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Niobium speciation in minerals revealed by L2,3-edges XANES spectroscopy

  • Quentin Bollaert , Mathieu Chassé , Hebatalla Elnaggar , Amélie Juhin , Alexandra Courtin , Laurence Galoisy ORCID logo , Cécile Quantin , Marius Retegan , Delphine Vantelon and Georges Calas ORCID logo
Published/Copyright: March 2, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 3

Abstract

The systematic mineralogy of niobium (Nb) is complex, with more than one hundred species dominated by multicomponent oxides of similar chemistry. The determination of Nb speciation in solids (i.e., the distribution between the phases and the crystal-chemical environment of Nb) is thus a challenge in geological contexts. Here, we present the first Nb L2,3-edges X-ray absorption near-edge structure (XANES) measurements on various Nb minerals and synthetic oxides with geological relevance. The interpretation of Nb L2,3-edges XANES spectra in the light of crystal-field theory shows the sensitivity of spectra to local site symmetry and electronic environment around Nb atoms. Crystal-field multiplet simulations give estimates of the 10Dq crystal-field parameter values for Nb5+, which range from 2.8 to 3.9 eV depending on Nb coordination and Nb‒O distances. Rather than a 10Dq vs. R–5 relationship (where R represents the average Nb‒O bond distance) expected in a point-charge model, we find a R–3 dependence with the crystal-field splitting for reference materials with octahedrally coordinated Nb. Complementary ligand-field multiplet simulations provide evidence of charge transfer between Nb and O. The contribution of the ionic and covalent characters to the Nb‒O bonds is equivalent, unlike more ionic 3d metal‒O bonds. This systematic characterization of the L2,3-edges XANES spectral properties of Nb provides information on the mechanisms by which Nb5+ substitutes for Fe3+, Ti4+, or Ce4+ in oxides common in geological contexts. Whereas the substitution of Nb5+ for Ce4+ does not modify the local structure of the cation site in cerianite, the substitution of Nb5+ for Ti4+ in rutile and anatase results in an increase of the cation-ligand distance and a decrease in the symmetry of the cation site. Conversely, the substitution of Nb5+ for Fe3+ in hematite and goethite results in a smaller cation site distortion. Our study demonstrates the usefulness of L2,3-edges XANES spectroscopy to determine Nb speciation in minerals to understand the processes of enrichment of this critical metal.

Keywords: Niobium; XANES; multiplet; 10Dq; local structure; speciation

Acknowledgments and Funding

We are grateful to Jean-Claude Boulliard and Éloïse Gaillou for the supply of rare mineral species from the Sorbonne Université (SU) and École Nationale Supérieure des Mines de Paris mineralogy (ENSMP) collections. We thank Alain Demourgues and Guillaume Gouget for providing the niobate samples and commenting on the manuscript, Sophie Cassaignon and Tsou Hsi Camille Chan Chang for the synthesis of Nb-substituted anatase, and Benoît Baptiste, Ludovic Delbes, Michel Fialin, and Nicolas Rividi for experimental support during XRD and EPMA analyses. We acknowledge SOLEIL for the provision of synchrotron radiation facilities and thank the staff of the LUCIA beamline for their help in the measurement of Nb L2,3-edges (Proposal No. 20191239).

References cited

Andersson, S. (1967) The crystal structure of N-Nb2O5, prepared in the presence of small amounts of LiF. Zeitschrift für Anorganische und Allgemeine Chemie, 351, 106–112, https://doi.org/10.1002/zaac.19673510114Search in Google Scholar

Andersson, S.S., Wagner, T., Jonsson, E., and Michallik, R.M. (2018) Mineralogy, paragenesis, and mineral chemistry of REEs in the Olserum-Djupedal REE-phosphate mineralization, SE Sweden. American Mineralogist, 103, 125–142, https://doi.org/10.2138/am-2018-6202Search in Google Scholar

Atanacio, A.J., Bak, T., and Nowotny, J. (2014) Niobium segregation in niobium-doped titanium dioxide (rutile). The Journal of Physical Chemistry C, 118, 11174–11185, https://doi.org/10.1021/jp4110536Search in Google Scholar

Bare, S.R., Mitchell, J.G.E., Maj, J.J., Vrieland, G.E., and Glands, J.L. (1993) Local site symmetry of dispersed molybdenum oxide catalysts: XANES at the Mo L2,3-edges. Journal of Physical Chemistry, 97, 6048–6053, https://doi.org/10.1021/j100124a043Search in Google Scholar

Baur, W.H. (1974) The geometry of polyhedral distortions. Predictive relationships for the phosphate group. Acta Crystallographica, B30, 1195–1215.Search in Google Scholar

Bhattacharyya, A., Schmidt, M.P., Stavitski, E., Azimzadeh, B., and Martínez, C.E. (2019) Ligands representing important functional groups of natural organic matter facilitate Fe redox transformations and resulting binding environments. Geochimica et Cosmochimica Acta, 251, 157–175, https://doi.org/10.1016/j.gca.2019.02.027Search in Google Scholar

Blake, R.L., Hessevick, R.E., and Finger, L.W. (1966) Refinement of the hematite structure. American Mineralogist, 51, 123–129.Search in Google Scholar

