ASTM C1432-03(2008)
(Test Method)Standard Test Method for Determination of Impurities in Plutonium: Acid Dissolution, Ion Exchange Matrix Separation, and Inductively Coupled Plasma-Atomic Emission Spectroscopic (ICP/AES) Analysis
Standard Test Method for Determination of Impurities in Plutonium: Acid Dissolution, Ion Exchange Matrix Separation, and Inductively Coupled Plasma-Atomic Emission Spectroscopic (ICP/AES) Analysis
SCOPE
1.1 This specification covers blended uranium trioxide (UO3), U3O8, or mixtures of the two, powders that are intended for conversion into a sinterable uranium dioxide (UO2) powder by means of a direct reduction process. The UO2 powder product of the reduction process must meet the requirements of Specification C 753 and be suitable for subsequent UO2 pellet fabrication by pressing and sintering methods. This specification applies to uranium oxides with a 235U enrichment less than 5 %.
1.2 This specification includes chemical, physical, and test method requirements for uranium oxide powders as they relate to the suitability of the powder for storage, transportation, and direct reduction to UO2 powder. This specification is applicable to uranium oxide powders for such use from any source.
1.3 The scope of this specification does not comprehensively cover all provisions for preventing criticality accidents, for health and safety, or for shipping. Observance of this specification does not relieve the user of the obligation to conform to all international, national, state, and local regulations for processing, shipping, or any other way of using uranium oxide powders (see 2.2 and 2.3).
1.4 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
1.5 The following safety hazards caveat pertains only to the test methods portion of the annexes in this specification: This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: C1432 − 03 (Reapproved2008)
Standard Test Method for
Determination of Impurities in Plutonium: Acid Dissolution,
Ion Exchange Matrix Separation, and Inductively Coupled
Plasma-Atomic Emission Spectroscopic (ICP/AES) Analysis
This standard is issued under the fixed designation C1432; 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 Nuclear-Grade Plutonium Nitrate Solutions
C1168 PracticeforPreparationandDissolutionofPlutonium
1.1 This test method covers the determination of 25 ele-
Materials for Analysis
ments in plutonium (Pu) materials.The Pu is dissolved in acid,
D1193 Specification for Reagent Water
the Pu matrix is separated from the target impurities by an ion
exchange separation, and the concentrations of the impurities
3. Summary of Test Method
aredeterminedbyinductivelycoupledplasma-atomicemission
spectroscopy (ICP-AES).
3.1 A sample of plutonium metal is dissolved in a small
volume of 6 M hydrochloric acid (HCl). Then, 10 M (HNO )/
1.2 This test method is specific for the determination of 3
0.03 M hydrofluoric acid (HF) is added to the dissolved
impurities in8MHNO solutions. Impurities in other pluto-
plutonium to oxidize the plutonium to the Pu (IV) state. The
nium materials, including plutonium oxide samples, may be
sample solution is loaded onto a nitrate anion exchange resin
determined if they are appropriately dissolved (see Practice
and eluted with8MHNO /0.006 M HF.The rinses contain the
C1168) and converted to8MHNO solutions.
target metallic impurities and less than 15 µg/mL Pu. The
1.3 The values stated in SI units are to be regarded as
plutonium is stripped from the anion exchange resin with 0.1
standard. No other units of measurement are included in this
M HCl. The rinses containing the metallic impurities are
standard.
analyzed by ICP-AES.
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
4. Significance and Use
responsibility of the user of this standard to establish appro-
4.1 This test method can be used on plutonium matrices in
priate safety and health practices and determine the applica-
nitrate solutions.
bility of regulatory limitations prior to use.
4.2 This test method has been validated for all elements
2. Referenced Documents listed in Test Methods C757 except sulfur (S) and tantalum
(Ta).
2.1 ASTM Standards:
C757 Specification for Nuclear-Grade Plutonium Dioxide
4.3 This test method has been validated for all of the cation
Powder, Sinterable
elements measured in Table 1. Phosphorus (P) requires a
C758 Test Methods for Chemical, Mass Spectrometric,
vacuum or an inert gas purged optical path instrument.
Spectrochemical, Nuclear, and RadiochemicalAnalysis of
Nuclear-Grade Plutonium Metal
5. Interferences
C759 Test Methods for Chemical, Mass Spectrometric,
5.1 Plutonium concentrations of less than 50 µg/mL in the
Spectrochemical, Nuclear, and RadiochemicalAnalysis of
final aqueous phase do not significantly affect the analytical
results for most elements. Interference studies should be made
todeterminethedegreeofPuandotherelementalinterferences
This test method is under the jurisdiction ofASTM Committee C26 on Nuclear
onthetargetanalytes;backgroundandinterelementcorrections
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of
Test.
may be required.
Current edition approved Dec. 1, 2008. Published January 2009. Originally
approved in 1999. Last previous edition approved in 2003 as C1432 – 03. DOI:
6. Apparatus
10.1520/C1432-03R08.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
6.1 An ICP-AES equipped with a Charge Injection Device
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
(CID) detector or an ICP-AES with a spectral bandpass of 0.05
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. nm or less is required to provide the necessary spectral
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
C1432 − 03 (2008)
TABLE 1 Percent Recovery and Repeatability Standard Deviation for Sixteen Spiked Samples
Wavelength/Order Actual Conc Mean Conc Average R.S.D.
