ABSTRACT

Experiments were carried out to determine molybdenum isotope fractionation associated with adsorption to pyrite. Results show that the Mo isotope composition of the aqueous solution becomes progressively heavier as Mo is adsorbed, with a Mo isotope fractionation as large as 2.9‰. This fractionation is larger than observed for typical anoxic continental margin marine sediments (e.g., ~0.7‰), suggesting that Mo adsorption to pyrite is not the dominant process operating in these environments. However, our adsorption results do suggest the possibility that anoxic fractionation processes could impart an isotope signature within the geologic record similar to the isotope fractionation observed under oxygenated conditions. Additional experiments were conducted at high (~100 μM) dissolved Mo concentrations, but at varying pH and ∑H₂S concentrations, and in each case these experiments promoted Mo-sulfide precipitation. Even though the experiments were conducted under differing conditions and produced different amounts of precipitate, the results suggest a constant fractionation of ~0.9‰ associated with this Mo removal process. This fractionation is more consistent with that inferred for anoxic continental margin marine sediments, suggesting that a process similar to Mo-sulfide precipitation, rather than an adsorption process, may be responsible for the Mo isotope compositions observed in these environments. The findings of this study suggest that, regardless of the geochemical mechanism employed, sediment Mo sequestration under anoxic conditions may impart a significant isotopic fractionation relative to parent seawater.