ASTM C1637-21

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Designation: C1637 − 13 C1637 − 21
Standard Test Method for
the Determination of Impurities in Plutonium Metal: Acid
Materials—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
1.1 This Test Methodtest method covers the determination of 58 trace elements in plutonium (Pu) metal. materials such as Pu
metal, Pu oxides, and Pu/uranium (U) mixed oxides. 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 Methodtest 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, where the samples are
dissolved and the oxidation state is adjusted to the Pu(IV) and, if applicable, the U(VI) state. It may be applied to other matrices;
however, it is the responsibility of the user to evaluate the performance of other matrices.
1.3 The use of a quadrupole ICP-MS or a high resolution ICP-MS (HR-ICP-MS) can be employed in all applications relevant to
this test method. HR-ICP-MS is a better option in many cases since it can reduce or potentially eliminate interferences encountered
in the following complex sample matrices.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 This standard does not purport to address all of the safety concerns concerns, if any, associated with its use. It is the
responsibility of the user of this methodstandard to establish appropriate safety safety, health, and healthenvironmental practices
and to determine the applicability of regulatory limitations prior to use of this standard.use.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
C757 Specification for Nuclear-Grade Plutonium Dioxide Powder for Light Water Reactors
C758 Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-
Grade Plutonium Metal
This test method is under the jurisdiction of ASTM Committee C26 on Nuclear Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of Test.
Current edition approved Jan. 1, 2013June 1, 2021. Published January 2013July 2021. Originally approved in 2006. Last previous edition approveapproved in 20062013
as D1637 – 06.13. DOI: 10.1520/C1637-13.10.1520/C1637-21.
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 Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
C1637 − 21
C759 Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-
Grade Plutonium Nitrate Solutions
C859 Terminology Relating to Nuclear Materials
C1168 Practice for Preparation and Dissolution of Plutonium Materials for Analysis
C1432 Test Method for Determination of Impurities in Plutonium: Acid Dissolution, Ion Exchange Matrix Separation, and
Inductively Coupled Plasma-Atomic Emission Spectroscopic (ICP/AES) Analysis
D1193 Specification for Reagent Water
E1154 Specification for Piston or Plunger Operated Volumetric Apparatus
3. Terminology
3.1 Except as otherwise defined herein, definitions of terms are as given in Terminology C859.
4. Summary of Test Method
4.1 Samples of plutonium materials are prepared and dissolved in accordance with an appropriate procedure in Practice C1168.
These procedures adjust the dissolved Pu to the Pu(IV) oxidation state.
4.2 A sample of Pu metal is weighed and dissolved as described in Practice C1168. An aliquot of the original sample is then taken
and diluted with 1 % HNO by volume to a prescribed volume. Aliquots from a second dilution of the original sample are used
to prepare run batch dilutions that are analyzed for trace impurities by ICP-MS (Section 10).
4.3 Plutonium oxide powders are weighed and then dissolved in a nitric acid / hydrofluoric acid or ammonium bifluoride solution
following the process described in Practice C1168. An aliquot of the dissolved sample is then taken and diluted with 0.1 M HNO
by volume to a prescribed volume in order to reach a certain concentration of Pu. In direct analysis mode, a second dilution of
the original sample is necessary to prepare run batch dilutions that are analyzed for trace impurities by ICP-MS (Section 11).
4.4 A sample of Pu metal is Mixed oxide powders are weighed and then dissolved in a small volume of 6 M hydrochloric acid
(HCl). Then, 10 M nitric acid (HNOnitric acid / )/0.03 M hydrofluoric acid (HF) is added to the hydrofluoric acid solution
following the process described in Practice C1168dissolved Pu to oxidize the Pu to the Pu(IV). Mixed oxide (U, Pu) pellets are
first crushed and then dissolved in a nitric acid / hydrofluoric acid solution following the process described in Practice C1168state.
An aliquot of the originaldissolved sample is then taken and diluted with 1 % 0.5 M HNO by volume to a prescribed volume.
Aliquots from a volume in order to reach a certain concentration of Pu. In direct analysis mode, a second dilution of the original
sample are usedis necessary to prepare to run batch dilutions that are analyzed for trace impurities by ICP-MS. For mixed oxide
powders and pellets, the standard additions method is recommended where standards at known concentration are added to the
diluted dissolved sample and the solutions are analyzed by ICP-MS (Section 12).
5. Significance and Use
5.1 This test method may be run together with Test Method C1432 to analyze for trace impurities in Pu metal. Using the technique
described in this test method and the technique described in Test Method C1432 will provide the analyst with a more thorough
verification of the impurity concentrations contained in the Pu metal sample. In addition, Test Method C1432 can be used to
determine impurity concentrations for analytes such as Ca, Fe, Na, and Si, which have not been determined using this test method.