Bonazzi, P. (2006) Single-crystal diffraction and transmission electron microscopy studies of “silicified” pyrochlore from Narssârssuk, Julianehaab district, Greenland. American Mineralogist, 91, 794–801.Search in Google Scholar

Borst, A.M., Smith, M.P., Finch, A.A., Estrade, G., Villanova-de-Benavent, C., Nason, P., Marquis, E., Horsburgh, N.J., Goodenough, K.M., Xu, C., and others. (2020) Adsorption of rare earth elements in regolith-hosted clay deposits. Nature Communications, 11, 4386, https://doi.org/10.1038/s41467-020-17801-5 PubMedSearch in Google Scholar

Bourdelle, F., Benzerara, K., Beyssac, O., Cosmidis, J., Neuville, D.R., Brown, G.E. Jr., and Paineau, E. (2013) Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges. Contributions to Mineralogy and Petrology, 166, 423–434, https://doi.org/10.1007/s00410-013-0883-4Search in Google Scholar

Brotton, S.J., Shapiro, R., van der Laan, G., Guo, J., Glans, P.-A., and Ajello, J.M. (2007) Valence state fossils in Proterozoic stromatolites by L-edge X-ray absorption spectroscopy. Journal of Geophysical Research. Biogeosciences, 112 (G3).Search in Google Scholar

Burns, R.G. (1993) Mineralogical Applications of Crystal Field Theory. 2nd edition. Cambridge University Press.Search in Google Scholar

Butler, P.H. (1981) Point Group Symmetry Applications, 576 p. Springer.Search in Google Scholar

Cartier, C., Hammouda, T., Boyet, M., Mathon, O., Testemale, D., and Moine, B.N. (2015) Evidence for Nb2+ and Ta3+ in silicate melts under highly reducing conditions: A XANES study. American Mineralogist, 100, 2152–2158, https://doi.org/10.2138/am-2015-5330Search in Google Scholar

Černý, P. and Ercit, T.S. (1989) Mineralogy of niobium and tantalum: Crystal chemical relationships, paragenetic aspects and their economic implications. In P. Möller, P. Černý, and F. Saupé, Eds., Lanthanides, tantalum and niobium, 27–79. Springer-Verlag.Search in Google Scholar

Chakhmouradian, A.R., and Mitchell R.H. (1998) A structural study of the perovskite series CaTi1–2xFexNbxO3. Journal of Solid State Chemistry, 138, 272–277.Search in Google Scholar

Chakrabarty, A., Mitchell, R.H., Ren, M., Sen, A.K., and Pruseth, K.L. (2013) Rinkite, cerianite-(Ce), and hingganite-(Ce) in syenite gneisses from the Sushina Hill Complex, India: Occurrence, compositional data and petrogenetic significance. Mineralogical Magazine, 77, 3137–3153, https://doi.org/10.1180/minmag.2013.077.8.08Search in Google Scholar

Chassé, M., Griffin, W.L., O’Reilly, S.Y., and Calas, G. (2017) Scandium speciation in a world-class lateritic deposit. Geochemical Perspectives Letters, 3, 105–114, https://doi.org/10.7185/geochemlet.1711Search in Google Scholar

Chassé, M., Griffin, W.L., O’Reilly, S.Y., and Calas, G. (2019) Australian laterites reveal mechanisms governing scandium dynamics in the critical zone. Geochimica et Cosmochimica Acta, 260, 292–310, https://doi.org/10.1016/j.gca.2019.06.036Search in Google Scholar

Chehreh Chelgani, S., Hart, B., Marois, J., and Ourriban, M. (2012) Study of pyrochlore matrix composition effects on froth flotation by SEM–EDX. Minerals Engineering, 30, 62–66, https://doi.org/10.1016/j.mineng.2012.02.009Search in Google Scholar

De Groot, F. (2005) Multiplet effects in X-ray spectroscopy. Coordination Chemistry Reviews, 249, 31–63, https://doi.org/10.1016/j.ccr.2004.03.018Search in Google Scholar

De Groot, F.M.F., Fuggle, J.C., Thole, B.T., and Sawatzky, G.A. (1990) L2,3 X-ray-absorption edges of d0 compounds: K+, Ca2+, Sc3+, and Ti4+ in Oh (octahedral) symmetry. Physical Review B, 41, 928–937.Search in Google Scholar

De Groot, F.M.F., Figueiredo, M.O., Basto, M.J., Abbate, M., Petersen, H., and Fuggle, J.C. (1992) 2p X-ray absorption of titanium in minerals. Physics and Chemistry of Minerals, 19, 140–147, https://doi.org/10.1007/BF00202101Search in Google Scholar

De Groot, F.M.F., Hu, Z.W., Lopez, M.F., Kaindl, G., Guillot, F., and Tronc, M. (1994) Differences between L3 and L2 X-ray absorption spectra of transition metal compounds. The Journal of Chemical Physics, 101, 6570–6576, https://doi.org/10.1063/1.468351Search in Google Scholar

