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

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, As^1--pyrite, in which As^1- 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: As^{3 +} + y Au⁺ + 1 - y (□) ⇔ 2 Fe^{2 +}; 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 As^1--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.