ASTM C1637-06
(Test Method)Standard Test Method for the Determination of Impurities in Plutonium Metal: Acid Digestion and Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS) Analysis
Standard Test Method for the Determination of Impurities in Plutonium Metal: Acid Digestion and Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS) Analysis
SCOPE
1.1 This Test Method covers the determination of 58 trace elements in plutonium (Pu) metal. The Pu sample is dissolved in acid, and the concentration of the trace impurities are determined by Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS).
1.2 This Test Method is specific for the determination of trace impurities in Pu metal. It may be applied to other types of Pu materials, such as Pu oxides, if the samples are dissolved and oxidized to the Pu(IV) state. However, it is the responsibility of the user to evaluate the performance of other matrices.
1.3 This standard does not purport to address all of the safety concerns associated with its use. It is the responsibility of the user of this method to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use of this standard.
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Designation: C1637 − 06
StandardTest Method for
the Determination of Impurities in Plutonium Metal: Acid
Digestion and Inductively Coupled Plasma-Mass
Spectroscopy (ICP-MS) Analysis
This standard is issued under the fixed designation C1637; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope Separation, and Inductively Coupled Plasma-Atomic
Emission Spectroscopic (ICP/AES) Analysis
1.1 This Test Method covers the determination of 58 trace
D1193 Specification for Reagent Water
elements in plutonium (Pu) metal. The Pu sample is dissolved
in acid, and the concentration of the trace impurities are
3. Summary of Test Method
determined by Inductively Coupled Plasma-Mass Spectros-
3.1 Asample of Pu metal is dissolved in a small volume of
copy (ICP-MS).
6 M hydrochloric acid (HCl). Then, 10 M nitric acid (HNO )/
1.2 This Test Method is specific for the determination of
0.03 M hydrofluoric acid (HF) is added to the dissolved Pu to
traceimpuritiesinPumetal.Itmaybeappliedtoothertypesof
oxidize the Pu to the Pu(IV) state. An aliquot of the original
Pu materials, such as Pu oxides, if the samples are dissolved
sample is taken and diluted with 1 % HNO by volume to a
and oxidized to the Pu(IV) state. However, it is the responsi-
prescribed volume. Aliquots from a second dilution of the
bility of the user to evaluate the performance of other matrices.
original sample are used to prepare run batch dilutions that are
1.3 This standard does not purport to address all of the
analyzed for trace impurities by ICP-MS.
safety concerns associated with its use. It is the responsibility
4. Significance and Use
of the user of this method to establish appropriate safety and
health practices and to determine the applicability of regula-
4.1 This test method may be run together with Test Method
tory limitations prior to use of this standard.
C1432 to analyze for trace impurities in Pu metal. Using the
technique described in this test method and the technique
2. Referenced Documents
described in Test Method C1432 will provide the analyst with
2.1 ASTM Standards: a more thorough verification of the impurity concentrations
C757 Specification for Nuclear-Grade Plutonium Dioxide contained in the Pu metal sample. In addition, Test Method
Powder, Sinterable C1432 can be used to determine impurity concentrations for
C758 Test Methods for Chemical, Mass Spectrometric, analytes such as Ca, Fe, Na, and Si, which have not been
determined using this test method.
Spectrochemical, Nuclear, and RadiochemicalAnalysis of
Nuclear-Grade Plutonium Metal
4.2 This test method can be used on Pu matrices in nitrate
C759 Test Methods for Chemical, Mass Spectrometric,
solutions.
Spectrochemical, Nuclear, and RadiochemicalAnalysis of
4.3 This test method has been validated for use on materials
Nuclear-Grade Plutonium Nitrate Solutions
that meet the specifications described in Specification C757
C1168 PracticeforPreparationandDissolutionofPlutonium
and Test Methods C758 and C759.
Materials for Analysis
C1432 Test Method for Determination of Impurities in 4.4 This test method has been validated for all elements
Plutonium: Acid Dissolution, Ion Exchange Matrix
listed in Table 1.
5. Interferences
This test method is under the jurisdiction ofASTM Committee C26 on Nuclear
5.1 Ionsfromdoublycharged(2+)speciesareformedinthe
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of
ICP-MS. The actinide related spectral interferences are from
Test.
actinide 2+ and actinide-oxide 2+. The spectral interferences
Current edition approved Jan. 1, 2006. Published February 2006. DOI: 10.1520/
C1637-06.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM “Inductively Coupled Plasma – Mass Spectrometry Using the VG Elemental
Standards volume information, refer to the standard’s Document Summary page on Plasma Quad,” Actinide Analytical Chemistry Procedures, Los Alamos National
the ASTM website. Laboratory, 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 States
C1637 − 06
TABLE 1 Impurity Elements, Mean Percent Recoveries and
5.3 Ions from plutonium cause a matrix related signal
Percent Relative Standard Deviations
suppression. Signal suppression increases as the Pu concentra-
Element N Mean R, % RSD, %
tion increases. In order to minimize signal suppression effects
Lithium 22 93.65 7.26
from Pu, samples are diluted so that the concentration of Pu in
Beryllium 22 96.46 8.14
the analyzed aliquot is less than 500 µg/mL. Three internal
Boron 22 98.48 6.97
Magnesium 22 98.30 7.58
standards are added to samples to correct for matrix related
Aluminium 22 99.66 8.62
signal suppression and signal drift. Scandium, rhodium and
Phosphorus 22 99.43 8.96
Titanium 22 99.25 2.44 thulium are used as internal standards.Analytes at the low end
Vanadium 22 94.44 7.38
of the mass range (below 75 amu) are referenced to scandium.
Chromium 22 97.29 3.90
Rhodium is a reference for analytes at the middle of the mass
Manganese 22 95.48 3.46
Cobalt 22 95.92 4.35 range (76-138) and all analytes at the high end of the mass
Nickel 22 96.78 3.98
range are referenced to thulium (139-238 amu).
