Calcium-Uranyl-Carbonato Species Kinetically Limit U(VI) Reduction by Fe(II) and Lead to U(V)-Bearing Ferrihydrite

Dewey, Christian; Sokaras, Dimosthenis; Kroll, Thomas; Bargar, John R.; Fendorf, Scott

doi:10.1021/acs.est.9b05870

Calcium-Uranyl-Carbonato Species Kinetically Limit U(VI) Reduction by Fe(II) and Lead to U(V)-Bearing Ferrihydrite

Journal Article · Tue Apr 21 00:00:00 EDT 2020 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.9b05870· OSTI ID:1638150

Dewey, Christian ^[1]; Sokaras, Dimosthenis ^[2]; Kroll, Thomas ^[2]; ^[2]; ^[1]

Stanford University, CA (United States)
SLAC National Accelerator Laboratory, Menlo Park, CA (United States)

Reaction conditions and mechanisms promoting or inhibiting U reduction exert a central control on U solubility and, therefore, U transport and its associated risks. Here, we vary and track common aqueous uranium species to show that a kinetic restriction inhibits homogeneous reduction of the calcium-uranyl-carbonato species (CaUO$$_2$$(CO$$_3$$)$$_3$$$$^{2–}$$ and Ca$$_2$$UO$$_2$$(CO$$_3$$)$$_3$$) by Fe(II)$$_{(aq)}$$, while ferrihydrite surface-catalyzed reduction of all aqueous uranyl by Fe(II) proceeds. Using U L$$_3$$ high energy resolution fluorescence detection (HERFD) X-ray absorption near edge structure (XANES) spectroscopy, U L$$_3$$ extended X-ray absorption fine structure (EXAFS) spectroscopy, and transmission electron microscopy (TEM), we also show that U(V) is generated and incorporated into ferrihydrite formed from homogeneous U(VI) reduction by Fe(II)(aq). Through elucidation of the mechanisms that inhibit reduction of the calcium-uranyl-carbonato species and promote stabilization of U(V), we advance our understanding of the controls on U solubility and thus improve prediction of U transport in surface and subsurface systems.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Stanford University, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-76SF00515; SC0016544

OSTI ID:: 1638150

Alternate ID(s):: OSTI ID: 1675267

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 10 Vol. 54; ISSN 1520-5851; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (48)