Element
(nm) (µg/mL) (µg/mL) (%R) (%)
Aluminum Al 396.152 {67} 2.5 2.4 95 6
Barium Ba 455.403 {58} 2.5 2.4 95 5
Beryllium Be 313.042 {84} 2.5 2.3 94 6
Boron B 249.773 {106} 2.5 2.5 100 7
Cadmium Cd 226.502 {116} 2.5 2.5 101 12
Calcium Ca 396.847 {66} 2.5 2.6 104 20
Chromium Cr 283.563 {93} 2.5 2.3 92 8
Cobalt Co 228.616 {115} 2.5 2.5 101 6
Copper Cu 324.754 {81} 2.5 2.4 97 6
Iron Fe 259.940 {101} 2.5 2.5 101 12
Lead Pb 220.353 {120} 2.5 3.1 122 12
Lithium Li 670.784 {39} 2.5 2.2 87 6
Magnesium Mg 280.270 {94} 2.5 2.4 95 6
Manganese Mn 257.610 {102} 2.5 2.5 98 5
Molybdenum Mo 202.030 {130} 2.5 2.6 103 10
Nickel Ni 231.604 {114} 2.5 2.5 100 11
Silicon Si 251.612 {104} 2.5 2.3 92 16
Sodium Na 588.995 {45} 25.0 24.7 97 16
Strontium Sr 421.552 {62} 2.5 2.4 95 5
Tin Sn 189.989 {139} 2.5 2.7 109 19
Titanium Ti 334.941 {79} 2.5 2.5 102 8
Tungsten W 207.911 {127} 2.5 2.5 99 11
Vanadium V 292.402 {90} 2.5 2.0 82 7
Zinc Zn 213.856 {123} 2.5 2.5 100 8
Zirconium Zr 339.198 {78} 2.5 2.5 101 10
resolution. The spectrometer may be either a simultaneous 6.7 1000 mL plastic volumetric flasks.
multielement or a sequential spectrometer. The spectrometer
may be either an inert gas-path or vacuum instrument; the 7. Reagents and Materials
appropriate spectral lines should be selected for each specific
7.1 Purity of Reagents—Reagent grade chemicals shall be
instrument. Either an analog or digital readout system may be
used in all tests. Unless otherwise indicated, it is intended that
used.
all reagents shall conform to the specifications of the Commit-
6.2 The ICP-AES is interfaced to a glovebox.The torch box
tee on Analytical Reagents of the American Chemical Society
is glovebox enclosed, since plutonium containing materials
(ACS), where such specifications are available. Other grades
comeindirectcontactwiththetorch.Thissetupisdescribedin
could be used, provided it is first ascertained that the reagent is
ASTM STP 951.
of sufficiently high purity to permit its use without lessening
the accuracy of the determination.
6.3 Vacuum manifold set at approximately 23 cm Hg (9 in.
Hg) is optional. A gravity system is also acceptable.
7.2 Purity of Water—Unless otherwise indicated, references
6.4 15 mL plastic disposable ion exchange columns. to water shall be understood to mean laboratory accepted
demineralized or deionized water as described by Type 1 of
6.5 50 mL plastic vials.
Specification D1193.
6.6 Plastic micro and macro pipettes.
7.3 Ultra high purity acids shall be used for sample disso-
lution and calibration standards preparation unless otherwise
The sole source of supply of the apparatus known to the committee at this time
noted.
is Thermo Jarrell Ash PolyScan Iris spectrometer (Thermo Electron Spectroscopy,
Franklin, MA), or an Applied Research Laboratories 3580 ICP-AES instrument
NOTE 1—The molarity of ultra high purity acids may vary from
(Dearborn, MI). If you are aware of alternative suppliers, please provide this
standard ACS specifications for concentrated acids.
information to ASTM International Headquarters. Your comments will receive
1 NOTE 2—All reagents are prepared and stored in polytetrafluoroethyl-
careful consideration at a meeting of the responsible technical committee, which
ene (PTFE) containers.
you may attend.
Edellson, M. C., and Daniel, J. Leland, “Plasma Spectroscopy of the Analysis
of Hazardous Materials: Design and Application of Enclosed Plasma Sources,”
Conference Proceedings, ASTM STP 951, ASTM, 1986.
The sole source of supply of the apparatus known to the committee at this time
is Eichrom Technologies Vacuum Box System (Part # AC-24-BOX), Eichrom
Technologies Inc., Darien. IL. If you are aware of alternative suppliers, please
provide this information toASTM International Headquarters. Your comments will
receive careful consideration at a meeting of the responsible technical committee,
which you may attend. Reagent Chemicals, American Chemical Society Specifications, American
The sole source of supply of the apparatus known to the committee at this time Chemical Society, Washington, DC. For suggestions on the testing of reagents not
is Ion exchange columns from eitherApplied Separation or Bio-Rad Inc. If you are listed by the American Chemical Society, see Analar Standards for Laboratory
aware of alternative suppliers, please provide this information to ASTM Interna- Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
tional Headquarters.Your comments will receive careful consideration at a meeting and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
of the responsible technical committee, which you may attend. MD.
C1432 − 03 (2008)
7.4 Hydrochloric Acid (HCl, 11.3 M), concentrated ultra 7.14.1 Calibration Stock Solution-2 (CSS-2), contains 5000
8 11
high purity HCl. µg/mL of Na in 0.8 M HNO .
