Dispersion of arsenic species from highly explosive historical volcanic eruptions in Patagonia

Andean volcanic rocks typically have low to moderate arsenic (As) concentrations. However, elevated levels of As in groundwaters of southern South America have been reported as a consequence of weathering of volcanic glass. This study discusses the abundance, speciation and dispersion of As species in fresh volcanic ash from highly explosive (Volcanic Explosivity Index: 4-5) Patagonian eruptions, as well as the potential of As release to aqueous reservoirs. Synchrotron-based X-ray absorption and micro-focused X-ray photoelectron spectroscopies were used to evaluate As solid speciation. Batch experiments at different pH conditions were performed with the aim of understanding the controls on As release to aqueous reservoirs. Bulk chemical and mineralogical characterizations were performed by inductively coupled plasma optical emission spectroscopy, X-ray diffraction and scanning electron microscopy/energy dispersive spectroscopy. Finally, to understand how As-bearing phases are spatially distributed after eruptions, simulations of volcanic ash emission, transport and deposition were performed. Results indicate that the concentration, speciation, and mobility of As in fresh Patagonian volcanic ash depend on the silica content of source magmas. Although the main As host in volcanic ash is Al-silicate glass, this phase is stable at neutral pH characteristic of most aqueous reservoirs. Higher contributions of As to water are associated with the more mobile As species that concentrate onto the surface of Al-silicate glass. Atmospheric dispersion simulations revealed that primary fallout of As-bearing ash has affected large areas in Patagonia, but also reached the ChacoPampean plain, where the presence of As-rich groundwater has been widely documented.