ASTM E267-90(2001)
(Test Method)Standard Test Method for Uranium and Plutonium Concentrations and Isotopic Abundances (Withdrawn 2006)
Standard Test Method for Uranium and Plutonium Concentrations and Isotopic Abundances (Withdrawn 2006)
SCOPE
1.1 This test method is applicable to the determination of uranium (U) and plutonium (Pu) concentrations and their isotopic abundances (Note 1) in solutions which result from the dissolution of nuclear reactor fuels either before or after irradiation. A minimum sample size of 50 [mu]g of irradiated U will contain sufficient Pu for measurement and will minimize the effects of cross contamination by environment U. Note 1—The isotopic abundance of Pu can be determined by this test method; however, interference from U may be encountered. This interference may be due to (1) inadequate chemical separation of uranium and plutonium, (2) uranium contamination within the mass spectrometer, and (3) uranium contamination in the filament. One indication of uranium contamination is a changing 238/239 ratio during the mass spectrometer run, in which case, a meaningful Pu analysis cannot be obtained on that run. If inadequate separation is the problem, a second pass through the separation may remove the uranium. If contamination in the mass spectrometer or on the filaments is the problem, use of a larger sample, for example, 1 μg, on the filament may ease the problem. A recommended alternative method of determining Pu isotopic abundance without U interference is alpha spectroscopy using Practice D3084. The Pu abundance should be obtained by determining the ratio of alpha particle activity of Pu to the sum of the activities of Pu and Pu. (1) The contribution of Pu and Pu to the alpha activity differs from their isotopic abundances due to different specific activities.
1.2 The procedure is applicable to dissolver solutions of uranium fuels containing plutonium, aluminum, stainless steel, or zirconium. Interference from other alloying constituents has not been investigated and no provision has been made in the test method for fuels used in the Th U fuel cycle.
1.3 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.
WITHDRAWN RATIONALE
This test method is applicable to the determination of uranium (U) and plutonium (Pu) concentrations and their isotopic abundances in solutions which result from the dissolution of nuclear reactor fuels either before or after irradiation.
Formerly under the jurisdiction of Committee C26 on Nuclear Fuel Cycle, this test method was discontinued in July 2006.
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:E267–90(Reapproved2001)
Standard Test Method for
Uranium and Plutonium Concentrations and Isotopic
Abundances
This standard is issued under the fixed designation E267; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
1.1 This test method is applicable to the determination of 2.1 ASTM Standards:
uranium (U) and plutonium (Pu) concentrations and their D1193 Specification for Reagent Water
isotopicabundances(Note1)insolutionswhichresultfromthe D3084 Practice for Alpha-Particle Spectrometry of Water
dissolution of nuclear reactor fuels either before or after E137 Practice for Evaluation of Mass Spectrometers for
irradiation. A minimum sample size of 50 µg of irradiated U Quantitative Analysis from a Batch Inlet
will contain sufficient Pu for measurement and will minimize E219 Test Method for Atom Percent Fission in Uranium
the effects of cross contamination by environment U. Fuel (Radiochemical Method)
E244 Test Method for Atom Percent Fission in Uranium
NOTE 1—The isotopic abundance of Pu can be determined by this
238 and Plutonium Fuel (Mass Spectrometric Method)
test method; however, interference from U may be encountered. This
interference may be due to (1) inadequate chemical separation of uranium
3. Summary of Test Method
and plutonium, (2) uranium contamination within the mass spectrometer,
and (3) uranium contamination in the filament. One indication of uranium 3.1 An aliquot of solution to be analyzed is spiked with
233 242
contamination is a changing 238/239 ratio during the mass spectrometer
known amounts of U and Pu (2–6). U and Pu are
run,inwhichcase,ameaningful Puanalysiscannotbeobtainedonthat
separated by ion exchange and analyzed mass spectrometri-
run. If inadequate separation is the problem, a second pass through the
cally.
separation may remove the uranium. If contamination in the mass
spectrometeroronthefilamentsistheproblem,useofalargersample,for
4. Significance and Use
example, 1 µg, on the filament may ease the problem. A recommended
238 238
4.1 This test method is specified for obtaining the atom
alternative method of determining Pu isotopic abundance without U
interference is alpha spectroscopy using Practice D3084. The Pu ratiosandUatompercentabundancesrequiredbyTestMethod
abundance should be obtained by determining the ratio of alpha particle
E244andtheUconcentrationrequiredbyTestMethodE219.