Evaluating the performance of parallel subsurface simulators: An illustrative example with PFLOTRAN: Evaluating the Parallel Performance of Pflotran Hammond, G. E.; Lichtner, P. C.; Mills, R. T. Water Resources Research, Vol. 50, Issue 1 https://doi.org/10.1002/2012WR013483	journal	January 2014
Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements Bargar, John R.; Reitmeyer, Rebecca; Lenhart, John J. Geochimica et Cosmochimica Acta, Vol. 64, Issue 16 https://doi.org/10.1016/S0016-7037(00)00398-7	journal	August 2000
Surface catalysis of uranium(VI) reduction by iron(II) Liger, Emmanuelle; Charlet, Laurent; Van Cappellen, Philippe Geochimica et Cosmochimica Acta, Vol. 63, Issue 19-20 https://doi.org/10.1016/S0016-7037(99)00265-3	journal	October 1999
Biogeochemical processes controlling the speciation and transport of arsenic within iron coated sands Herbel, Mitchell; Fendorf, Scott Chemical Geology, Vol. 228, Issue 1-3 https://doi.org/10.1016/j.chemgeo.2005.11.016	journal	April 2006
Competing retention pathways of uranium upon reaction with Fe(II) Massey, Michael S.; Lezama-Pacheco, Juan S.; Jones, Morris E. Geochimica et Cosmochimica Acta, Vol. 142 https://doi.org/10.1016/j.gca.2014.07.016	journal	October 2014
Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe Geochimica et Cosmochimica Acta, Vol. 157 https://doi.org/10.1016/j.gca.2015.02.006	journal	May 2015
Local structure and oxidation state of uranium in some ternary oxides: X-ray absorption analysis Soldatov, A. V.; Lamoen, D.; Konstantinović, M. J. Journal of Solid State Chemistry, Vol. 180, Issue 1 https://doi.org/10.1016/j.jssc.2006.08.038	journal	January 2007
Ferrozine---a new spectrophotometric reagent for iron Stookey, Lawrence L. Analytical Chemistry, Vol. 42, Issue 7, p. 779-781 https://doi.org/10.1021/ac60289a016	journal	June 1970
Tetra- and Hexavalent Uranium Forms Bidentate-Mononuclear Complexes with Particulate Organic Matter in a Naturally Uranium-Enriched Peatland Mikutta, Christian; Langner, Peggy; Bargar, John R. Environmental Science & Technology, Vol. 50, Issue 19 https://doi.org/10.1021/acs.est.6b03688	journal	September 2016
Uranium Redox Transformations after U(VI) Coprecipitation with Magnetite Nanoparticles Pidchenko, Ivan; Kvashnina, Kristina O.; Yokosawa, Tadahiro Environmental Science & Technology, Vol. 51, Issue 4 https://doi.org/10.1021/acs.est.6b04035	journal	February 2017
Trace Uranium Partitioning in a Multiphase Nano-FeOOH System McBriarty, Martin E.; Soltis, Jennifer A.; Kerisit, Sebastien Environmental Science & Technology, Vol. 51, Issue 9 https://doi.org/10.1021/acs.est.7b00432	journal	April 2017
Complexation by Organic Matter Controls Uranium Mobility in Anoxic Sediments Bone, Sharon E.; Cliff, John; Weaver, Karrie Environmental Science & Technology, Vol. 54, Issue 3 https://doi.org/10.1021/acs.est.9b04741	journal	December 2019
Natural Uranium Contamination in Major U.S. Aquifers Linked to Nitrate Nolan, Jason; Weber, Karrie A. Environmental Science & Technology Letters, Vol. 2, Issue 8 https://doi.org/10.1021/acs.estlett.5b00174	journal	July 2015
Uranium(V) Incorporation Mechanisms and Stability in Fe(II)/Fe(III) (oxyhydr)Oxides Roberts, Hannah E.; Morris, Katherine; Law, Gareth T. W. Environmental Science & Technology Letters, Vol. 4, Issue 10 https://doi.org/10.1021/acs.estlett.7b00348	journal	September 2017
Ab Initio Molecular Dynamics of Uranium Incorporated in Goethite (α-FeOOH): Interpretation of X-ray Absorption Spectroscopy of Trace Polyvalent Metals Kerisit, Sebastien; Bylaska, Eric J.; Massey, Michael S. Inorganic Chemistry, Vol. 55, Issue 22 https://doi.org/10.1021/acs.inorgchem.6b01773	journal	November 2016
Mechanisms and Rates of U(VI) Reduction by Fe(II) in Homogeneous Aqueous Solution and the Role of U(V) Disproportionation Collins, Richard N.; Rosso, Kevin M. The Journal of Physical Chemistry A, Vol. 121, Issue 35 https://doi.org/10.1021/acs.jpca.7b05965	journal	August 2017
