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Licensed Unlicensed Requires Authentication Published by De Gruyter September 20, 2020

A multi-methodological study of kernite, a mineral commodity of boron

  • G. Diego Gatta ORCID logo , Alessandro Guastoni , Paolo Lotti , Giorgio Guastella , Oscar Fabelo and Maria Teresa Fernandez-Diaz
From the journal American Mineralogist

Abstract

Kernite, ideally Na2B4O6(OH)2∙3H2O, is a major constituent of borate deposits and one of the most important mineral commodities of B. The chemical composition and crystal structure of kernite from the Kramer Deposit (Kern County, California) were investigated by a suite of analytical techniques (i.e., titrimetric determination of B content, gravimetric method for Na, ion selective electrode for F, high-T mass loss for H2O content, inductively coupled plasma atomic emission spectroscopy for REE and other minor elements, elemental analysis for C, N, and H contents) and single-crystal X‑ray (at 293 K) and neutron (at 20 K) diffraction. The concentrations of more than 50 elements were measured. The general experimental formula of the kernite sample used in this study is Na1.99B3.99O6(OH)2∙3.01H2O. The fraction of other elements is, overall, insignificant: excluding B, kernite from the Kramer Deposit does not act as geochemical trap of other technologically relevant elements (e.g., Li, Be, or REE). The X‑ray and neutron structure model obtained in this study confirms that the structure of kernite is built up by: two (crystallographically independent) triangular BO2OH groups and two tetrahedral BO4 groups, which share corner-bridging O atoms to form threefold rings, giving chains running along [010], and NaO4(OH)(OH2) and NaO2(OH)(OH2)3 polyhedra. Positional disorder of two H sites of H2O molecules was observed by the neutron structure refinement and corroborated by the maximum-entropy method calculation, which consistently provided a model based on a static disorder, rather than a dynamic one. The H-bonding network in the structure of kernite is complex, pervasive, and plays a primary role on its structural stability: the majority of the oxygen sites are involved in H-bonding, as donors or as acceptors. The potential utilizations of kernite, as a source of B (B2O3 ~50 wt%), are discussed, on the basis of the experimental findings of this study.

Acknowledgments

The Associate Editor and an anonymous reviewer are thanked for their suggestions aimed to improve the quality of the manuscript.

  1. Funding

    The authors thank the Institut Laue-Langevin (Grenoble, France) for the allocation of the neutron beamtime; further information is available under the identifier DOI:10.5291/ILL-DATA.DIR-179. G.D.G. and P.L. acknowledge the support of the Italian Ministry of Education (MIUR) through the projects “Dipartimenti di Eccellenza 2018–2022” and “PRIN2017—Mineral reactivity, a key to understand large-scale processes”. P.L. acknowledges the support of the University of Milan through the project “PSR2018—Georisorse e Geomateriali”.

References cited

Amoros, J.L.P. (1945) La estructura de la kernita. Euclides, 57-58, 599–608.Search in Google Scholar

Archer, J., and Lehmann, M.S. (1986) A simple adjustable mount for a two-stage cryorefrigerator on an Eulerian cradle. Journal of Applied Crystallography, 19, 456–459.10.1107/S0021889886088957Search in Google Scholar

Bove, L.E., Klotz, S., Paciaroni, A., and Sacchetti, F. (2009) Anomalous proton dynamics in ice at low temperatures. Physical Review Letters, 103, 165901–165904.10.1103/PhysRevLett.103.165901Search in Google Scholar PubMed

Busing, W.R., and Levy, H.A. (1964) The effect of thermal motion on the estimation of bond lengths from diffraction measurements. Acta Crystallographica, 17, 142–146.10.1107/S0365110X64000408Search in Google Scholar

Carter, R.S., Palevsky, H., Myers, V.W., and Hughes, D.J. (1953) Thermal neutron absorption cross sections of boron and gold. Physical Review, 96, 716–721.10.1103/PhysRev.92.716Search in Google Scholar

Christ, C.L., and Garrels, R.M. (1959) Relations among sodium borate hydrates at the Kramer deposit, Born, California. American Journal of Science, 257, 516–528.10.2475/ajs.257.7.516Search in Google Scholar

Cialdi, G., Corazza, E., and Sabelli, C. (1967) La struttura cristallina della kernite, Na2B4O6(OH)2∙3H2O. Rendiconti dell’Accademia Nazionale dei Lincei, Ser. VIII, 42, 236–251.Search in Google Scholar

Cipriani, C. (1958) Ricerche sulla disidratazione di alcuni borati naturali. Atti della Società Toscana di Scienze Naturali, 65A, 284–322.Search in Google Scholar