Dietzel, C.A.F., Kristandt, T., Dahlgren, S., Giebel, R.J., Marks, M.A.W., Wenzel, T., and Markl, G. (2019) Hydrothermal processes in the Fen alkaline-carbonatite complex, southern Norway. Ore Geology Reviews, 111, 102969, https://doi.org/10.1016/j.oregeorev.2019.102969Search in Google Scholar

Dufour, F., Cassaignon, S., Durupthy, O., Colbeau-Justin, C., and Chanéac, C. (2012) Do TiO2 nanoparticles really taste better when cooked in a microwave oven? European Journal of Inorganic Chemistry, 2012, 2707–2715, https://doi.org/10.1002/ejic.201101269Search in Google Scholar

European Commission (2020) Directorate-General for Internal Market, Industry, Entrepreneurship and SMEs, Blengini, G., El Latunussa, C., Eynard, U., et al., Study on the EU’s list of critical raw materials: final report. Publications Office, https://data.europa.eu/doi/10.2873/11619Search in Google Scholar

Ewing, R.C. (1975) The crystal chemistry of complex niobium and tantalum oxides: IV. The metamict state. (Discussion) American Mineralogist, 60, 728–733.Search in Google Scholar

Friis, H. and Casey, W.H. (2018) Niobium is highly mobile as a polyoxometalate ion during natural weathering. Canadian Mineralogist, 56, 905–912, https://doi.org/10.3749/canmin.1800058Search in Google Scholar

Fu, Y., Dong, C.-L., Lee, W.-Y., Chen, J., Guo, P., Zhao, L., and Shen, S. (2016) Nb-doped hematite nanorods for efficient solar water splitting: Electronic structure evolution versus morphology alteration. ChemNanoMat: Chemistry of Nanomaterials for Energy, Biology and More, 2, 704–711, https://doi.org/10.1002/cnma.201600024Search in Google Scholar

Galoisy, L., Pélegrin, E., Arrio, M.-A., Ildefonse, P., Calas, G., Ghaleb, D., Fillet, C., and Pacaud, F. (1999) Evidence for 6-coordinated zirconium in inactive nuclear waste glasses. Journal of the American Ceramic Society, 82, 2219–2224, https://doi.org/10.1111/j.1151-2916.1999.tb02065.xSearch in Google Scholar

Gardecka, A.J., Goh, G.K.L., Sankar, G., and Parkin, I.P. (2015) On the nature of niobium substitution in niobium doped titania thin films by AACVD and its impact on electrical and optical properties. Journal of Materials Chemistry A, 3, 17755–17762, https://doi.org/10.1039/C5TA03772GSearch in Google Scholar

Gibson, C., Aghamirian, M., and Kelebek, S. (2015) Challenges in niobium flotation. In P. Blatter and J. Zinck, Eds., Proceedings of the 47th Annual Canadian Mineral Processors Operators Conference, p. 244–254. Canadian Institute of Mining, Metallurgy and Petroleum, Ottawa, Ontario, Canada.Search in Google Scholar

Giovannini, A.L., Bastos Neto, A.C., Porto, C.G., Pereira, V.P., Takehara, L., Barbanson, L., and Bastos, P.H.S. (2017) Mineralogy and geochemistry of laterites from the Morro dos Seis Lagos Nb (Ti, REE) deposit (Amazonas, Brazil). Ore Geology Reviews, 88, 461–480, https://doi.org/10.1016/j.oregeorev.2017.05.008Search in Google Scholar

Giovannini, A.L., Mitchell, R.H., Bastos Neto, A.C., Moura, C.A.V., Pereira, V.P., and Porto, C.G. (2020) Mineralogy and geochemistry of the Morro dos Seis Lagos siderite carbonatite, Amazonas, Brazil. Lithos, 360–361, 105433, https://doi.org/10.1016/j.lithos.2020.105433Search in Google Scholar

Gouget, G., Duttine, M., Chung, U.-C., Fourcade, S., Mauvy, F., Braida, M.-D., Le Mercier, T., and Demourgues, A. (2019) High ionic conductivity in oxygen-deficient Ti-substituted sodium niobates and the key role of structural features. Chemistry of Materials, 31, 2828–2841, https://doi.org/10.1021/acs.chemmater.8b05292Search in Google Scholar

Guimarães, H.N., and Weiss, R.A. (2001) The complexity of the niobium deposits in the alkaline-ultramafic intrusions Catalao I and II—Brazil. Proceedings of International Symposium on Niobium, p. 37–51. Sao Paulo, Brazil.Search in Google Scholar

Haverkort, M.W. (2016) Quanty for core level spectroscopy—excitons, resonances and band excitations in time and frequency domain. Journal of Physics: Conference Series, 712, 012001.Search in Google Scholar

Haverkort, M.W., Zwierzycki, M., and Andersen, O.K. (2012) Multiplet ligand-field theory using Wannier orbitals. Physical Review B, 85, 165113.Search in Google Scholar

Henderson, G.S., de Groot, F.M.F., and Moulton, B.J.A. (2014) X-ray absorption near-edge structure (XANES) spectroscopy. Reviews in Mineralogy and Geochemistry, 78, 75–138, https://doi.org/10.2138/rmg.2014.78.3Search in Google Scholar