238 239 240 2
activity of Pu to the sum of the activities of Pu and Pu. (1) The
239 240
NOTE 2—The isotopic abundance of Pu normally is not required for
contribution of Pu and Pu to the alpha activity differs from their
burnup analysis of conventional light-water reactor fuel.
isotopic abundances due to different specific activities.
4.2 The separated heavy element fractions placed on mass
1.2 The procedure is applicable to dissolver solutions of
spectrometric filaments must be very pure. The quantity
uranium fuels containing plutonium, aluminum, stainless steel,
required depends upon the sensitivity of the instrument detec-
or zirconium. Interference from other alloying constituents has
tion system. If a scintillator (7) or an electron multiplier
not been investigated and no provision has been made in the
232 233
detector is used, only a few nanograms are required. If a
test method for fuels used in the Th- U fuel cycle.
Faraday cup is used, a few micrograms are needed. Chemical
1.3 This standard does not purport to address all of the
purity of the sample becomes more important as the sample
safety concerns, if any, associated with its use. It is the
size decreases, because the ion emission of the sample is
responsibility of the user of this standard to establish appro-
repressed by impurities.
priate safety and health practices and determine the applica-
4.3 Operation at elevated temperature (for example, 50 to
bility of regulatory limitations prior to use.
60°C)(Note3)willgreatlyimprovetheseparationefficiencyof
ionexchangecolumns.Suchhigh-temperatureoperationyields
ThistestmethodisunderthejurisdictionofASTMCommitteeC26onNuclear
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of
Test.
Current edition approved July 27, 1990. Published December 1990. Originally Annual Book of ASTM Standards, Vol 11.01.
e1 4
published as E267–65T. Last previous edition E267–78(1985) . Annual Book of ASTM Standards, Vol 11.02.
2 5
The boldface numbers in parentheses refer to the list of references appended to Annual Book of ASTM Standards, Vol 05.03.
this test method. Annual Book of ASTM Standards, Vol 12.02.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
E267
an iron-free U fraction and U-free Pu fraction, each of which 5.3.3 Aminimumofonestageofmagneticdeflection.Since
has desirable emission characteristics. the resolution is not affected, the angle of deflection may vary
with the instrument design,
NOTE 3—Asimpleglasstubecolumncanbeheatedbyaninfraredlamp
5.3.4 A mechanism for changing samples,
until it is warm to the touch.
5.3.5 A direct-current, electron multiplier, scintillation or
4.4 Extreme care must be taken to avoid contamination of
semi-conductor detector (7) followed by a current-measuring
the sample by environmental U. The level of U contamination
device, such as a vibrating-reed electrometer or a fast counting
should be measured by analyzing an aliquot of 8 M nitric acid
system for counting individual ions,
(HNO ) reagent as a blank and computing the amount of U it
5.3.6 A pumping system to attain a vacuum of 2 or 3 310
contains.
−7torrinthesource,theanalyzer,andthedetectorregions,and
4.4.1 The U blank is normally 0.2 ng of total U. Blanks 5.3.7 Amechanismtoscanmassesofinterestbyvaryingthe
larger than 0.5 ng are undesirable, because as much as 5 ng of
magnetic field or the accelerating voltage.
natural U contamination in a 50 µg sample of fully enriched U
235 238
6. Reagents and Materials
will change its U-to- U ratio from 93.3-to-5.60 to 93.3-
to-5.61 (that is, 16.661 to 16.631) or 0.18%.
6.1 Purity of Reagents—Reagent grade chemicals shall be
235 238
4.4.2 Where a 10% decrease in U-to- U ratio from
used in all tests. Unless otherwise indicated, it is intended that
neutron irradiation of a fuel is being measured, such contami- all reagents shall conform to the specifications of the Commit-
nation introduces a 1.8% error in the difference measurement.
tee onAnalytical Reagents of theAmerican Chemical Society,
It is clear that larger blanks or smaller samples cannot be where such specifications are available. Other grades may be
tolerated. In the analysis of small samples, environmental U
used, provided it is first ascertained that the reagent is of
contamination can introduce the largest single source of error. sufficiently high purity to permit its use without lessening the
accuracy of the determination.
