ASTM C1845-16

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.
Designation: C1845 − 16
Standard Practice for
The Separation of Lanthanide Elements from Uranium
Matrices Using High Pressure Ion Chromatography (HPIC)
for Isotopic Analyses by Inductively Coupled Plasma Mass
Spectrometry (ICP-MS)
This standard is issued under the fixed designation C1845; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
1.1 This practice provides instructions for the rapid separa- 2.1 ASTM Standards:
tion of lanthanide elements using high pressure ion chroma- C859Terminology Relating to Nuclear Materials
tography (HPIC) from dissolved uranium materials such as: C1052Practice for Bulk Sampling of Liquid Uranium
nuclear fuels, uranium ores, hydrolyzed UF , and depleted, Hexafluoride
natural, or enriched oxides/powders, or metals. When C1075Practices for Sampling Uranium-Ore Concentrate
optimized, this technique will produce purified elemental C1168PracticeforPreparationandDissolutionofPlutonium
fractions of the lanthanide elements isolated from the bulk Materials for Analysis
uranium matrix allowing for isotopic assay using inductively C1347Practice for Preparation and Dissolution of Uranium
coupled plasma mass spectrometry (ICP-MS). Materials for Analysis
C1689Practice for Subsampling of Uranium Hexafluoride
1.2 This practice is most applicable for analyte concentra-
C1769Practice for Analysis of Spent Nuclear Fuel to De-
tions of nanograms per gram uranium or higher. For ICP-MS
termine Selected Isotopes and Estimate Fuel Burnup
detection and measurement of analyte concentrations lower
D1193Specification for Reagent Water
than this, it would be necessary to perform additional pre-
E105Practice for Probability Sampling of Materials
cleanup or concentration techniques, or both, which are not
addressed in this practice.
3. Terminology
1.3 When combined with isotope dilution, this practice can
3.1 Definitions—For definitions of terms used in this
also be used for improved precision assays of the lanthanide
practice, refer to Terminology C859.
elementsusingtheprincipleofisotopedilutionmassspectrom-
etry (IDMS). 4. Summary of Practice
1.4 The values stated in SI units are to be regarded as
4.1 Solid samples are dissolved according to Practices
standard. No other units of measurement are included in this C1168, C1347, or other appropriate methods. Uranium
practice.
hexafluoride can be sampled in accordance with Practices
C1052 and C1689. The resulting dissolver solution is pro-
1.5 This standard does not purport to address all of the
cessed to produce solutions of isolated lanthanide elements for
safety concerns, if any, associated with its use. It is the
mass spectrometric isotopic analysis. The elements are selec-
responsibility of the user of this standard to establish appro-
tivelyseparatedfromthedissolversolutionandcollectedusing
priate safety and health practices and determine the applica-
HPIC instrumentation equipped with automated fraction col-
bility of regulatory limitations prior to use.
lection. Appropriate aliquots of the unseparated dissolutions
This practice is under the jurisdiction of ASTM Committee C26 on Nuclear
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Test. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Current edition approved June 1, 2016. Published June 2016. DOI: 10.1520/ Standards volume information, refer to the standard’s Document Summary page on
C1845-16. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
C1845 − 16
are taken to provide up to 100 ng/mL of a lanthanide element compartment should be employed to maintain consistency
on the analytical column to be separated from 3.5 mg/mL or between sample analyses.
less of uranium. In a strong nitric acid matrix, no pre-
7. Apparatus
separation valence adjustments are necessary.
7.1 High pressure ion chromatograph equipped with a
NOTE 1—This practice has been verified to separate 0.7 mg of total
singlevariablespeedgradientpumpcapableofdeliveringflow
uraniumfromthelanthanideanalytes.20ngtotalofeachanalytehasbeen
rates of 0.001 to 10 mL/min.The system requires eluent degas
shown to have efficient resolution on the column to yield purified
capabilityandalowpressuregradientmixercapableofmixing
elemental samples. If larger uranium and analytes sample sizes are being
considered, it is suggested that these be verified by the lab for efficient
four independent eluent streams.
uranium removal and analyte resolution.