7.14.2 Calibration Stock Solution-3 (CSS-3), contains 500
7.5 Hydrochloric Acid (HCl, 6 M)—Add 531 mL of con-
µg/mLofMo,Si,Sn,Ti,W,andZrin0.3MHNO /0.1MHF.
centrated ultra high purity HCl (11.3 M) to less than 450 mLof
7.14.3 Calibration Stock Solution-5 (CSS-5), contains 500
water and dilute to 1 L with water.
µg/mL of Al, Ba, and Sr in 0.8 M HNO .
7.6 Hydrochloric Acid (HCl, 0.1 M)—Add 8.8 mL of
7.14.4 Calibration Stock Solution-6 (CSS-6), contains 500
concentrated ultra high purity HCl (11.3 M) to water, while
µg/mL of Be, B, Cd, Ca, Cr, Co, Cu, Fe, Li, Mg, Mn, Ni, Pb,
stirring, and dilute to 1 L with water. (Reagent grade HCl can
V, and Zn in 0.8 M HNO .
be used in preparing this reagent.)
7.15 Prepare the multielement impurity standards and
7.7 Hydrofluoric Acid (HF, 28.3 M), concentrated ultra high
blanks as described in 7.15.1-7.15.5. All calibration standard
purity HF.
solutions are stored in PTFE containers.
7.15.1 Calibration Standard One High (CAL 1 HI)—Pipette
7.8 Nitric Acid (HNO , 15.8 M), concentrated ultra high
purity nitric acid. 20 mL each, of stock solutions CSS-3, and CSS-5 into a 1 L
volumetric flask. Dilute to 1 L with8MHNO /0.006 M HF.
7.9 Nitric Acid-Hydrofluoric Acid Mixture, 10 M HNO /
This standard solution contains the target analytes at a concen-
0.03 M HF—Add 1 mL of concentrated ultra high purity HF
tration of 10 µg/mL.
(28.3 M) to water; using a plastic pipette, while stirring, add
7.15.2 Calibration Standard One Low (CAL 1 LO)—Pipette
633 mL concentrated ultra high purity HNO (15.8 M) and
10 mL each, of stock solutions CSS-3, and CSS-5 into a 1 L
dilute to 1 L with water.
volumetric flask. Dilute to 1 L with8MHNO /0.006 M HF.
7.10 Nitric Acid-Hydrofluoric Acid Mixture, 8 M HNO /
This standard solution contains the target analytes at a concen-
0.006 M HF—Add 0.21 mL of concentrated ultra high purity
tration of 5 µg/mL.
HF (28.3 M) to water; using a plastic pipette, while stirring,
7.15.3 Calibration Standard Two High (CAL 2 HI)—Pipette
add 506 mL of concentrated ultra high purity HNO (15.8 M)
20 mL each, of stock solutions CCS-2, and CSS-6 intoa1L
and dilute to 1 L with water.
volumetric flask. Dilute to 1 L with8MHNO /0.006 M HF.
This standard solution contains the target analytes at a concen-
7.11 Nitric Acid (HNO,4M)—Add 253 mL of concen-
tration of 10 µg/mL, except Na. Na is 100 µg/mL.
trated ultra high purity nitric acid (15.8 M) to water, while
7.15.4 Calibration Standard Two Low (CAL 2 LO)—Pipette
stirring, and dilute to 1 L with water.
10 mL each, of stock solutions CCS-2, and CCS-6 intoa1L
7.12 Anion Exchange Resin, macroporous-1 (MP-1), 200-
volumetric flask. Dilute to 1 L with8MHNO /0.006 M HF.
400 mesh, either nitrate form or chloride form, high purity.
This standard solution contains the target analytes at a concen-
7.13 Stock Solutions, traceable to a national standard, of
tration of 5 µg/mL, except Na. Na is 50 µg/mL.
multielement spike solutions are available from a commercial
7.15.5 Calibration Standard Blank (CAL BL)—Thisblankis
vendor. The stock solutions of multielement spike solutions
an 8 M HNO /0.006 M HF solution.
can also be prepared in-house.
7.13.1 Spike Solution 1 (SS-1), contains 500 µg/mL of Al,
8. Hazards
Ba, Be, Ca, Li, Mg, Sr, and Na in 0.8 M HNO .
8.1 Plutonium bearing materials are radioactive and toxic.
7.13.2 Spike Solution 2 (SS-2), contains 500 µg/mL of B,
Adequate laboratory facilities, gloveboxes and fume hoods
Mo, Si, Sn, Ti, W, and Zr in 0.8 M HNO .
along with safe techniques, must be used in handling samples
7.13.3 Spike Solution 3 (SS-3), contains 500 µg/mL of Cd,
containing these materials. A detailed discussion of all the
Cr, Co, Cu, Fe, Pb, Mn, Ni, V, and Zn in 0.8 M HNO .
precautions necessary is beyond the scope of this test method;
7.14 Stock Solutions, traceable to a national standard, of
however, personnel who handle these materials should be
multielement impurity standards are available from a commer- familiar with such safe handling practices.
cial vendor. The stock solutions of multielement standards can
9. Procedure
also be prepared in-house.
9.1 Preparation of Anion Exchange Resin Slurry:
8 9.1.1 If the anion exchange resin was purchased in the
The sole source of supply of the apparatus known to the committee at this time
is Ultrex (J. T. Baker, Inc.) and Seastar brands of ultra high purity acids. If you are nitrate form, prepare a 1:1 (volume:volume) slurry of the resin
aware of alternative suppliers, please provide this information to ASTM Interna-
in 4 M HNO and proceed to 9.2.
tional Headquarters.Your comments will receive careful consideration at a meeting
9.1.2 If the anion resin was purchased in the chloride form,
of the responsible technical committee, which you may attend.
convert it to the nitrate form.