Hiley, C.I., Playford, H.Y., Fisher, J.M., Felix, N.C., Thompsett, D., Kashtiban, R.J., and Walton, R.I. (2018) Pair distribution function analysis of structural disorder by Nb5+ inclusion in ceria: Evidence for enhanced oxygen storage capacity from under-coordinated oxide. Journal of the American Chemical Society, 140, 1588–1591, https://doi.org/10.1021/jacs.7b12421Search in Google Scholar

Hill, I.G., Worden, R.H., and Meighan, I.G. (2000) Geochemical evolution of a palaeolaterite: The Interbasaltic Formation, Northern Ireland. Chemical Geology, 166, 65–84, https://doi.org/10.1016/S0009-2541(99)00179-5Search in Google Scholar

Höche, T., Ikeno, H., Mader, M., Henderson, G.S., Blyth, R.I.R., Sales, B.C., and Tanaka, I. (2013) Vanadium L2,3 XANES experiments and first-principles multielectron calculations: Impact of second-nearest neighboring cations on vanadium-bearing fresnoites. American Mineralogist, 98, 665–670, https://doi.org/10.2138/am.2013.4335Search in Google Scholar

Horn, M., Schwerdtfeger, C.F., and Meagher, E.P. (1972) Refinement of the structure of anatase at several temperatures. Zeitschrift für Kristallographie, 136, 273–281.Search in Google Scholar

Ikeno, H., Mizoguchi, T., and Tanaka, I. (2011) Ab initio charge transfer multiplet calculations on the L2,3 XANES and ELNES of 3d transition metal oxides. Physical Review B: Condensed Matter and Materials Physics, 83, 155107, https://doi.org/10.1103/PhysRevB.83.155107Search in Google Scholar

Ikeno, H., Krause, M., Höche, T., Patzig, C., Hu, Y., Gawronski, A., Tanaka, I., and Rüssel, C. (2013) Variation of Zr-L2,3 XANES in tetravalent zirconium oxides. Journal of Physics Condensed Matter, 25, 165505, https://doi.org/10.1088/0953-8984/25/16/165505Search in Google Scholar

Ismael, M. (2020) A review and recent advances in solar-to-hydrogen energy conversion based on photocatalytic water splitting over doped-TiO2 nanoparticles. Solar Energy, 211, 522–546, https://doi.org/10.1016/j.solener.2020.09.073Search in Google Scholar

Janots, E., Bernier, F., Brunet, F., Muñoz, M., Trcera, N., Berger, A., and Lanson, M. (2015) Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge. Geochimica et Cosmochimica Acta, 153, 134–148, https://doi.org/10.1016/j.gca.2015.01.009Search in Google Scholar

Jehng, J.M., and Wachs, I.E. (1991) Structural chemistry and Raman spectra of niobium oxides. Chemistry of Materials, 3, 100–107.Search in Google Scholar

Jollivet, P., Calas, G., Galoisy, L., Angeli, F., Bergeron, B., Gin, S., Ruffoni, M.P., and Trcera, N. (2013) An enhanced resolution of the structural environment of zirconium in borosilicate glasses. Journal of Non-Crystalline Solids, 381, 40–47, https://doi.org/10.1016/j.jnoncrysol.2013.09.013Search in Google Scholar

Kalfoun, F., Ionov, D., and Merlet, C. (2002) HFSE residence and Nb/Ta ratios in metasomatised, rutile-bearing mantle peridotites. Earth and Planetary Science Letters, 199, 49–65, https://doi.org/10.1016/S0012-821X(02)00555-1Search in Google Scholar

Kolodiazhnyi, T., Sakurai, H., Belik, A.A., and Gornostaeva, O.V. (2016) Unusual lattice evolution and magnetochemistry of Nb doped CeO2. Acta Materialia, 113, 116–123, https://doi.org/10.1016/j.actamat.2016.04.052Search in Google Scholar

König, E., and Kremer, S. (1977) Ligand-Field Energy Diagrams. Springer.Search in Google Scholar

Krause, M.O. and Oliver, J.H. (1979) Natural widths of atomic K and L levels, Kα X-ray lines and several KLL Auger lines. Journal of Physical and Chemical Reference Data, 8, 329–338, https://doi.org/10.1063/1.555595Search in Google Scholar

Kubouchi, Y., Hayakawa, S., Namatame, H., and Hirokawa, T. (2012) Direct observation of fractional change of niobium ionic species in a solution by means of X-ray absorption fine structure spectroscopy. X-Ray Spectrometry, 41, 259–263, https://doi.org/10.1002/xrs.2390Search in Google Scholar

Kunz, M. and Brown, I.D. (1995) Out-of-center distortions around octahedrally coordinated d0 transition metals. Journal of Solid State Chemistry, 115, 395–406, https://doi.org/10.1006/jssc.1995.1150Search in Google Scholar

Kurtz, A.C., Derry, L.A., Chadwick, O.A., and Alfano, M.J. (2000) Refractory element mobility in volcanic soils. Geology, 28, 683–686, https://doi.org/10.1130/0091-7613(2000)28<683:REMIVS>2.0.CO;2Search in Google Scholar

