Lithium isotope systematics and water/rock interactions in a shallow-water hydrothermal system at Milos Island, Greece

Abstract

The active venting fluids of Milos Island, located within the southern Aegean Sea, belong to a shallow-water hydrothermal system (< 200 m depth) that shows chemical compositions and evolution processes comparable to those of mid-ocean ridges (MOR). In this study, we analyze Li and δ7Li in 69 vent water samples, grouped into two types based on their salt content. The low-Cl end-member (EM) Cave fluids show a relatively high Li content (0.39–0.54 mM) with MORB-like δ7Li (∼4.5 ‰, MORB = 3.7 ‰) compared to that of seawater, and the high-Cl brine fluids contain remarkably high Li (6.14–10.6 mM) and variable δ7Li (1.4–8.7 ‰). The latter fluids may have derived from metamorphic basement modified by seawater interactions at ∼300 °C. A scenario using a steady-state dissolution/precipitation model can generate consistent Li and δ7Li patterns, where linear correlations of Cl and Li suggest phase separation occurred after water/rock interaction at depth. On the contrary, no significant δ7Li variation in most Milos fluids suggests limited isotopic fractionation occurred during phase separation. More importantly, the detected Li enrichment in the high-Cl fluids implies a large Li flux, ∼3.4 × 107 mol/yr, to the ocean from the Milos system. Assuming that 10% of the world's shallow-water systems discovered to date have similar Li outputs to those of Milos, this Li flux would represent ∼1.8% of MOR hydrothermal fluxes which is on the order of ∼13 × 109 mol/yr. These results emphasize the importance of Li flux derived from shallow-water hydrothermal systems, which should not be excluded from the calculation of the marine Li budget and its impact on the global silicate weathering cycles.