Diverse early diagenetic processes of ferromanganese nodules from the eastern Pacific Ocean: evidence from mineralogy and in-situ geochemistry

Ferromanganese nodules are a potential energy resource because of their high contents of economically interesting elements (i.e. Mn, Ni, Cu, and Zn). These are higher in diagenetic layers than in hydrogenetic layers. The study of the causes of elemental accumulation in the diagenetic layer is useful for the exploration metal-rich nodules. A diagenetic-dominant ferromanganese nodule, from the central Clarion–Clipperton Fracture Zone of the eastern Pacific Ocean was studied from core to rim. It was divided into four layers and seven sublayers, of the four typical diagenetic sublayers (L1, L2-1, L2-2, and L3-1). Differences were observed in these diagenetic sublayers. L1 presents the highest Mn/Fe ratio (54), the lowest Co content (2262 ppm), and a positive Ce anomaly. L2-1 exhibits high Co (3122 ppm) and Ba contents (4020 ppm), a positive Ce anomaly, and an obvious peak for 10 Å manganate minerals. L2-2 contains the lowest Ni+Cu contents (3.2 wt%), the highest Ba and Co contents (5110 ppm), and the strongest positive Ce anomaly. In L2-2, the δCe value can be positively correlated to the Mn/Fe ratio and a pronounced peak for 10 Å manganate minerals indicates that this layer has the highest mineral crystallinity. L3-1 shows the highest Ni+Cu contents (5.4 wt%), the lowest Ba (1247ppm), and Co (1725 ppm), a weakly positive Ce anomaly, and the poorest mineral crystallization. Diagenetic- and hydrogenetic-endmember mixing models reveal that hydrogenetic input contributes minimally to these chemical changes, whereas diagenetic input contributes greatly. The changes in diagenetic input may be caused by the changes in primary productivity brought about by movement of tectonic plates and the intense activity of the diagenetic pore fluid. The activity may provide a metal source for the diagenetic sublayer (anomalously high Co and Ce content) via the incorporation of metals released from dissolved buried nodules and micronodules under a suboxic or reducing environments.