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Title: Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

Abstract

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondary uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K+ and Pb2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported betweenmore » the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.« less

Authors:
 [1];  [2];  [2];  [2];  [3]
  1. Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Science; Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Glenn T. Seaborg Inst.
  2. Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Science
  3. Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Science, Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1416495
Alternate Identifier(s):
OSTI ID: 1549381
Report Number(s):
LLNL-JRNL-725124
Journal ID: ISSN 0883-2927
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Applied Geochemistry
Additional Journal Information:
Journal Volume: 87; Journal Issue: C; Journal ID: ISSN 0883-2927
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; uranium ore; uranium ore alteration; extraction chromatography; ICP-MS; rare-earth elements fractionation

Citation Formats

Balboni, Enrica, Spano, T, Cook, N, Simonetti, A, and Burns, P C. Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals. United States: N. p., 2017. Web. https://doi.org/10.1016/j.apgeochem.2017.10.007.
Balboni, Enrica, Spano, T, Cook, N, Simonetti, A, & Burns, P C. Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals. United States. https://doi.org/10.1016/j.apgeochem.2017.10.007
Balboni, Enrica, Spano, T, Cook, N, Simonetti, A, and Burns, P C. Fri . "Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals". United States. https://doi.org/10.1016/j.apgeochem.2017.10.007. https://www.osti.gov/servlets/purl/1416495.
@article{osti_1416495,
title = {Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals},
author = {Balboni, Enrica and Spano, T and Cook, N and Simonetti, A and Burns, P C},
abstractNote = {We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondary uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K+ and Pb2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.},
doi = {10.1016/j.apgeochem.2017.10.007},
journal = {Applied Geochemistry},
number = C,
volume = 87,
place = {United States},
year = {2017},
month = {10}
}

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Works referenced in this record:

Chemical and Sr isotopic characterization of North America uranium ores: Nuclear forensic applications
journal, November 2016


Alpha Spectrometric Determination of Trace Level of 239-240Pu and 238Pu Uranium Compounds and Solutions
journal, January 1999


Methodology for Rare Earth Element Determinations of Uranium Oxides by Ion Microprobe
journal, September 2007


Migration in the Nile Valley during the New Kingdom period: a preliminary strontium isotope study
journal, September 2007

  • Buzon, Michele R.; Simonetti, Antonio; Creaser, Robert A.
  • Journal of Archaeological Science, Vol. 34, Issue 9
  • DOI: 10.1016/j.jas.2006.10.029

Continuous precipitation of uranium with hydrogen peroxide
journal, October 1990

  • Cahill, Allen E.; Burkhart, Lawrence E.
  • Metallurgical Transactions B, Vol. 21, Issue 5
  • DOI: 10.1007/BF02657806

Sodium uranates: Preparation and thermochemical properties
journal, August 1971


SIMS U–Pb dating of uranium mineralization in the Katanga Copperbelt: Constraints for the geodynamic context
journal, September 2011


Fate of trace elements during alteration of uraninite in a hydrothermal vein-type U-deposit from Marshall Pass, Colorado, USA
journal, October 2007

  • Deditius, Artur P.; Utsunomiya, Satoshi; Ewing, Rodney C.
  • Geochimica et Cosmochimica Acta, Vol. 71, Issue 20
  • DOI: 10.1016/j.gca.2007.08.008

Analytical techniques for the separation and determination of transuranium element ultratraces in depleted uranium ammunitions
journal, April 2004

  • Desideri, Donatella; Meli, Maria Assunta; Roselli, Carla
  • International Journal of Environmental Analytical Chemistry, Vol. 84, Issue 5
  • DOI: 10.1080/03067310001640410

Site-selective time-resolved laser fluorescence spectroscopy of Eu3+ in calcite
journal, May 2008

  • Marques Fernandes, M.; Schmidt, M.; Stumpf, T.
  • Journal of Colloid and Interface Science, Vol. 321, Issue 2
  • DOI: 10.1016/j.jcis.2008.01.017

Uraninite chemistry as forensic tool for provenance analysis
journal, September 2014


The Solubility of Uranium Peroxide in Acidic and Basic Media at 25 °c
journal, December 1958

  • Gayer, Karl H.; Thompson, Lancelot C.
  • Canadian Journal of Chemistry, Vol. 36, Issue 12
  • DOI: 10.1139/v58-239

Sub-surface charging, a source of error in microprobe analysis
journal, March 1984

  • Graham, J.; Butt, C. R. M.; Vigers, R. B. W.
  • X-Ray Spectrometry, Vol. 13, Issue 3
  • DOI: 10.1002/xrs.1300130308

Measurement of the sulphur isotope ratio (34S/32S) in uranium ore concentrates (yellow cakes) for origin assessment
journal, January 2013

  • Han, Sun-Ho; Varga, Zsolt; Krajkó, Judit
  • Journal of Analytical Atomic Spectrometry, Vol. 28, Issue 12
  • DOI: 10.1039/c3ja50231g