5. Apparatus 6.2 Purity of Water— Unless otherwise indicated, refer-
ences to water shall be understood to mean reagent water
5.1 Shielding—To work with highly irradiated fuel, shield-
conforming to Specification D1193.
ingisrequiredforprotectionofpersonnelduringpreparationof
6.3 Anion Exchange Resin.
the primary dilution of dissolver solution. The choice of
239 238
6.4 Blended Pu and U Calibration Standard—Prepare
shielding is dependent upon the type and level of the radioac-
a solution containing about 0.25 mg Pu/liter and 25 mg
tivity of the samples being handled.
U/liter in 8 M HNO , as follows. With a new, calibrated,
5.2 Glassware—To avoid cross contamination, use only
clean Kirk-type micropipet, add 0.500 mL of Pu known
new glassware (beakers, pipets, and columns) from which
solution (see 6.12) to a calibrated 1-L volumetric flask. Rinse
surface U has been removed by boiling in HNO (1+1) for 1
the micropipet into the flask three times with 8 M HNO .Ina
to2h.Glasswareisremovedfromtheleachingsolution,rinsed
similar manner, add 0.100 mL of U known solution (see
inredistilledwater,oven-dried,andcovereduntilusedtoavoid
6.14). Dilute exactly to the 1-Lmark with 8 M HNO and mix
recontamination with U from atmospheric dust. Wrapping
thoroughly. From the value K (see 6.12), calculate the atoms
clean glassware in aluminum foil or plastic film will protect it
of Pu/mL of calibration standard, C , as follows:
against dust.
C 5~mL Pusolution/1000mLcalibrationstandard!
5.2.1 For accurate delivery of 500-µL volumes specified in 239
3 K (1)
thisprocedureforspikeandsample,aKirk-typemicropipet (8)
(also known as a “lambda” transfer pipet) is required. Such a From the value K (see 6.14), calculate the atoms of
23 8
pipetiscalibratedtocontain500µLwith 60.2%accuracyand
U/mL of calibration standard, C , as follows:
is designed to be rinsed out with dilute acid to recover its
C 5~mL Usolution/1000mLcalibrationstandard!
contents. Volumetric, measuring, and other type pipets are not
3 K (2)
sufficiently accurate for measuring spike and sample volumes.
Flame-seal 3 to 5-mL portions in glass ampoules to prevent
5.3 Mass Spectrometer—The suitability of mass spectrom-
evaporation after preparation until time of use. For use, break
etersforusewiththistestmethodofanalysisshallbeevaluated
off the tip of an ampoule, pipet promptly the amount required,
by means of performance tests described in this test method
and discard any unused solution. If more convenient, the
and in Practice E137. The mass spectrometer used should
possess the following characteristics:
5.3.1 A thermal-ionization source with single or multiple
“ReagentChemicals,AmericanChemicalSocietySpecifications,”Am.Chemi-
filaments of rhenium (Re),
cal Soc., Washington, DC. For suggestions on the testing of reagents not listed by
5.3.2 An analyzer radius sufficient to resolve adjacent
theAmericanChemicalSociety,see“ReagentChemicalsandStandards,”byJoseph
Rosin, D. Van Nostrand Co., Inc., New York, NY and the “United States
masses in the mass-to-charge range being studied, that is,
+ + Pharmacopeia.”
m/e=233 to 238 for U or m/e=265 to 270 for UO ions.
2 8
Dowex-1-type resins (eitherAG 1-X2 orAG 1-X4, 200 to 400 mesh) obtained
Resolution must be great enough to measure one part of U
from Bio-Rad Laboratories 32nd St. and Griffin Ave., Richmond, CA, have been
in 250 parts of U, found satisfactory.
E267
calibration standard can be flame-sealed in premeasured por- 6.8 Hydrofluoric Acid—Reagent grade concentrated HF (28
tions for quantitative transfer when needed. M).
