Kendrick, Mark; Arculus, R.; Burnard, P.; Honda, M.
Volatiles are critically important in controlling the chemical and physical properties of the mantle. However, determining mantle volatile abundances via the preferred proxy of submarine volcanic glass can be hampered by seawater assimilation. This study shows how combined Cl, Br, I, K and H2O abundances can be used to unambiguously constrain the dominant mechanism by which melts assimilate seawater-derived components, and provide an improved method for determining mantle H2O and Cl abundances....[Show more] We demonstrate that melts from the northwest part of the Lau Basin, the Galápagos Spreading Centre and melts from other locations previously shown to have anomalously high Cl contents, all assimilated excess Cl and H2O from ultra-saline brines with estimated salinities of 55±15wt.% salts. Assimilation probably occurs at depths of ~3-6km in the crust when seawater-derived fluids come into direct contact with deep magmas. In addition to their ultra-high salinity, the brines are characterised by K/Cl of <0.2, I/Cl of close to the seawater value (~3×10-6) and distinctive Br/Cl ratios of 3.7-3.9×10-3, that are higher than both the seawater value of 3.5×10-3 and the range of Br/Cl in 43 pristine E-MORB and OIB glasses that are considered representative of diverse mantle reservoirs [Br/Clmantle=(2.8±0.6)×10-3 and I/Clmantle=(60±30)×10-6 (2σ)]. The ultra-saline brines, with characteristically elevated Br/Cl ratios, are produced by a combination of fluid-rock reactions during crustal hydration and hydrothermal boiling. The relative importance of these processes is unknown; however, it is envisaged that a vapour phase will be boiled off when crustal fluids are heated to magmatic temperatures during assimilation. Furthermore, the ultra-high salinity of the residual brine that is assimilated may be partly determined by the relative solubilities of H2O and Cl in basaltic melts. The most contaminated glasses from the Galápagos Spreading Centre and Lau Basin have assimilated ~95% of their total Cl and up to 35-40% of their total H2O, equivalent to the melts assimilating 1000-2000ppm brine at an early stage of their evolution. Dacite glasses from Galapagos contain even higher concentrations of brine components (e.g. 12,000ppm), but the H2O and Cl in these melts was probably concentrated by fractional crystallisation after assimilation. The Cl, Br, I and K data presented here confirm the proportion of seawater-derived volatiles assimilated by submarine magmas can vary from zero to nearly 100%, and that assimilation is closely related to hydrothermal activity. Assimilation of seawater components has previously been recognised as a possible source of atmospheric noble gases in basalt glasses. However, hydrothermal brines have metal and helium concentrations up to hundreds of times greater than seawater, and brine assimilation could also influence the helium isotope systematics of some submarine glasses