Naturally acid waters from Copahue volcano, Argentina

Volcanic acid sulfate–chloride brines form through absorption of volcanic vapors in shallow reservoirs of meteoric water. Reaction with surrounding volcanic rocks leads to partial neutralization of the fluids and precipitation of secondary minerals. Chemical data of such acid waters from Copahue volcano, Argentina, covering 8 years of observations, show evidence for changes in composition related to water rock interaction at depth prior to emergence of the fluids at the surface. The chemical composition changed dramatically during the 2000 eruption of Copahue, with enhanced concentrations and fluxes of Mg, Na, Fe and Al, followed in 2001 by rapidly declining concentrations and element fluxes. The subsequent 5 years saw more variable element ratios and strong depletions in K and Al. Most incompatible elements are released from the rock matrix stochiometrically, whereas some elements are enriched through vapor input from the magma (As, Pb, Zn). Most fluids have LREE enrichments relative to the rock matrix, but during periods of new magma intrusion the LREE enrichment decreases as does the magnitude of the negative Eu anomaly in the fluids. These observations are interpreted assuming early dissolution of plagioclase, olivine and volcanic glass that occurs during intrusion of new magma into the hydrothermal system. The high field strength elements are virtually immobile even in these hot acid fluids, with Nb and Ta more so than Hf and Zr. The mobility of U and Th in these fluids is comparable, at variance with Th behavior in neutral fluids. The local rivers and lakes of Copahue are fertilized by volcanic dissolved P, and most surface waters with pH < 3 have high levels of As. The acid fluids from Copahue may be surficial analogs for deep subduction fluids that evolve below zones of arc magma generation as well as for early Mars environments that are thought to have had large acid lakes.