The sole source of supply of the apparatus known to the committee at this time
is AG MP-1 anion exchange resin, Bio-Rad, Richmond, CA. If you are aware of
9.2 Sample Dissolution and Preparation:
alternative suppliers, please provide this information to ASTM International
Headquarters.Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend.
10 11
Thesolesourceofsupplyoftheapparatusknowntothecommitteeatthistime Thesolesourceofsupplyoftheapparatusk
...
This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:C1432–03 Designation: C 1432 – 03 (Reapproved 2008)
Standard Test Method for
Determination of Impurities in Plutonium: Acid Dissolution,
Ion Exchange Matrix Separation, and Inductively Coupled
Plasma-Atomic Emission Spectroscopic (ICP/AES) Analysis
This standard is issued under the fixed designation C 1432; 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 method covers the determination of 25 elements in plutonium (Pu) materials. The Pu is dissolved in acid, the Pu
matrix is separated from the target impurities by an ion exchange separation, and the concentrations of the impurities are
determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES).
1.2 This test method is specific for the determination of impurities in8MHNO solutions. Impurities in other plutonium
materials, including plutonium oxide samples, may be determined if they are appropriately dissolved (see Practice C 1168) and
converted to 8 M HNO solutions.
1.3
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
C 757 Specification for Nuclear-Grade Plutonium Dioxide Powder, Sinterable
C 758 Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-
Grade Plutonium Metal
C 759 Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-
Grade Plutonium Nitrate Solutions
C 1168 Practice for Preparation and Dissolution of Plutonium Materials for Analysis
D 1193 Specification for Reagent Water
3. Summary of Test Method
3.1 Asample of plutonium metal is dissolved in a small volume of 6 M hydrochloric acid (HCl). Then, 10 M (HNO )/0.03 M
hydrofluoric acid (HF) is added to the dissolved plutonium to oxidize the plutonium to the Pu (IV) state. The sample solution is
loadedontoanitrateanionexchangeresinandelutedwith8MHNO /0.006MHF.Therinsescontainthetargetmetallicimpurities
and less than 15 µg/mL Pu. The plutonium is stripped from the anion exchange resin with 0.1 M HCl. The rinses containing the
metallic impurities are analyzed by ICP-AES.
4. Significance and Use
4.1 This test method can be used on plutonium matrices in nitrate solutions.
4.2 This test method has been validated for all elements listed in Test Methods C 757 except sulfur (S) and tantalum (Ta).
4.3 This test method has been validated for all of the cation elements measured in Table 1. Phosphorus (P) requires a vacuum
or an inert gas purged optical path instrument.
5. Interferences
5.1 Plutonium concentrations of less than 50 µg/mL in the final aqueous phase do not significantly affect the analytical results
This test method is under the jurisdiction ofASTM Committee C26 on Nuclear Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of Test.
Current edition approved Feb. 10, 2003. Published April 2003. Originally approved in 1999. Last previous edition approved in 1999 as C1432–99.
Current edition approved Dec. 1, 2008. Published January 2009. Originally approved in 1999. Last previous edition approved in 2003 as C 1432 – 03.
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
, Vol 12.01.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.
C 1432 – 03 (2008)
TABLE 1 Percent Recovery and Repeatability Standard Deviation for Sixteen Spiked Samples
Wavelength/Order Actual Conc Mean Conc Average R.S.D.
Element
(nm) (µg/mL) (µg/mL) (%R) (%)
Aluminum Al 396.152 {67} 2.5 2.4 95 6
Barium Ba 455.403 {58} 2.5 2.4 95 5
Beryllium Be 313.042 {84} 2.5 2.3 94 6
Boron B 249.773 {106} 2.5 2.5 100 7
Cadmium Cd 226.502 {116} 2.5 2.5 101 12
Calcium Ca 396.847 {66} 2.5 2.6 104 20
Chromium Cr 283.563 {93} 2.5 2.3 92 8
Cobalt Co 228.616 {115} 2.5 2.5 101 6
Copper Cu 324.754 {81} 2.5 2.4 97 6
Iron Fe 259.940 {101} 2.5 2.5 101 12
Lead Pb 220.353 {120} 2.5 3.1 122 12
Lithium Li 670.784 {39} 2.5 2.2 87 6
Magnesium Mg 280.270 {94} 2.5 2.4 95 6
Manganese Mn 257.610 {102} 2.5 2.5 98 5
Molybdenum Mo 202.030 {130} 2.5 2.6 103 10
Nickel Ni 231.604 {114} 2.5 2.5 100 11
Silicon Si 251.612 {104} 2.5 2.3 92 16
Sodium Na 588.995 {45} 25.0 24.7 97 16
Strontium Sr 421.552 {62} 2.5 2.4 95 5
Tin Sn 189.989 {139} 2.5 2.7 109 19
Titanium Ti 334.941 {79} 2.5 2.5 102 8
Tungsten W 207.911 {127} 2.5 2.5 99 11
Vanadium V 292.402 {90} 2.5 2.0 82 7
Zinc Zn 213.856 {123} 2.5 2.5 100 8
Zirconium Zr 339.198 {78} 2.5 2.5 101 10
for most elements. Interference studies should be made to determine the degree of Pu and other elemental interferences on the
target analytes; background and interelement corrections may be required.
