An experimental and ab initio study on the abiotic reduction of uranyl by ferrous iron

Taylor, S. D.; Marcano, M. C.; Rosso, K. M.; Becker, U.

doi:10.1016/j.gca.2015.01.021

An experimental and ab initio study on the abiotic reduction of uranyl by ferrous iron

Journal Article · Mon Feb 23 00:00:00 EST 2015 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2015.01.021· OSTI ID:1700520

Taylor, S. D. ^[1]; Marcano, M. C. ^[1]; Rosso, K. M. ^[2]; Becker, U. ^[1]

Univ. of Michigan, Ann Arbor, MI (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

It is important to understand the mechanisms controlling the removal of uranyl from solution from an environmental standpoint, particularly whether soluble Fe(II) is capable of reducing soluble U(VI) to insoluble U(IV). Experiments were performed to shed light into discrepancies of recent studies about precipitation of U-containing solids without changing oxidation states versus precipitation/reduction reactions, especially with respect to the kinetics of these reactions. To understand the atomistic mechanisms, thermodynamics, and kinetics of these redox processes, ab initio electron transfer (ET) calculations, using Marcus theory, were applied to study the reduction of U(VI)_aq to U(V)_aq by Fe(II)_aq (the first rate-limiting ET-step). Outer-sphere (OS) and inner-sphere (IS) Fe–U complexes were modeled to represent simple species within a homogeneous environment through which ET could occur.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1700520

Report Number(s):: PNNL-SA--153389

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 156; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

