Identification of Simultaneous U(VI) Sorption Complexes and U(IV) Nanoprecipitates on the Magnetite (111) Surface

Singer, David M.; Chatman, Shawn M.; Ilton, Eugene S.; Rosso, Kevin M.; Banfield, Jillian F.; Waychunas, Glenn A.

doi:10.1021/es203877x

Identification of Simultaneous U(VI) Sorption Complexes and U(IV) Nanoprecipitates on the Magnetite (111) Surface

Journal Article · Mon Feb 27 00:00:00 EST 2012 · Environmental Science and Technology

DOI:https://doi.org/10.1021/es203877x· OSTI ID:1508074

Singer, David M. ^[1]; Chatman, Shawn M. ^[2]; Ilton, Eugene S. ^[2]; Rosso, Kevin M. ^[2]; Banfield, Jillian F. ^[3]; Waychunas, Glenn A. ^[4]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); The University of Chicago
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sequestration of uranium (U) by magnetite is a likely important sink for U in natural and contaminated environments. Nonetheless, molecular-scale controls that favor U(VI) uptake including both adsorption of U(VI) and reduction to U(IV) by magnetite remain poorly understood, in particular, the role of U(VI)–CO₃–Ca complexes in inhibiting U(VI) reduction. To investigate U uptake pathways on magnetite as a function of U(VI) aqueous speciation, we performed batch sorption experiments on (111) surfaces of natural single crystals under a range of solution conditions (pH 5 and 10; 0.1 mM U(VI); 1 mM NaNO₃; and with or without 0.5 mM CO₃ and 0.1 mM Ca) and characterized surface-associated U using grazing incidence extended X-ray absorption fine structure spectroscopy (GI-EXAFS), grazing incidence X-ray diffraction (GI-XRD), and scanning electron microscopy (SEM). In the absence of both carbonate ([CO₃]T, denoted here as CO₃) and calcium (Ca), or in the presence of CO₃ only, coexisting adsorption of U(VI) surface species and reduction to U(IV) occurs at both pH 5 and 10. In the presence of both Ca and CO₃, only U(VI) adsorption (VI) occurs. When U reduction occurs, nanoparticulate UO₂ forms only within and adjacent to surface microtopographic features such as crystal boundaries and cracks. This result suggests that U reduction is limited to defect-rich surface regions. Further, at both pH 5 and 10 in the presence of both CO₃ and Ca, U(VI)–CO₃–Ca ternary surface species develop and U reduction is inhibited. These findings extend the range of conditions under which U(VI)–CO₃–Ca complexes inhibit U reduction.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Chicago, Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-94ER14466

OSTI ID:: 1508074

Alternate ID(s):: OSTI ID: 1037911
OSTI ID: 1040672

Report Number(s):: DOE-UCHICAGO-14466--14

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 7 Vol. 46; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

