Adsorption of Neodymium, Dysprosium, and Ytterbium to Goethite under Varying Aqueous Chemistry Conditions

He, Xicheng; Sharma, Neha; Stagg, Olwen; Flynn, Elaine D.; Catalano, Jeffrey G.; Giammar, Daniel E.

doi:10.1021/acsearthspacechem.4c00032

Title: Adsorption of Neodymium, Dysprosium, and Ytterbium to Goethite under Varying Aqueous Chemistry Conditions

Journal Article · 21 May 2024 · ACS Earth and Space Chemistry

DOI: https://doi.org/10.1021/acsearthspacechem.4c00032 · OSTI ID:2352722

He, Xicheng ^[1]; Sharma, Neha ^[2]; Stagg, Olwen ^[2];

^[2];

^[2]

Washington University in St. Louis, MO (United States); Washington University in St. Louis
Washington University in St. Louis, MO (United States)

The adsorption of rare earth elements (REEs) to iron oxides can regulate the mobility of REEs in the environment and is heavily influenced by water chemistry. This study utilized batch experiments to examine the adsorption of Nd, Dy, and Yb to goethite under varying pH, electrolyte (type and concentration), and concentrations of dissolved inorganic carbon and citrate. REE adsorption was strongly influenced by pH, with an increase from essentially no adsorption at pH 3.0 to nearly complete adsorption at pH 6.5 and higher. Citrate enhanced the adsorption of REEs at low pH (<5.0), likely by forming goethite-REE-citrate ternary surface complexes. However, citrate inhibited the adsorption of REEs at higher pH (>5.0) by forming aqueous REE-citrate complexes. Ionic strength had a small influence on REE adsorption, and the presence of dissolved inorganic carbon had no discernible effect. Equilibrium adsorption was interpreted with a triple-layer surface complexation model (SCM). The selection of surface complexation reactions was guided by extended X-ray absorption fine structure spectra. An SCM with a single bidentate inner-sphere surface complexation reaction for Nd and two inner-sphere surface complexation reactions (one monodentate and one bidentate reaction) for Dy and Yb effectively simulated adsorption across a broad range of conditions in the absence of citrate. Accounting for the effects of citrate on REE adsorption required the addition of up to two ternary REE-citrate-goethite surface complexes. The SCM can enable predictions of REE transport in subsurface environments that have goethite as an important adsorbent mineral. Furthermore, this predictive capability could contribute to identifying potential REE sources and facilitating efficient extraction of REEs.

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Research Organization:: Washington University in St. Louis, MO (United States)

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

Grant/Contract Number:: AC02-76SF00515; SC0022213

OSTI ID:: 2352722

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 6 Vol. 8; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