Inhibition of Bacterial U(VI) Reduction by Calcium Brooks, Scott C.; Fredrickson, James K.; Carroll, Sue L. Environmental Science & Technology, Vol. 37, Issue 9 https://doi.org/10.1021/es0210042	journal	May 2003
Kinetics of Uranium(VI) Reduction by Hydrogen Sulfide in Anoxic Aqueous Systems Hua, Bin; Xu, Huifang; Terry, Jeff Environmental Science & Technology, Vol. 40, Issue 15, p. 4666-4671 https://doi.org/10.1021/es051804n	journal	August 2006
Thermodynamic Constraints on the Oxidation of Biogenic UO ₂ by Fe(III) (Hydr)oxides Ginder-Vogel, Matthew; Criddle, Craig S.; Fendorf, Scott Environmental Science & Technology, Vol. 40, Issue 11 https://doi.org/10.1021/es052305p	journal	June 2006
Determination of the Formation Constants of Ternary Complexes of Uranyl and Carbonate with Alkaline Earth Metals (Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , and Ba ²⁺ ) Using Anion Exchange Method Dong, Wenming; Brooks, Scott C. Environmental Science & Technology, Vol. 40, Issue 15 https://doi.org/10.1021/es0606327	journal	August 2006
Speciation-Dependent Microbial Reduction of Uranium within Iron-Coated Sands Neiss, Jim; Stewart, Brandy D.; Nico, Peter S. Environmental Science & Technology, Vol. 41, Issue 21 https://doi.org/10.1021/es0706697	journal	November 2007
Atomistic Simulations of Uranium Incorporation into Iron (Hydr)Oxides Kerisit, Sebastien; Felmy, Andrew R.; Ilton, Eugene S. Environmental Science & Technology, Vol. 45, Issue 7 https://doi.org/10.1021/es1037639	journal	April 2011
Reduction of Uranium(VI) by Soluble Iron(II) Conforms with Thermodynamic Predictions Du, Xin; Boonchayaanant, Benjaporn; Wu, Wei-Min Environmental Science & Technology, Vol. 45, Issue 11 https://doi.org/10.1021/es2006012	journal	June 2011
Reduction of U(VI) Incorporated in the Structure of Hematite Ilton, Eugene S.; Pacheco, Juan S. Lezama; Bargar, John R. Environmental Science & Technology, Vol. 46, Issue 17 https://doi.org/10.1021/es3015502	journal	August 2012
Fate of Arsenic during Microbial Reduction of Biogenic versus Abiogenic As–Fe(III)–Mineral Coprecipitates Muehe, E. Marie; Scheer, Lukas; Daus, Birgit Environmental Science & Technology https://doi.org/10.1021/es400801z	journal	July 2013
Stability of Uranium Incorporated into Fe (Hydr)oxides under Fluctuating Redox Conditions Stewart, Brandy D.; Nico, Peter S.; Fendorf, Scott Environmental Science & Technology, Vol. 43, Issue 13 https://doi.org/10.1021/es803317w	journal	June 2009
Incorporation of Oxidized Uranium into Fe (Hydr)oxides during Fe(II) Catalyzed Remineralization Nico, Peter S.; Stewart, Brandy D.; Fendorf, Scott Environmental Science & Technology, Vol. 43, Issue 19 https://doi.org/10.1021/es900515q	journal	October 2009
Influence of Dynamical Conditions on the Reduction of U ^VI at the Magnetite−Solution Interface Ilton, Eugene S.; Boily, Jean-François; Buck, Edgar C. Environmental Science & Technology, Vol. 44, Issue 1 https://doi.org/10.1021/es9014597	journal	January 2010
Impact of Uranyl−Calcium−Carbonato Complexes on Uranium(VI) Adsorption to Synthetic and Natural Sediments Stewart, Brandy D.; Mayes, Melanie A.; Fendorf, Scott Environmental Science & Technology, Vol. 44, Issue 3 https://doi.org/10.1021/es902194x	journal	February 2010
Spectroscopic Confirmation of Uranium(VI)−Carbonato Adsorption Complexes on Hematite Bargar, John R.; Reitmeyer, Rebecca; Davis, James A. Environmental Science & Technology, Vol. 33, Issue 14 https://doi.org/10.1021/es990048g	journal	July 1999
Redox Energetics and Kinetics of Uranyl Coordination Complexes in Aqueous Solution Morris, David E. Inorganic Chemistry, Vol. 41, Issue 13 https://doi.org/10.1021/ic0201708	journal	July 2002
Environmental Speciation of Actinides Maher, Kate; Bargar, John R.; Brown, Gordon E. Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic301686d	journal	June 2012
Field-scale model for the natural attenuation of uranium at the Hanford 300 Area using high-performance computing: MODEL FOR NATURAL ATTENUATION OF URANIUM Hammond, Glenn E.; Lichtner, Peter C. Water Resources Research, Vol. 46, Issue 9 https://doi.org/10.1029/2009WR008819	journal	September 2010
