Chemical and morphological characterization of polymetallic (Mn-Fe) nodules from the Clarion-Clipperton Zone in the Pacific Ocean

Abstract

Geochemical studies (WD-XRF, ICP-MS, and GF-AAS) have shown that polymetallic nodules from the eastern Clarion-Clipperton Zone (CCZ) in the Pacific Ocean are enriched in several metals such as Cu (mean 1.16%), Ni (1.15%), Co (0.15%), and Zn (0.14%), as well as remarkable contents of Mo (0.059%), V (0.04%), Ce (0.019%), Nd (0.011%), Li (0.015), and Pt (43 ppb). The average content of REE, together with Y and Sc, is 620 ppm. In nodules from the CCZ metal concentrations are often much higher than those reported in nodules from other ocean basins in the world. The bulk-nodule mean value of the Mn/Fe ratio is 5.3, which is characteristic for a mixed (hydrogenetic and diagenetic) origin of the nodules. Microprobe investigation revealed two different chemical compositions of the layers, and ascertained their general metal content. The nodules analyzed are composed mainly of concentric-collomorphic laminae of Mn and Fe (oxy)hydroxides which crystallized around mineral nuclei (e.g., quartz, clay minerals), bioclasts or rock fragments. They are from 3.3 to 7.6 cm in diameter. The chemical and physical properties of the laminae allowed distinction of two genetic types: hydrogenetic and diagenetic. Those formed as a result of hydrogenesis had increased values of Co, Si, Cl and S, while formed diagenetically showed increased levels of Cu, Ni, Mg, Zn and K. These lamina types are characterized by different growth structures, reflectivity, density and Mn/Fe ratios. The ratio of the diagenetic layers to hydrogenetic layers (192/53) in representative polymetallic nodules shows that the nodules of this study are of mixed hydrogenetic-diagenetic type. A mixed genesis was also shown by discriminant diagrams, with these CCZ samples being located at the transition between typical hydrogenetic and diagenetic fields.