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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

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