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Licensed Unlicensed Requires Authentication Published by De Gruyter August 28, 2018

Segerstromite, Ca3(As5+O4)2[As3+(OH)3]2, the first mineral containing As3+(OH)3, the arsenite molecule, from the Cobriza mine in the Atacama Region, Chile

  • Hexiong Yang EMAIL logo , Robert T. Downs , Robert A. Jenkins and Stanley H. Evans
From the journal American Mineralogist

Abstract

A new mineral species, segerstromite, ideally Ca3(As5+O4)2[As3+(OH)3]2, has been discovered at the Cobriza mine in the Sacramento district in the Copiapó Province, Chile. Crystals of segerstromite occur as tetrahedra, dodecahedra (up to 0.50 × 0.50 × 0.50 mm), or in blocky aggregates. Associated minerals include talmessite, vladimirite, and Sr-bearing hydroxylapatite. Similar to the associated minerals, segerstromite is a secondary mineral. The new mineral is colorless in transmitted light, transparent with a white streak and vitreous luster. It is brittle and has a Mohs hardness of ~4.5. No cleavage, parting, or twinning was observed. The measured and calculated densities are 3.44(3) and 3.46 g/cm3, respectively. Optically, segerstromite is isotropic, with n = 1.731(5). It is insoluble in water or hydrochloric acid. An electron microprobe analysis yielded an empirical formula (based on 14 O apfu) Ca2.98(AsO4)2.00[As(OH)3]2.00.

Segerstromite is cubic, with space group I213 and unit-cell parameters a = 10.7627(2) Å, V = 1246.71(4) Å3, and Z = 4. Its crystal structure is constructed from three different polyhedral units: distorted CaO8 cubes, rigid As5+O4 arsenate tetrahedra, and neutral As3+(OH)3 arsenite triangular pyramids. The Ca-groups form layers of corrugated crankshaft chains that lie parallel to the cubic axes. These chains are linked by the isolated As5+O4 and As3+(OH)3 groups. Segerstromite is the first known crystalline compound that contains the As3+(OH)3 arsenite molecule, pointing to a new potential approach to remove highly toxic and mobile As3+(OH)3 from drinking water.

Acknowledgments

This study was funded by the Science Foundation Arizona. The constructive comments by Anthony R. Kampf and an anonymous reviewer are greatly appreciated.

References cited

Arai, Y., Elzinga, E.J., and Sparks, D. (2001) X-ray absorption spectroscopic investigation of arsenite and arsenate adsorption at the aluminum oxide-water interface. Journal of Colloid and Interfacial Science, 235, 80–88.10.1006/jcis.2000.7249Search in Google Scholar PubMed

Brese, N.E., and O’Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica, B47, 192–197.10.1107/S0108768190011041Search in Google Scholar

Ciardelli, M.C., Xu, H., and Sahai, N. (2008) Role of Fe(II), phosphate, silicate, sulfate, and carbonate in arsenic uptake by coprecipitation in synthetic and natural groundwater. Water Research, 42, 615–624.10.1016/j.watres.2007.08.011Search in Google Scholar PubMed

Dickson, D., Liu, G., and Cai, Y. (2017) Adsorption kinetics and isotherms of arsenite and arsenate on hematite nanoparticles and aggregates. Journal of Environmental Management, 186, 261–267.10.1016/j.jenvman.2016.07.068Search in Google Scholar PubMed

Đorđević, T. (2015) Crystal chemistry of the M11+,2+-M22+,3+-H-arsenites: the first cadmium(II) arsenite, Na4Cd7(AsO3)6. Zeitschrift für Anorganische und Allgemeine Chemie, 641, 1863–1868.10.1002/zaac.201500252Search in Google Scholar

Đorđević, T., Kolitsch, U., and Nasadala, L. (2016) A single-crystal X-ray and Raman spectroscopic study of hydrothermally synthesized arsenates and vanadates with the descloizite and adelite structure types. American Mineralogist, 101, 1135–1149.10.2138/am-2016-5422Search in Google Scholar

