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Thermodynamic properties of mansfieldite (AlAsO4·2H2O), angelellite (Fe4(AsO4)2O3) and kamarizaite (Fe3(AsO4)2(OH)3·3H2O)

Published online by Cambridge University Press:  15 May 2018

Juraj Majzlan ,
Ulla Gro Nielsen ,
Edgar Dachs ,
Artur Benisek ,
Petr Drahota ,
Uwe Kolitsch ,
Julia Herrmann ,
Ralph Bolanz  and
Martin Števko
Juraj Majzlan*
Affiliation:
Institute of Geosciences, Friedrich-Schiller University, Burgweg 11, D-07749 Jena, Germany
Ulla Gro Nielsen
Affiliation:
Department of Physics, Chemistry, and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark
Edgar Dachs
Affiliation:
Department of Material Research and Physics, Division Mineralogy, University of Salzburg, Hellbrunnerstrasse 34, A-5020 Salzburg, Austria
Artur Benisek
Affiliation:
Department of Material Research and Physics, Division Mineralogy, University of Salzburg, Hellbrunnerstrasse 34, A-5020 Salzburg, Austria
Petr Drahota
Affiliation:
Institute of Geochemistry, Mineralogy and Mineral Resources, Charles University, Albertov 6, 128 43 Prague, Czech Republic
Uwe Kolitsch
Affiliation:
Mineralogisch-Petrographische Abt., Naturhistorisches Museum, Burgring 7, 1010 Wien, Austria
Julia Herrmann
Affiliation:
Institute of Geosciences, Friedrich-Schiller University, Burgweg 11, D-07749 Jena, Germany
Ralph Bolanz
Affiliation:
Institute of Geosciences, Friedrich-Schiller University, Burgweg 11, D-07749 Jena, Germany
Martin Števko
Affiliation:
Department of Mineralogy and Petrology, National Museum, Cirkusová 1740, CZ-19300 Praha 9, Czech Republic
*
*E-mail: Juraj.Majzlan@uni-jena.de
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Abstract

Thermodynamic data for the arsenates of various metals are necessary to calculate their solubilities and to evaluate their potential as arsenic storage media. If some of the less common arsenate minerals have been shown to be less soluble than the currently used options for arsenic disposal (especially scorodite and arsenical iron oxides), they should be further investigated as promising storage media. Furthermore, the health risk associated with arsenic minerals is a function of their solubility and bioavailability, not merely their presence. For all these purposes, solubilities of such minerals need to be known. In this work, a complete set of thermodynamic data has been determined for mansfieldite, AlAsO4·2H2O; angelellite, Fe4(AsO4)2O3; and kamarizaite, Fe3(AsO4)2(OH)3·3H2O, using a combination of high-temperature oxide-melt calorimetry, relaxation calorimetry, solubility measurements, and estimates where possible and appropriate. Several choices for the reference compounds for As for the high-temperature oxide-melt calorimetry were assessed. Scorodite was selected as the best one. The calculated Gibbs free energy of formation (all data in kJ·mol–1) is –1733.4 ± 3.5 for mansfieldite, –2319.2 ± 7.9 for angelellite and –3056.8 ± 8.5 for kamarizaite. The solubility products for the dissolution reactions are –21.4 ± 0.5 for mansfieldite, –43.4 ± 1.5 for angelellite and –50.8 ± 1.6 for kamarizaite. Available, but limited, chemical data for the natural scorodite–mansfieldite solid-solution series hint at a miscibility gap; hence the non-ideal nature of the series. However, no mixing parameters were derived because more data are needed. The solubility of mansfieldite is several orders of magnitude higher than that of scorodite. The solubility of kamarizaite, on the other hand, is comparable to that of scorodite, and kamarizaite even has a small stability field in a pH-pε diagram. It is predicted to form under mildly acidic conditions in acid drainage systems that are not subject to rapid neutralization and sudden strong supersaturation. The solubility of angelellite is high, and the mineral is obviously restricted to unusual environments, such as fumaroles. Its crystallization may be enhanced via its epitaxial relationship with the much more common hematite. The use of the scorodite–mansfieldite solid solution for arsenic disposal, whether the solid solution is ideal or not, is not practical. The difference in solubility products of the two end-members (scorodite and mansfieldite) is so large that almost any system will drive the precipitation of essentially pure scorodite, leaving the aluminium in the aqueous phase.