6. Apparatus
6.1 An ICP-AES equipped with a Charge Injection Device (CID) detector or an ICP-AES with a spectral bandpass of 0.05 nm
or less is required to provide the necessary spectral resolution. The spectrometer may be either a simultaneous multielement or
a sequential spectrometer. The spectrometer may be either an inert gas-path or vacuum instrument; the appropriate spectral lines
should be selected for each specific instrument. Either an analog or digital readout system may be used.
6.2 The ICP-AES is interfaced to a glovebox. The torch box is glovebox enclosed, since plutonium containing materials come
in direct contact with the torch. This setup is described in ASTM STP 951.
6.3 Vacuum manifold set at approximately 23 cm Hg (9 in. Hg) is optional. A gravity system is also acceptable.
6.4 15 mL plastic disposable ion exchange columns.
6.5 50 mL plastic vials.
6.6 Plastic micro and macro pipettes.
6.7 1000 mL plastic volumetric flasks.
7. Reagents and Materials
7.1 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),
Annual Book of ASTM Standards, Vol 11.01.
The sole source of supply of the apparatus known to the committee at this time is Thermo Jarrell Ash PolyScan Iris spectrometer (Thermo Electron Spectroscopy,
Franklin, MA), or anApplied Research Laboratories 3580 ICP-AES instrument (Dearborn, MI). If you are aware of alternative suppliers, please provide this information to
ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, which you may attend.
A Thermo Jarrell Ash PolyScan Iris spectrometer (Thermo Electron Spectroscopy, Franklin, MA), or an Applied Research Laboratories 3580 ICP-AES instrument
(Dearborn, MI) have been found to be acceptable.
Edellson, M. C., and Daniel, J. Leland, “Plasma Spectroscopy of the Analysis of Hazardous Materials: Design and Application of Enclosed Plasma Sources,”
Conference Proceedings, ASTM STP 951, ASTM, 1986.
Edellson, M. C., and Daniel, J. Leland, “Plasma Spectroscopy of theAnalysis of Hazardous Materials: Design andApplication of Enclosed Plasma Sources,” Conference
Proceedings, ASTM STP 951, ASTM, 1986.
ThesolesourceofsupplyoftheapparatusknowntothecommitteeatthistimeisEichromTechnologiesVacuumBoxSystem(Part#AC-24-BOX),EichromTechnologies
Inc., Darien. IL. If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful
consideration at a meeting of the responsible technical committee, which you may attend.
Eichrom Technologies Vacuum Box System (Part # AC-24-BOX), Eichrom Technologies Inc., Darien. IL, has been found to be acceptable.
The sole source of supply of the apparatus known to the committee at this time is Ion exchange columns from eitherApplied Separation or Bio-Rad Inc. If you are aware
ofalternativesuppliers,pleaseprovidethisinformationtoASTMInternationalHeadquarters.Yourcommentswillreceivecarefulconsiderationatameetingoftheresponsible
technical committee, which you may attend.
C 1432 – 03 (2008)
wheresuchspecificationsareavailable. Othergradescouldbeused,provideditisfirstascertainedthatthereagentisofsufficiently
high purity to permit its use without lessening the accuracy of the determination.
7.2 Purity of Water— Unless otherwise indicated, references to water shall be understood to mean laboratory accepted
demineralized or deionized water as described by Type 1 of Specification D 1193.
7.3 Ultra high purity acids shall be used for sample dissolution and calibration standards preparation unless otherwise noted.
NOTE 1—The molarity of ultra high purity acids may vary from standard ACS specifications for concentrated acids.
NOTE 2—All reagents are prepared and stored in polytetrafluoroethylene (PTFE) containers.
7.4 Hydrochloric Acid (HCl, 11.3 M), concentrated ultra high purity HCl.
7.5 Hydrochloric Acid (HCl, 6 M)—Add 531 mL of concentrated ultra high purity HCl (11.3 M) to less than 450 mL of water
and dilute to 1 L with water.
7.6 Hydrochloric Acid (HCl, 0.1 M)—Add 8.8 mL of concentrated ultra high purity HCl (11.3 M) to water, while stirring, and
dilute to 1 L with water. (Reagent grade HCl can be used in preparing this reagent.)
7.7 Hydrofluoric Acid (HF, 28.3 M), concentrated ultra high purity HF.
7.8 Nitric Acid (HNO , 15.8 M), concentrated ultra high purity nitric acid.
7.9 Nitric Acid-Hydrofluoric Acid Mixture,10MHNO /0.03 M HF—Add 1 mLof concentrated ultra high purity HF (28.3 M)
to water; using a plastic pipette, while stirring, add 633 mL concentrated ultra high purity HNO (15.8 M) and dilute to 1 L with
water.
7.10 Nitric Acid-Hydrofluoric Acid Mixture,8MHNO /0.006 M HF—Add 0.21 mLof concentrated ultra high purity HF (28.3
M) to water; using a plastic pipette, while stirring, add 506 mL of concentrated ultra high purity HNO (15.8 M) and dilute to 1
L with water.
7.11 Nitric Acid (HNO ,4M)—Add 253 mLof concentrated ultra high purity nitric acid (15.8 M) to water, while stirring, 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.
7.13 Stock Solutions, traceable to a national standard, of multielement spike solutions are available from a commercial vendor.
The stock solutions of multielement spike solutions can also be prepared in-house.
