Nickel exchange between aqueous Ni(II) and deep-sea ferromanganese nodules and crusts

摘要

Deep-sea ferromanganese (Fe-Mn) nodules and crusts are rich in traditional and non-traditional metals with both current and emerging economic value. Mn(III,IV) oxides (e.g., phyllomanganates) are important host phases for these metals (e.g., Ni), which are structurally incorporated during nodule and Fe-Mn crust formation. Recrystallization of phyllomanganates can be catalyzed by aqueous Mn(II) (Mn(II)(aq)) during (bio)geochemical Mn redox cycling. The fate of structurally incorporated metals during such recrystallization of Mn(III,IV) oxides remains, however, poorly constrained. Here, we use a Ni-62 isotope tracer to determine the exchangeability of dissolved Ni with structurally incorporated Ni in two deep-sea Fe-Mn nodules and one Fe-Mn crust. Ni exchange between solid and solution was investigated during reactions in 1 mM Mn(II)(aq) and in Mn(II)-free solutions under variable pH conditions (pH 5.5 and 7.5) over time. Sample characterization shows that all samples are of hydrogenetic or mixed hydrogenetic-diagenetic origin and Ni is preferentially associated with the phyllomanganates. Our Ni exchange experiments reveal that in some samples up to 25% of incorporated Ni is exchangeable with the fluid after 14 days. The prevalent reaction pathways exhibit pH-dependent behavior during phyllomanganate recrystallization and differ between sample types, with Mn(II)(aq) enhancing Ni exchange in the Fe-Mn crust-fluid system and Ni exchange being independent of Mn(II)(aq) concentrations in the Fe-Mn nodule-fluid systems. The exchangeability of structurally-incorporated Ni in Fe-Mn nodules and crusts indicates a labile behavior that potentially makes it available for biogeochemical processes in the marine environment.