Influence of calcium on microbial reduction of solid phase uranium(VI) Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M. Biotechnology and Bioengineering, Vol. 97, Issue 6 https://doi.org/10.1002/bit.21357	journal	January 2007
The crystal structure of Liebigite, Ca2UO2(CO3)3�?11H2O Mereiter, K. TMPM Tschermaks Mineralogische und Petrographische Mitteilungen, Vol. 30, Issue 4 https://doi.org/10.1007/BF01087173	journal	January 1982
Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: arsenate on hematite (0001) and (10–12) Waychunas, G.; Trainor, T.; Eng, P. Analytical and Bioanalytical Chemistry, Vol. 383, Issue 1 https://doi.org/10.1007/s00216-005-3393-z	journal	September 2005
The structure of uranium (VI) sorption complexes on silica, alumina, and montmorillonite Sylwester, E. R.; Hudson, E. A.; Allen, P. G. Geochimica et Cosmochimica Acta, Vol. 64, Issue 14 https://doi.org/10.1016/S0016-7037(00)00376-8	journal	July 2000
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
Uranium (VI) sorption on colloidal magnetite under anoxic environment: experimental study and surface complexation modelling Missana, Tiziana; García-Gutiérrez, Miguel; Fernńdez, Victor Geochimica et Cosmochimica Acta, Vol. 67, Issue 14 https://doi.org/10.1016/S0016-7037(02)01350-9	journal	July 2003
Surface reactions kinetics between nanocrystalline magnetite and uranyl Missana, Tiziana; Maffiotte, César; Garcı́a-Gutiérrez, Miguel Journal of Colloid and Interface Science, Vol. 261, Issue 1 https://doi.org/10.1016/S0021-9797(02)00227-8	journal	May 2003
Study of the interaction between U(VI) and the anoxic corrosion products of carbon steel Duro, Lara; El Aamrani, Souad; Rovira, Miquel Applied Geochemistry, Vol. 23, Issue 5 https://doi.org/10.1016/j.apgeochem.2008.01.004	journal	May 2008
Removal of uranium(VI) from the aqueous phase by iron(II) minerals in presence of bicarbonate Regenspurg, Simona; Schild, Dieter; Schäfer, Thorsten Applied Geochemistry, Vol. 24, Issue 9 https://doi.org/10.1016/j.apgeochem.2009.04.029	journal	September 2009
Inhibition of the reduction of Cr(VI) at the magnetite–water interface by calcium carbonate coatings Doyle, Colin S.; Kendelewicz, Tom; Brown, Gordon E. Applied Surface Science, Vol. 230, Issue 1-4 https://doi.org/10.1016/j.apsusc.2004.02.035	journal	May 2004
Spectroscopic investigation of magnetite surface for the reduction of hexavalent chromium Jung, Yoojin; Choi, Jeongyun; Lee, Woojin Chemosphere, Vol. 68, Issue 10 https://doi.org/10.1016/j.chemosphere.2007.02.028	journal	August 2007
Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation Catalano, Jeffrey G.; Brown, Gordon E. Geochimica et Cosmochimica Acta, Vol. 69, Issue 12 https://doi.org/10.1016/j.gca.2005.01.025	journal	June 2005
CTR diffraction and grazing-incidence EXAFS study of U(VI) adsorption onto α-Al2O3 and α-Fe2O3 (11̄02) surfaces Catalano, Jeffrey G.; Trainor, Thomas P.; Eng, Peter J. Geochimica et Cosmochimica Acta, Vol. 69, Issue 14 https://doi.org/10.1016/j.gca.2005.03.044	journal	July 2005
Reduction of U(VI) to U(IV) on the surface of magnetite Scott, T. B.; Allen, G. C.; Heard, P. J. Geochimica et Cosmochimica Acta, Vol. 69, Issue 24 https://doi.org/10.1016/j.gca.2005.07.003	journal	December 2005
The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz Fox, Patricia M.; Davis, James A.; Zachara, John M. Geochimica et Cosmochimica Acta, Vol. 70, Issue 6 https://doi.org/10.1016/j.gca.2005.11.027	journal	March 2006
X-ray absorption spectroscopy identifies calcium-uranyl-carbonate complexes at environmental concentrations Kelly, Shelly D.; Kemner, Kenneth M.; Brooks, Scott C. Geochimica et Cosmochimica Acta, Vol. 71, Issue 4 https://doi.org/10.1016/j.gca.2006.10.013	journal	February 2007
Biogenic nanoparticulate UO2: Synthesis, characterization, and factors affecting surface reactivity Singer, David M.; Farges, François; Brown, Gordon E. Geochimica et Cosmochimica Acta, Vol. 73, Issue 12 https://doi.org/10.1016/j.gca.2009.03.031	journal	June 2009
Uranyl–chlorite sorption/desorption: Evaluation of different U(VI) sequestration processes Singer, David M.; Maher, Kate; Brown, Gordon E. Geochimica et Cosmochimica Acta, Vol. 73, Issue 20 https://doi.org/10.1016/j.gca.2009.07.002	journal	October 2009