Lebernegg, S., Amthauer, G., and Grodzicki, M. (2008) Single-centre MO theory of transition metal complexes. Journal of Physics. B, Atomic, Molecular, and Optical Physics, 41, 035102, https://doi.org/10.1088/0953-4075/41/3/035102Search in Google Scholar

Lee, M.J., Lee, J.I., Garcia, D., Moutte, J., Williams, C.T., Wall, F., and Kim, Y. (2006) Pyrochlore chemistry from the Sokli phoscorite-carbonatite complex, Finland: Implications for the genesis of phoscorite and carbonatite association. Geochemical Journal, 40, 1–13, https://doi.org/10.2343/geochemj.40.1Search in Google Scholar

Lian, Z., Liu, F., He, H., and Liu, K. (2015) Nb-doped VOx/CeO2 catalyst for NH3- SCR of NOx at low temperatures. RSC Advances, 5, 37675–37681, https://doi.org/10.1039/C5RA02752GSearch in Google Scholar

Linnen, R.L. and Cuney, M. (2005) Granite-related rare-element deposits and experimental constraints on Ta-Nb-W-Sn-Zr-Hf mineralization, 45–68. In R.L. Linnen and I.M. Samson, Eds., Rare-Element Geochemistry and Mineral Deposits, 17, p. 45–68. Geological Association of Canada Short Course NotesSearch in Google Scholar

Lottermoser, B.G. and England, B.M. (1988) Compositional variation in pyrochlores from the Mt Weld carbonatite laterite, Western Australia. Mineralogy and Petrology, 38, 37–51, https://doi.org/10.1007/BF01162480Search in Google Scholar

Lü, X., Mou, X., Wu, J., Zhang, D., Zhang, L., Huang, F., Xu, F., and Huang, S. (2010) Improved-performance dye-sensitized solar cells using Nb-doped TiO2 electrodes: Efficient electron injection and transfer. Advanced Functional Materials, 20, 509–515, https://doi.org/10.1002/adfm.200901292Search in Google Scholar

Ma, J., Guo, X., Xue, H., Pan, K., Liu, C., and Pang, H. (2020) Niobium/tantalum-based materials: Synthesis and applications in electrochemical energy storage. Chemical Engineering Journal, 380, 122428, https://doi.org/10.1016/j.cej.2019.122428Search in Google Scholar

MacLean, W.H. and Barrett, T.J. (1993) Lithogeochemical techniques using immobile elements. Journal of Geochemical Exploration, 48, 109–133, https://doi.org/10.1016/0375-6742(93)90002-4Search in Google Scholar

Meagher, E.P., and Lager, G.A. (1979) Polyhedral thermal expansion in the TiO2 polymorphs: Refinement of the crystal structures of rutile and brookite at high temperature. Canadian Mineralogist, 17, 77–85.Search in Google Scholar

Mellini, M. (1982) Niocalite revised: Twinning and crystal structure. TMPM Tschermaks Mineralogische und Petrographische Mitteilungen, 30, 249–266.Search in Google Scholar

Miedema, P.S., and de Groot, F.M.F. (2013) The iron L edges: Fe 2p X-ray absorption and electron energy loss spectroscopy. Journal of Electron Spectroscopy and Related Phenomena, 187, 32–48.Search in Google Scholar

Mitchell, R.H. (2015) Primary and secondary niobium mineral deposits associated with carbonatites. Ore Geology Reviews, 64, 626–641, https://doi.org/10.1016/j.oregeorev.2014.03.010Search in Google Scholar

Mitchell, R.H., Choi, J.B., Hawthorne, F.C., McCammon, C.A., and Burns, P.C. (1998) Latrappite: A re-investigation. Canadian Mineralogist, 36, 107–116.Search in Google Scholar

Nabi, M.M., Wang, J., Meyer, M., Croteau, M.-N., Ismail, N., and Baalousha, M. (2021) Concentrations and size distribution of TiO2 and Ag engineered particles in five wastewater treatment plants in the United States. The Science of the Total Environment, 753, 142017, https://doi.org/10.1016/j.scitotenv.2020.142017Search in Google Scholar

Neumann, R. and Medeiros, E.B. (2015) Comprehensive mineralogical and technological characterisation of the Araxá (SE Brazil) complex REE (Nb-P) ore, and the fate of its processing. International Journal of Mineral Processing, 144, 1–10, https://doi.org/10.1016/j.minpro.2015.08.009Search in Google Scholar

Newville, M. (2013) Larch: An analysis package for XAFS and related spectroscopies. Journal of Physics: Conference Series, 430, 012007, https://doi.org/10.1088/1742-6596/430/1/012007Search in Google Scholar

Ogasawara, K., Iwata, T., Koyama, Y., Ishii, T., Tanaka, I., and Adachi, H. (2001) Relativistic cluster calculation of ligand-field multiplet effects on cation L2,3 X-ray-absorption edges of SrTiO3, NiO, and CaF2. Physical Review B: Condensed Matter, 64, 115413, https://doi.org/10.1103/PhysRevB.64.115413Search in Google Scholar