Keywords

mansfielditeangelellitekamarizaitehigh-temperature oxide-melt calorimetryrelaxation calorimetry
Type
Article
Information
Mineralogical Magazine , Volume 82 , Issue 6 , December 2018 , pp. 1333 - 1354
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2019 

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Footnotes

Associate Editor: Jason Harvey

References

Akopyan, K., Petrosyan, V., Grigoryan, R. and Melkomian, D.M. (2018) Assessment of residential soil contamination with arsenic and lead in mining and smelting towns of northern Armenia. Journal of Geochemical Exploration, 184, 97–109.Google Scholar
Alcantar, S., Ledbetter, H.R. and Ranmohotti, K.G.S. (2017) Crystal structure of BaMn2(AsO4)2 containing discrete [Mn4O18]28− units. Acta Crystallographica E, 73, 1855–1860.Google Scholar
Baghurst, D.R., Barrett, J.B. and Mingos, D.M.P. (1995) The hydrothermal microwave synthesis of scorodite: Iron(III) arsenate(V) dihydrate, FeAsO4·2H2O. Journal of the Chemical Society, Chemical Communications, 323–324.Google Scholar
Benisek, A., Kroll, H. and Dachs, E. (2012) The heat capacity of fayalite at high temperatures. American Mineralogist, 97, 657–660.Google Scholar
Bhowmick, S., Pramanik, S., Singh, P., Mondal, P., Chatterjee, D. and Nriagu, J. (2018) Arsenic in groundwater of West Bengal, India: A review of human health risks and assessment of possible intervention options. Science of the Total Environment, 612, 148–169.Google Scholar
Bolanz, R.M., Wierzbicka-Wieczorek, M., Uhlík, P., Čaplovičová, M., Göttlicher, J., Steininger, R. and Majzlan, J. (2013) Structural incorporation of As5+ into hematite. Environmental Science & Technology, 47, 9140–9147.Google Scholar
Borčinová Radková, A., Jamieson, H., Lalinská-Voleková, B., Majzlan, J., Števko, M. and Chovan, M. (2017) Mineralogical controls on antimony and arsenic mobility during tetrahedrite-tennantite weathering at historic mine sites Špania Dolina-Piesky and Ľubietová-Svätodušná, Slovakia. American Mineralogist, 102, 1091–1100.Google Scholar
Bozau, E., Licha, T. and Ließmann, W. (2017) Hydrogeochemical characteristics of mine water in the Harz Mountains, Germany. Chemie der Erde – Geochemistry, 77, 614–624.Google Scholar
Chukanov, N.V., Pekov, I.V., Möckel, S., Mukhanova, A.A., Belakovsky, D.I., Levitskaya, L.A. and Bekenova, G.K. (2010) Kamarizaite, ${\rm Fe}_{\rm 3}^{3 +} $(AsO4)2(OH)3·3H2O, a new mineral species, arsenate analogue of tinticite. Geology of Ore Deposits, 52, 599–605.Google Scholar
Chukhlantsev, V.G. (1956) The solubility products of a number of arsenates. Journal of Analytical Chemistry (USSR), 11, 565–571.Google Scholar
Cornelis, G., Johnson, C.A., van Gerven, T. and Vandecasteele, C. (2008) Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review. Applied Geochemistry, 23, 955–976.Google Scholar
Cui, J.L., Zhao, Y.P., Li, J.S., Beiyuan, J.Z., Tsang, D.C.W., Poon, C.S., Chan, T.S., Wang, W.X. and Li, X.D. (2018) Speciation, mobilization, and bioaccessibility of arsenic in geogenic soil profile from Hong Kong. Environmental Pollution, 232, 375–384.Google Scholar
Đorđević, T., Gerger, S. and Karanović, L. (2017) Hydrothermal and ionothermal synthesis of mineral-related arsenates in the system CdO–MO–As2O5 (M 2+ = Mg, Co, Ni, Cu, Zn) and their crystal structures. European Journal of Mineralogy, 29, 73–89.Google Scholar
