Oxidation of Ni-Rich Mangrove Sediments after Isolation from the Sea (Dumbea Bay, New Caledonia): Fe and Ni Behavior and Environmental Implications

Formation of Fe-sulfides in anoxic horizons of mangrove sediments makes this ecosystem a potential long-term sink for metal contaminants in the intertropical region. Increasing anthropogenic pressure on coastal areas can alter the physicochemical of mangrove sediments by modifying their redox state, affecting directly the rate of Fe-sulfides that mediate accumulation of metal contaminant. Here, we show that isolation from the sea, due to land use planning, directly modify the redox state of mangrove sediments from reducing condition to oxidizing condition, affecting the stability of Ni-accumulating Fe-sulfides. Unusual suboxic/oxic conditions are indeed observed at intermediate depths in these mangrove sediments and favor the oxidative dissolution of Ni-pyrite (Fe1-xNixS2) that initially formed under anoxic/suboxic conditions. This reaction leads to a significant release of aqueous HS-, Fe2+ and Ni2+ at the redox boundary. HS- and Fe2+ oxidize into SO42- and Fe3+ and precipitate as schwertmannite (Fe8O8(OH)(6)SO4), leading to acidification of the pore-waters. Meanwhile, aqueous Ni2+ is mostly leached downward in the underlying anoxic layers of the sediment where it sorbs at the surface of pyrite and/or incorporates in the structure of newly formed pyrites. These results emphasize the potential of Fe-sulfides for mitigating the impact of the oxidation of former Ni-rich mangrove sediments, as long as the anoxic conditions are preserved at depth. This assumption can be expanded to other divalent metals and should be applicable to a larger set of mangrove ecosystems worldwide.