Okada, K. and Kotani, A. (1993) Theory of core level X-ray photoemission and photoabsorption in Ti compounds. Journal of Electron Spectroscopy and Related Phenomena, 62, 131–140, https://doi.org/10.1016/0368-2048(93)80010-JSearch in Google Scholar

Olegário, R.C., Ferreira de Souza, E.C., Marcelino Borges, J.F., Marimon da Cunha, J.B., Chaves de Andrade, A.V., Masetto Antunes, S.R., and Antunes, A.C. (2013) Synthesis and characterization of Fe3+ doped cerium–praseodymium oxide pigments. Dyes and Pigments, 97, 113–117, https://doi.org/10.1016/j.dyepig.2012.12.011Search in Google Scholar

Oliveira, L.C.A., Ramalho, T.C., Souza, E.F., Gonçalves, M., Oliveira, D.Q.L., Pereira, M.C., and Fabris, J.D. (2008) Catalytic properties of goethite prepared in the presence of Nb on oxidation reactions in water: Computational and experimental studies. Applied Catalysis B: Environmental, 83, 169–176, https://doi.org/10.1016/j.apcatb.2008.01.038Search in Google Scholar

Perrault, G. (1968) La composition chimique et la structure cristalline du pyrochlore d’Oka. Canadian Mineralogist, 9, 383–402.Search in Google Scholar

Piilonen, P.C., Farges, F., Linnen, R.L., Brown, G.E., Pawlak, M., and Pratt, A. (2006) Structural environment of Nb5+ in dry and fluid-rich (H2O,F) silicate glasses: A combined XANES and EXAFS study. Canadian Mineralogist, 44, 775–794.Search in Google Scholar

Retegan, M. (2019) Core-level spectroscopy simulations in Python. Crispy: v0.7.3. https://doi.org/10.5281/zenodo.1008184Search in Google Scholar

Ribeiro, J.M., Correia, F.C., Kuzmin, A., Jonane, I., Kong, M., Goñi, A.R., Reparaz, J.S., Kalinko, A., Welter, E., and Tavares, C.J. (2020) Influence of Nb-doping on the local structure and thermoelectric properties of transparent TiO2:Nb thin films. Journal of Alloys and Compounds, 838, 155561, https://doi.org/10.1016/j.jallcom.2020.155561Search in Google Scholar

Ruck, R., Babkine, J., Nguyen, C., Marnier, G., and Dusausoy, Y. (1986) Geochemical association of Fe and Nb in synthetic and natural cassiterites and rutiles. Proceedings of Experimental Mineralogy and Geochemistry, p. 122–123. Nancy, France.Search in Google Scholar

Rudnick, R.L. and Gao, S. (2003) Composition of the continental crust. In H.D. Holland and K.K. Turekian, Eds., The Crust, 3, 1–64. Treatise on Geochemistry, Elsevier-Pergamon.Search in Google Scholar

Schaaffs, W., Sandström, A.E., Tomboulian, D.H., Kirkpatrick, P., Pattee, H.H., and Stephenson, S.T. (1957) Röntgenstrahlen /X-Rays Vol. 6 /30. Springer.Search in Google Scholar

Schaefers, F., Mertin, M., and Gorgoi, M. (2007) KMC-1: A high resolution and high flux soft x-ray beamline at BESSY. The Review of Scientific Instruments, 78, 123102, https://doi.org/10.1063/1.2808334Search in Google Scholar

Schaube, M., Merkle, R., and Maier, J. (2019) Oxygen exchange kinetics on systematically doped ceria: A pulsed isotope exchange study. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 7, 21854–21866, https://doi.org/10.1039/C9TA05908CSearch in Google Scholar

Scherz, A., Gross, E.K.U., Appel, H., Sorg, C., Baberschke, K., Wende, H., and Burke, K. (2005) Measuring the kernel of time-dependent density functional theory with X-ray absorption spectroscopy of 3d transition metals. Physical Review Letters, 95, 253006.Search in Google Scholar

Schulz, K.J., Piatak, N.M., and Papp, J.F. (2017) Niobium and tantalum. In K.J. Schulz, J.H. DeYoung Jr., R.R. Seal II, and D.W. Bradley., Eds., Critical Mineral Resources of the United States. U. S. Geological Survey, Professional Paper 1802-M, 34 p.Search in Google Scholar

Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chaleogenides. Acta Crystallographica. Section B, Structural Crystallography and Crystal Chemistry, A32, 751–767.Search in Google Scholar

Sheppard, L., Bak, T., Nowotny, J., Sorrell, C.C., Kumar, S., Gerson, A.R., Barnes, M.C., and Ball, C. (2006) Effect of niobium on the structure of titanium dioxide thin films. Thin Solid Films, 510, 119–124, https://doi.org/10.1016/j.tsf.2005.12.272Search in Google Scholar

Silva, A.C., Oliveira, D.Q.L., Oliveira, L.C.A., Anastácio, A.S., Ramalho, T.C., Lopes, J.H., Carvalho, H.W.P., and Torres, C.E.R. (2009) Nb-containing hematites Fe2−xNbxO3: The role of Nb5+ on the reactivity in presence of the H2O2 or ultraviolet light. Applied Catalysis A, General, 357, 79–84, https://doi.org/10.1016/j.apcata.2009.01.014Search in Google Scholar