Drahota, P., Kulakowski, O., Culka, A., Knappová, M., Rohovec, J., Veselovský, F. and Racek, M. (2018) Arsenic mineralogy of near-neutral soils and mining waste at the Smolotely-Líšnice historical gold district, Czech Republic. Applied Geochemistry, 89, 243–254.Google Scholar
Flis, J., Manecki, M. and Bajda, T. (2011) Solubility of pyromorphite Pb5(PO4)3Cl – mimetite Pb5(AsO4)3Cl solid solution series. Geochimica et Cosmochimica Acta, 75, 1858–1868.Google Scholar
Forray, F.L. and Navrotsky, A. (2005) Thermochemistry of arsenic minerals. Goldschmidt Conference Section: Acid Mine Drainage, A773 [abstracts].Google Scholar
Forray, F.L., Smith, A.M.L., Navrotsky, A., Wright, K., Hudson-Edwards, K.A. and Dubbin, W.E. (2014) Synthesis, characterization and thermochemistry of synthetic Pb–As, Pb–Cu and Pb–Zn jarosites. Geochimica et Cosmochimica Acta, 127, 107–119.Google Scholar
Gamble, A.V., Givens, A.K. and Sparks, D.L. (2018) Arsenic speciation and availability in orchard soils historically contaminated with lead arsenate. Journal of Environmental Quality, 47, 121–128.Google Scholar
Gomez-Parrales, I., Bellinfante, N. and Tejada, M. (2011) Study of mineralogical speciation of arsenic in soils using X ray microfluorescence and scanning electronic microscopy. Talanta, 84, 853–858.Google Scholar
Gonzalez-Contreras, P., Weijma, J., van der Weijden, R. and Buisman, C.J.N. (2010) Biogenic scorodite crystallization by Acidianus sulfidivorans for arsenic removal. Environmental Science & Technology, 44, 675–680.Google Scholar
Harrison, W.T.A. (2000) Synthetic mansfieldite, AlAsO4·2H2O. Acta Crystallographica C, 56, e421.Google Scholar
Hawthorne, F.C. (1976) The hydrogen positions in scorodite. Acta Crystallographica B, 32, 2891–2892.Google Scholar
Hebbard, E.R., Wilson, S.A., Jowitt, S.M., Tait, A.W., Turvey, C.C. and Wilson, H.L. (2017) Regrowth of arsenate-sulfate efflorescences on processing plant walls at the Ottery arsenic-tin mine, New South Wales, Australia: Implications for arsenic mobility and remediation of mineral processing sites. Applied Geochemistry, 79, 91–106.Google Scholar
Iuliano, M., Ciavatta, L. and De Tommaso, G. (2007) On the solubility constant of strengite. Soil Science Society of America Journal, 71, 1137–1140.Google Scholar
Jambor, J.L. (1994) Mineralogy of sulfide-rich tailings and their oxidation products. Pp. 59–102 in: Short Course Handbook on Environmental Geochemistry of Sulfide Mine-Waste (Jambor, J.L. and Blowes, D.W., editors). Mineralogical Association of Canada, 22.Google Scholar
Johnston, S., Burton, E., Keene, A.F., Planer-Friedrich, B., Voegelin, A., Blackford, M.G. and Lumpkin, G.R. (2012) Arsenic mobilization and iron transformations during sulfidization of As(V)-bearing jarosite. Chemical Geology, 334, 9–24.Google Scholar
Kocourková, E., Sracek, O., Houzar, S., Cempírek, J., Losos, Z., Filip, J. and Hršelová, P. (2011) Geochemical and mineralogical control on the mobility of arsenic in a waste rock pile at Dlouhá Ves, Czech Republic. Journal of Geochemical Exploration, 110, 61–73.Google Scholar
Kennedy, C.A., Stancescu, M., Marriott, R.A. and White, M.A. (2007) Recommendations for accurate heat capacity measurements using a Quantum Design physical property measurement system. Cryogenics, 47, 107–112.Google Scholar