Surface Complexation Model Parameters for Goethite (α-FeOOH) Lumsdon, David O.; Evans, Leslie J. Journal of Colloid and Interface Science, Vol. 164, Issue 1 https://doi.org/10.1006/jcis.1994.1150	journal	April 1994
Geochemical and mineralogical characteristics of ion-adsorption type REE mineralization in Phuket, Thailand Sanematsu, Kenzo; Kon, Yoshiaki; Imai, Akira Mineralium Deposita, Vol. 48, Issue 4 https://doi.org/10.1007/s00126-011-0380-5	journal	August 2011
Toward the Circular Economy of Rare Earth Elements: A Review of Abundance, Extraction, Applications, and Environmental Impacts Dang, Duc Huy; Thompson, Karen A.; Ma, Lan Archives of Environmental Contamination and Toxicology, Vol. 81, Issue 4 https://doi.org/10.1007/s00244-021-00867-7	journal	June 2021
Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: evidence from Y/Ho, Zr/Hf, and lanthanide tetrad effect Bau, Michael Contributions to Mineralogy and Petrology, Vol. 123, Issue 3 https://doi.org/10.1007/s004100050159	journal	April 1996
Evaluation of ionic strength and salinity of groundwaters: effect of the ionic composition Polemio, Mario; Bufo, Sabino; Paoletti, Sergio Geochimica et Cosmochimica Acta, Vol. 44, Issue 6 https://doi.org/10.1016/0016-7037(80)90262-8	journal	June 1980
Rare earth elements in hydrothermal systems: Estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth elements at high pressures and temperatures Haas, Johnson R.; Shock, Everett L.; Sassani, David C. Geochimica et Cosmochimica Acta, Vol. 59, Issue 21 https://doi.org/10.1016/0016-7037(95)00314-P	journal	November 1995
Surface ionization and complexation at the oxide/water interface II. Surface properties of amorphous iron oxyhydroxide and adsorption of metal ions Davis, James A.; Leckie, James O. Journal of Colloid and Interface Science, Vol. 67, Issue 1 https://doi.org/10.1016/0021-9797(78)90217-5	journal	October 1978
Surface ionization and complexation at the oxide/water interface. 3. Adsorption of anions Davis, James A.; Leckie, James O. Journal of Colloid and Interface Science, Vol. 74, Issue 1 https://doi.org/10.1016/0021-9797(80)90168-X	journal	March 1980
Composition of the Continental Crust Rudnick, R. L.; Gao, S. Treatise on Geochemistry https://doi.org/10.1016/B0-08-043751-6/03016-4	book	January 2003
REE(III) adsorption onto Mn dioxide (δ-MnO2) and Fe oxyhydroxide: Ce(III) oxidation by δ-MnO2 Ohta, Atsuyuki; Kawabe, Iwao Geochimica et Cosmochimica Acta, Vol. 65, Issue 5 https://doi.org/10.1016/S0016-7037(00)00578-0	journal	March 2001
Carbonate complexation of yttrium and the rare earth elements in natural waters Luo, Yu-Ran; Byrne, Robert H. Geochimica et Cosmochimica Acta, Vol. 68, Issue 4 https://doi.org/10.1016/S0016-7037(03)00495-2	journal	February 2004
Scavenging of dissolved yttrium and rare earths by precipitating iron oxyhydroxide: experimental evidence for Ce oxidation, Y-Ho fractionation, and lanthanide tetrad effect Bau, Michael Geochimica et Cosmochimica Acta, Vol. 63, Issue 1 https://doi.org/10.1016/S0016-7037(99)00014-9	journal	January 1999
Modeling the adsorption of citric acid onto Muloorina illite and related clay minerals Lackovic, Kurt; Johnson, Bruce B.; Angove, Michael J. Journal of Colloid and Interface Science, Vol. 267, Issue 1 https://doi.org/10.1016/S0021-9797(03)00693-3	journal	November 2003
Surface ionization and complexation at the oxide/water interface Davis, James A.; James, Robert O.; Leckie, James O. Journal of Colloid and Interface Science, Vol. 63, Issue 3 https://doi.org/10.1016/S0021-9797(78)80009-5	journal	March 1978
Effect of organic acids on adsorption and desorption of rare earth elements Shan, Xiao-quan; Lian, Jun; Wen, Bei Chemosphere, Vol. 47, Issue 7 https://doi.org/10.1016/S0045-6535(02)00032-2	journal	May 2002