Singh, S.K., Eng, J., Atanasov, M., and Neese, F. (2017) Covalency and chemical bonding in transition metal complexes: An ab initio based ligand field perspective. Coordination Chemistry Reviews, 344, 2–25, https://doi.org/10.1016/j.ccr.2017.03.018Search in Google Scholar

Sugiura, C., Kitamura, M., and Muramatsu, S. (1987) Ruthenium LII and rhodium LII,III X-ray absorption-edge structures. Physica status solidi (b), 140, 631–636Search in Google Scholar

Sugiura, C., Kitamura, M., and Muramatsu, S. (1988) Niobium LIIl and LII X-ray absorption-edge spectra of Nb2O5 and NH4NbF6. Journal of Physics and Chemistry of Solids, 49, 1095–1099, https://doi.org/10.1016/0022-3697(88)90159-XSearch in Google Scholar

Usui, H., Yoshioka, S., Wasada, K., Shimizu, M., and Sakaguchi, H. (2015) Nb-doped rutile TiO2: A potential anode material for Na-ion battery. ACS Applied Materials & Interfaces, 7, 6567–6573, https://doi.org/10.1021/am508670zSearch in Google Scholar

Vantelon, D., Trcera, N., Roy, D., Moreno, T., Mailly, D., Guilet, S., Metchalkov, E., Delmotte, F., Lassalle, B., Lagarde, P., and others. (2016) The LUCIA beamline at SOLEIL. Journal of Synchrotron Radiation, 23, 635–640, https://doi.org/10.1107/S1600577516000746Search in Google Scholar

Wall, F., Williams, C.T., Woolley, A.R., and Nasraoui, M. (1996) Pyrochlore from weathered carbonatite at Lueshe, Zaire. Mineralogical Magazine, 60, 731–750, https://doi.org/10.1180/minmag.1996.060.402.03Search in Google Scholar

Walter, B.F., Parsapoor, A., Braunger, S., Marks, M.A.W., Wenzel, T., Martin, M., and Markl, G. (2018) Pyrochlore as a monitor for magmatic and hydrothermal processes in carbonatites from the Kaiserstuhl volcanic complex (SW Germany). Chemical Geology, 498, 1–16, https://doi.org/10.1016/j.chemgeo.2018.08.008Search in Google Scholar

Wang, B., Zhao, Y., Banis, M.N., Sun, Q., Adair, K.R., Li, R., Sham, T.-K., and Sun, X. (2018a) Atomic layer deposition of lithium niobium oxides as potential solid-state electrolytes for lithium-ion batteries. ACS Applied Materials & Interfaces, 10, 1654–1661, https://doi.org/10.1021/acsami.7b13467Search in Google Scholar

Wang, S., Song, Z., Kong, Y., Xia, Z., and Liu, Q. (2018b) Crystal field splitting of 4f n–15d-levels of Ce3+ and Eu2+ in nitride compounds. Journal of Luminescence, 194, 461–466, https://doi.org/10.1016/j.jlumin.2017.10.073Search in Google Scholar

Waring, J.L., Roth, R.S., and Parker, H.S. (1973) Temperature-pressure phase relationships in niobium pentoxide. Journal of Research of the National Bureau of Standards. Section A. Physics and Chemistry, 77A, 705–711, https://doi.org/10.6028/jres.077A.042 PubMedSearch in Google Scholar

Weng, T.-C., Waldo, G. S., and Penner-Hahn, J.E. (2005) A method for normalization of X-ray absorption spectra. Journal of Synchrotron Radiation, 12, 506–510, https://doi.org/10.1107/S0909049504034193Search in Google Scholar

Wenger, M., Armbruster, T., and Geiger, C.A. (1991) Cation distribution in partially ordered columbite from the Kings Mountain pegmatite, North Carolina. American Mineralogist, 76, 1897–1904.Search in Google Scholar

Wu, B., Hu, Y.-Q., Bonnetti, C., Xu, C., Wang, R.-C., Zhang, Z.-S., Li, Z.-Y., and Yin, R. (2021) Hydrothermal alteration of pyrochlore group minerals from the Miaoya carbonatite complex, central China and its implications for Nb mineralization. Ore Geology Reviews, 132, 104059, https://doi.org/10.1016/j.oregeorev.2021.104059Search in Google Scholar

Wyckoff, R.W.G. (1963) Crystal Structures, 2nd ed. Vol. 1. Interscience Publishers, New York.Search in Google Scholar

Yang, H., Lu, R., Downs, R.T., and Costin, G. (2006) Goethite, α-FeO(OH), from single-crystal data. Acta Crystallographica, E62, i250–i252.Search in Google Scholar

Zietlow, P., Beirau, T., Mihailova, B., Groat, L.A., Chudy, T., Shelyug, A., Navrotsky, A., Ewing, R.C., Schlüter, J., Škoda, R., and others. (2017) Thermal annealing of natural, radiation-damaged pyrochlore. Zeitschrift für Kristallographie. Crystalline Materials, 232, 25–38, https://doi.org/10.1515/zkri-2016-1965Search in Google Scholar
Received: 2021-09-08
Accepted: 2022-03-28
Published Online: 2023-03-02
Published in Print: 2023-03-28

