Mineralogy and the Incorporation Mechanism of Economic Relevant Metals Such As Ni, Cu, Co and Mo of Mn-Nodules from the German License Area within the Clarion-Clipperton Zone

"INTRODUCTIONPolymetallic nodules from the Clarion and Clipperton Zone (CCZ) within the equatorial NE Pacific Ocean show high concentration of economic important strategic metals such as Ni, Cu, Co, Mo and Rare Earth Elements (REE). The content of those metals in nodules is depending on (i) the supply during individual growing periods, (ii) the environment conditions as well as (iii) on different manganese minerals, which occur in nodules. The incorporation of the metals can vary within the structure (incorporated into the structure / over vacancies of the structure) and this can be relevant for the further metallurgical treatment.Mineralogy of Mn-nodules from the CCZ and the incorporation of metalsManganese nodules consist of nm to µm thick layer growth structures (LGS) of different genetic origin (hydrogenetic/suboxic-diagenetic). Those LGS form due to the precipitation of Mn-and Fe-(oxy) hydroxide colloids from the oxygen rich near-bottom water and/or pore water (hydrogenetic growth; Halbach et al., 1988) or from suboxic (depleted in O2 <5µmol O2/l; Hein and Koschinsky 2013)) near-bottom water/pore water (suboxicdiagenetic growth; Halbach et al., 1988; Wegorzewski and Kuhn, 2014).In general, metals dissolved in seawater will be adsorbed and complexed on the oxide surfaces according to their different surface charge. The surface charge of the Mn-Fe (oxy) hydroxides depends on the pHzpc (zpc: zero point of charge). In seawater dissolved hydrated cations (Ni2+, Cu2+, Co2+) are adsorbed preferentially on the negatively charged Mn-oxide (MnO2 -) surface (pHzpc 2.8). In contrast, negatively and neutrally charged complexes (e.g., Ti(OH4); REE(CO3)2 -, MoO4 2-) are adsorbed on the surface of Fe-oxy hydroxide colloids (FeOOH+) which have a slightly positively charged surface (pHzpc 8.5; Stumm and Morgan, 1981; Koschinsky and Halbach 1995)."