Structure, charge distribution, and electron hopping dynamics in magnetite (Fe3O4) (100) surfaces from first principles Skomurski, Frances N.; Kerisit, Sebastien; Rosso, Kevin M. Geochimica et Cosmochimica Acta, Vol. 74, Issue 15 https://doi.org/10.1016/j.gca.2010.04.063	journal	August 2010
Products of abiotic U(VI) reduction by biogenic magnetite and vivianite Veeramani, Harish; Alessi, Daniel S.; Suvorova, Elena I. Geochimica et Cosmochimica Acta, Vol. 75, Issue 9 https://doi.org/10.1016/j.gca.2011.02.024	journal	May 2011
The effects of uranium speciation on the rate of U(VI) reduction by Shewanella oneidensis MR-1 Sheng, Ling; Szymanowski, Jennifer; Fein, Jeremy B. Geochimica et Cosmochimica Acta, Vol. 75, Issue 12 https://doi.org/10.1016/j.gca.2011.03.039	journal	June 2011
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
Spectroscopic characterization of alkaline earth uranyl carbonates Amayri, Samer; Reich, Tobias; Arnold, Thuro Journal of Solid State Chemistry, Vol. 178, Issue 2 https://doi.org/10.1016/j.jssc.2004.07.050	journal	February 2005
Surface structure of magnetite (111) under hydrated conditions by crystal truncation rod diffraction Petitto, Sarah C.; Tanwar, Kunaljeet S.; Ghose, Sanjit K. Surface Science, Vol. 604, Issue 13-14 https://doi.org/10.1016/j.susc.2010.03.014	journal	July 2010
Mechanisms of Uranium Interactions with Hydroxyapatite: Implications for Groundwater Remediation Fuller, C. C.; Bargar, J. R.; Davis, J. A. Environmental Science & Technology, Vol. 36, Issue 2 https://doi.org/10.1021/es0108483	journal	January 2002
Iron Oxide Surface-Catalyzed Oxidation of Ferrous Iron by Monochloramine: Implications of Oxide Type and Carbonate on Reactivity Vikesland, Peter J.; Valentine, Richard L. Environmental Science & Technology, Vol. 36, Issue 3 https://doi.org/10.1021/es010935v	journal	February 2002
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
Adsorption of Aqueous Uranyl Complexes onto Bacillus subtilis Cells Gorman-Lewis, Drew; Elias, Patricia E.; Fein, Jeremy B. Environmental Science & Technology, Vol. 39, Issue 13 https://doi.org/10.1021/es047957c	journal	July 2005
Chemical Reduction of U(VI) by Fe(II) at the Solid−Water Interface Using Natural and Synthetic Fe(III) Oxides Jeon, Byong-Hun; Dempsey, Brian A.; Burgos, William D. Environmental Science & Technology, Vol. 39, Issue 15 https://doi.org/10.1021/es0487527	journal	August 2005
Pilot-Scale in Situ Bioremediation of Uranium in a Highly Contaminated Aquifer. 1. Conditioning of a Treatment Zone Wu, Wei-Min; Carley, Jack; Fienen, Michael Environmental Science & Technology, Vol. 40, Issue 12 https://doi.org/10.1021/es051954y	journal	June 2006
Changes in Uranium Speciation through a Depth Sequence of Contaminated Hanford Sediments Catalano, Jeffrey G.; McKinley, James P.; Zachara, John M. Environmental Science & Technology, Vol. 40, Issue 8 https://doi.org/10.1021/es0520969	journal	April 2006
Non-uraninite Products of Microbial U(VI) Reduction Bernier-Latmani, Rizlan; Veeramani, Harish; Vecchia, Elena Dalla Environmental Science & Technology, Vol. 44, Issue 24 https://doi.org/10.1021/es101675a	journal	December 2010
Solution and Microbial Controls on the Formation of Reduced U(IV) Species Boyanov, Maxim I.; Fletcher, Kelly E.; Kwon, Man Jae Environmental Science & Technology, Vol. 45, Issue 19 https://doi.org/10.1021/es2014049	journal	October 2011
U(VI) Sorption and Reduction Kinetics on the Magnetite (111) Surface Singer, David M.; Chatman, Shawn M.; Ilton, Eugene S. Environmental Science & Technology, Vol. 46, Issue 7 https://doi.org/10.1021/es203878c	journal	March 2012
Uranium Speciation As a Function of Depth in Contaminated Hanford Sediments - A Micro-XRF, Micro-XRD, and Micro- And Bulk-XAFS Study Singer, David M.; Zachara, John M.; Brown Jr, Gordon E. Environmental Science & Technology, Vol. 43, Issue 3 https://doi.org/10.1021/es8021045	journal	February 2009
Reduction of Hg(II) to Hg(0) by Magnetite Wiatrowski, Heather A.; Das, Soumya; Kukkadapu, Ravi Environmental Science & Technology, Vol. 43, Issue 14 https://doi.org/10.1021/es9003608	journal	July 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
Redox Behavior of Magnetite: Implications for Contaminant Reduction Gorski, Christopher A.; Nurmi, James T.; Tratnyek, Paul G. Environmental Science & Technology, Vol. 44, Issue 1 https://doi.org/10.1021/es9016848	journal	January 2010