Downs, R.T., Bartelmehs, K.L., Gibbs, G.V., and Boisen, M.B. Jr. (1993) Interactive software for calculating and displaying X-ray or neutron powder diffractometer patterns of crystalline materials. American Mineralogist, 78, 1104–1107.Search in Google Scholar

Fazal, M. A., Kawachi, T., amd Ichion, E. (2001) Extent and severity of ground-water arsenic contamination in Bangladesh. Water International, 26, 370–379.10.1080/02508060108686929Search in Google Scholar

Frost, R.L., Čejka, J., Sejkora, J., Plášil, J., Bahfenne, S., and Keeffe, E.C. (2011) Raman spectroscopy of hydrogen arsenate group (AsO3OH)2 in solid-state compounds: cobalt-containing zinc arsenate mineral, koritnigite (Zn,Co) (AsO3OH)·H2O. Journal of Raman Spectroscopy, 42, 534–539.10.1002/jrs.2690Search in Google Scholar

Goldberg, S., and Johnston, C.T. (2001) Mechanisms of arsenic adsorption on amorphous oxides evaluated using macroscopic measurements, vibrational spectroscopy, and surface complexation modeling. Journal of Colloid and Interfacial Science, 234, 204–216.10.1006/jcis.2000.7295Search in Google Scholar PubMed

Hawthorne, F.C., Cooper, M.A., Abdu, Y.A., Ball, N.A., Back, M.E., and Tait, K.T. (2012) Davidlloydite, ideally Zn3(AsO4)2(H2O)4, a new arsenate mineral from the Tsumeb mine, Otjikoto (Oshikoto) region, Namibia: description and crystal structure. Mineralogical Magazine, 76, 45–57.10.1180/minmag.2012.076.1.45Search in Google Scholar

Hernández-Cobos, J., Cristina Vargas, M., Ramírez-Solís, A. and Ortega-Blake, I. (2010) Aqueous solvation of As(OH)3: A Monte Carlo study with flexible polarizable classical interaction potentials. The Journal of Chemical Physics, 133, 114501.10.1063/1.3483619Search in Google Scholar

Hill, R.J. (1979) Crystal structure refinement and electron density distribution in diaspore. Physics and Chemistry of Minerals, 5, 179–200.10.1007/BF00307552Search in Google Scholar

Hughes, M.F. (2002) Arsenic toxicity and potential mechanisms of action. Toxicology Letter, 133, 1–16.10.1016/S0378-4274(02)00084-XSearch in Google Scholar

Itakura, T., Sasai, R., and Itoh, H. (2007) Arsenic recovery from water containing arsenite and arsenate ions by hydrothermal mineralization. Journal of Hazardous Materials, 328–333.10.1016/j.jhazmat.2006.12.025Search in Google Scholar PubMed

Itakura, T., Sasai, R., and Itoh, H. (2008) A precipitation method for arsenite ion in aqueous solution as natural mineral by hydrothermal mineralization. Journal of the Ceramic Society of Japan, 116, 234–238.10.2109/jcersj2.116.234Search in Google Scholar

Kampf, A.R., Mills, S.J., Nash, B.P., Dini, M., and Donoso, A.A.M. (2015) Tapiaite, Ca5Al2(AsO4)4(OH)4·12H2O, a new mineral from the Jote mine, Tierra Amarilla, Chile. Mineralogical Magazine, 79, 345–354.10.1180/minmag.2015.079.2.12Search in Google Scholar

Kharbish, S. (2012) Raman spectra of minerals containing interconnected As(Sb)O3 pyramids: trippkeite and schafarzikite. Journal of Geosciences, 57, 53–62.10.3190/jgeosci.111Search in Google Scholar