5.2 This test method can be used on Pu matrices in nitrate solutions.
5.3 This test method has been validated for use on materials that meet the specifications described in Specification C757 and Test
Methods C758 and C759.
5.4 This test method has been validated for all elements listed in Table 1.
6. Interferences
6.1 Ions from doubly charged (2+) species are formed in the ICP-MS. The actinide related spectralisobaric interferences are from
“Inductively Coupled Plasma – Mass Spectrometry Using the VG Elemental Plasma Quad,” Actinide Analytical Chemistry ProceduresProcedures, LA-UR-05-7605, Los
Alamos National Laboratory, ANC102 R.1.2, LA-UR-05-7605, 20020044. .
C1637 − 21
TABLE 1 Impurity Elements, Mean Percent Recoveries and
Percent Relative Standard Deviations
Element N Mean R, % RSD, %
Lithium 22 93.65 7.26
Beryllium 22 96.46 8.14
Boron 22 98.48 6.97
Magnesium 22 98.30 7.58
Aluminium 22 99.66 8.62
Phosphorus 22 99.43 8.96
Titanium 22 99.25 2.44
Vanadium 22 94.44 7.38
Chromium 22 97.29 3.90
Manganese 22 95.48 3.46
Cobalt 22 95.92 4.35
Nickel 22 96.78 3.98
Zinc 22 94.24 4.12
Copper 22 96.66 3.70
Germanium 22 98.16 4.54
Arsenic 22 101.38 8.67
Selenium 22 101.15 8.00
Rubidium 22 100.24 5.36
Strontium 22 98.89 4.16
Yttrium 22 98.07 3.81
Zirconium 22 98.10 3.41
Niobium 22 96.92 3.65
Molybdenum 22 97.82 3.81
A
Molybdenum 21 98.36 2.90
Ruthenium 22 98.32 2.14
Palladium 22 97.69 2.49
Silver 22 105.14 7.88
A
Silver 21 106.56 4.26
Cadmium 22 96.03 3.72
Indium 22 98.01 3.57
Tin 22 97.25 3.94
Antimony 22 95.05 6.21
Tellurium 22 100.10 6.86
Caesium 22 101.81 6.93
Barium 22 97.99 3.68
Lanthanum 22 98.31 3.84
Cerium 22 97.57 3.72
Praeseodymium 22 97.32 3.00
Neodymium 22 97.22 3.56
Samarium 22 98.39 3.34
Europium 22 97.43 3.02
Gadolinium 22 100.04 2.78
Terbium 22 97.62 2.72
Dysprosium 22 98.18 2.20
Holmium 22 98.61 2.21
Erbium 22 98.05 2.29
Ytterbium 22 99.59 2.43
Lutetium 22 97.06 5.00
A
Lutetium 21 97.79 3.72
Hafnium 22 100.32 3.95
Tantalum 22 93.42 3.21
A
Tantalum 21 93.89 2.43
Tungsten 22 96.29 3.54
Rhenium 22 99.75 3.28
Iridium 22 99.88 3.70
Platinum 22 100.57 3.93
Gold 22 101.20 5.35
A
Gold 21 100.41 3.96
Thallium 22 100.09 5.02
Lead 22 101.58 5.54
Bismuth 22 100.70 5.43
Thorium 22 103.30 6.89
Uranium 22 104.14 9.11
TABLE 1 Impurity Elements, Mean Percent Recoveries and
Percent Relative Standard Deviations
Element N Mean R, % RSD, %
Lithium 22 93.65 7.26
Beryllium 22 96.46 8.14
Boron 22 98.48 6.97
Magnesium 22 98.30 7.58
Aluminium 22 99.66 8.62
Phosphorus 22 99.43 8.96
Titanium 22 99.25 2.44
C1637 − 21
Vanadium 22 94.44 7.38
Chromium 22 97.29 3.90
Manganese 22 95.48 3.46
Cobalt 22 95.92 4.35
Nickel 22 96.78 3.98
Zinc 22 94.24 4.12
Copper 22 96.66 3.70
Germanium 22 98.16 4.54
Arsenic 22 101.38 8.67
Selenium 22 101.15 8.00
Rubidium 22 100.24 5.36
Strontium 22 98.89 4.16
Yttrium 22 98.07 3.81
Zirconium 22 98.10 3.41
Niobium 22 96.92 3.65
Molybdenum 22 97.82 3.81
A
Molybdenum 21 98.36 2.90
Ruthenium 22 98.32 2.14
Palladium 22 97.69 2.49
Silver 22 105.14 7.88
A
Silver 21 106.56 4.26
Cadmium 22 96.03 3.72
Indium 22 98.01 3.57
Tin 22 97.25 3.94
Antimony 22 95.05 6.21
Tellurium 22 100.10 6.86
Caesium 22 101.81 6.93
Barium 22 97.99 3.68
Lanthanum 22 98.31 3.84
Cerium 22 97.57 3.72
Praeseodymium 22 97.32 3.00
Neodymium 22 97.22 3.56
Samarium 22 98.39 3.34
Europium 22 97.43 3.02
Gadolinium 22 100.04 2.78
Terbium 22 97.62 2.72
Dysprosium 22 98.18 2.20
Holmium 22 98.61 2.21
Erbium 22 98.05 2.29
Ytterbium 22 99.59 2.43
Lutetium 22 97.06 5.00
A
Lutetium 21 97.79 3.72
Hafnium 22 100.32 3.95
Tantalum 22 93.42 3.21
A
Tantalum 21 93.89 2.43
Tungsten 22 96.29 3.54
Rhenium 22 99.75 3.28
Iridium 22 99.88 3.70
Platinum 22 100.57 3.93
Gold 22 101.20 5.35
A
Gold 21 100.41 3.96
Thallium 22 100.09 5.02
Lead 22 101.58 5.54
Bismuth 22 100.70 5.43
Thorium 22 103.30 6.89
Uranium 22 104.14 9.11
A
Without Outlying Valueoutlying value.