Kolitsch, U., Rieck, B., Brandstätter, F., Schreiber, F., Fabritz, K. H., Blass, G. and Gröbner, J. (2014) Neufunde aus dem altem Bergbau und den Schlacken von Lavrion (I). Mineralien-Welt, 25, 60–75.Google Scholar
Kolitsch, U., Lengauer, C.L. and Giester, G. (2016) Crystal structures and isotypism of the iron(III) arsenate kamarizaite and the iron(III) phosphate tinticite. European Journal of Mineralogy, 28, 71–81.Google Scholar
Krivovichev, S.V., Zhitova, E.S., Ismagilova, R.M. and Zolotarev, A.A. (2018) Site-selective As-P substitution and hydrogen bonding in the crystal structure of philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O. Physics and Chemistry of Minerals, https://doi.org/10.1007/s00269-018-0972-zGoogle Scholar
Kumarathasan, P., McCarthy, G.J., Hasset, D.J. and Pflughoeft-Hassett, D.F. (1990) Oxyanion substituted ettringites: synthesis and characterization, and their potential role in immobilization of As, B, Cr, Se, and V. MRS Online Proceeding Library, 178, 83–104.Google Scholar
Langmuir, D., Mahoney, J. and Rowson, J. (2006) Solubility products of amorphous ferric arsenate and crystalline scorodite (FeAsO4·2H2O) and their application to arsenic behavior in buried mine tailings. Geochimica et Cosmochimica Acta, 70, 2942–2956.Google Scholar
Le Berre, J.F., Cheng, T.C., Gauvin, R. and Demopoulos, G.P. (2007) Hydrothermal synthesis and stability evaluation of iron(III)-aluminum(III) arsenate solid solutions. Metallurgical and Materials Transactions B, 38, 159–166.Google Scholar
Lintnerová, O., Šucha, V. and Streško, V. (1999) Mineralogy and geochemistry of acid mine Fe-precipitates from the main Slovak mining regions. Geologica Carpathica, 50, 395–404.Google Scholar
Luo, Z.Q., Zhou, X.T., Jia, Q.M., Chen, X.F., Tao, Z.C. and Liu, S.Q. (2015) Preparation of arsenical-natroalunite solid solutions with high crystallinity by hydrothermal method. Materials Research Innovations, 19, S6-26-S6-29.Google Scholar
Luptáková, J., Milovská, S., Jeleň, S., Mikuš, T., Milovský, R. and Biroň, A. (2016) Primary ore Cu mineralization at the Ľubietová-Podlipa locality (Slovakia). Acta Geologica Slovaca, 8, 175–194.Google Scholar
Majzlan, J., Drahota, P., Filippi, M., Grevel, K.-D., Kahl, W.-A., Plášil, J., Woodfield, B.F. and Boerio-Goates, J. (2012) Thermodynamic properties of scorodite and parascorodite (FeAsO4·2H2O), kaňkite (FeAsO4·3.5H2O), and FeAsO4. Hydrometallurgy, 117–118, 47–56.Google Scholar
Majzlan, J., Števko, M., Dachs, E., Benisek, A., Plášil, J. and Sejkora, J. (2016) Thermodynamics, stability, crystal structure, and phase relations among euchroite, Cu2(AsO4)(OH)·3H2O, and related minerals. European Journal of Mineralogy, 29, 5–16.Google Scholar
Majzlan, J. (2017) Solution calorimetry on minerals related to acid mine drainage – methodology, checks, and balances. Acta Geologica Slovaca, 9, 171–183.Google Scholar
Moore, P.B. and Araki, T. (1978) Angelellite, ${\rm Fe}_{\rm 4}^{3 +} $O3(As5+O4)2: a novel cubic close-packed oxide structure. Neues Jahrbuch für Mineralogie, Abhandlungen, 132, 91–100.Google Scholar
Navrotsky, A. (1997) Progress and new directions in high temperature calorimetry revisited. Physics and Chemistry of Minerals, 24, 222–241.Google Scholar