Kolozsi, A., Lakatos, A., Galbács, G., Madsen, A.Ø., Larsen, E., and Gyurcsik, B. (2008) A pH-Metric, UV, NMR, and X-ray crystallographic study on arsenous acid reacting with dithioerythritol. Inorganic Chemistry, 47, 3832–3840.10.1021/ic7024439Search in Google Scholar PubMed

Kreidie, N., Armiento, G., Cibin, G., Cinque, G., Crovato, C., Nardi, E., Pacifico, R., Cremisini, C., and Mottana, A. (2011) An integrated geochemical and mineralogical approach for the evaluation of arsenic mobility in mining soils. Journal of Soils and Sediments, 11, 37–52.10.1007/s11368-010-0274-7Search in Google Scholar

Ladeira, A.C.Q., and Ciminelli, V.S.T. (2004) Adsorption and desorption of arsenic on an oxisol and its constituents. Water Research, 38, 2087–2094.10.1016/j.watres.2004.02.002Search in Google Scholar PubMed

Libowitzky, E. (1999) Correlation of O-H stretching frequencies and O-H···O hydrogen bond lengths in minerals. Monatshefte für Chemie, 130, 1047–1059.10.1007/978-3-7091-6419-8_7Search in Google Scholar

Liu, J., Jia, R., and Liu, J. (2014) The vibration characterization of synthetic crystalline lead hydrogen arsenite chloride precipitates Pb2(HAsO3)Cl2-implications of solidification of As (III) and Pb (II). Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 117, 658–661.10.1016/j.saa.2013.09.042Search in Google Scholar

Loehr, T.M., and Plane, R.A. (1968) Raman spectra and structures of arsenious acid and arsenites in aqueous solution. Inorganic Chemistry, 7, 1708–1714.10.1021/ic50067a004Search in Google Scholar

Majzlan, J., Drahota, P., and Filippi, M. (2014) Parageneses and crystal chemistry of arsenic minerals. Reviews in Mineralogy and Geochemistry, 79, 17–184.10.1515/9781614517979.17Search in Google Scholar

Mohan, D., and Pittman, C.U. Jr. (2007) Arsenic removal from water/wastewater using adsorbents—A critical review. Journal of Hazardous Materials, 142, 1–53.10.1016/j.jhazmat.2007.01.006Search in Google Scholar

Müller, K., Ciminelli, V.S.T., Dantas, M.S.S., and Willscher, S. (2010) A comparative study of As(III) and As(V) in aqueous solutions and adsorbed on iron oxy-hydroxides by Raman spectroscopy. Water Research, 44, 5660–5672.10.1016/j.watres.2010.05.053Search in Google Scholar

Pokrovski, G.D., Bény, J-M., and Zotov, A. (1999) Solubility and Raman spectroscopic study of As(III) speciation in organic compound-water solutions. A hydration approach for aqueous arsenic in complex solutions. Journal of Solution Chemistry, 28, 1307–1327.10.1023/A:1021795924067Search in Google Scholar

Pokrovski, G.S., Zakirov, I., Roux, J., Testemale, D., Hazemann, J.-L., Bychkov, A. Yu., and Golikova, G.V. (2002) Experimental study of arsenic speciation in vapor phase to 500 °C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases. Geochimica et Cosmochimica Acta, 66, 3453–3480.10.1016/S0016-7037(02)00946-8Search in Google Scholar

Porquet, A., and Filella, M. (2007) Structural evidence of the similarity of Sb(OH)3 and As(OH)3 with glycerol: Implications for their uptake. Chemical Research of Toxicology, 20, 1269–1276.10.1021/tx700110mSearch in Google Scholar PubMed

Ramirez-Solis, A., Mukopadhyay, R., Rosen, B.P., and Stemmler, T.L. (2004) Experimental and theoretical characterization of arsenite in water: insights into the coordination environment of As-O. Inorganic Chemistry, 43, 2954–2959.10.1021/ic0351592Search in Google Scholar PubMed PubMed Central