Electron Transfer Reactions in Chemistry: Theory and Experiment (Nobel Lecture) Marcus, Rudolph A. Angewandte Chemie International Edition in English, Vol. 32, Issue 8 https://doi.org/10.1002/anie.199311113	journal	August 1993
XPS determination of uranium oxidation states: XPS determination of uranium oxidation states Ilton, Eugene S.; Bagus, Paul S. Surface and Interface Analysis, Vol. 43, Issue 13 https://doi.org/10.1002/sia.3836	journal	October 2011
The influence of polarization functions on molecular orbital hydrogenation energies Hariharan, P. C.; Pople, J. A. Theoretica Chimica Acta, Vol. 28, Issue 3 https://doi.org/10.1007/BF00533485	journal	January 1973
Electron transfer in environmental systems: a frontier for theoretical chemistry Rosso, Kevin M.; Dupuis, Michel Theoretical Chemistry Accounts, Vol. 116, Issue 1-3 https://doi.org/10.1007/s00214-005-0016-x	journal	October 2005
U(VI) reduction by Fe(II) on hematite nanoparticles Zeng, Hui; Giammar, Daniel E. Journal of Nanoparticle Research, Vol. 13, Issue 9 https://doi.org/10.1007/s11051-011-0296-0	journal	February 2011
Redox processes catalyzed by hydrous oxide surfaces Wehrli, Bernhard; Sulzberger, Barbara; Stumm, Werner Chemical Geology, Vol. 78, Issue 3-4 https://doi.org/10.1016/0009-2541(89)90056-9	journal	December 1989
The synchronous-transit method for determining reaction pathways and locating molecular transition states Halgren, Thomas A.; Lipscomb, William N. Chemical Physics Letters, Vol. 49, Issue 2 https://doi.org/10.1016/0009-2614(77)80574-5	journal	July 1977
Interaction between aqueous uranium (VI) and sulfide minerals: Spectroscopic evidence for sorption and reduction Wersin, Paul; Hochella, Michael F.; Persson, Per Geochimica et Cosmochimica Acta, Vol. 58, Issue 13 https://doi.org/10.1016/0016-7037(94)90117-1	journal	July 1994
Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model Waite, T. D.; Davis, J. A.; Payne, T. E. Geochimica et Cosmochimica Acta, Vol. 58, Issue 24 https://doi.org/10.1016/0016-7037(94)90243-7	journal	December 1994
Electron transfers in chemistry and biology Marcus, R. A.; Sutin, Norman Biochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, Vol. 811, Issue 3 https://doi.org/10.1016/0304-4173(85)90014-X	journal	August 1985
Natural attenuation of TCE, As, Hg linked to the heterogeneous oxidation of Fe(II): an AFM study Charlet, Laurent; Bosbach, Dirk; Peretyashko, Tanya Chemical Geology, Vol. 190, Issue 1-4 https://doi.org/10.1016/S0009-2541(02)00122-5	journal	October 2002
N-compound reduction and actinide immobilisation in surficial fluids by Fe(II): the surface FeIIIOFeIIOH° species, as major reductant Charlet, L.; Silvester, E.; Liger, E. Chemical Geology, Vol. 151, Issue 1-4 https://doi.org/10.1016/S0009-2541(98)00072-2	journal	October 1998
Reactive transport of uranyl in a goethite column: an experimental and modelling study Gabriel, U.; Gaudet, J. -P.; Spadini, L. Chemical Geology, Vol. 151, Issue 1-4 https://doi.org/10.1016/S0009-2541(98)00074-6	journal	October 1998
Reduction of U(VI) in goethite (α-FeOOH) suspensions by a dissimilatory metal-reducing bacterium Fredrickson, James K.; Zachara, John M.; Kennedy, David W. Geochimica et Cosmochimica Acta, Vol. 64, Issue 18 https://doi.org/10.1016/S0016-7037(00)00397-5	journal	September 2000
The proximity effect on semiconducting mineral surfaces: a new aspect of mineral surface reactivity and surface complexation theory? Becker, Udo; Rosso, Kevin M.; Hochella, Michael F. Geochimica et Cosmochimica Acta, Vol. 65, Issue 16 https://doi.org/10.1016/S0016-7037(01)00624-X	journal	August 2001
Uranium co-precipitation with iron oxide minerals Duff, Martine C.; Coughlin, Jessica Urbanik; Hunter, Douglas B. Geochimica et Cosmochimica Acta, Vol. 66, Issue 20 https://doi.org/10.1016/S0016-7037(02)00953-5	journal	October 2002
Proximity effects on semiconducting mineral surfaces II: Rosso, Kevin M.; Becker, Udo Geochimica et Cosmochimica Acta, Vol. 67, Issue 5 https://doi.org/10.1016/S0016-7037(02)00990-0	journal	March 2003
Outer-sphere electron transfer kinetics of metal ion oxidation by molecular oxygen Rosso, Kevin M.; Morgan, James J. Geochimica et Cosmochimica Acta, Vol. 66, Issue 24 https://doi.org/10.1016/S0016-7037(02)01040-2	journal	December 2002
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
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations Valiev, M.; Bylaska, E. J.; Govind, N. Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489 https://doi.org/10.1016/j.cpc.2010.04.018	journal	September 2010
Computer simulation of electron transfer at hematite surfaces Kerisit, Sebastien; Rosso, Kevin M. Geochimica et Cosmochimica Acta, Vol. 70, Issue 8 https://doi.org/10.1016/j.gca.2005.12.021	journal	April 2006
Reduction of pertechnetate [Tc(VII)] by aqueous Fe(II) and the nature of solid phase redox products Zachara, John M.; Heald, Steve M.; Jeon, Byong-Hun Geochimica et Cosmochimica Acta, Vol. 71, Issue 9 https://doi.org/10.1016/j.gca.2006.10.025	journal	May 2007
Surface complexation of U(VI) on goethite (α-FeOOH) Sherman, David M.; Peacock, Caroline L.; Hubbard, Christopher G. Geochimica et Cosmochimica Acta, Vol. 72, Issue 2 https://doi.org/10.1016/j.gca.2007.10.023	journal	January 2008
Heterogeneous reduction of Tc(VII) by Fe(II) at the solid–water interface Peretyazhko, T.; Zachara, J. M.; Heald, S. M. Geochimica et Cosmochimica Acta, Vol. 72, Issue 6 https://doi.org/10.1016/j.gca.2008.01.004	journal	March 2008
A first principles study of the oxidation energetics and kinetics of realgar Renock, Devon; Becker, Udo Geochimica et Cosmochimica Acta, Vol. 74, Issue 15 https://doi.org/10.1016/j.gca.2010.05.003	journal	August 2010
Heterogeneous reduction of U6+ by structural Fe2+ from theory and experiment Skomurski, F. N.; Ilton, E. S.; Engelhard, M. H. Geochimica et Cosmochimica Acta, Vol. 75, Issue 22 https://doi.org/10.1016/j.gca.2011.08.006	journal	November 2011
Solubility of schoepite: Comparison and selection of complexation constants for U(VI) Jang, Je-Hun; Dempsey, Brian A.; Burgos, William D. Water Research, Vol. 40, Issue 14 https://doi.org/10.1016/j.watres.2006.04.014	journal	August 2006
Chromate removal from aqueous wastes by reduction with ferrous ion Eary, L. E.; Rai, Dhanpat. Environmental Science & Technology, Vol. 22, Issue 8 https://doi.org/10.1021/es00173a018	journal	August 1988
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
Reduction of Uranyl in the Interlayer Region of Low Iron Micas under Anoxic and Aerobic Conditions Ilton, Eugene S.; Heald, Steve M.; Smith, Steven C. Environmental Science & Technology, Vol. 40, Issue 16 https://doi.org/10.1021/es0522478	journal	August 2006
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
Molecular-Scale Structure of Uranium(VI) Immobilized with Goethite and Phosphate Singh, Abhas; Catalano, Jeffrey G.; Ulrich, Kai-Uwe Environmental Science & Technology, Vol. 46, Issue 12 https://doi.org/10.1021/es300494x	journal	May 2012
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
Reductive Immobilization of Uranium(VI) by Amorphous Iron Sulfide Hua, Bin; Deng, Baolin Environmental Science & Technology, Vol. 42, Issue 23 https://doi.org/10.1021/es801225z	journal	December 2008
Comment on “Reductive Immobilization of Uranium(VI) by Amorphous Iron Sulfide” Noubactep, C. Environmental Science & Technology, Vol. 43, Issue 4 https://doi.org/10.1021/es803175g	journal	January 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
Relativistic and correlation effects for element 105 (hahnium, Ha): a comparative study of M and MO (M = Nb, Ta, Ha) using energy-adjusted ab initio pseudopotentials Dolg, Michael; Stoll, Hermann; Preuss, Heinzwerner The Journal of Physical Chemistry, Vol. 97, Issue 22 https://doi.org/10.1021/j100124a012	journal	June 1993
Electric-field induced intramolecular electron transfer in spiro .pi.-electron systems and their suitability as molecular electronic devices. A theoretical study Farazdel, Abbas; Dupuis, Michel; Clementi, Enrico Journal of the American Chemical Society, Vol. 112, Issue 11 https://doi.org/10.1021/ja00167a016	journal	May 1990
Aspects of Aqueous Iron and Manganese (II/III) Self-Exchange Electron Transfer Reactions Rosso, Kevin M.; Smith, Dayle M. A.; Dupuis, Michel The Journal of Physical Chemistry A, Vol. 108, Issue 24 https://doi.org/10.1021/jp037470a	journal	June 2004
Kinetics of Triscarbonato Uranyl Reduction by Aqueous Ferrous Iron: A Theoretical Study Wander, Matthew C. F.; Kerisit, Sebastien; Rosso, Kevin M. The Journal of Physical Chemistry A, Vol. 110, Issue 31 https://doi.org/10.1021/jp062325t	journal	August 2006
Green Rust Reduction of Chromium Part 2: Comparison of Heterogeneous and Homogeneous Chromate Reduction Wander, Matthew C. F.; Schoonen, Martin A. A. The Journal of Physical Chemistry C, Vol. 114, Issue 39 https://doi.org/10.1021/jp1021328	journal	September 2010
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient Klamt, A.; Schüürmann, G. J. Chem. Soc., Perkin Trans. 2, Issue 5 https://doi.org/10.1039/P29930000799	journal	January 1993
X-Ray photoelectron spectroscopy of some uranium oxide phases Allen, Geoffrey C.; Crofts, John A.; Curtis, Michael T. Journal of the Chemical Society, Dalton Transactions, Issue 12 https://doi.org/10.1039/dt9740001296	journal	January 1974
An ab initio model of electron transport in hematite (α-Fe₂O₃) basal planes Rosso, Kevin M.; Smith, Dayle M. A.; Dupuis, Michel The Journal of Chemical Physics, Vol. 118, Issue 14, p. 6455-6466 https://doi.org/10.1063/1.1558534	journal	April 2003
Fully optimized contracted Gaussian basis sets for atoms Li to Kr Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 97, Issue 4 https://doi.org/10.1063/1.463096	journal	August 1992
Ab initio pseudopotentials for Hg through Rn : I. Parameter sets and atomic calculations Küchle, W.; Dolg, M.; Stoll, H. Molecular Physics, Vol. 74, Issue 6 https://doi.org/10.1080/00268979100102941	journal	December 1991
The conductor-like screening model for polymers and surfaces Delley, B. Molecular Simulation, Vol. 32, Issue 2 https://doi.org/10.1080/08927020600589684	journal	February 2006
Interfacial reactivity of radionuclides: emerging paradigms from molecular-level observations Felmy, A. R.; Ilton, E. S.; Rosso, K. M. Mineralogical Magazine, Vol. 75, Issue 4 https://doi.org/10.1180/minmag.2011.075.4.2379	journal	August 2011
A solution chemists view of surface chemistry Schindler, P. W. Pure and Applied Chemistry, Vol. 63, Issue 12 https://doi.org/10.1351/pac199163121697	journal	January 1991