Navrotsky, A. (2014) Progress and new directions in calorimetry: A 2014 perspective. Journal of the American Ceramic Society, 97, 3349–3359.Google Scholar
Navrotsky, A. and Kleppa, O.J. (1968) Thermodynamics of formation of simple spinels. Journal of Inorganic and Nuclear Chemistry, 30, 479–498.Google Scholar
Nordstrom, D.K. and Archer, D.G. (2003) Arsenic thermodynamic data and environmental geochemistry. Pp. 1–25 in: Arsenic in Ground Water (Welch, A.H. and Stollenwerk, K.G., editors). Springer.Google Scholar
Nordstrom, D.K., Königsberger, E. and Majzlan, J. (2014) Thermodynamic properties for arsenic minerals and aqueous species. Pp. 217–255 in: Arsenic: Environmental Geochemistry, Mineralogy, and Microbiology (Bowell, R.J., Alpers, C.N., Jamieson, H.E., Nordstrom, D.K. and Majzlan, J., editors). Reviews in Mineralogy & Geochemistry, 79. Mineralogical Society of America and the Geochemical Society, Chantilly, Virginia, USA.Google Scholar
Nriagu, J.O. (1972) Solubility equilibrium constant of strengite. American Journal of Science, 272, 476–484.Google Scholar
Pantuzzo, F.L., Santos, L.R.G. and Ciminelli, V.S.T. (2014) Solubility-product constant of an amorphous aluminum-arsenate phase (AlAsO4·3.5H2O) at 25°C. Hydrometallurgy, 144–145, 63–68.Google Scholar
Parkhurst, D.L. and Appelo, C.A.J. (1999) User's guide to PHREEQC (Version 2) – a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. U.S. Geol. Survey Water-Resources Investigation Report, 99–4259, 312 pp.Google Scholar
Pinisakul, A., Polprasert, C., Parkpian, P. and Satayavivad, J. (2002) Arsenic removal efficiency and mechanisms by electro-chemical precipitation process. Water Science and Technology, 46, 247–254.Google Scholar
Prasanna, S.V. and Kamath, P.V. (2009) Synthesis and characterization of arsenate-intercalated layered double hydroxides (LDHs): Prospects for arsenic mineralization. Journal of Colloid and Interface Science, 331, 439–445.Google Scholar
Rahman, M.S., Clark, M.W., Yee, L.H., Comarmond, M.J., Payne, T.E., Kappen, P. and Mokhber-Shahin, L. (2017) Arsenic solid-phase speciation and reversible binding in long-term contaminated soils. Chemosphere, 168, 1324–1336.Google Scholar
Ramdohr, P., Ahlfeld, F. and Berndt, F. (1959) Angelellit, ein natürliches triklines Eisen-Arsenat, 2Fe2O3·As2O5. Neues Jahrbuch für Mineralogie, Monatshefte, 145–151.Google Scholar
Riveros, P.A., Dutrizac, J.E. and Spencer, P. (2001) Arsenic disposal practices in the metallurgical industry. Canadian Metallurgical Quarterly, 40, 395–420.Google Scholar
Robie, R.A. and Hemingway, B.S. (1995) Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (105 pascals) and at higher temperatures. US Geological Survey Bulletin, 2131, 461 pp.Google Scholar
Savage, K.S., Bird, D.K. and O'Day, P.A. (2005) Arsenic speciation in synthetic jarosite. Chemical Geology, 215, 473–498.Google Scholar
Schwendtner, K. and Kolitsch, K. (2017) MIn(HAsO4)2 (M = K, Rb, Cs): three new hydrogenarsenates adopting two different structure types. Acta Crystallographica E, 73, 1580–1586.Google Scholar
Sejkora, J., Ondruš, P., Fikar, M., Veselovský, F., Mach, Z., Gabašová, A., Škoda, R. and Beran, P. (2006) Supergene minerals at the Huber stock and Schnöd deposits, Krásno ore district, the Slavkovský les area, Czech Republic. Journal of the Czech Geological Society, 51, 57–101.Google Scholar
