Enargite oxidation: A review

• Published in: Earth-science reviews 2008, Vol.86 (1), p.62-88
• Main Authors: Lattanzi, Pierfranco, Da Pelo, Stefania, Musu, Elodia, Atzei, Davide, Elsener, Bernhard, Fantauzzi, Marzia, Rossi, Antonella
• Format: Article
• Language: English
• Subjects: Acidithiobacillus ferrooxidans; Chemical bonds; Chemical compounds; Dissolution; enargite; laboratory experiments; Minerals; Oxidation; secondary minerals; Spectrum analysis; Sulfolobus; surface oxidation
• ISSN: 0012-8252; 1872-6828
• DOI: 10.1016/j.earscirev.2007.07.006

Enargite, Cu 3AsS 4, is common in some deposit types, e.g. porphyry systems and high sulphidation epithermal deposits. It is of environmental concern as a potential source of arsenic. In this communication, we review the current knowledge of enargite oxidation, based on the existing literature and our own original data. Explicit descriptions of enargite oxidation in natural environments are scarce. The most common oxidized alteration mineral of enargite is probably scorodite, FeAsO 4.2H 2O, with iron provided most likely by pyrite, a phase almost ubiquitously associated with enargite. Other secondary minerals after enargite include arsenates such as chenevixite, Cu 2Fe 2(AsO 4) 2(OH) 4.H 2O, and ceruleite, Cu 2Al 7(AsO 4) 4.11.5H 2O, and sulphates such as brochantite, Cu 4(SO 4)(OH) 6, and posnjakite, Cu 4(SO 4)(OH) 6·H 2O. Detailed studies of enargite field alteration at Furtei, Sardinia, suggest that most alteration occurs through dissolution, as testified by the appearance of etch pits at the surface of enargite crystals. However, apparent replacement by scorodite and cuprian melanterite was observed. Bulk oxidation of enargite in air is a very slow process. However, X-ray photoelectron spectroscopy (XPS) reveals subtle surface changes. From synchrotron-based XPS it was suggested that surface As atoms react very fast, presumably by forming bonds with oxygen. Conventional XPS shows the formation, on aged samples, of a nanometer-size alteration layer with an appreciably distinct composition with respect to the bulk. Mechanical activation considerably increases enargite reactivity. In laboratory experiments at acidic to neutral pH, enargite oxidation/dissolution is slow, although it is accelerated by the presence of ferric iron and/or bacteria such as Acidithiobacillus ferrooxidans and Sulfolobus BC. In the presence of sulphuric acid and ferric iron, the reaction involves dissolution of Cu and formation of native sulphur, subsequently partly oxidized to sulphate. At alkaline pH, the reactivity of enargite is apparently slightly greater. XPS spectra of surfaces conditioned at pH 11 have been interpreted as evidence of formation of a number of surface species, including cupric oxide and arsenic oxide. Treatment with hypochlorite solutions at pH 12.5 quickly produces a coating of cupric oxide. Electrochemical oxidation of enargite typically involves low current densities, confirming that the oxidation process is slow. Important surface changes occur only at h