7.13.1 Spike Solution 1 (SS-1), contains 500 µg/mL of Al, Ba, Be, Ca, Li, Mg, Sr, and Na in 0.8 M HNO .
7.13.2 Spike Solution 2 (SS-2), contains 500 µg/mL of B, Mo, Si, Sn, Ti, W, and Zr in 0.8 M HNO .
7.13.3 Spike Solution 3 (SS-3), contains 500 µg/mL of Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, V, and Zn in 0.8 M HNO .
7.14 Stock Solutions, traceable to a national standard, of multielement impurity standards are available from a commercial
vendor. The stock solutions of multielement standards can also be prepared in-house.
7.14.1 Calibration Stock Solution-2 (CSS-2), contains 5000 µg/mL of Na in 0.8 M HNO .
7.14.2 Calibration Stock Solution-3 (CSS-3), contains 500 µg/mL of Mo, Si, Sn, Ti, W, and Zr in 0.3 M HNO /0.1 M HF.
7.14.3 Calibration Stock Solution-5 (CSS-5), contains 500 µg/mL of Al, Ba, and Sr in 0.8 M HNO .
7.14.4 Calibration Stock Solution-6 (CSS-6), contains 500 µg/mLof Be, B, Cd, Ca, Cr, Co, Cu, Fe, Li, Mg, Mn, Ni, Pb, V, and
Zn in 0.8 M HNO .
7.15 Prepare the multielement impurity standards and blanks as described in 7.15.1-7.15.5. All calibration standard solutions
are stored in PTFE containers.
7.15.1 Calibration Standard One High (CAL 1 HI)—Pipette 20 mL each, of stock solutions CSS-3, and CSS-5 intoa1L
volumetric flask. Dilute to 1 Lwith 8 M HNO /0.006 M HF. This standard solution contains the target analytes at a concentration
of 10 µg/mL.
Ion exchange columns from either Applied Separation or Bio-Rad Inc., have been found to be acceptable.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed by
the American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
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 Joseph Rosin, D. Van Nostrand Co., New York, NY and the United States Pharmacopeia.
The sole source of supply of the apparatus known to the committee at this time is Ultrex (J. T. Baker, Inc.) and Seastar brands of ultra high purity acids. If you are aware
ofalternativesuppliers,pleaseprovidethisinformationtoASTMInternationalHeadquarters.Yourcommentswillreceivecarefulconsiderationatameetingoftheresponsible
technical committee, which you may attend.
The Ultrex (J. T. Baker, Inc.) and Seastar brands of ultra high purity acids have been found to be acceptable.
ThesolesourceofsupplyoftheapparatusknowntothecommitteeatthistimeisAGMP-1anionexchangeresin,Bio-Rad,Richmond,CA.Ifyouareawareofalternative
suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical
committee, which you may attend.
AG MP-1 anion exchange resin, Bio-Rad, Richmond, CA, has been found to be acceptable.
The sole source of supply of the apparatus known to the committee at this time is Multielement spike solutions, Inorganic Ventures, NJ. If you are aware of alternative
suppliers, please provide this information to ASTM International Headquarters. Y
...
This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:C1432–99 Designation: C 1432 – 03 (Reapproved 2008)
Standard Test Method for
Determination of Impurities in Plutonium: Acid Dissolution,
Ion Exchange Matrix Separation, and Inductively Coupled
Plasma-Atomic Emission Spectroscopic (ICP/AES) Analysis
This standard is issued under the fixed designation C 1432; 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 method covers the determination of 25 elements in plutonium (Pu) materials. The Pu is dissolved in acid, the Pu
matrix is separated from the target impurities by an ion exchange separation, and the concentrations of the impurities are
determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The elements determined are listed in Table
2.
1.2 This test method is specific for the determination of impurities in Pu in 8 M nitric acid (HNOHNO ) solutions. Impurities
in other plutonium materials, including plutonium oxide samples, may be determined if they are appropriately dissolved (see
PracticesPractice C 1168) and converted to8MHNO solutions.
1.3Plutonium bearing materials are radioactive and toxic. Adequate laboratory facilities, glove boxes, and fume hoods, along
with safe techniques, must be used in handling samples containing these materials. A detailed discussion of all the precautions
necessary is beyond the scope of this test method; however, personnel who handle these materials should be familiar with such
safe handling practices.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
oftheuserofthismethodstandardtoestablishappropriatesafetyandhealthpracticesanddeterminetheapplicabilityofregulatory
limitations prior to use of this standard.use.
2. Referenced Documents
2.1 ASTM Standards:
C697Test Methods for Chemical, Mass Spectrometric, and Spectrochemical Analysis of Nuclear-Grade Plutonium Dioxide
Powers and Pellets
C 757 Specification for Nuclear-Grade Plutonium Dioxide Powder, Sinterable
C 758 Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-
Grade Plutonium Metal
C 759 Test Methods for Chemical, Mass Spectrometric, Spectrochemical, Nuclear, and Radiochemical Analysis of Nuclear-
Grade Plutonium Nitrate Solutions
C 1168 Practice for Preparation and Dissolution of Plutonium Materials for Analysis
D 1193 Specification for Reagent Water
3. Summary of Test Method
3.1 A sample of Puplutonium metal is dissolved in a small volume of 6 M hydrochloric acid (HCl). Then, 1 mL of 10 M
(HNO )/0.2)/0.03 M hydrofluoric acid (HF) is added to the dissolved Puplutonium to oxidize the Puplutonium to the Pu (IV) state.