actinide 2+ and actinide-oxide 2+. The spectralisobaric interferences are observed at 120.5 and 127.5 atomic mass unit
(amu),(AMU), when analyzing plutonium-239.
6.2 SpectralIsobaric interferences occur from the argon plasma and the acid used to transport the sample to the plasma. These
spectralisobaric interferences occur between 12 and 80 amu. AMU.
6.3 Ions from plutonium cause a matrix related signal suppression. Signal suppression increases as the Pu concentration increases.
In order to minimize signal suppression effects from Pu, samples are diluted so that the concentration of Pu in the analyzed aliquot
is less than 500 μg/mL. Three internal standards are added to samples to correct for matrix related signal suppression and signal
drift. Scandium, rhodium and thulium are used as internal standards. Analytes at the low end of the mass range (below 75
amu)AMU) are referenced to scandium. Rhodium is a reference for analytes at the middle of the mass range (76-138) (76 to 138)
and all analytes at the high end of the mass range are referenced to thulium (139-238 amu). (139 to 238 AMU).
C1637 − 21
6.4 The use of a collision/reaction system, or similar technology, with a quadrupole ICP-MS, or the use of a high-resolution
ICP-MS, may reduce or eliminate some of these interferences.
7. Apparatus
7.1 ICP-MS Instrument—An ICP-MS instrument with a quadrupole mass spectrometer and a electron multiplier that operates at
1 amu resolution is used for this determination. The instrument can also be a magnetic sector instrument or a time of flight
instrument. One of the following:
7.1.1 An ICP-MS instrument with a quadrupole mass spectrometer and an electron multiplier that operates at 1 AMU resolution
can be used. A collision/reaction system, or similar technology, can be used to reduce interferences.
7.1.2 A high-resolution (also known as magnetic sector) ICP-MS.
7.1.3 A time-of-flight mass spectrometer.
7.2 The ICP-MS is interfaced to a glovebox. The torch box, and the analyzer region of the mass spectrometer are glovebox
enclosed, enclosed in an appropriate containment unit, since Pu containing materials come in direct contact with these sections of
the instrument. Methods for enclosing plasma spectroscopic sources so that hazardous materials can be analyzed safely are
described in ASTM STP 951.
7.3 Graduated 14 mL disposable plastic round bottom tubes and caps or similar.
7.4 Piston-operated Volumetric Pipettors and Dispensers, Electronic pipettes. complying with the requirements of Specification
E1154, for pipetting and dispensing of solutions, acids, and so forth.
8. Reagents and Materials
8.1 Ultra high purity acids (such as spectroscopic grade) shall be used for sample dissolution and calibration standards preparation
unless otherwise noted.
8.2 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society (ACS),
where such specification are available.
8.3 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean laboratory accepted
demineralized or deionized water as described by Type I of Specification D1193.
NOTE 1—The molarity of ultra high purity acids may vary from standard ACS specifications for concentrated acids.
NOTE 1—All reagents are prepared and stored in polytetrafluoroethylene (PTFE) containers.
8.4 Hydrochloric Acid (HCl, 11.3 M), concentrated HCl.
8.5 Hydrochloric Acid (HCl, 6 M)—(HCl, 6 M), Add 531 mL of concentrated HCl (11.3 M) to less than 450 mL of water and dilute
to 1 liter with water.
8.6 Nitric Acid (HNO , 15.8 M)—M), concentrated nitric acid.
Edellson, M. C., and Daniel, J. Leland,C. and L
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