Surface complexation modeling of Yb(III) sorption and desorption on hematite and alumina Marmier, N.; Dumonceau, J.; Fromage, F. Journal of Contaminant Hydrology, Vol. 26, Issue 1-4 https://doi.org/10.1016/S0169-7722(96)00065-4	journal	April 1997
Recent development in bonded NdFeB magnets Ma, B. M.; Herchenroeder, J. W.; Smith, B. Journal of Magnetism and Magnetic Materials, Vol. 239, Issue 1-3 https://doi.org/10.1016/S0304-8853(01)00609-6	journal	February 2002
Rare earth elements sorption to iron oxyhydroxide: Model development and application to groundwater Liu, Haiyan; Pourret, Olivier; Guo, Huaming Applied Geochemistry, Vol. 87 https://doi.org/10.1016/j.apgeochem.2017.10.020	journal	December 2017
Recent advances in dysprosium-based single molecule magnets: Structural overview and synthetic strategies Zhang, Peng; Guo, Yun-Nan; Tang, Jinkui Coordination Chemistry Reviews, Vol. 257, Issue 11-12 https://doi.org/10.1016/j.ccr.2013.01.012	journal	June 2013
Kinetics of Ni reaction with organic matter-ferrihydrite composites: Experiments and modeling Wang, Pei; Lu, Yang; Hu, Shiwen Chemical Engineering Journal, Vol. 379 https://doi.org/10.1016/j.cej.2019.122306	journal	January 2020
Prediction of the speciation of alkaline earths adsorbed on mineral surfaces in salt solutions Sverjensky, Dimitri A. Geochimica et Cosmochimica Acta, Vol. 70, Issue 10 https://doi.org/10.1016/j.gca.2006.01.006	journal	May 2006
Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: Influence of solution complexation with carbonate Quinn, Kelly A.; Byrne, Robert H.; Schijf, Johan Geochimica et Cosmochimica Acta, Vol. 70, Issue 16 https://doi.org/10.1016/j.gca.2006.06.014	journal	August 2006
Speciation of adsorbed yttrium and rare earth elements on oxide surfaces Piasecki, Wojciech; Sverjensky, Dimitri A. Geochimica et Cosmochimica Acta, Vol. 72, Issue 16 https://doi.org/10.1016/j.gca.2008.05.049	journal	August 2008
Ion-adsorption REEs in regolith of the Liberty Hill pluton, South Carolina, USA: An effect of hydrothermal alteration Bern, Carleton R.; Yesavage, Tiffany; Foley, Nora K. Journal of Geochemical Exploration, Vol. 172 https://doi.org/10.1016/j.gexplo.2016.09.009	journal	January 2017
A review of platinum group element (PGE) geochemistry and a study of the changes of PGE contents in the topsoil of Berlin, Germany, between 1992 and 2013 Birke, Manfred; Rauch, Uwe; Stummeyer, Jens Journal of Geochemical Exploration, Vol. 187 https://doi.org/10.1016/j.gexplo.2017.09.005	journal	April 2018
Rare earth elements: A review of applications, occurrence, exploration, analysis, recycling, and environmental impact Balaram, V. Geoscience Frontiers, Vol. 10, Issue 4 https://doi.org/10.1016/j.gsf.2018.12.005	journal	July 2019
Variability in goethite surface site density: evidence from proton and carbonate sorption Villalobos, Mario; Trotz, Maya A.; Leckie, James O. Journal of Colloid and Interface Science, Vol. 268, Issue 2 https://doi.org/10.1016/j.jcis.2003.07.044	journal	December 2003
Impact of humate complexation on the adsorption of REE onto Fe oxyhydroxide Davranche, Mélanie; Pourret, Olivier; Gruau, Gérard Journal of Colloid and Interface Science, Vol. 277, Issue 2 https://doi.org/10.1016/j.jcis.2004.04.007	journal	September 2004
Effects of pH and ionic strength on the adsorption of phosphate and arsenate at the goethite–water interface Antelo, Juan; Avena, Marcelo; Fiol, Sarah Journal of Colloid and Interface Science, Vol. 285, Issue 2 https://doi.org/10.1016/j.jcis.2004.12.032	journal	May 2005
Goethite surface reactivity: II. A microscopic site-density model that describes its surface area-normalized variability Villalobos, Mario; Cheney, Marcos A.; Alcaraz-Cienfuegos, Jorge Journal of Colloid and Interface Science, Vol. 336, Issue 2 https://doi.org/10.1016/j.jcis.2009.04.052	journal	August 2009
