Geochemistry of trace metals and Rare Earth Elements in shallow marine water affected by hydrothermal fluids at Vulcano (Aeolian Islands, Italy)

Abstract

Trace metals and Rare Earth Element (REE) are amply discharged by submarine hydrothermal vents, sometimes leading to the formation of ore deposits of economic interest. We report on first data on the geochemical processes involving REE and trace metals, at the solid-liquid interface, in the hydrothermal area of Levante Bay at Vulcano Island (Aeolian Archipelago, Italy). Samples were collected from several submarine springs and seeps, a mud pool and one thermal well, and analyzed for Al, Si, Ti, V, Cr, Mn, Fe, Co, As, Rb, Sr, Cs, Ba, U and REE, besides major ions. Within the bay, hydrothermal fluids contaminate seawater and promote the leaching of metals from sediments through the dissolution of CO2 and H2S, while the particulate matter removes several elements from the water. The leaching of the bottom sediments and the contribution of steam-heated water produce an enrichment of some metals and REE in the Levante Bay with respect to the concentrations expected in the ambient seawater. An enrichment up to one order of magnitude is measured for Fe, Al, Ba, Cs and Rb, and up to two orders of magnitude for Mn in the submarine samples. Other transition metals (Ti, V, Co, Cr), U, As and Sr have concentrations similar or slightly lower than the ambient seawater. REE are in concentrations higher than in ambient seawater up to two orders of magnitude. Despite being significantly higher than uncontaminated seawater, the concentrations of some metals (namely Fe, Al, Ti, Cr, V, Co, U) and REE in most samples are lower than expected by the mixing between seawater and the steam-heated water, discharging from submarine springs. Indeed, equilibrium and reaction path modeling indicate the likely precipitation of Fe-oxyhydroxides, able to remove minor elements, such as Ti, Cr, Co, V and As, and REE. The last ones are significantly removed by newly-forming solid phases, due to the presence of a large amount of Fe released by the acidic fluids through the leaching of sediments. The low pH limits the formation of solution complexes of REE with carbonate ions (the main complexing agent for REE in seawater), whereas the sorption onto particles is still effective, even at close distance from the submarine springs and seeps. This study brings new insights on the geochemical processes occurring in submarine hydrothermal systems, in particular, those in subduction-related context.