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A proposed new type of arsenian pyrite: Composition, nanostructure and geological significance
Journal article   Peer reviewed

A proposed new type of arsenian pyrite: Composition, nanostructure and geological significance

A.P. Deditius, S. Utsunomiya, D. Renock, R.C. Ewing, C.V. Ramana, U. Becker and S.E. Kesler
Geochimica et Cosmochimica Acta, Vol.72(12), pp.2919-2933
2008
DOI: https://doi.org/10.1016/j.gca.2008.03.014
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Abstract

This report describes a new form of arsenian pyrite, called As3+-pyrite, in which As substitutes for Fe [(Fe,As)S2], in contrast to the more common form of arsenian pyrite, As1--pyrite, in which As1- substitutes for S [Fe(As,S)2]. As3+-pyrite has been observed as colloformic overgrowths on As-free pyrite in a hydrothermal gold deposit at Yanacocha, Peru. XPS analyses of the As3+-pyrite confirm that As is present largely as As3+. EMPA analyses show that As3+-pyrite incorporates up to 3.05 at % of As and 0.53 at. %, 0.1 at. %, 0.27 at. %, 0.22 at. %, 0.08 at. % and 0.04 at. % of Pb, Au, Cu, Zn, Ni, and Co, respectively. Incorporation of As3+ in the pyrite could be written like: As3 + + y Au+ + 1 - y (□) ⇔ 2 Fe2 +; where Au+ and vacancy (□) help to maintain the excess charge. HRTEM observations reveal a sharp boundary between As-free pyrite and the first overgrowth of As3+-pyrite (20-40 nm thick) and co-linear lattice fringes indicating epitaxial growth of As3+-pyrite on As-free pyrite. Overgrowths of As3+-pyrite onto As-free pyrite can be divided into three groups on the basis of crystal size, 8-20 nm, 100-300 nm and 400-900 nm, and the smaller the crystal size the higher the concentration of toxic arsenic and trace metals. The Yanacocha deposit, in which As3+-pyrite was found, formed under relatively oxidizing conditions in which the dominant form of dissolved As in the stability field of pyrite is As3+; in contrast, reducing conditions are typical of most environments that host As1--pyrite. As3+-pyrite will likely be found in other oxidizing hydrothermal and diagenetic environments, including high-sulfidation epithermal deposits and shallow groundwater systems, where probably kinetically controlled formation of nanoscale crystals such as observed here would be a major control on incorporation and release of As3+ and toxic heavy metals in oxidizing natural systems.

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Citation topics
8 Earth Sciences
8.8 Geochemistry, Geophysics & Geology
8.8.1 Geochemical Petrogenesis
Web Of Science research areas
Geochemistry & Geophysics
ESI research areas
Geosciences
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