Cited By (3)

Density functional theory (DFT) calculations of VI/V reduction potentials of uranyl coordination complexes in non-aqueous solutions Arumugam, Krishnamoorthy; Burton, Neil A. Physical Chemistry Chemical Physics, Vol. 21, Issue 6 https://doi.org/10.1039/c8cp05412f	journal	January 2019
The basis for reevaluating the reactivity of pyrite surfaces: spin states and crystal field d-orbital splitting energies of bulk, terrace, edge, and corner Fe( ii ) ions Arumugam, Krishnamoorthy; Renock, Devon; Becker, Udo Physical Chemistry Chemical Physics, Vol. 21, Issue 12 https://doi.org/10.1039/c8cp05459b	journal	January 2019
Electrochemical, Spectroscopic, and Computational Investigations on Redox Reactions of Selenium Species on Galena Surfaces Cook, Peter; Kim, YoungJae; Yuan, Ke Minerals, Vol. 9, Issue 7 https://doi.org/10.3390/min9070437	journal	July 2019

Similar Records

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

Journal Article · Mon Apr 20 20:00:00 EDT 2020 · Environmental Science and Technology · OSTI ID:1638150

Kinetics of Triscarbonato Uranyl Reduction by Aqueous Ferrous Iron: A Theoretical Study

Journal Article · Tue Aug 01 00:00:00 EDT 2006 · Journal of Physical Chemistry A, 110(31):9691-9701 · OSTI ID:891123

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

An experimental and ab initio study on the abiotic reduction of uranyl by ferrous iron

Citation Formats

References (49)

Cited By (3)

Similar Records

Related Subjects