The Cl−Br−I− composition of ∼3.23 Ga modified seawater: implications for the geological evolution of ocean halide chemistry

Fluid inclusion leachates obtained from vug and vein quartz samples from an Archean (∼3.23 Ga) Fe-oxide hydrothermal deposit in the west-central part of the Barberton greenstone belt, South Africa, were analyzed by ion chromatography for chloride, bromide, and iodide. The deposit, known as the ironstone pods, formed by seafloor hydrothermal activity and fluid discharge. Quartz is dominated by type I liquid-vapor, aqueous inclusions with a bimodal salinity distribution (0–0.25 MCl− and 0.9–1.8 MCl−). Bulk analytical salinities range from 0.45 to 0.99 MCl− represent averages of type I inclusions. Bulk fluid inclusion bromide and iodide concentrations are 1.44–3.32 mM and 0.01–0.12 mM, respectively. For comparison, modern seawater has halogen contents of 590 mM chloride, 0.9 mM bromide, and 0.5 μM total iodine. In the fluids from the ironstone pods, bromide and iodide are enriched relative to chloride, when compared with modern seawater. imate Br−Cl− and I−Cl− ratios of 3.2 Ga Barberton seawater are 2.5 × 10−3 and 40 × 10−6, respectively. Dispersion to higher values was caused principally by reaction with organic sediments whose trends are similar to those seen for modern vent fluids at unsedimented and sedimented ridges, relative to modern seawater. These halide ratios are greater than those of modern seawater, suggesting a change in the halide ratios of seawater over geological time. The analytical data are consistent with a model in which marine organic sedimentation has fractionated bromine and iodine out of seawater relative to chloride, thereby causing the halide ratios of seawater to decrease from high early and mid-Archean values towards their present day values.