Roy, E., Patra, S., Rashmi Madhuri, R., and Sharma, P.K. (2016) A single solution for arsenite and arsenate removal from drinking water using cysteine@ZnS:TiO2 nanoparticle modified molecularly imprinted biofouling-resistant filtration membrane. Chemical Engineering Journal, 304, 259–270.10.1016/j.cej.2016.06.064Search in Google Scholar

Ruan, H.D., Frost, R.L., and Kloprogge, J.T. (2001) Comparison of Raman spectra in characterizing gibbsite, bayerite, diaspore and boehmite. Journal of Raman Spectroscopy, 32, 745–750.10.1002/jrs.736Search in Google Scholar

Sasaki, K., Nakano, H., Wilopo, W., Miura, Y., and Hirajima, T. (2009) Sorption and speciation of arsenic by zero-valent iron. Colloids and Surfaces A: Physicochemical Engineering Aspects, 347, 8–17.10.1016/j.colsurfa.2008.10.033Search in Google Scholar

Sheldrick, G.M. (2015a) SHELXT—Integrated space-group and crystal structure determination. Acta Crystallographica, A71, 3–8.10.1107/S2053273314026370Search in Google Scholar PubMed PubMed Central

Sheldrick, G.M. (2015b) Crystal structure refinement with SHELX. Acta Crystallographica, C71, 3–8.Search in Google Scholar

Testamale, D., Hazemann, J.-L., Pokrovski, G.S., Joly, Y., Roux, J., Argoud, R., and Geaymond, O. (2004) Structural and electronic evolution of the As(OH)3 molecule in high temperature aqueous solutions: an X-ray absorption investigation. Journal of Chemical Physics, 121, 8973–8982.10.1063/1.1785150Search in Google Scholar PubMed

Tossell, J.A., and Zimmermann, M.D. (2008) Calculation of the structures, stabilities, and vibrational spectra of arsenites, thioarsenites and thioarsenates in aqueous solution. Geochimica et Cosmochimica Acta, 72, 5232–5242.10.1016/j.gca.2008.08.013Search in Google Scholar

Vaughan, D.J. (2011) Arsenic. Elements, 2, 71–75.10.2113/gselements.2.2.71Search in Google Scholar

Wood, S.A., Tait, C.D., and Janecky, D.R. (2002) A Raman spectroscopic study of arsenite and thioarsenite species in aqueous solution at 25 °C. Geochemical Transactions, 3, 31–39.10.1186/1467-4866-3-31Search in Google Scholar PubMed PubMed Central

Yadav, M.K., Gupta, A.K., Ghosal, P.S., and Mukherjee, A. (2017) pH mediated facile preparation of hydrotalcite based adsorbent for enhanced arsenite and arsenate removal: Insights on physicochemical properties and adsorption mechanism. Journal of Molecular Liquids, 240, 240–252.10.1016/j.molliq.2017.05.082Search in Google Scholar

Yang, H., Evans, S.H., Downs, R.T., and Jenkins, R.A. (2011) The crystal structure of vladimirite, with a revised chemical formula, Ca4(AsO4)2(AsO3OH)·4H2O. Canadian Mineralogist, 49, 1055–1064.10.3749/canmin.49.4.1055Search in Google Scholar

Yokoyama, Y., Kazuya Tanaka, K., and Takahashi, Y. (2012) Differences in the immobilization of arsenite and arsenate by calcite. Geochimica et Cosmochimica Acta, 91, 202–219.10.1016/j.gca.2012.05.022Search in Google Scholar

Zhang, G., Qu, J., Liu, H., Liu, R., and Li, G. (2007) Removal mechanism of As(III) by a novel Fe-Mn binary oxide adsorbent: Oxidation and sorption. Environmental Science & Technology, 41, 4613–4619.10.1021/es063010uSearch in Google Scholar PubMed

Received: 2017-10-12
Accepted: 2018-05-11
Published Online: 2018-08-28
Published in Print: 2018-09-25

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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