The sample solution is loaded onto a nitrate anion exchange resin and eluted with 8 M HNO /0.2/0.006 M HF. The rinses contain
the target metallic impurities and less than 15 µg/mL Pu. The Puplutonium is stripped from the anion exchange resin with 0.1 M
HCl. The rinses containing the metallic impurities are analyzed by ICP-AES.
This guide is under the jurisdiction of ASTM Committee C-26 on Nuclear Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of Test.
Current edition approved June 10, 1999. Published August 1999.
This test method is under the jurisdiction ofASTM Committee C26 on Nuclear Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of Test.
Current edition approved Dec. 1, 2008. Published January 2009. Originally approved in 1999. Last previous edition approved in 2003 as C 1432 – 03.
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at service@astm.org. For Annual Book ofASTM Standards
, Vol 12.01.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.
C 1432 – 03 (2008)
4. Significance and Use
4.1This test method measures all elements listed in Specification C757, except sulfur (S) and tantalum (Ta).
4.2This test method measures all of the cation elements measured in Test Methods C697, except silver (Ag), gold (Au), and
bismuth (Bi). Phosphorus (P) requires a vacuum instrument.
4.1 This test method can be used on plutonium matrices in nitrate solutions.
4.2 This test method has been validated for all elements listed in Test Methods C 757 except sulfur (S) and tantalum (Ta).
4.3 This test method has been validated for all of the cation elements measured in Table 1. Phosphorus (P) requires a vacuum
or an inert gas purged optical path instrument.
5. Interferences
5.1 Plutonium concentrations of less than 50 µg/mL in the final aqueous phase do not significantly affect the analytical results
for most elements. Interference studies should be made to determine the degree of Pu and other elemental interferences on the
target analytes; background and interelement corrections may be required.
6. Apparatus
6.1An ICP-AES with a spectral bandpass of 0.05 nm or less is required to provide the necessary spectral resolution.
6.1 An ICP-AES equipped with a Charge Injection Device (CID) detector or an ICP-AES with a spectral bandpass of 0.05 nm
or less is required to provide the necessary spectral resolution. The spectrometer may be either a simultaneous multielement or
a sequential spectrometer. The spectrometer may be either an inert gas-path or vacuum instrument; the appropriate spectral lines
should be selected for each specific instrument. Either an analog or digital readout system may be used.
6.2The ICP-AES is interfaced to a glovebox. The torchbox is glovebox enclosed since Pu containing materials come in direct
contact with the torch. The torchbox offers several safety features, such as a shielded window for observing the plasma, which
Annual Book of ASTM Standards, Vol 11.01.
The sole source of supply of the apparatus known to the committee at this time is Thermo Jarrell Ash PolyScan Iris spectrometer (Thermo Electron Spectroscopy,
Franklin, MA), or anApplied Research Laboratories 3580 ICP-AES instrument (Dearborn, MI). If you are aware of alternative suppliers, please provide this information to
ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, which you may attend.
TABLE 1 ICP-AES Opercent Recovery and Repeatability Stang Condard Deviation for Sixteen Spiked SamplesA
Wavelength/Order Actual Conc Mean Conc Average R.S.D.
ParaElementer
(nm) (µg/mL) (µg/mL) (%R) (%)
Valueminum Al 396.152 {67} 2.5 2.4 95 6
Aluminum Al 396.152 {67} 2.5 2.4 95 6
Forward rf power 1.4 kW03 {58} 2.5 2.4 95 5
Barium Ba 455.403 {58} 2.5 2.4 95 5
Reflectedrf power <10 W42 {84} 2.5 2.3 94 6
Beryllium Be 313.042 {84} 2.5 2.3 94 6
Outer argon flow 106} 2.5 L/min 2.5 100 7
Boron B 249.773 {106} 2.5 2.5 100 7
Auxiliary argon flow 02 {116} 2.8L/min5 2.5 101 12
Cadmium Cd 226.502 {116} 2.5 2.5 101 12
Carrier argon flow 0.7 L/min {66} 2.5 2.6 104 20
Calcium Ca 396.847 {66} 2.5 2.6 104 20
Observation height 15 mm above load coil63 {93} 2.5 2.3 92 8
Chromium Cr 283.563 {93} 2.5 2.3 92 8
Nebulizer Cross flow type 228.616 {115} 2.5 2.5 101 6
Cobalt Co 228.616 {115} 2.5 2.5 101 6
Solution uptakerate 1} 2.5 2.4 97 6
Copper Cu 324.754 {81} 2.5 2.4 97 6
Iron Fe 259.940 {101} 2.5 2.5 101 12
Lead Pb 220.353 {120} 2.5 3.1 122 12
Lithium L/i 670.784 {39} 2.5 2.2 87 6
Lithium Li 670.784 {39} 2.5 2.2 87 6
Magnesium Mg 280.270 {94} 2.5 2.4 95 6
Manganese Mn 257.610 {102} 2.5 2.5 98 5
Molybdenum Mo 202.030 {130} 2.5 2.6 103 10
Nickel Ni 231.604 {114} 2.5 2.5 100 11
Silicon Si 251.612 {104} 2.5 2.3 92 16
Sodium Na 588.995 {45} 25.0 24.7 97 16
Strontium Sr 421.552 {62} 2.5 2.4 95 5
Tin Sn 189.989 {139} 2.5 2.7 109 19
Titanium Ti 334.941 {79} 2.5 2.5 102 8
Tungsten W 207.911 {127} 2.5 2.5 99 11
Vanadium V 292.402 {90} 2.5 2.0 82 7
Zinc Zn 213.856 {123} 2.5 2.5 100 8
Zirconium Zr 339.198 {78} 2.5 2.5 101 10
A
These conditions are typical for an ARL #3580.
