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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. 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 ± 15 wt. % salts. Assimilation probably occurs at depths of ~3-6 km 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 35-40 % of their total H2O, equivalent to the melts assimilating 1000-2000 ppm brine at an early stage of their evolution. Dacite glasses from Galapagos contain even higher concentrations of brine components (e.g. 12,000 ppm), 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 3 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.

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Kendrick-11Dec'12.docx Click here to view linked References serpentinites trap noble gases and halogens that originate from seawater, diverse crustal lithologies and organic matter. Combined with previous analyses of metamorphosed serpentinites, the new data suggest that approximately 60-70% of the 36 Ar entering subduction zones in serpentinites is lost from chrysotile and/or antigorite and could potentially escape through the forearc. An additional, ~20-30 % of the 36 Ar entering subduction zones in serpentinites is lost during antigorite breakdown and may be cycled through the arc or back-arc, and ~1-10 % of the 36 Ar entering subduction zones in serpentinites may be subducted into the deeper mantle. The data demonstrate decoupling of noble gases, halogens and water during subduction and suggest that subduction-zone fluid fluxes may concentrate noble gases and iodine in newly formed forearc serpentinites. The distinctive I/Cl enrichment of forearc serpentinites suggest that halogen abundance ratios provide a plausible means for inferring the geotectonic setting of serpentinisation in ophiolite samples. The exceptional Cl, Br, I and noble gas concentrations of serpentinites, the potential subduction of the forearc serpentinites and the stability of serpentine minerals to mantle depths of >200 km, imply that serpentinites could dominate the deep recycling budgets of both the heavy halogens and atmospheric noble gases.

[1980] and Kyser and Rison [1982]. The present study also has shown that the nucleogenic 2•Ne production from the 24Mg(n,00 reaction is only about one-fifth the previous estimate. The contribution of nucleogenic 21Ne from the 24Mg(n,00 reaction is insignificant compared with nucleogenic 2•Ne production from 180(o•,n). Our estimate of the nucleogenic 2•Ne/radiogenic 4He production ratio both in the mantle and in the crust is 4.5 x 10 -8. This production ratio is quite consistent with nucleogenic 21Ne/radiogenic 4He ratios actually observed in crustal fluid samples ((4.6 + 0.8) x 10-8). The error in calculation of the nucleogenic neon production, resulting from a random statistical variation of the entry neutron yields and cross sections, is estimated to be less than 5%.

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