Neoformation of exotic copper minerals from gel-like precursors at the Exótica deposit, Chuquicamata, Chile

Abstract

At the Exótica deposit, south of the giant porphyry copper deposit of Chuquicamata (Atacama Desert, Chile), Cu-rich groundwater seeped out at several locations in the Exótica open pit (Mina Sur) during sampling in 2009–2011. At their outflows, these solutions formed blueish and greenish copper-bearing gel-like precipitates. These gels contained atacamite and copper sulfate hydroxides such as devilline, spangolite, posnjakite, schulenbergite, and brochantite, which were identified by XRD, SEM, ESEM, and FTIR. The formation of the gel materials was studied under humid and dry conditions during and after maturation and water evaporation. Atacamite was found associated to outflowing saline solutions with pH 5.7, SO4/Cl weight ratios of 0.42–0.48, SO4/NO3 ratios of 0.48–0.50. These solutions are seen as an expression of the the lower aquifer of the Calama basin. Most copper sulfate hydroxides (spangolite, posnjakite, schulenbergite) were associated with slightly acidic freshwaters (pH 6.0 to 6.5, SO4/Cl ratios of 3.08–4.99, SO4/NO3 ratios of 2.52–3.13). In contrast, devilline formed in gels with near neutral to slightly alkaline water (pH 7.2 to 7.8, SO4/Cl ratio of 8.34, and SO4/NO3 ratio of 6.05). Non-copper-bearing precipitates formed by evaporation of the supernatant solutions from the gel. Gypsum precipitated first, then blödite (sodium-magnesium sulfate), and finally halite. Slightly negative sulfur isotope values suggest that the sulfur source in the neoformed gels is primarily the oxidation of sulfides rather than sulfate of sedimentary origin. The studied copper-gel seeps suggest that they might represent a modern precursor of the latest atacamite-brochantite-gypsum mineralization event at Exótica. These data support that the atacamite-brochantite-gypsum mineralization at Exótica is linked to the inflow of Cl-SO4-dominated groundwater from the lower saline aquifer of the Calama basin into the Chuquicamata-Exótica-Radomiro Tomic complex.