Analytical Atomic Spectrometry for Nuclear Forensics
journal, August 2005

  • Hou, Xiandeng; Chen, Wen; He, Yihua
  • Applied Spectroscopy Reviews, Vol. 40, Issue 3
  • DOI: 10.1081/ASR-200064495

Structural formula of uraninite
journal, August 1992


An investigation into heterogeneity in a single vein-type uranium ore deposit: Implications for nuclear forensics
journal, December 2015


The provenance of Australian uranium ore concentrates by elemental and isotopic analysis
journal, April 2008


Nuclear forensic analysis of an unknown uranium ore concentrate sample seized in a criminal investigation in Australia
journal, July 2014


A new Rare-Earth-Element Uranyl Carbonate Sheet in the Structure of Bijvoetite-(Y)
journal, February 2000


Estimation of trace impurities in reactor-grade uranium using ICP-AES
journal, October 1999


Rare earth element patterns and crustal evolution—II. Archean sedimentary rocks from Kalgoorlie, Australia
journal, February 1977


Mobility and fractionation of rare earth elements during weathering of a granodiorite
journal, May 1979


Decoupling of O and Pb isotope systems of uraninite in the early Proterozoic Conglomerates in the Elliot Lake district
journal, September 2011


Near infrared reflectance spectroscopy as a process signature in uranium oxides
journal, August 2012

  • Plaue, J. W.; Klunder, G. L.; Hutcheon, I. D.
  • Journal of Radioanalytical and Nuclear Chemistry, Vol. 296, Issue 1
  • DOI: 10.1007/s10967-012-2027-0

Cation-exchange isolation and ICP-AES determination of rare earth elements in geological silicate materials
journal, March 1997

  • Rucandio, M. I.
  • Fresenius' Journal of Analytical Chemistry, Vol. 357, Issue 6
  • DOI: 10.1007/s002160050231

Incorporation versus adsorption: substitution of Ca2+ by Eu3+ and Cm3+ in aragonite and gypsum
journal, January 2009

  • Schmidt, Moritz; Stumpf, Thorsten; Walther, Clemens
  • Dalton Transactions, Issue 33
  • DOI: 10.1039/b822656c

IN-SITU ELEMENTAL AND Sr ISOTOPE INVESTIGATION OF HUMAN TOOTH ENAMEL BY LASER ABLATION-(MC)-ICP-MS: SUCCESSES AND PITFALLS
journal, April 2008


Trace element and U isotope analysis of uraninite and ore concentrate: Applications for nuclear forensic investigations
journal, September 2017


Application of Lead and Strontium Isotope Ratio Measurements for the Origin Assessment of Uranium Ore Concentrates
journal, October 2009

  • Varga, Zsolt; Wallenius, Maria; Mayer, Klaus
  • Analytical Chemistry, Vol. 81, Issue 20
  • DOI: 10.1021/ac901100e

Determination of rare-earth elements in uranium-bearing materials by inductively coupled plasma mass spectrometry
journal, March 2010


Rare earths in Archean graywackes from Wyoming and from the Fig Tree Group, South Africa
journal, March 1973


Uranium release and secondary phase formation during unsaturated testing of UO2 at 90°C
journal, August 1992


Ten-year results from unsaturated drip tests with UO2 at 90°C: implications for the corrosion of spent nuclear fuel
journal, October 1996


    Works referencing / citing this record:

    What’s that yellow powder? A nuclear forensic case study
    journal, August 2018

    • Xu, Ning; Worley, Christopher; Rim, Jung
    • Journal of Radioanalytical and Nuclear Chemistry, Vol. 318, Issue 1
    • DOI: 10.1007/s10967-018-6084-x

    Characterization of uraninite using a FIB–SEM approach and its implications for LA–ICP–MS analyses
    journal, October 2018

    • Lewis, Stefanie R.; Simonetti, Antonio; Corcoran, Loretta
    • Journal of Radioanalytical and Nuclear Chemistry, Vol. 318, Issue 2
    • DOI: 10.1007/s10967-018-6232-3

    Avoiding polyatomic interferences in measurements of lanthanides in uranium material for nuclear forensic purposes
    journal, June 2019

    • Vesterlund, Anna; Ramebäck, Henrik
    • Journal of Radioanalytical and Nuclear Chemistry, Vol. 321, Issue 2
    • DOI: 10.1007/s10967-019-06623-5

    Happy Jack Uraninite: A New Reference Material for High Spatial Resolution Analysis of U‐Rich Matrices
    journal, September 2019

    • Dorais, Corinne; Simonetti, Antonio; Corcoran, Loretta
    • Geostandards and Geoanalytical Research, Vol. 44, Issue 1
    • DOI: 10.1111/ggr.12293

    Multivariate Analysis Based on Geochemical, Isotopic, and Mineralogical Compositions of Uranium-Rich Samples
    journal, September 2019

    • Corcoran, Loretta; Simonetti, Antonio; Spano, Tyler L.
    • Minerals, Vol. 9, Issue 9
    • DOI: 10.3390/min9090537