SGTE (1999) Thermodynamic properties of inorganic materials compiled by SGTE. In: Numerical Data and Functional Relationships in Science and Technology (Martienssen, W., editor). Group IV, Physical Chemistry Vol. 19. Springer.Google Scholar
Shen, M., Guo, H., Jia, Y., Cao, Y. and Zhang, D. (2018) Partitioning and reactivity of iron oxide minerals in aquifer sediments hosting high arsenic groundwater from the Hetao basin, P. R. China. Applied Geochemistry, 89, 190–201.Google Scholar
Skarpelis, N. and Argyraki, A. (2009) The geology and origin of supergene ores in Lavrion (Attica, Greece). Resource Geology, 59, 1–14.Google Scholar
Števko, M., Sejkora, J. and Malíková, R. (2016) New data on supergene minerals from the Rainer mining field, Ľubietová-Podlipa deposit (Slovak Republic). Bulletin Mineralogicko-Petrologického Oddělení Národního Muzea, 24, 1–12 [in Slovak with English abstract].Google Scholar
Števko, M., Sejkora, J. and Súľovec, Š. (2017) Contribution to the chemical composition of libethenite from the type locality: Podlipa copper deposit, Ľubietová (Slovak Republic). Bulletin Mineralogie a Petrologie, 25, 252–259. [in Slovak with English abstract].Google Scholar
Sunyer, A., Currubi, M. and Vinals, J. (2016) Arsenic immobilization as alunite-type phases: The arsenate substitution in alunite and hydronium alunite. Journal of Hazardous Materials, 261, 559–569.Google Scholar
Swash, P.M. and Monhemius, A.J. (1998) The scorodite process: A technology for the disposal of arsenic in the 21st century. Pp. 119–161 in: Effluent Treatment in the Mining Industry (Castro, S.H., Vergara, F. and Sánchez, M.A., editors). Universidad de Concepción, Chile.Google Scholar
Ushakov, S.V., Helean, K.B., Navrotsky, A. and Boatner, L.A. (2001) Thermochemistry of rare-earth orthophosphates. Journal of Materials Research, 16, 2623–2633.Google Scholar
Vinals, J., Sunyer, A., Molera, P., Cruells, M. and Llorca, N. (2010) Arsenic stabilization of calcium arsenate waste by hydrothermal precipitation of arsenical natroalunite. Hydrometallurgy, 104, 247–259.Google Scholar
Voudouris, P., Melfos, V., Spry, P.G., Bonsall, T.A., Tarkian, M. and Solomos, C. (2008) Carbonate-replacement Pb–Zn–Ag ± Au mineralization in the Kamariza area, Lavrion, Greece: Mineralogy and thermochemical conditions of formation. Mineralogy and Petrology, 94, 85–106.Google Scholar
Wagman, D.D., Evans, W.H., Parker, V.B., Halow, I., Bailey, S.M. and Schumm, R.H. (1968) Selected values of chemical thermodynamic properties. Tables for the first thirty-four elements in the standard order of arrangement. NBS Technical Note, 270–3.Google Scholar
Weber, K. (1959) Eine kristallographische Untersuchung des Angelellits, 2Fe2O3·As2O5. Neues Jahrbuch für Mineralogie, Monatshefte, 152–158 [in German].Google Scholar
Welham, N.J., Malatt, K.A. and Vukcevic, S. (2000) The stability of iron phases presently used for disposal from metallurgical systems – A review. Minerals Engineering, 13, 911–931.Google Scholar
Wright, J.P., McLaughlin, A.C. and Attfield, J.P. (2000) Partial frustration of magnetic order in synthetic angelellite, Fe4As2O11. Journal of the Chemical Society, Dalton Transactions, 3663–3668.Google Scholar
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