7.1.1 Optionally the HPIC may be equipped with a post-
4.2 For the separation HPIC sample aliquots are injected column reaction coil using a chromophore for detection via a
using a 200 µL sample loop and loaded ontoa4by250mm single or multi-wavelength UV/Vis absorption detector to
high pressure cation exchange column with sulfonic acid measure the appropriate wavelength emission.
functional groups and an ion exchange capacity of ~80 7.1.2 Usinganintegratedonlinedetectorisusefulforinitial
micro-equivalents/columns. First, complexation and removal instrument testing and setup of the parameters for the lan-
of the bulk dissolved uranium matrix is accomplished using a
thanide separations and determining initial time intervals for
dilute hydrochloric acid eluent which is directed to waste. thecollectionoffractions.Also,withthedetectoronlineduring
Next, the lanthanide elements are selectively eluted off of the
fraction collection it could be used as a trigger for the fraction
columnbychelationchromatographyusingadilutesolutionof collector. CAUTION: The nature of the post-column chro-
2-hydroxyisobutyric acid (α-HIBA). Fractions are collected at
mophore solution may have an impact in post separation
automated 20 s time intervals to allow for recovery of the analyses.
separated analytes, producing purified aliquots of each lan-
7.2 Autosampler for sample injection equipped with a 10-
thanide element from the bulk uranium matrix of the dissolver
port injections switching valve is recommended.Alternately, a
solution for isotopic measurements using ICP-MS.
manual injection setup can be used.
5. Significance and Use 7.3 Sample loop. A200 µLsample loop is considered to be
optimal for this practice; however, injection loops can vary
5.1 The measurement of isotopic distributions for the lan-
from 25 to 1000 µL depending on sample concentrations.
thanide series elements is of important to all phases of the
nuclear fuels cycle. Examples include the purification of the NOTE 3—Matrix effects with regard to peak resolution must be
considered when choosing large sample loop volumes.
Nd isotopes from Ce and Sm isotopes for the determination of
atom percent fission through the production of Nd in
7.4 Analytical column. Standard bore high pressure analyti-
irradiatednuclearfuelsusingPracticeC1769,determinationof
cal column (250×4mm I.D.) with sulfonic acid functional
rare earth content and isotopic distribution in Uranium Ore
groupsandanionexchangecapacityof~80micro-equivalents/
Concentrates (UOC) for source term and production of lan-
columns.Standardboreisrequiredovermicroborecolumnsto
thanide fission products in irradiated nuclear fuels for determi-
support greater resolution for complex sample matrices.
nation of performance, improvements of depletion codes, and
7.5 Guard column.Standardboreguardcolumn(50×4mm
analysis of burnup indicators.
I.D.) is required to protect the analytical column from sample
contaminates which will degrade the performance of the
6. Interferences
column.
6.1 Highsaltcontentinthesamplecanpotentiallyinfluence
7.6 Fraction collector. Automated fraction collector either
both the retention times and the resolution of the analytes.The
as a standalone system that communicates with the HPIC unit
concentration of the nitric acid in the sample matrix does not
or integrated into the instrument.
necessarily influence the retention times and the resolution of
the analytes, but it can influence the removal of uranium. 2 M
8. Reagents and Materials
nitricacidhasbeensuccessfulinefficientlyremovinguranium.
8.1 PurityofReagents—Highpuritygradeacidsandreagent
6.2 The presence of high concentrations of sulfate,
grade chemicals shall be used for the preparation of eluent
phosphate, oxalate, and halides in the sample matrix will
stock solutions. High concentrations of ionic impurities in
potentially have an effect on the retention times and the
eluents will degrade column performance over time and
resolution of the analytes.
adversely affect the separation chemistry resulting in inconsis-
tentretentiontimesorunacceptableoverlaps,orboth,between
NOTE 2—Using a smaller sample injection loop volume with a higher
the rare earth elemental fractions. It is intended that all acids
analyte concentration can reduce the effects of the matrix on the retention
times and the resolution of the analytes.
andreagentsconformtothespecificationsoftheCommitteeon
Analytical Reagents of theAmerican Chemical Society where
6.3 Temperature can impact the retention times and the
such specifications are available.
resolution of the analytes and, where possible, a thermal
8.2 Purity of Water—Type II Reagent Grade Water with a
specific resistance of 18.2 MΩ-cm, according to Specification
Re-evaluation of Spent Nuclear FuelAssay Data for the Three Mile Island Unit
D1193,shallbeusedinthepreparationofallhighpurityacids,
1 Reactor and Application to Code Validation, Annals of Nuclear Energy, Vol 87,
Part 2, January 2016, pp. 267–281. reagents, and eluents.
