Platinum enrichment and phase associations in marine ferromanganese crusts and nodules based on a multi-method approach

Abstract Marine ferromanganese crusts and nodules host high concentrations of many economically interesting metals such as platinum (Pt), with Pt concentrations in the range of 44 to 3207 ppb in 182 analyzed samples from various locations in the global ocean. Different mechanisms have been proposed to explain this strong enrichment in the Mn Fe oxide phases compared to seawater, including reduction of seawater Pt(II) to Pt(0) or oxidation to Pt(IV) and surface adsorption on the Fe-oxyhydroxide or Mn-oxide phases. To shed more light on the process of Pt enrichment in nodules and crusts, we applied a multi-method approach including bulk analyses, statistics (correlations and Q-mode factor analyses), sequential leaching, sorption experiments, and XANES and EXAFS measurements. Our analyses lend new support to the heterogeneous oxidation/sorption mechanism advanced by Maeno et al. (2016) to explain the initial Pt(II) enrichment on FeMn crusts, with Pt oxidation only taking place on the Mn-oxide phase but not on the Fe-oxyhydroxide phase of crusts. Nodules show lower concentrations and a lesser association of Pt with the Mn phase as the latter is partly of diagenetic origin while the origin of Pt is hydrogenetic. Our results also indicate that sorption of Pt2+(aq) to FeO(OH) is possible if Pt2+(aq) exists under conditions typical of nodule and crust growth in the oceans. Platinum concentrations are consistently highest in phosphatized Fe Mn crusts where they appear to be related to the occurrence of a 10 A manganate, so they are likely to be the best exploration target for Pt globally in marine Fe Mn crusts. However, further work is needed to understand the geochemical reactions that dominate mass transfer of Pt under conditions under which crusts are phosphatized and to identify the exact mineral type which hosts the Pt enrichment. The complex Pt geochemistry in marine FeMn crusts and nodules due to the different phase associations and enrichment processes on the different carrier phases make a straightforward interpretation of Pt data in specific samples difficult. Our findings suggest that only spatially resolved, species-specific methods available via synchrotron-based X-ray and modern electron-probe micro-analyzers (in development) could provide the combination of spatial resolution and species-specificity to determine which of several proposed mechanisms are actually responsible for Pt enrichment in FeMn crusts.