The effect of chemical variability and weathering on Raman spectra of enargite and fahlore

Enargite (Cu3AsS4) and tennantite (Cu12As4S13) are typical As-bearing sulfides in intermediate- and high-sulfidation epithermal deposits. Trace and major element variations in enargite and tennantite and their substitution mechanisms are widely described. However, Raman spectra of the minerals with correlative quantitative chemical information are rarely documented, especially for enargite. Therefore, comparative electron and μ-Raman microprobe analyses were performed on enargite and fahlore grains. These spectra can be used in the industrial detection and subsequent removal of As-bearing sulfides prior to ore beneficiation in order to diminish the environmental impact of the metallurgical technologies. A simple Sb5+–As5+ substitution in enargite was confirmed by Raman analyses. Similarly, a complete solid solution series from tetrahedrite to tennantite (i.e., Sb3+–As3+ substitution) can be correlated with a gradual evolution in their Raman spectra. In turn, Te4+ occupies the As3+ and Sb3+ sites in fahlore by the coupled substitution Te4+ + Cu+ → (As, Sb)3+ + (Cu, Fe, Zn)2+. Accordingly, Raman bands of goldfieldite (Te-rich member) are strongly broadened compared with those of tetrahedrite and tennantite. A secondary phase with high porosity and a fibrous or wormlike texture was found in enargite in a weathered sample. The chemical composition, Raman spectrum, and X-ray diffraction signature of the secondary phase resemble tennantite. A gradual transformation of the primary enargite into this secondary phase was visualized by comparative electron and Raman microprobe mapping.</p