Effect of fulvic acid on neodymium uptake by goethite Armstrong, Christopher R.; Wood, Scott A. Journal of Colloid and Interface Science, Vol. 387, Issue 1 https://doi.org/10.1016/j.jcis.2012.07.060	journal	December 2012
Distribution of rare earth elements and oxyhydroxide phases within a weathered felsic igneous profile in Hong Kong Duzgoren-Aydin, N. S.; Aydin, A. Journal of Asian Earth Sciences, Vol. 34, Issue 1 https://doi.org/10.1016/j.jseaes.2008.03.010	journal	January 2009
Nature of parent rocks, mineralization styles and ore genesis of regolith-hosted REE deposits in South China: An integrated genetic model Li, Yan Hei Martin; Zhao, Wen Winston; Zhou, Mei-Fu Journal of Asian Earth Sciences, Vol. 148 https://doi.org/10.1016/j.jseaes.2017.08.004	journal	October 2017
Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: Influence of pH and ionic strength Quinn, Kelly A.; Byrne, Robert H.; Schijf, Johan Marine Chemistry, Vol. 99, Issue 1-4 https://doi.org/10.1016/j.marchem.2005.05.011	journal	March 2006
Geochemistry of mineralization with exchangeable REY in the weathering crusts of granitic rocks in South China Bao, Zhiwei; Zhao, Zhenhua Ore Geology Reviews, Vol. 33, Issue 3-4 https://doi.org/10.1016/j.oregeorev.2007.03.005	journal	June 2008
REE concentration processes in ion adsorption deposits: Evidence from the Ambohimirahavavy alkaline complex in Madagascar Estrade, Guillaume; Marquis, Eva; Smith, Martin Ore Geology Reviews, Vol. 112 https://doi.org/10.1016/j.oregeorev.2019.103027	journal	September 2019
Enrichment of ion-exchangeable rare earth elements by felsic volcanic rock weathering in South China: Genetic mechanism and formation preference Fu, Wei; Luo, Peng; Hu, Zuoying Ore Geology Reviews, Vol. 114 https://doi.org/10.1016/j.oregeorev.2019.103120	journal	November 2019
On thermal effects in solid-state lasers: The case of ytterbium-doped materials Chénais, Sébastien; Druon, Frédéric; Forget, Sébastien Progress in Quantum Electronics, Vol. 30, Issue 4 https://doi.org/10.1016/j.pquantelec.2006.12.001	journal	January 2006
Origins, roles and fate of organic acids in soils: A review Adeleke, R.; Nwangburuka, C.; Oboirien, B. South African Journal of Botany, Vol. 108 https://doi.org/10.1016/j.sajb.2016.09.002	journal	January 2017
Ferrihydrite Transformation Impacted by Adsorption and Structural Incorporation of Rare Earth Elements Yang, Meijun; Liang, Xiaoliang; Li, Ying ACS Earth and Space Chemistry, Vol. 5, Issue 10 https://doi.org/10.1021/acsearthspacechem.1c00159	journal	September 2021
Uptake of rare earth elements from solution by metal oxides Koeppenkastrop, Dirk; De Carlo, Eric H. Environmental Science & Technology, Vol. 27, Issue 9 https://doi.org/10.1021/es00046a006	journal	September 1993
Ion Adsorption at the Rutile−Water Interface: Linking Molecular and Macroscopic Properties Zhang, Z.; Fenter, P.; Cheng, L. Langmuir, Vol. 20, Issue 12 https://doi.org/10.1021/la0353834	journal	June 2004
REY-Th-U Dynamics in the Critical Zone: Combined Influence of Reactive Bedrock Accessory Minerals, Authigenic Phases, and Hydrological Sorting (Mule Hole Watershed, South India) Braun, Jean-Jacques; Riotte, Jean; Battacharya, Shrema Geochemistry, Geophysics, Geosystems, Vol. 19, Issue 5 https://doi.org/10.1029/2018GC007453	journal	May 2018
Microscopic analyses of weathered granite in ion-adsorption rare earth deposit of Jianxi Province, China Mukai, Hiroki; Kon, Yoshiaki; Sanematsu, Kenzo Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-76981-8	journal	November 2020
Site-binding model of the electrical double layer at the oxide/water interface Yates, David E.; Levine, Samuel; Healy, Thomas W. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 70, Issue 0 https://doi.org/10.1039/f19747001807	journal	January 1974
