Metal and acidity fluxes controlled by precipitation/dissolution cycles of sulfate salts in an anthropogenic mine aquifer

Abstract

Underground mine drainages are extremely difficult to study due to the lack of information about the flow path and source proximity in relation to the outflow adit. Geochemical processes controlling metals and acidity fluxes in a complex anthropogenic mine aquifer in SW Spain during the dry and rainy season were investigated by geochemical and statistical tools. High concentrations of acidity, sulfate, metals and metalloids (e.g. Fe, Cu, Zn, As, Cd, Ni, Co) were observed due to intense sulfide oxidation processes. The high residence time inside the anthropogenic aquifer, around 40days, caused the release of significant quantities of metals linked to host rocks (e.g. Al, Ca, Ge, Li, Mg, REE). The most outstanding characteristic of the acid mine drainage (AMD) outflows is the existence of higher Fe/SO4 molar ratios than those theoretical of pyrite (0.50) during most of the monitored period, due to a fire which occurred in 1949 and remained active for decades. Permanent and temporal retention mechanisms of acidity and metals were observed in the galleries. Once released from sulfide oxidation, Pb and As are sorbed on Fe oxyhydroxysulfate or precipitated as low solubility minerals (i.e. anglesite) inside the galleries. The precipitation of evaporitic sulfate salts during the dry season and the subsequent re-dissolution after rainfall control the fluxes of acidity and main metals (i.e. Fe, Mg, Al) from this anthropogenic aquifer. Some elements, such as Cd, Cu, Ni, REE and Zn, are retained in highly soluble sulfate salts while other elements, such as Ge, Pb and Sc, have a lower response to washout processes due to its incorporation in less soluble sulfate salts. In this way, metal concentration during the washout processes would be controlled by the proportion and solubility of each type of evaporitic sulfate salt stored during the dry season. The recovery of metals of economic interest contained in the AMD could help to self-finance the remediation of these waters in derelict mines worldwide.