The adsorption of cerium on synthetic δ-MnO2: Implications for Ce uptake behavior of hydrogenetic and early diagenetic ferromanganese nodules from the Western Pacific

Cerium (Ce) anomalies can be used to distinguish diagenetic and hydrogenetic nodules, making them an important discriminator for the genesis of marine ferromanganese nodules. To understand the enrichment and adsorption mechanisms of Ce in different types of ferromanganese nodules, we conducted mineralogical and geochemical studies on ferromanganese nodule layers formed through both hydrogenetic and early diagenetic processes as well as adsorption experiments on synthetic δ-MnO2 to monitor the Ce uptake during the different processes. The major and trace element contents of natural ferromanganese nodule layers were investigated by SEM, EPMA and LA-ICP-MS analysis. The marine nodule studied in this study consisted of a core of fish tooth and a rim that could be divided into the hydrogenetic (type I) and early diagenetic (type II) layers based on their mineralogy and Mn/Fe ratios. The Mn oxide mineral assemblage is composed of todorokite, buserite, birnessite, and vernadite (δ-MnO2) and occurred in both type I and II layers. The type I layer has laminated structures with a low Mn/Fe ratio (1.1–3.2; averaging at 1.7), and low Cu, Ni and Mg contents consistent with a hydrogenetic genesis. The type II layer has a columnar and stromatolitic structure with a high Mn/Fe ratio (5.1–54.0; averaging at 23.3) and high Cu, Ni and Mg contents that are similar to early diagenetic nodules. The ΣREE contents in type I and type II layers are 1405–3506 ppm (averaging at 2091 ppm) and 199–1232 ppm (averaging at 674 ppm), respectively, indicating that the REE is enriched in the hydrogenetic type I layers. Strong positive Ce anomalies are present type I layers ranging from 1.2 to 2.5 (averaging 1.9), but only slightly positive are seen in type II ranging from 0.4 to 2.4 (averaging at 1.0). Synthetic experiments to monitor the Ce uptake process show that Ce can be adsorbed onto δ-MnO2 with the XRD and FTIR patterns suggesting that the structure of δ-MnO2 did not change significantly, consistent with Ce behavior in hydrogenetic nodules. The results suggest that Ce is predominantly concentrated in hydrogenetic nodules in an oxic environment, whereas in the early diagenetic layer, there is less oxidation and fixation of Ce due to the suboxic conditions. Our findings are consistent with Ce anomalies in marine Fe-Mn nodules being the result of Mn oxide oxidation adsorption and then fixation (oxidation) after adsorption.