Spectroelectrochemistry of Enargite I: Reactivity in Alkaline Solutions (6a333428-5a01-42f0-a4a9-2757a37008bb)

"The presence of enargite (Cu3AsS4) is problematic in gold processing not only because it is environmentally hazardous due to its arsenic content but also because it is refractory, causing both cyanide and oxygen consumption to increase. Selective leaching and treatment of the arsenic would prove advantageous prior to applying conventional gold leaching methods. The reactivity of enargite samples from Butte in Montana and Quiruvilca in Peru were spectroelectrochemically studied under alkaline conditions – pH range of 8-13 – using Raman spectroscopy and cyclic voltammetry. Raman spectra of the surface were collected during and after potentially cycled voltammograms in order to determine and compare surface species against theoretical EH-pH diagrams constructed from mass-balanced thermodynamic calculations using STABCAL software. Under slightly oxidizing conditions, covellite (CuS) peaks were found in a short matter of time, above ~100mV vs. SHE for pH 9-13, suggesting arsenic leaching specifically occurred. At longer conditioning times, elemental sulfur was observed and tended to passivate the surface. The presence of elemental sulfur suggests that copper was eventually leached from the surface. By operating above pH 12, under slightly reducing conditions near -300mV vs. SHE, arsenic can be selectively leached as thioarsenate (AsS4 3-) or thiosulfate (AsO4 3-) without sulfur formation.IntroductionEnvironmental limitations on the pyrometallurgical processing of ores and concentrates bearing arsenic and other hazardous elements often outweigh those in hydrometallurgical processing, particularly when minerals like enargite (Cu3AsS4) are present. The hydrometallurgical processing of enargite-bearing materials can be broken down into two categories: the co-dissolution of arsenic and copper under acidic conditions, and the selective leaching of arsenic under alkaline conditions. The selective leaching of arsenic would preferably leave behind copperrich sulfide phases, typically chalcocite (Cu2S) and covellite (CuS), which then become more amenable to conventional copper (and gold) processing. Furthermore, selective leaching often employs sulfide (S2-), bisulfide (HS-) or polysulfides (Sx 2-) to first extract the arsenic as AsS4 3- and AsS3 3- (Delfini et al., 2003; Anderson and Twidwell, 2008; Tongamp et al., 2010a,b). However, hypochlorite leaching (Viñals et al., 2003; Curreli et al., 2005; Mihajlovic et al., 2007), ammoniacal leaching (Gajam and Raghavan, 1983), and finegrinding to mechanically activate the enargite surface (Balaz and Achimovicova, 2006) have been investigated to increase the normally slow reaction kinetics. Because gold ores are becoming more refractory due to increasing arsenic contents as a result of enargite, these methods are being examined more closely by the gold-mining industry."