© 2023 by Mineralogical Society of America

Articles in the same Issue

  1. Mineralogy and bulk geochemistry of a fumarole at Hverir, Iceland: Analog for acid-sulfate leaching on Mars
  2. The crystal structure and chemistry of natural giniite and implications for Mars
  3. Solid solution of CaSiO3 and MgSiO3 perovskites in the lower mantle: The role of ferrous iron
  4. Secondary ion mass spectrometer analyses for trace elements in glass standards using variably charged silicon ions for normalization
  5. Raman shifts of c-BN as an ideal P-T sensor for studying water-rock interactions in a diamond-anvil cell
  6. Resetting of the U-Pb and Th-Pb systems in altered bastnäsite: Insight from the behavior of Pb at nanoscale
  7. X-ray diffraction reveals two structural transitions in szomolnokite
  8. Contamination of heterogeneous lower crust in Hannuoba tholeiite: Evidence from in situ trace elements and strontium isotopes of plagioclase
  9. Oxygen fugacity buffering in high-pressure solid media assemblies from IW-6.5 to IW+4.5 and application to the V K-edge oxybarometer
  10. Trace element partitioning between anhydrite, sulfate melt, and silicate melt
  11. Chemical reaction between ferropericlase (Mg,Fe)O and water under high pressure-temperature conditions of the deep lower mantle
  12. Composition-dependent thermal equation of state of B2 Fe-Si alloys at high pressure
  13. Effects of thermal annealing on water content and δ18O in zircon
  14. Tourmaline and zircon trace the nature and timing of magmatic-hydrothermal episodes in granite-related Sn mineralization: Insights from the Libata Sn ore field
  15. Cation ordering, twinning, and pseudo-symmetry in silicate garnet: The study of a birefringent garnet with orthorhombic structure
  16. The occurrence of monoclinic jarosite in natural environments
  17. Niobium speciation in minerals revealed by L2,3-edges XANES spectroscopy
  18. The first occurrence of the carbide anion, C4–, in an oxide mineral: Mikecoxite, ideally (CHg4)OCl2, from the McDermitt open-pit mine, Humboldt County, Nevada, U.S.A
  19. Hydrothermal alteration of Ni-rich sulfides in peridotites of Abu Dahr, Eastern Desert, Egypt: Relationships among minerals in the Fe-Ni-Co-O-S system, fO2 and fS2
  20. New Mineral Names: Arsenic and Lead
https://doi.org/10.2138/am-2022-8293
Keywords for this article
Niobium; XANES; multiplet; 10Dq; local structure; speciation

Articles in the same Issue

  1. Mineralogy and bulk geochemistry of a fumarole at Hverir, Iceland: Analog for acid-sulfate leaching on Mars
  2. The crystal structure and chemistry of natural giniite and implications for Mars
  3. Solid solution of CaSiO3 and MgSiO3 perovskites in the lower mantle: The role of ferrous iron
  4. Secondary ion mass spectrometer analyses for trace elements in glass standards using variably charged silicon ions for normalization
  5. Raman shifts of c-BN as an ideal P-T sensor for studying water-rock interactions in a diamond-anvil cell
  6. Resetting of the U-Pb and Th-Pb systems in altered bastnäsite: Insight from the behavior of Pb at nanoscale
  7. X-ray diffraction reveals two structural transitions in szomolnokite
  8. Contamination of heterogeneous lower crust in Hannuoba tholeiite: Evidence from in situ trace elements and strontium isotopes of plagioclase
  9. Oxygen fugacity buffering in high-pressure solid media assemblies from IW-6.5 to IW+4.5 and application to the V K-edge oxybarometer
  10. Trace element partitioning between anhydrite, sulfate melt, and silicate melt
  11. Chemical reaction between ferropericlase (Mg,Fe)O and water under high pressure-temperature conditions of the deep lower mantle
  12. Composition-dependent thermal equation of state of B2 Fe-Si alloys at high pressure
  13. Effects of thermal annealing on water content and δ18O in zircon
  14. Tourmaline and zircon trace the nature and timing of magmatic-hydrothermal episodes in granite-related Sn mineralization: Insights from the Libata Sn ore field
  15. Cation ordering, twinning, and pseudo-symmetry in silicate garnet: The study of a birefringent garnet with orthorhombic structure
  16. The occurrence of monoclinic jarosite in natural environments
  17. Niobium speciation in minerals revealed by L2,3-edges XANES spectroscopy
  18. The first occurrence of the carbide anion, C4–, in an oxide mineral: Mikecoxite, ideally (CHg4)OCl2, from the McDermitt open-pit mine, Humboldt County, Nevada, U.S.A
  19. Hydrothermal alteration of Ni-rich sulfides in peridotites of Abu Dahr, Eastern Desert, Egypt: Relationships among minerals in the Fe-Ni-Co-O-S system, fO2 and fS2
  20. New Mineral Names: Arsenic and Lead
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