242 233
6.5 Blended Pu and U Spike Solution—Prepare a
6.9 Ion Exchange Column—One method of preparing such
solution containing about 0.25 mg Pu/liter and 5 mg acolumnistodrawouttheendofa(150-mm)(6-in.)lengthof
U/liter in 8 M HNO . Standardize the spike solution as
4-mm inside diameter glass tubing and force a glass wool plug
follows: into the tip tightly enough to restrict the linear flow rate of the
6.5.1 In a 5-mL beaker, place about 0.1 mL of ferrous
finished column to less than 10 mm/min. By means of a
solution, exactly 500 µL of calibration standard (see 6.4), and capillary pipet add resin (see 6.3) suspended in water to the
exactly 500µ Lof spike solution (see 6.5). In a second beaker,
required bed length. Since the diameter of glass tubing may
place about 0.1 mLof ferrous solution and 1 mLof calibration vary from piece to piece, the quantities of resin and of liquid
standard without any spike. In a third beaker, place 0.1 mL of
reagentsusedarespecifiedinmillimetersofcolumnlength.To
ferrous solution and 1 mLof spike without standard. Mix well simplify use, mark the tubing above the resin bed in millime-
andallowtostandfor5mintoreducePutoPu(III)orPu(IV)
terswithamarkingpenorbackwithastripofmillimetergraph
to promote Pu isotopic exchange. paper. Dispense liquid reagents into the column from a
6.5.2 Follow the procedure described in 8.5.2-8.8.6. On the
polyethylene wash bottle to the length specified in the proce-
242 239
Pu fraction, record the isotopic ratios of Pu to Pu in the
dure.Thus 500 mm of wash solution can be added by filling to
calibration standard, C ; in the spike solution, S ; and in the
the 100-mm mark five times.
2/9 2/9
standard-plus-spike mixture, M . On the U fraction, record
6.10 Nitric Acid (sp gr 1.42)—Distill to obtain a 16 M
2/9
233 238
the corresponding U-to- U ratios, C , S , and M .
reagent low in U and dissolved solids. Dilute further with
3/8 3/8 3/8
Correct all ratios for mass discrimination bias (see Section 7).
redistilled water to 8 M,3 M, 0.5 M, and 0.05 M concentra-
6.5.3 Calculate the number of atoms of Pu/mL of spike,
tions.
S , as follows:
6.11 Nitrite Solution (0.1 M)—Add 0.69 g of sodium
nitrite (NaNO ) and 0.2 g of NaOH to 50 mL of redistilled
S 5 C M 2 C / 1 2 M /S (3)
$~ ! @ ~ !#% 2
2 239 2/9 2/9 2/9 2/9
water, dilute to 100 mL with redistilled water, and mix.
6.5.4 Calculate the number of atoms of U/mL of spike,
6.12 Pu Known Solution—Add 10 mL of 6 M HCL to a
S , as follows:
clean calibrated 1-L flask. Cool the flask in an ice water bath.
S 5 C $~M 2 C !/@1 2 ~M /S !#% (4)
3 238 3/8 3/8 3/8 3/8
Allow time for the acid to reach approximately 0°C and place
242 233
6.5.5 Calculatetheratioof Puatomsto Uatomsinthe in a glove box. Displace the air in the flask with inert gas (A,
He, or N ). Within the glove box, open the U.S. New
spike, S , as follows:
2/3 2
Brunswick Laboratory Plutonium Metal Standard Sample 126,
S 5 S /S (5)
2/3 2 3
containingabout0.5gPu(actualweightindividuallycertified)
6.5.6 Store in the same manner as the calibration standard
and add the metal to the cooled HCl. After dissolution of the
(see 6.4), that is, flame-seal 3 to 5-mL portions in glass
metal is complete, add 10 drops of concentrated HF and 400
ampoules. For use, break off the tip of an ampoule, pipet
mLof 8 M HNO and swirl. Place the flask in a stainless-steel
promptly the amount required, and discard any unused solu-
beaker for protection and invert a 50-mL beaker over the top
tion. If more convenient, spike solution can be flame-sealed in
and let it stand for at least 8 days to allow any gaseous
premeasured portions for quantitative transfer to individual
oxidation products to escape. Dilute to the mark with 8 M
samples.
HNO and mix thoroughly. By using the individual weight of
6.6 Ferrous Solution (0.001 M)—Add 40 mg of reagent
Pu in grams, the purity, and the molecular weight of the Pu
grade ferrous ammonium
...
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