Comboni, D., Pagliaro, F., Gatta, G.D., Lotti, P., Milani, S., Merlini, M., Battiston, T., Glazyrin, K., and Liermann, H.-P. (2020) High-pressure behavior and phase stability of Na2B4O6(OH)2·3H2O (kernite). Journal of the American Ceramic Society, 103, 5291–5301.10.1111/jace.17185Search in Google Scholar

Cooper, W.F., Larsen, F.K., and Coppens, P. (1973) Electron population analysis of accurate diffraction data. V. Structure and one-center charge refinement of the light-atom mineral kernite, Na2B4O6(OH)2∙3H2O. American Mineralogist, 58, 21–31.Search in Google Scholar

European Commission (2017) Critical Raw Materials for the EU. Document 52017DC0490. https://ec.europa.eu/growth/sectors/raw-materials/specific-interest/critical_en.Search in Google Scholar

Farrugia, L.J. (1999) WinGX suite for small-molecule single-crystal crystallography. Journal of Applied Crystallography, 32, 837–838.10.1107/S0021889899006020Search in Google Scholar

Gatta, G.D., Rotiroti, N., McIntyre, G.J., Guastoni, A., and Nestola, F. (2008) New insights into the crystal chemistry of epididymite and eudidymite from Malosa, Malawi: a single-crystal neutron diffraction study. American Mineralogist, 93, 1158–1165.10.2138/am.2008.2965Search in Google Scholar

Gatta, G.D., McIntyre, G.J., Swanson, G.J., and Jacobsen, S.D. (2012) Minerals in cement chemistry: a single-crystal neutron diffraction and Raman spectroscopic study of thaumasite, Ca3Si(OH)6(CO3(SO4∙12H2O. American Mineralogist, l, 97, 1060–1069.10.2138/am.2012.4058Search in Google Scholar

Gatta G.D., Guastoni A., Lotti P., Guastella G., Fabelo O., and Fernandez-Diaz. M.T. (2019a) A multi-methodological study of kurnakovite: A potential B-rich aggregate. American Mineralogist, 104, 1315–1322.10.2138/am-2019-7072Search in Google Scholar

Gatta, G.D., Fabelo-Rosa O.R., and Fernandez-Diaz M.T. (2019b) Crystal chemistry of kernite mineral [Na2B4O6(OH)2∙3H2O]: a sustainable approach for boron-based cements. Experimental Report, Institut Laue-Langevin (ILL), doi:10.5291/ILL-DATA.DIR-179.10.5291/ILL-DATA.DIR-179Search in Google Scholar

Giese, R.F. Jr. (1966) Crystal structure of kernite, Na2B4O6(OH)2∙3H2O. Science, 154, 1453–1454.10.1126/science.154.3755.1453Search in Google Scholar

Grice, J.D., Burns, P.C., and Hawthorne, F.C. (1999) Borate minerals. II. A hierarchy of structures based upon the borate fundamental building block. Canadian Mineralogist, 37, 731–762.Search in Google Scholar

Heller, G. (1986) A survey of structural types of borates and polyborates. Topics in Current Chemistry, 131, 39–98.10.1007/3-540-15811-1_2Search in Google Scholar

Hurlbut, C.S. Jr., Aristarain, L.F., and Erd, R.C. (1973) Kernite from Tincalayu, Salta, Argentina. American Mineralogist, 58, 308–313.Search in Google Scholar

Jun, L., Shuping, X., and Shiyang, G. (1995) FT-IR and Raman spectroscopic study of hydrated borates. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 51, 519–532.10.1016/0584-8539(94)00183-CSearch in Google Scholar

Kloprogge, J.T., and Frost, R.L. (1999) Raman microscopic study of some borate minerals: Ulexite, kernite, and inderite. Applied Spectroscopy, 53, 356–364.10.1366/0003702991946587Search in Google Scholar

Larson, A.C. (1967) Inclusion of secondary extinction in least-squares calculations. Acta Crystallographica, 23, 664–665.10.1107/S0365110X67003366Search in Google Scholar

Lotti, P., Gatta, G.D., Comboni, D., Guastella, G., Merlini, M., Guastoni, A., and Liermann, H.P. (2017) High-pressure behavior and P-induced phase transition of CaB3O4(OH)3∙H2O (colemanite). Journal of American Ceramic Society, 100, 2209–2220.10.1111/jace.14730Search in Google Scholar

Lotti, P., Gatta, G.D., Demitri, N., Guastella, G., Rizzato, S., Ortenzi, M.A., Magrini, F., Comboni, D., Guastoni, A., and Fernandez-Diaz, M.T. (2018) Crystal-chemistry and temperature behavior of the natural hydrous borate colemanite, a mineral commodity of boron. Physics and Chemistry of Minerals, 45, 405–422.10.1007/s00269-017-0929-7Search in Google Scholar