U(VI) Sorption and Reduction by Fe(II) Sorbed on Montmorillonite Chakraborty, Sudipta; Favre, Fabienne; Banerjee, Dipanjan Environmental Science & Technology, Vol. 44, Issue 10 https://doi.org/10.1021/es903493n	journal	May 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
Glancing-angle x-ray absorption spectroscopy of corroded borosilicate glass surfaces containing uranium Greaves, G. N.; Barrett, N. T.; Antonini, G. M. Journal of the American Chemical Society, Vol. 111, Issue 12 https://doi.org/10.1021/ja00194a024	journal	June 1989
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
Magnetic domain structures on a natural single crystal of magnetite Özdemir, Özden; Dunlop, David J. Geophysical Research Letters, Vol. 20, Issue 17 https://doi.org/10.1029/93GL01936	journal	September 1993
Closure domains in magnetite Özdemir, Özden; Xu, Song; Dunlop, David J. Journal of Geophysical Research: Solid Earth, Vol. 100, Issue B2 https://doi.org/10.1029/94JB02874	journal	February 1995
Effect of crystal defects and internal stress on the domain structure and magnetic properties of magnetite Özdemir, Özden; Dunlop, David J. Journal of Geophysical Research: Solid Earth, Vol. 102, Issue B9 https://doi.org/10.1029/97JB01779	journal	September 1997
Microbial reduction of uranium Lovley, Derek R.; Phillips, Elizabeth J. P.; Gorby, Yuri A. Nature, Vol. 350, Issue 6317 https://doi.org/10.1038/350413a0	journal	April 1991
Fenton-Like Soil Remediation Catalyzed by Naturally Occurring Iron Minerals Watts, Richard J.; Udell, Matthew D.; Kong, Sungho Environmental Engineering Science, Vol. 16, Issue 1 https://doi.org/10.1089/ees.1999.16.93	journal	January 1999
Relativistic calculations of spin-dependent x-ray-absorption spectra Ankudinov, A. L.; Rehr, J. J. Physical Review B, Vol. 56, Issue 4 https://doi.org/10.1103/PhysRevB.56.R1712	journal	July 1997
The importance of accurate crystal structure determination of uranium minerals. II. Soddyite (UO2)2(SiO4).2H2O Demartin, F.; Gramaccioli, C. M.; Pilati, T. Acta Crystallographica Section C Crystal Structure Communications, Vol. 48, Issue 1 https://doi.org/10.1107/S0108270191004481	journal	January 1992
Structure of phuralumite Piret, P.; Piret-Meunier, J.; Declercq, J. P. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 35, Issue 8 https://doi.org/10.1107/S0567740879007950	journal	August 1979
The structure of magnetite Fleet, M. E. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 37, Issue 4 https://doi.org/10.1107/S0567740881004597	journal	April 1981
IFEFFIT : interactive XAFS analysis and FEFF fitting Newville, Matthew Journal of Synchrotron Radiation, Vol. 8, Issue 2 https://doi.org/10.1107/S0909049500016964	journal	March 2001
Micro-beam X-ray absorption and fluorescence spectroscopies at GSECARS: APS beamline 13ID Newville, M.; Sutton, S. R.; Rivers, M. L. Journal of Synchrotron Radiation, Vol. 6, Issue 3 https://doi.org/10.1107/S0909049598016185	journal	May 1999
Influence of chemical composition on the crystalline morphologies of magnetite Clark, T. M.; Evans, B. J. IEEE Transactions on Magnetics, Vol. 33, Issue 5 https://doi.org/10.1109/20.619728	journal	January 1997
Uranyl(VI) carbonate complex formation: Validation of the Ca2UO2(CO3)3(aq.) species Bernhard, G.; Geipel, Gerhard; Reich, T. Radiochimica Acta, Vol. 89, Issue 8 https://doi.org/10.1524/ract.2001.89.8.511	journal	January 2001
Adsorption of arsenic to magnetite nanoparticles: Effect of particle concentration, pH, ionic strength, and temperature Shipley, Heather J.; Yean, Sujin; Kan, Amy T. Environmental Toxicology and Chemistry, Vol. 28, Issue 3, p. 509-515 https://doi.org/10.1897/08-155.1	journal	December 2009
Quantifying Constraints Imposed by Calcium and Iron on Bacterial Reduction of Uranium(VI) Stewart, Brandy D.; Neiss, Jim; Fendorf, Scott Journal of Environment Quality, Vol. 36, Issue 2 https://doi.org/10.2134/jeq2006.0058	journal	January 2007
Continuous Cauchy wavelet transform analyses of EXAFS spectra: A qualitative approach Muñoz, Manuel; Argoul, Pierre; Farges, François American Mineralogist, Vol. 88, Issue 4 https://doi.org/10.2138/am-2003-0423	journal	April 2003
Analysis of uranyl-bearing phases by EXAFS spectroscopy: Interferences, multiple scattering, accuracy of structural parameters, and spectral differences Catalano, Jeffrey G.; Brown, Gordon E. American Mineralogist, Vol. 89, Issue 7 https://doi.org/10.2138/am-2004-0711	journal	July 2004

