93.89 2.43Tungsten 22 96.29 3.54Rhenium 22 99.75
30、3.28Iridium 22 99.88 3.70Platinum 22 100.57 3.93Gold 22 101.20 5.35GoldA21 100.41 3.96Thallium 22 100.09 5.02Lead 22 101.58 5.54Bismuth 22 100.70 5.43Thorium 22 103.30 6.89Uranium 22 104.14 9.11AWithout Outlying ValueC1637 1327.3 Purity of WaterUnless otherwise indicated, referencesto water shall be
31、 understood to mean laboratory accepteddemineralized or deionized water as described by Type I ofSpecification D1193.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 (P
32、TFE) containers.7.4 Hydrochloric Acid (HCl, 11.3 M), concentrated HCl.7.5 Hydrochloric Acid (HCl, 6 M), Add 531 mL of concen-trated HCl (11.3 M) to less than 450 mL of water and dilute to1 liter with water.7.6 Nitric Acid (HNO3, 15.8 M) concentrated nitric acid.7.7 Nitric Acid, 1 % by volume One vol
33、ume of concen-trated nitric acid (HNO3, 15.8 M) brought to one hundredvolumes with water.7.8 Hydrofluoric Acid (HF, 28.3 M), concentrated HF.7.9 Nitric Acid-Hydrofluoric Acid Mixture, 10 M HNO3/0.03 M HFAdd 1 mL of concentrated HF (28.3 M) to water;using a plastic pipette, while stirring, add 633 mL
34、 concentratedHNO3(15.8 M) and dilute to 1 L with water.7.10 Stock solutions, traceable to a national standardsorganization, of multielement spike solutions are availablefrom commercial vendors. The stock solutions of mulielementspike solutions can also be prepared in-house.7.10.1 Spike Solution 1 (S
35、S-1)contains 500 g/mL of Al,As, Ba, Be, Bi, Cs, In, Li, Mg, Rb, Se and Sr in 0.8 M HNO3.77.10.2 Spike Solution 2 (SS-2)contains 500 g/mL of B,Ge, Hf, Mo, Nb, P, Re, Sb, Sn, Ta, Ti, W and Zr in 0.8 MHNO3.77.10.3 Spike Solution 3 (SS-3)contains 500 g/mL of Ag,Cd, Cr, Co, Cu, Mn, Ni, Pb, Tl, V and Zn i
36、n 0.8 M HNO3.77.10.4 Spike Solution 4 (SS-4)contains 500 g/mL of Ce,Dy, Er, Eu, Gd, Ho, La, Lu, Nd, Pr, Sm, Tb, Th, U, Yb and Yin 0.8 M HNO3.77.10.5 Spike Solution 5 (SS-5)contains 500 g/mL of Au,Ir, Pd, Pt, Ru and Te in 0.8 M HNO3.77.11 Stock solutions, traceable to a national standardsorganization
37、, of multielement impurity standards are availablefrom commercial vendors. The stock solutions of multielementstandards can also be prepared in-house.7.11.1 Inductively Coupled Plasma Calibration Standard-One (ICPCS-1) contains 10 g/mLofAg,Al,As, Be, B, Cr, Co,Cu, Ge, Li, Mg, Mn, Ni, P, Pr, Rb, Se,
38、Ti, V, and Zn in 10 %HNO3by volume and 0.5 % HF by volume.87.11.2 Inductively Coupled Plasma Calibration Standard-Two (ICPCS-2) contains 10 g/mL of Ba, Bi, Cd, Cs, Ce, Dy,Er, Eu, Gd, Ho, La, Lu, Nd, Pb, Re, Sm, Sr, Tb, Tl, Th, U, Yb,and Y in 10 % HNO3by volume.87.11.3 Inductively Coupled Plasma Cali
39、bration Standard-Three (ICPCS-3) contains 10 g/mL of Au, Hf, In, Ir, Mo, Nb,Pd, Pt, Ru, Ta, Te, Sb, Sn, W, and Zr in 10 % HCl by volume,2 % HF by volume and 0.5 % HNO3by volume.87.12 Stock solutions, traceable to a national standardsorganization, of single element internal standard are availablefrom
40、 commercial vendors.7.12.1 Internal Standard-One (IS-1), contains 10 g/mL ofSc in 2 % HNO3by volume.7.12.2 Internal Standard-Two (IS-2), contains 10 g/mL ofRh in 2 % HCl by volume.7.12.3 Internal Standard-Three (IS-3), contains 10 g/mLofTm in 2 % HNO3by volume.8. Hazards8.1 Plutonium bearing materia
41、ls are radioactive and toxic.Adequate laboratory facilities, gloveboxes and fumehoodsalong 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 the
42、se materials should befamiliar with such safe handling practices.8.2 Extreme care should be exercised in using concentratedacids.8.3 Warning Hydrofluoric acid is a highly corrosiveacid that can severely burn skin, eyes, and mucous membranes.Hydrofluoric acid is similar to other acids in that the ini
43、tialextent 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 neutralized, hydr
44、ofluoricacid reactions with tissue may continue for days if leftunattended. Due to the serious consequences of hydrofluoricacid burns, prevention of exposure or injury of personnel is theprimary goal. Utilization of appropriate laboratory controls(hoods) and wearing adequate personal protective equi
45、pment toprotect from skin and eye contact is essential. Acute exposureto HF can cause painful and severe burns upon skin contact thatrequire special medical attention. Chronic or prolonged expo-sure to low levels on the skin may cause fluorosis.9. Procedure9.1 Sample Dissolution9.1.1 Obtain an aliqu
46、ot of Pu metal of approximately 0.25 gfor every sample that will be analyzed. For one of the samplesthat will be analyzed obtain a second aliquot to be analyzed asa “spiked sample.” A “spiked sample” should be analyzed witheach batch of samples.9.1.2 Label (using the sample identification) a clean 1
47、4 mLplastic tube for each sample to be analyzed. Label twoadditional tubes as follows: 1) “spiked sample” (include theidentification of the Pu sample that will be used) and 2)“blank”. These tubes will be used as “dissolution tubes”. Weighand record the weight of each of the Pu metal aliquots to60.00
48、01 g. Place the weighed Pu metal aliquot into theappropriately labeled plastic tube.9.1.3 Pipette 0.1 mL each of the SS-1, SS-2, SS-3, SS-4 andSS-5 into the tube labeled “SPIKED SAMPLE”.7Multielement spike solutions, Inorganic Ventures, NJ, has been found to beacceptable.8Multielement impurity stand
49、ards, High Purity Standards, Charleston, SC, hasbeen found to be acceptable.C1637 1339.1.4 Pipette 1 mL of 6 M HCl into each of the “dissolutiontubes”, including the one labeled “blank” (see Practice C1168).NOTE 3Addition of the dissolution acid (6 M HCl) to the samplesshould be performed by slowly adding a few drops at a time and swirlingthe sample tube; if the reaction becomes too vigorous the solution maybubble out of the plastic tube. Do not cap and do not vigorously shake thetubes containing samples.9.1.5 Add enough 10 M HNO3/ 0.03 M HF so that the