Lotti, P., Comboni, D., Gigli, L., Carlucci, L., Mossini, E., Macerata, E., Mariani, M., and Gatta, G.D. (2019) Thermal stability and high-temperature behavior of the natural borate colemanite: An aggregate in radiation-shielding concretes. Construction and Building Materials, 203, 679–686.10.1016/j.conbuildmat.2019.01.123Search in Google Scholar

Momma, K., and Izumi, F. (2011) Vesta 3 for three-dimensional visualization of crystal, volumetric and morphology data. Journal of Applied Crystallography, 44, 1272–1276.10.1107/S0021889811038970Search in Google Scholar

Momma, K., Ikeda, T., Belik, A.A., and Izumi, F. (2013) Dysnomia, a computer program for maximum-entropy method (MEM) analysis and its performance in the MEM-based pattern fitting. Powder Diffraction, 28, 184–193.10.1017/S088571561300002XSearch in Google Scholar

Morgan, V., and Erd, R.C. (1969) Minerals of the Kramer borate district, California. California Division of Mines and Geology Mineral Information Service, 22, pp. 143–153 and 165–172.Search in Google Scholar

Noble, L.F. (1926) Borate deposits in the Kramer district, Kern County, California. U.S. Geological Survey Bulletin, 785, 45–61.Search in Google Scholar

Obert, L., and Long, A.E. (1962) Underground borate mining, Kern County, California. U.S. Bureau of Mines Report of Investigation, 6110, 1–12.Search in Google Scholar

Palmer, M.R., and Swihart, G.H. (1996) Boron isotope geochemistry: An overview. In L.M. Anovitz and E.S. Grew, Eds., Boron: Mineralogy, Petrology, and Geochemistry, 33, p. 709–744. Reviews in Mineralogy, Mineralogical Society of America, Chantilly.10.1515/9781501509223-015Search in Google Scholar

Puffer, J.H. (1975) The Kramer borate mineral assemblage. Mineralogical Record, 6, 84–91.Search in Google Scholar

Rauch, H., and Waschkowski, W. (2002) Neutron Scattering Lengths. In A.J. Dianoux and G. Lander, Eds., Neutron Data Booklet, 1st ed., pp. 1–18. Institut Laue Langevin, Grenoble.Search in Google Scholar

Schaller, W.T. (1927) Kernite, a new sodium borate. American Mineralogist, 12, 24–25.Search in Google Scholar

Schaller, W.T. (1930) Borate minerals from the Kramer district, Mohave Desert, California. U.S. Geological Survey Professional Paper, 158, 137–170.10.3133/pp158ISearch in Google Scholar

Sears, V.F. (1986) Neutron scattering lengths and cross-sections. In K. Sköld and D.L. Price, Eds., Neutron Scattering, Methods of Experimental Physics, vol. 23A, p. 521–550. Academic Press.10.1016/S0076-695X(08)60561-XSearch in Google Scholar

Sennova, N.A., Bubnova, R.S., Filatov, S.K., Paufler, P., Meyer, D.C., Levin, A.A., and Polyakova, I.G. (2005) Room, low, and high temperature dehydration and phase transition of kernite in vacuum and in air. Crystal Research and Technology, 40, 563–572.10.1002/crat.200410384Search in Google Scholar

Sheldrick, G.M. (1997) SHELXL-97. Programs for crystal structure determination and refinement. University of Göttingen, Germany.Search in Google Scholar

Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112–122.10.1107/S0108767307043930Search in Google Scholar PubMed

Siefke, J.W. (1991) The Boron open Pit Mine at the Kramer Borate Deposit. The Diversity of Mineral and Energy Resources of Southern California. In M.A. McKibben, Ed., Society of Economic Geologist Guidebook Series, 12, 4–15.Search in Google Scholar

Silva, M., O’Bannon, E.F., and Williams, Q. (2018) A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra. American Mineralogist, 103, 1306–1318.10.2138/am-2018-6253Search in Google Scholar

Steiner, T. (1998) Opening and narrowing of the water H-O-H angle by hydrogen-bonding effects: Re-inspection of neutron diffraction data. Acta Crystallographica, B54, 464–470.10.1107/S0108768197018193Search in Google Scholar

USGS (2018) Mineral commodity summaries 2018, 200 p. U.S. Geological Survey, Reston, Virginia, U.S.A.Search in Google Scholar

USGS (2019) Mineral commodity summaries 2019, 200 p. U.S. Geological Survey, Reston, Virginia, U.S.A.Search in Google Scholar

Yen, F., and Gao, T. (2015) Dielectric anomaly in ice near 20 K: Evidence of macroscopic quantum phenomena. Journal of Physical Chemistry Letters, 6, 2822–2825.10.1021/acs.jpclett.5b00797Search in Google Scholar PubMed

Received: 2020-01-08
Accepted: 2020-02-22
Published Online: 2020-09-20
Published in Print: 2020-09-25

© 2020 Walter de Gruyter GmbH, Berlin/Boston

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