Experimental investigation of the reactions between pyrite and aqueous Cu(I) chloride solution at 100–250 °C

Abstract

Replacement of pyrite by copper-bearing sulfides is widespread in mineral deposits, with zonation of chalcocite, bornite, and chalcopyrite being a common result of this process. Copper occurs predominantly as Cu(I) in hydrothermal fluids, but the mechanistic details of reactions between pyrite and aqueous Cu(I) and their relevance to the zonation of Cu sulfides in hydrothermal deposits remain poorly understood, because of a lack of relevant experimental constraints. In this study, we investigated the reactions between pyrite and aqueous Cu(I) chloride solutions over a wide range of physicochemical conditions (100–250 °C; pH = 1–8; saturated vapor pressure). The experimental results show that Cu-bearing sulfides form at temperatures of >150 °C, and that pH exerts an important control on the mineralogy of the reaction products. In strongly acidic conditions (pH = 1.1), pyrite dissolution occurs; in acidic-to-neutral conditions (pH = 3.0–6.0), chalcopyrite and bornite are the main products; in weakly alkaline conditions (pH = 8.2), the replacement products are chalcocite and bornite. Chalcopyrite, bornite, and chalcocite generally occur in a zoned sequence outward from the pyrite reaction front to the bulk solution, and the replacement of pyrite by chalcopyrite is heterogeneous. In situ Raman observation and S isotope analyses suggest that pyrite replacement by chalcopyrite is a redox-coupled dissolution–precipitation reaction, with the oxidative dissolution of pyrite to form sulfate, generating the electrons that maintain the reductive replacement of pyrite by chalcopyrite. The sites of oxidative dissolution and reductive replacement can be spatially separated, but coupled by electron transfer. By contrast, the further replacement of chalcopyrite by bornite and chalcocite does not involve the oxidative dissolution of sulfur, but release of iron and H+, which could be promoted at higher pH. Notably, when the zonation of sulfides is established in a hydrothermal experiment of pyrite replacement by Cu(I) solution, gradients of H2S (or HS–), Cu(I), and Fe(II) are developed between the pyrite reaction front and bulk solution via diffusion through interstitial pore space. As such, the inner zones of chalcopyrite and bornite are not in equilibrium with the bulk solution as confirmed by thermodynamic calculations. The results imply that the zonation of Cu-bearing sulfides in mineral deposits records heterogeneous chemical environments, from the mineral interface- to the ore deposit-scale during dynamic mineralization processes.