Solubility and speciation of rhenium in anoxic environments at ambient temperature and applications to the Black Sea

The aqueous speciation of rhenium at the temperatures on or near the Earthʹs surface, especially in anoxic environments, is not well known. For the first time, the relative importance of ReO4− and the neutral rhenium species, Re(OH)40, is thermodynamically modeled in anoxic environments at ambient temperature where ReS2 or its solid solution(s) is likely to control the solubility. This thermodynamic model suggests that ReO4− is an insignificant species in anoxic environments. In comparison to observed total rhenium concentrations in anoxic waters (from ∼3 to ∼30 pmol/kg), the contribution from ReO4− would be less than 10−8 ppb (∼4×10−5 pmol/kg). In contrast, the neutral rhenium species is an important species in anoxic environments. At ΣH2S=10−4 molal, 10−2 ppb (∼40 pmol/kg) of Re(OH)40 can exist in equilibrium with ReS2 in the HS− field at a pH of about 9 or under the oxygen fugacity conditions imposed by the HS−/SO42− redox couple, demonstrating its importance in anoxic environments. Applications of the present study to the Black Sea indicate that rhenium concentrations in the anoxic water column at depths ranging from 105 to ∼390 m can be successfully modeled as Re(OH)40, implying that the dominant species in solution may be Re(OH)40.