1、Designation: C 1637 06Standard 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 C 1637; the number immediately following the designation indicates the
2、 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 Method covers the determination of 58 tr
3、aceelements 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 ot
4、her 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 This standard does not purport to address all of thesafety concerns associated with its use. It
5、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 this standard.2. Referenced Documents2.1 ASTM Standards:2C 757 Specification for Nuclear-Grade Plutonium DioxidePowder, Si
6、nterableC 758 Test Methods for Chemical, Mass Spectrometric,Spectrochemical, Nuclear, and Radiochemical Analysis ofNuclear-Grade Plutonium MetalC 759 Test Methods for Chemical, Mass Spectrometric,Spectrochemical, Nuclear, and Radiochemical Analysis ofNuclear-Grade Plutonium Nitrate SolutionsC 1168 P
7、ractice for Preparation and Dissolution of Pluto-nium Materials for AnalysisC 1432 Test Method for Determination of Impurities inPlutonium: Acid Dissolution, Ion Exchange Matrix Sepa-ration, and Inductively Coupled Plasma-Atomic EmissionSpectroscopic (ICP/AES) AnalysisD 1193 Specification for Reagen
8、t 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 to the dissolved Pu tooxidize the Pu to the Pu(IV) state. An aliquot of the originalsample is taken and diluted
9、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.34. Significance and Use4.1 This test method may be run together with Test MethodC 1432 to analyze for trace imp
10、urities in Pu metal. Using thetechnique described in this test method and the techniquedescribed in Test Method C 1432 will provide the analyst witha more thorough verification of the impurity concentrationscontained in the Pu metal sample. In addition, Test MethodC 1432 can be used to determine imp
11、urity 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 test method has been validated for use on materialsthat meet the specifications described in Specification C
12、757and Test Methods C 758 and C 759.4.4 This test method has been validated for all elementslisted in Table 1.5. Interferences5.1 Ions from doubly charged (2+) species are formed in theICP-MS. The actinide related spectral interferences are fromactinide 2+ and actinide-oxide 2+. The spectral interfe
13、rences1This test method is under the jurisdiction ofASTM Committee C26 on NuclearFuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods ofTest.Current edition approved Jan. 1, 2006. Published February 2006.2For referenced ASTM standards, visit the ASTM website, www.astm.org, o
14、rcontact 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 Procedures, Los Ala
15、mos NationalLaboratory, ANC102 R.1.2, LA-UR-05-7605, 2004.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.are observed at 120.5 and 127.5 atomic mass unit (amu), whenanalyzing plutonium-239.5.2 Spectral interferences from the argon p
16、lasma and theacid used to transport the sample to the plasma. These spectralinterferences occur 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
17、 Pu, samples are diluted so that the concentration of Pu inthe analyzed aliquot is less than 500 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
18、 the mass range (below 75 amu) are referenced to scandium.Rhodium is a reference for analytes at 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 an
19、d a electron multiplier that operates at 1 amuresolution is used for this determination. The instrument 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 gloveboxenclose
20、d, since Pu containing materials come in direct contactwith these sections of the instrument. Methods 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 simila
21、r.6.4 Electronic pipettes.7. Reagents and Materials7.1 Ultra high purity acids shall be used for 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 thatal
22、l reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society(ACS), where such specification are available.67.3 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean laboratory accepteddemineralized or dei
23、onized water as described by Type I ofSpecification D 1193.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), conce
24、ntrated HCl.4Edellson, 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) and INSTRUMENT QUALITY (SeastarChemicals) lines of ultra high
25、 purity acids have been found satisfactory for thispurpose.”6“Reagent Chemicals, American Chemical Society Specification,” Am. Chem.Soc., Washington, DC. For suggestions on the testing of reagents not listed by theAmerican Chemical Society, see “Reagents Chemicals and Standards,” by JosephRosin D. V
26、an Nostrand Co., New York, NY and the “United States Phamacopeia.”TABLE 1 Impurity Elements, Mean Percent Recoveries andPercent Relative Standard DeviationsElement 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 8.62Phosphoru
27、s 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 4.12Copper 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 4.16Yttr
28、ium 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 22 105.14 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 6.8
29、6Caesium 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 3.34Europium 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
30、 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 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 2
31、2 100.70 5.43Thorium 22 103.30 6.89Uranium 22 104.14 9.11AWithout Outlying ValueC16370627.5 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 %
32、 by volume One volume 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,10MHNO3/0.03 M HFAdd 1 mL of concentrated HF (28.3 M) to water;using a plastic pipette, while stirr
33、ing, add 633 mL concentratedHNO3(15.8 M) and dilute to 1 L with water.7.10 Stock solutions, traceable to a national standards orga-nization, of multielement spike solutions are available fromcommercial vendors. The stock solutions of mulielement spikesolutions can also be prepared in-house.7.10.1 Sp
34、ike Solution 1 (SS-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, P
35、b, Tl, V and Zn in 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 stan
36、dards orga-nization, of multielement impurity standards are available fromcommercial 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,
37、Ni, P, Pr, Rb, Se, 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
38、Coupled Plasma Calibration 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 standards orga-nization, of single element internal stand
39、ard are available fromcommercial 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 Plut
40、onium bearing materials 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, per
41、sonnel who handle these materials should befamiliar with such safe handling practices.8.2 Extreme care should be exercised in using concentratedacids. In particular, hydrofluoric acid should be used with careby persons familiar with its hazards through review of theMaterial Data Safety Sheet (MSDS)
42、and who are properlyequipped to respond to cases of skin contact.9. Procedure9.1 Sample Dissolution9.1.1 Obtain an aliquot 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.
43、” A “spiked sample” should be analyzed witheach batch of samples.9.1.2 Label (using the sample identification) a clean 14 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)“blan
44、k”. These tubes will be used as “dissolution tubes”. Weighand record the weight of each of the Pu metal aliquots to +/-0.0001 g. Place the weighed Pu metal aliquot into the appro-priately 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 “SPIK
45、ED SAMPLE”.9.1.4 Pipette 1 mL of 6 M HCl into each of the “dissolutiontubes”, including the one labeled “blank” (see PracticeC 1168).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
46、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 finalvolume is 3.0 mL and mix thoroughly.9.1.6 Label another set of tubes as in 9.1.2.9.1.7 Pipette 0.3 mL from ea
47、ch of the dissolution tubes intoeach of the identically labeled tubes in step 9.1.6.9.1.8 Dilute to 5 mL with 1 % HNO3by volume and mixthoroughly (the samples will be analyzed from further dilutionsof this second dilution).NOTE 4The remainder of the sample in the dissolution tubes may beused for ana
48、lysis using Test Method C 1432 or can be disposed of usingthe appropriate laboratory protocol.9.2 Internal Standard and Calibration Standard PreparationNOTE 5Steps 9.2.1-9.2.7 may be performed in a fumehood; the tubescan be introduced into a glovebox after the internal standard mixture isadded to ea
49、ch tube in the analytical run and the calibration standards areprepared.9.2.1 Pipette equal volumes of IS-1, IS-2 and IS-3 into aclean 14 mL plastic tube. The concentration of the internalstandard mixture will be 3.333 g/mL.7Multielement spike solutions, Inorganic Ventures, NJ, has been found to beacceptable.8Multielement impurity standards, High Purity Standards, Charleston, SC, hasbeen found to be acceptable.C16370639.2.2 Label another set of 14 mL tubes as in 9.1.2.9.2.3 Label 14 mL plastic tubes for calibration standards.9.2.4 Add ; 5mLof1%HNO3by volum