Cited By (7)

Biogeochemical aspects of uranium mineralization, mining, milling, and remediation Campbell, Kate M.; Gallegos, Tanya J.; Landa, Edward R. Applied Geochemistry, Vol. 57 https://doi.org/10.1016/j.apgeochem.2014.07.022	journal	June 2015
Effects of pH, carbonate, calcium ion and humic acid concentrations, temperature, and uranium concentration on the adsorption of uranium on the CTAB-modified montmorillonite Hui, Junjie; Wang, Youqun; Liu, Yuhui Journal of Radioanalytical and Nuclear Chemistry, Vol. 319, Issue 3 https://doi.org/10.1007/s10967-019-06415-x	journal	January 2019
MOF catalysis of Fe ^II -to-Fe ^III reaction for an ultrafast and one-step generation of the Fe ₂ O ₃ @MOF composite and uranium( vi ) reduction by iron( ii ) under ambient conditions Xiong, Yang Yang; Li, Jian Qiang; Yan, Chang Sheng Chemical Communications, Vol. 52, Issue 61 https://doi.org/10.1039/c6cc04597a	journal	January 2016
Reduction of Hg(II) to Hg(0) by Biogenic Magnetite from two Magnetotactic Bacteria Liu, Songnian; Wiatrowski, Heather A. Geomicrobiology Journal, Vol. 35, Issue 3 https://doi.org/10.1080/01490451.2017.1362076	journal	December 2017
Reduction of Hg(II) to Hg(0) by Biogenic Magnetite from two Magnetotactic Bacteria Liu, Songnian; Wiatrowski, Heather A. Taylor & Francis https://doi.org/10.6084/m9.figshare.5533192	text	January 2017
Reduction of Hg(II) to Hg(0) by biogenic magnetite from two magnetotactic bacteria Liu, Songnian; Wiatrowski, Heather A. Taylor & Francis https://doi.org/10.6084/m9.figshare.5533192.v1	text	January 2017
Reduction of Hg(II) to Hg(0) by Biogenic Magnetite from two Magnetotactic Bacteria Liu, Songnian; Wiatrowski, Heather A. Taylor & Francis https://doi.org/10.6084/m9.figshare.5533192.v2	text	January 2017

Similar Records

Identification of Simultaneous U(VI) Sorption Complexes and U(IV) Nanoprecipitates on the Magnetite (111) Surface

Journal Article · Thu May 10 00:00:00 EDT 2012 · Environmental Science and Technology · OSTI ID:1037911

Identification of simultaneous U(VI) sorption complexes and U(IV) nanoprecipitates on the magnetite (111) surface

Journal Article · Tue Apr 03 00:00:00 EDT 2012 · Environmental Science & Technology, 46(7):3811-3820 · OSTI ID:1040672

U(VI) Sorption and Reduction Kinetics on the Magnetite (111) Surface

Journal Article · Tue Apr 03 00:00:00 EDT 2012 · Environmental Science and Technology · OSTI ID:1040673

Related Subjects

58 GEOSCIENCES
Synchrotron radiation

Identification of Simultaneous U(VI) Sorption Complexes and U(IV) Nanoprecipitates on the Magnetite (111) Surface

Citation Formats

References (59)

Cited By (7)

Similar Records

Related Subjects