Theoretical analysis of the U L ₃ -edge NEXAFS in U oxides Nelin, Connie J.; Bagus, Paul S.; Ilton, Eugene S. RSC Adv., Vol. 4, Issue 14 https://doi.org/10.1039/C3RA46738D	journal	January 2014
A seven-crystal Johann-type hard x-ray spectrometer at the Stanford Synchrotron Radiation Lightsource Sokaras, D.; Weng, T. -C.; Nordlund, D. Review of Scientific Instruments, Vol. 84, Issue 5 https://doi.org/10.1063/1.4803669	journal	May 2013
The effect of symmetry on the U L ₃ NEXAFS of octahedral coordinated uranium( vi ) Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S. The Journal of Chemical Physics, Vol. 146, Issue 11 https://doi.org/10.1063/1.4978481	journal	March 2017
Uranium(IV) adsorption by natural organic matter in anoxic sediments Bone, Sharon E.; Dynes, James J.; Cliff, John Proceedings of the National Academy of Sciences, Vol. 114, Issue 4 https://doi.org/10.1073/pnas.1611918114	journal	January 2017
Speciation-Dependent Kinetics of Uranium(VI) Bioreduction Ulrich, Kai-Uwe; Veeramani, Harish; Bernier-Latmani, Rizlan Geomicrobiology Journal, Vol. 28, Issue 5-6 https://doi.org/10.1080/01490451.2010.507640	journal	June 2011
Influence of Uranyl Speciation and Iron Oxides on Uranium Biogeochemical Redox Reactions Stewart, Brandy D.; Amos, Richard T.; Nico, Peter S. Geomicrobiology Journal, Vol. 28, Issue 5-6 https://doi.org/10.1080/01490451.2010.507646	journal	June 2011
Actinide and lanthanide speciation with high-energy resolution X-ray techniques Vitova, T.; Denecke, M. A.; Göttlicher, J. Journal of Physics: Conference Series, Vol. 430 https://doi.org/10.1088/1742-6596/430/1/012117	journal	April 2013
Polarized x-ray-absorption spectroscopy of the uranyl ion: Comparison of experiment and theory Hudson, E. A.; Allen, P. G.; Terminello, L. J. Physical Review B, Vol. 54, Issue 1 https://doi.org/10.1103/PhysRevB.54.156	journal	July 1996
Relativistic XANES calculations of Pu hydrates Ankudinov, A. L.; Conradson, S. D.; Mustre de Leon, J. Physical Review B, Vol. 57, Issue 13 https://doi.org/10.1103/PhysRevB.57.7518	journal	April 1998
High energy resolution x-ray absorption spectroscopy study of uranium in varying valence states Vitova, T.; Kvashnina, K. O.; Nocton, G. Physical Review B, Vol. 82, Issue 23 https://doi.org/10.1103/PhysRevB.82.235118	journal	December 2010
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
CaUO2CO3 Complexation Implications for Bioremediation of UVI Kelly, S. D.; Kemner, K. M.; Brooks, S. C. Physica Scripta https://doi.org/10.1238/Physica.Topical.115a00915	journal	January 2005
SIXPack a Graphical User Interface for XAS Analysis Using IFEFFIT Webb, S. M. Physica Scripta https://doi.org/10.1238/Physica.Topical.115a01011	journal	January 2005
Effect of Uranium(VI) Speciation on Simultaneous Microbial Reduction of Uranium(VI) and Iron(III) Stewart, Brandy D.; Amos, Richard T.; Fendorf, Scott Journal of Environmental Quality, Vol. 40, Issue 1 https://doi.org/10.2134/jeq2010.0304	journal	January 2011
XAFS spectroscopic study of uranyl coordination in solids and aqueous solution Thompson, Hillary A.; Brown, Gordon E.; Parks, George A. American Mineralogist, Vol. 82, Issue 5-6 https://doi.org/10.2138/am-1997-5-607	journal	June 1997

Similar Records

Competing retention pathways of uranium upon reaction with Fe(II)

Journal Article · Wed Oct 01 00:00:00 EDT 2014 · Geochimica et Cosmochimica Acta, 142:166-185 · OSTI ID:1167628

The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz

Journal Article · Sun Jan 29 23:00:00 EST 2006 · Geochimica et Cosmochimica Acta · OSTI ID:944778

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cations
Extended X-ray absorption fine structure
Reaction products
Redox reactions
Transfer reactions

Calcium-Uranyl-Carbonato Species Kinetically Limit U(VI) Reduction by Fe(II) and Lead to U(V)-Bearing Ferrihydrite

Citation Formats

References (48)

Similar Records

Related Subjects