Nonconservative behavior of Br/Cl ratios during alteration of volcaniclastic sediments

Other than halite diagenesis and organic matter degradation, Cl and Br are considered to be conservative in marine pore fluids. Consequently, Br/Cl ratios should remain constant during most diagenetic reactions. Nonetheless, Br/Cl molar ratios decrease to 1.27 3 10 ('18% less than seawater value) in pore fluids from Site 833 in the Aoba Basin of the New Hebrides convergent margin despite the lack of halite diagenesis and little organic matter. Sediment at this site is largely volcanic ash, which becomes hydrated with depth as it converts to clay and zeolite minerals. These hydration reactions remove sufficient water to increase the concentrations of most solutes including Cl and Br. The resulting concentration gradients drive diffusion, but calculations indicate that diffusion does not decrease the Br/Cl ratio. Some Cl may be leached from the ash, but insufficient amounts are available to cause the observed decrease in Br/Cl ratio. The limited source of Cl suggests that proportionately more Br than Cl is lost from the fluids to the diagenetic solids. Similar nonconservative behavior of Cl and Br may occur during fluid circulation at ridge crests and flanks, thereby influencing the halide distribution in the crust. Copyright © 1999 Elsevier Science Ltd