Formation mechanism of Fe oxyhydroxides and behavior of metals during the oxidation of submarine sulfides at the Wocan-1 hydrothermal field, Carlsberg Ridge

Hydrothermal sulfides undergo complex oxidation process under seawater conditions, which has the potential to impact resource values and marine environments. However, the oxidation process is not fully explored, particularly regarding the transformation of minerals and the behavior of metals. In this paper, we conducted detailed mineralogical and geochemical analyses on a series of samples with varying degrees of oxidation, collected from the Wocan-1 hydrothermal field, Carlsberg Ridge, Northwest Indian Ocean. The principal purpose is to illuminate the formation and transformation of Fe (oxyhydr)oxides, and further to reveal the migration and redistribution of key metals throughout the oxidation process. We identified four types of Fe(−Si) (oxyhydr)oxides with two distinct formation mechanisms. Three Fe (oxyhydr)oxides are the direct oxidation products of pyrite and marcasite, while Fe-Si (oxyhydr)oxide precipitates from low-temperature hydrothermal fluids. Thin Fe (oxyhydr)oxide forms as the secondary product of euhedral pyrite at the early stage of oxidation. Pseudomorphic Fe (oxyhydr)oxide with low Fe contents, occurs as the replacement of euhedral marcasite. Filamentous Fe (oxyhydr)oxide, enriched in trace metals, is attributed to the uniform oxidation of subhedral pyrite-marcasite intergrowth. Moreover, major and trace elements occur multiple migrations and redistributions among primary sulfides, secondary products, and seawater. Notably, Fe (oxyhydr)oxides, through the sequestration mechanism, not only retain Cu and Zn released by the oxidation of primary sulfide minerals, but also scavenge Cu from seawater. However, the dissolution of Pb, As, Mo, and Co exceeds the amount retained during the oxidation, indicating that the potential release of toxic metals into the environment could pose a threat to the local ecosystem. These new insights can provide an initial foundation for the effect of submarine oxidation on economic values of sulfides and ecological environments of deep sea.