C1845 − 16
8.3 Nitric Acid (HNO ), concentrated, ρ ~1.42 g/mL~70% 10.3.4 Once dry, add 0.5 mL of2MHNO and repeat the
3 3
(m⁄m). dry down process.
10.3.5 Add 1 mL of 2 M HNO to the hot vial, cap, and
8.4 Nitric Acid (HNO ), 2.0 M—Dilute 125 mL concen-
allow the sample to cool.
trated HNO to a final volume of 1000 mL with water.
NOTE 6—Preferably perform the dry down steps in a trace clean
8.5 Hydrochloric Acid (HCl), concentrated, ρ ~1.18 g/mL,
environmentorinaHEPA-filteredenclosuretominimizeexternalsources
~36% (m/m).
of elemental contamination.
8.6 Hydrochloric Acid (HCl), 1.0 M—Dilute 100 mL con-
10.3.6 Transfer the sample to the appropriate autosampler
centrated HCl to a final volume of 1000 mL with water.
vial and label accordingly.
8.7 Ammonium Hydroxide, 28% NH in H O, ≥99.99%
3 2 10.4 Blanks:
purity.
10.4.1 Prepare method blanks that were taken through the
dissolutionprotocolwiththesamplesbyfollowingsteps10.3.1
8.8 α-Hydroxyisobutyric acid (α-HIBA), 0.4 M, reagent
through 10.3.6 above.
grade, 99 %—Dissolve 41.6 g α-HIBAin 500 mLwater (8.2),
10.4.2 Prepare instrument blanks by adding 1 mL of 2 M
buffer to a pH of 4.5 with Ammonium Hydroxide, approxi-
HNO to the appropriate autosampler vial and label.
mately 18 mL, and bring to a final volume of 1000 mL. 3
11. Preparation of Apparatus
9. Hazards
11.1 After extended use or noticeable degradation of col-
9.1 Strong acids are used for the preparation of reagents.
umn performance, or both, the guard and analytical columns
Wear appropriate personal protective equipment while han-
shall be cleaned. It is recommended that they be cleaned
dlingnitricandhydrochloricacids.Labcoat,gloves,andsafety
separately following the manufacturer’s recommendation so
glasses with side shields are considered to be the minimum
that contaminants on the guard column do not elute onto the
requirement. When handling large volumes of acid, a full face
analytical column.
shield should be used.
NOTE 7—If the column is unused for any significant length of time low
9.2 Hydrochloric acid (HCl) vapors are very corrosive. All
molarity HCl (10~50 mM) is a suitable storage solution that does not
dilutions of HCl solutions should be made in a fume hood to
require changing any of the eluents. For long term storage, follow the
avoid inhalation of vapors.
column manufacturer’s instructions.
11.2 If the columns are to be used after long-term storage,
9.3 Ammonium hydroxide is corrosive. Wear appropriate
personal protective equipment when handling and perform prepare them for use following manufacturer’s instructions.
work within a chemical fume hood to avoid inhalation of
11.3 Minimize void volumes in the sample flow path per
vapors.
manufacturer’s recommendations and ensure that all tubing
connections are tightened to manufacturer’s recommendations
10. Sampling, Test Specimens, and Test Units
and are leak free.
10.1 Sampling of UOC in a processing environment is
11.4 Configure the instrument with a 200 µL sample loop
performed according to Practices C1075 and liquid uranium
for optimum sample loading and a flow rate of 1.0 mL/min.
hexafluoride by Practice C1052. All others should follow
NOTE8—Foroptimumseparationperformancereferformanufacturer’s
Practice E105.
manual for ideal column pressure and adjust the eluent flow rate
accordingly.
10.2 Test specimens are obtained through acid dissolution
according to Practices C1347, C1168, or other appropriate
11.5 Verify that all modules of the HPIC system are active
methods. The dissolution of uranium-plutonium mixed oxides
and respond to the control computer per manufacturer’s in-
is covered in Practice C1168.
structions.
NOTE 4—Many uranium-containing materials such as high-purity
11.6 Program the gradient pumping profile into the instru-
metals and oxides dissolve readily in various inorganic acids. Nitric acid
ment control software as show
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