Effects of citric acid and the siderophore desferrioxamine B (DFO-B) on the mobility of germanium and rare earth elements in soil and uptake in Phalaris arundinacea Wiche, Oliver; Tischler, Dirk; Fauser, Carla International Journal of Phytoremediation, Vol. 19, Issue 8 https://doi.org/10.1080/15226514.2017.1284752	journal	May 2017
Larch: An Analysis Package for XAFS and Related Spectroscopies Newville, Matthew Journal of Physics: Conference Series, Vol. 430 https://doi.org/10.1088/1742-6596/430/1/012007	journal	April 2013
Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure Ankudinov, A. L.; Ravel, B.; Rehr, J. J. Physical Review B, Vol. 58, Issue 12 https://doi.org/10.1103/PhysRevB.58.7565	journal	September 1998
Synchrotron X-ray study of the electron density in RFeO₃ (R = Nd, Dy) Streltsov, Victor A.; Ishizawa, Nobuo Acta Crystallographica Section B Structural Science, Vol. 55, Issue 1 https://doi.org/10.1107/S0108768198005400	journal	February 1999
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
The crystal chemistry of the rare earth orthoferrites Marezio, M.; Remeika, J. P.; Dernier, P. D. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 26, Issue 12 https://doi.org/10.1107/S0567740870005319	journal	December 1970
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
Ore Deposits of the Platinum-Group Elements Mungall, J. E.; Naldrett, A. J. Elements, Vol. 4, Issue 4 https://doi.org/10.2113/GSELEMENTS.4.4.253	journal	August 2008
The role of clay minerals in formation of the regolith-hosted heavy rare earth element deposits Li, Martin Yan Hei; Zhou, Mei-Fu American Mineralogist, Vol. 105, Issue 1 https://doi.org/10.2138/am-2020-7061	journal	January 2020
Influence of multi-electron excitation on EXAFS spectroscopy of trivalent rare-earth ions and elucidation of change in hydration number through the series Ohta, A.; Kagi, H.; Tsuno, H. American Mineralogist, Vol. 93, Issue 8-9 https://doi.org/10.2138/am.2008.2628	journal	August 2008
Coordination study of rare earth elements on Fe oxyhydroxide and Mn dioxides: Part I. Influence of a multi-electron excitation on EXAFS analyses of La, Pr, Nd, and Sm Ohta, A.; Kagi, H.; Nomura, M. American Mineralogist, Vol. 94, Issue 4 https://doi.org/10.2138/am.2009.2986	journal	April 2009
Coordination study of rare earth elements on Fe oxyhydroxide and Mn dioxides: Part II. Correspondence of structural change to irregular variations of partitioning coefficients and tetrad effect variations appearing in interatomic distances Ohta, A.; Kagi, H.; Nomura, M. American Mineralogist, Vol. 94, Issue 4 https://doi.org/10.2138/am.2009.2987	journal	April 2009
Adsorption isotherms of lanthanum to soil constituents and effects of pH, EDTA and fulvic acid on adsorption of lanthanum onto goethite and humic acid Zhenghua, Wu; Jun, Luo; Hongyan, Guo Chemical Speciation & Bioavailability, Vol. 13, Issue 3 https://doi.org/10.3184/095422901782775444	journal	January 2001
Rare Earth and Critical Elements in Ore Deposits Verplanck, Philip L.; Hitzman, Murray W. https://doi.org/10.5382/REV.18	book	January 2016
The Genesis of Regolith-Hosted Heavy Rare Earth Element Deposits: Insights from the World-Class Zudong Deposit in Jiangxi Province, South China Li, Martin Yan Hei; Zhou, Mei-Fu; Williams-Jones, Anthony E. Economic Geology, Vol. 114, Issue 3 https://doi.org/10.5382/econgeo.4642	journal	May 2019
Controls on the Dynamics of Rare Earth Elements During Subtropical Hillslope Processes and Formation of Regolith-Hosted Deposits Li, Martin Yan Hei; Zhou, Mei-Fu; Williams-Jones, Anthony E. Economic Geology, Vol. 115, Issue 5 https://doi.org/10.5382/econgeo.4727	journal	August 2020

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Title: Adsorption of Neodymium, Dysprosium, and Ytterbium to Goethite under Varying Aqueous Chemistry Conditions

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