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[1] Abstract: Molybdenum isotopic compositions are precisely determined by MC-ICP-MS measurements using a Mo double spike. The double spike is added prior to chemical purification, so that laboratory and instrumental mass fractionations are separated from natural mass-dependent fractionation. Fractionation is determined on four Mo mass ratios, providing an internal consistency check.

Molybdenum (Mo) isotope fractionation has recently been introduced as a new proxy in oceanography and biogeochemistry. It is therefore fundamental to understand the processes controlling Mo partitioning into modern marine environments. This study identifi es the availability of dissolved sulfi de as the dominant control on overall Mo removal from the water column in euxinic systems. Mo isotopic composition of surface sediments from different localities of the Black Sea demonstrates complete fi xation of Mo only below 400 m water depth, above a critical concentration of 11 µmol l -1 aqueous hydrogen sulfi de in the bottom water. The Mo isotopic composition of these sediments refl ects the homogeneous seawater isotopic composition of 2.3‰. In contrast, signifi cant Mo isotope fractionation into less euxinic sediments is evident at shallower depths in the Black Sea, as well as in temporarily euxinic deeps of the Baltic Sea, consistent with the observed lower maximum sulfi de concentrations in the respective water columns. Therefore, Mo isotope signatures in the modern Black Sea constrain the processes responsible for global Mo removal from the ocean by euxinic sediments. Furthermore, models of past ocean anoxia reconstruction have to consider that the seawater Mo isotopic composition is not per se archived in euxinic sediments.

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Abstract-The

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In this study, we present first results from an ongoing investigation on the stable barium (Ba) isotope fractionation in the natural barium cycle. Stable Ba isotope signatures of international IAEA reference materials (synthetic barium sulfate, IAEA-SO-5, -6, and barium carbonate, IAEA-CO-9), natural Ba minerals and experimental Ba precipitates have been analyzed as a first approach to evaluate potential discriminating processes in the global geochemical barium cycle. Ba = − 0.5‰ was found in a diagenetic barite sample from ODP Leg 207. The observed natural discriminations are clearly larger than the analytical uncertainty of the stable isotope measurements, indicating significant isotope discrimination in the natural barium cycle. Precipitation experiments from aqueous barium chloride solutions at temperatures of~21°C and 80°C indicate that the light Ba isotope is enriched in pure barium carbonate and barium sulfate compared to the aqueous solution. A maximum isotope fractionation of − 0.3‰ is observed for both barium carbonate and sulfate, that -in the case of BaCO 3 -seems to be influenced by precipitation rate and/or the aqueous speciation, but less by temperature.

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