Zinc 22 94.24 4.12
Copper 22 96.66 3.70
6. Apparatus
Germanium 22 98.16 4.54
Arsenic 22 101.38 8.67
6.1 An ICP-MS instrument with a quadrupole mass spec-
Selenium 22 101.15 8.00
trometer and a electron multiplier that operates at 1 amu
Rubidium 22 100.24 5.36
Strontium 22 98.89 4.16
resolution is used for this determination. The instrument can
Yttrium 22 98.07 3.81
also be a magnetic sector instrument or a time of flight
Zirconium 22 98.10 3.41
instrument.
Niobium 22 96.92 3.65
Molybdenum 22 97.82 3.81
6.2 The ICP-MS is interfaced to a glovebox. The torch box,
A
Molybdenum 21 98.36 2.90
Ruthenium 22 98.32 2.14 and the analyzer region of the mass spectrometer are glovebox
Palladium 22 97.69 2.49
enclosed, since Pu containing materials come in direct contact
Silver 22 105.14 7.88
A with these sections of the instrument. Methods for enclosing
Silver 21 106.56 4.26
plasma spectroscopic sources so that hazardous materials can
Cadmium 22 96.03 3.72
Indium 22 98.01 3.57
be analyzed safely are described in ASTM STP 951.
Tin 22 97.25 3.94
Antimony 22 95.05 6.21
6.3 Graduated 14 mLdisposable plastic round bottom tubes
Tellurium 22 100.10 6.86
and caps or similar.
Caesium 22 101.81 6.93
Barium 22 97.99 3.68
6.4 Electronic pipettes.
Lanthanum 22 98.31 3.84
Cerium 22 97.57 3.72
7. Reagents and Materials
Praeseodymium 22 97.32 3.00
Neodymium 22 97.22 3.56
7.1 Ultra high purity acids shall be used for sample disso-
Samarium 22 98.39 3.34
lution and calibration standards preparation unless otherwise
Europium 22 97.43 3.02
Gadolinium 22 100.04 2.78 noted.
Terbium 22 97.62 2.72
7.2 Purity of Reagents—Reagent grade chemicals shall be
Dysprosium 22 98.18 2.20
Holmium 22 98.61 2.21
used in all tests. Unless otherwise indicated, it is intended that
Erbium 22 98.05 2.29
all reagents shall conform to the specifications of the Commit-
Ytterbium 22 99.59 2.43
tee on Analytical Reagents of the American Chemical Society
Lutetium 22 97.06 5.00
A 6
Lutetium 21 97.79 3.72
(ACS), where such specification are available.
Hafnium 22 100.32 3.95
Tantalum 22 93.42 3.21 7.3 Purity of Water—Unless otherwise indicated, references
A
Tantalum 21 93.89 2.43
to water shall be understood to mean laboratory accepted
Tungsten 22 96.29 3.54
demineralized or deionized water as described by Type I of
Rhenium 22 99.75 3.28
Iridium 22 99.88 3.70 Specification D1193.
Platinum 22 100.57 3.93
Gold 22 101.20 5.35 NOTE 1—The molarity of ultra high purity acids may vary from
A
Gold 21 100.41 3.96 standard ACS specifications for concentrated acids.
Thallium 22 100.09 5.02
NOTE 2—All reagents are prepared and stored in polytetrafluoroethyl-
Lead 22 101.58 5.54
ene (PTFE) containers.
Bismuth 22 100.70 5.43
Thorium 22 103.30 6.89
Uranium 22 104.14 9.11
Edellson, M. C., and Daniel, J. Leland, “Plasma Spectroscopy of the Analysis
A
Without Outlying Value
of Hazardous Materials: Design and Application of Enclosed Plasma Sources,”
Conference Proceedings, ASTM 951, ASTM, 1986.
“The ULTREX II (J. T. Baker) and INSTRUMENT QUALITY (Seastar
Chemicals) lines of ultra high purity acids have been found satisfactory for this
purpose.”
are observed at 120.5 and 127.5 atomic mass unit (amu), when
Reagent Chemicals, American Chemical Society Specifications, American
analyzing plutonium-239.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
5.2 Spectral interferences from the argon plasma and the
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
acid used to transport the sample to the plasma. These spectral
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
interferences occur between 12 and 80 amu. MD.
C1637 − 06
7.4 Hydrochloric Acid (HCl, 11.3 M), concentrated HCl. 7.12.2 Internal Standard-Two (IS-2), contains 10 µg/mL of
Rh in 2 % HCl by volume.
7.5 Hydrochloric Acid (HCl, 6 M),Add 531 mL of concen-
7.12.3 Internal Standard-Three (IS-3),contains10µg/mLof
trated HCl (11.3 M) to less than 450 mLof water and dilute to
Tm in 2 % HNO by volume.
1 liter with water. 3
7.6 Nitric Acid (HNO , 15.8 M)— concentrated nitric acid.
8. Hazards
7.7 Nitric Acid, 1 % by volume— One volume of concen-
8.1 Plutonium bearing materials are radioactive and toxic.
trated nitric acid (HNO , 15.8 M) brought to one hundred
Adequate laboratory facilities, gloveboxes and fumehoods
volumes with water.
along with safe techniques, must be used in handling samples
7.8 Hydrofluoric Acid (HF, 28.3 M), concentrated HF.
containing these materials. A detailed discussion of all the
precautions necessary is beyond the scope of this test method;
7.9 Nitric Acid-Hydrofluoric Acid Mixture, 10 M HNO /
however, personnel who handle these materials should be
0.03 M HF—Add 1 mLof concentrated HF (28.3 M) to water;
familiar with such safe handling practices.
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