C 1432 – 03 (2008)
allows the operator to view the plasma without risking damage to the eyes. The torchbox is equipped with an interlock that shuts
off high voltage power to the torchbox when the torchbox door is open. The interlock prevents the operator from being exposed
to high voltages during routine cleaning. This setup is described in ASTM STP 951.
6.2 The ICP-AES is interfaced to a glovebox. The torch box is glovebox enclosed, since plutonium containing materials come
in direct contact with the torch. This setup is described in ASTM STP 951.
6.3 Vacuum manifold set at approximately 23 cm Hg (9 in. Hg) is optional.
6.3Vacuum manifold set at approximately 9 in. Hg (optional).A gravity system is also acceptable.
6.4 15 mL plastic disposable ion exchange columns. A gravity system is acceptable.
6.415-mL plastic disposable ion exchange columns.
6.530-mL plastic vials.
6.5 50 mL plastic vials.
6.6 Plastic micro and macro pipettes.
6.7A 500-mL fritted column.
6.7 1000 mL plastic volumetric flasks.
7. Reagents and Materials
7.1 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 specifications are available. Other grades shouldcould be used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the accuracy of the determination.
7.2 Purity of Water— Unless otherwise indicated, references to water shall be understood to mean laboratory accepted
demineralized or deionized water as described by Type 1 of Specification D 1193.
7.3 Ultra high purity acids shall be used for sample dissolution and calibration standards preparation unless otherwise noted.
NOTE1—All reagents are prepared and stored in polytetrafluoroethylene (PTFE) containers. 1—The molarity of ultra high purity acids may vary from
standard ACS specifications for concentrated acids.
NOTE 2—All reagents are prepared and stored in polytetrafluoroethylene (PTFE) containers.
7.4 Hydrochloric Acid ((HCl) (sp gr 1.18))(HCl, 11.3 M), concentrated ultra high purity HCl.
7.5 Hydrochloric Acid (HCl, 6 M)—Add 500531 mL of concentrated ultra high purity HCl (sp gr 1.18) (11.3 M) to less than
500450 mL of water and dilute to 1 L with water.
7.6 HydrochloricAcid (HCl, 0.1 M)—Add 8.38.8 mLof concentrated ultra high purity HCl (sp gr 1.18)(11.3 M) to water, while
stirring, and dilute to 1 L with water. (Reagent grade HCl can be used in preparing this reagent.)
9 8
7.7 Hydrofluoric Acid ((HF) (sp gr 1.15)), concentrated ultra high purity (HF, 28.3 M), concentrated ultra high purity HF.
7.8Nitric Acid ((HNO ) (sp gr 1.42)), concentrated ultra high purity HNO .
3 3
7.8 Nitric Acid (HNO , 15.8 M), concentrated ultra high purity nitric acid.
7.9 Nitric Acid-Hydrofluoric Acid Mixture,10MHNO /0.2 M HF—Add 7.2 mL of concentrated ultra high purity HF (sp gr
1.15) to water, using a plastic pipet, while stirring; add 637-mLconcentrated ultra high purity HNO
/0.03 M HF—Add 1 mL of concentrated
ultra high purity HF (28.3 M) to water; using a plastic pipette, while stirring, add 633 mL concentrated ultra high purity HNO (sp gr 1.42);(15.8 M) and dilute
to 1 L with water.
An Applied Research Laboratories 3580 ICP-AES instrument (Fisons Instruments, Dearborn, MI) has been found to be acceptable. The ARL 3580 is a combination
Pashen-Runge type spectrometer containing a 58 channel simultaneous spectrometer and a sequential spectrometer, both with a 1-m focal length and capable of operating
in the 165 to 800-nm range.
Edellson, M. C., and Daniel, J. Leland, “Plasma Spectroscopy of theAnalysis of Hazardous Materials: Design andApplication of Enclosed Plasma Sources,” Conference
Proceedings, ASTM STP 951, ASTM, 1986.
Edelson, M. C., and Daniel, J. Leland, “Plasma Spectroscopy of theAnalysis of Hazardous Materials: Design andApplication of Enclosed Plasma Sources,” Conference
Proceedings, ASTM STP 951, ASTM, 1986.
ThesolesourceofsupplyoftheapparatusknowntothecommitteeatthistimeisEichromTechnologiesVacuumBoxSystem(Part#AC-24-BOX),EichromTechnologies
Inc., Darien. IL. If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful
consideration at a meeting of the responsible technical committee, which you may attend.
Speed Mate 10 Vacuum Extraction System, Applied Separations, Bethlehem, PA, has been found to be acceptable.
The sole source of supply of the apparatus known to the committee at this time is Ion exchange columns from eitherApplied Separation or Bio-Rad Inc. If you are aware
ofalternativesuppliers,pleaseprovidethisinformationtoASTMInternationalHeadquarters.Yourcommentswillreceivecarefulconsiderationatameetingoftheresponsible
technical committee, which you may attend.
Ion exchange columns from either Applied Separation or Bio-Rad Inc. have been found to be acceptable.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed by
the American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, D.C. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
The sole source of supply of the apparatus known to the committee at this time is Ultrex (J. T. Baker, Inc.) and Seastar brands of ultra high purity acids. If you are awar
...
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