Due to the multiple and poorly-crystallized phases in ferromanganese (Fe–Mn) nodules, research on the variability of micro-layers in nodules is limited and the accumulation of various elements with the growth of micro-layers have not been well documented. To address this gap, we examined the spatial distributions of elements in cross-sections of nodules from the Northwestern Pacific Ocean using in-situ electron microprobe analyses coupled with backscattered electron imaging and high-resolution X-ray elemental intensity mapping. Results suggest their significant selective enrichment of metal elements is similar to that of typical hydrogenetic nodules and diagenetic nodules. Moreover, W_Mn+Fe of Fe–Mn oxyhydroxide is equal to 50% after normalization and Co and Ni show positive relationships with Mn/Fe ratio, suggesting Fe oxyhydroxide would serve as a diluter at exposed surface during nodule growth. In suboxic conditions, Mn, Ni, and Co start to release, and the remaining Fe oxyhydroxide may react with the surrounding sediment to form Si-rich layers. Our studies reveal the diverse growth processes and show a much larger chemical heterogeneity of individual layers, which extend the models about the mechanisms of chemical precipitation and environmental conditions that existed during nodule growth.

Enrichments of critical metals in ferromanganese (Fe–Mn) nodules have received increasing attention in both deep-sea research and mineral exploration. To better assess the controls on the resource potential of Fe–Mn nodules, we conducted a comprehensive and detailed study of twelve nodules from the Philippine Sea collected from water depths of 4400 to 6000 m by investigating their microstructures, bulk geochemistry, and in situ Fe–Mn oxyhydroxide geochemistry, using XRF, ICP-MS, EMPA, and LA-ICP-MS coupled with BSE images. We successfully resolved different controls on the element enrichments, of which significant selective enrichment of metal elements in seawater is similar to that of typical hydrogenetic nodules. An enhanced supply of iron hydroxide due to calcite dissolution resulted in a dilution effect on Co, Ni, and Mn but an enrichment effect on rare earth elements plus yttrium (REE + Y) and Fe in nodules near topographic highs close to the carbonate compensation depth. While the supply of diagenetic Mn resulted in a dilution on Co and REE + Y, it resulted in enrichment on Ni, Cu, Li, and Mn on nodules on the seafloor. Moreover, via micro-layer analyses we confirmed the growth rate is a major determinant for the correlations of Co and REE with Fe-oxyhydroxides in these Philippine Sea nodules.