Concentrations and fractionation of REEs in marine ferromanganese crust deposits controlled by water depth

"Ferromanganese crusts contain hydrous Mn and Fe oxides as main metal compounds together with some economically interesting minor elements such as Co, Ni, Ti and Cu and trace metals such as Mo, W, Nb, Te, Ga, Pt, and REEs. Some of these metals or semimetals have a great future potential as innovative high-technology constituents. All of them are highly enriched in the crusts compared to seawater composition.The Mn in the crusts mainly originates from the O2 - minimum zone in the oceanic water column. The agent for Mn2+ oxidation is dissolved oxygen, transported upwards from colder deep water layers by turbulent eddy diffusion. The Mn itself descends from surface waters and is carried down to the O2-minimum zone by fecal pellet transport. In contrast, Fe is mainly supplied from carbonate dissolution of planktonic skeletons in the water column. These relationships result in the fact that the oceanic water depth strongly controls the metal composition of ferromanganese crusts: the Mn - group metals are more enriched in shallower water, whereas the concentration of the Fe - group metals increase with water depth. The REEs play a very important role with regard to the trace metal composition of the crusts: their concentrations increase with water depth mainly controlled by a decreasing Mn/Fe ratio.In seawater, REEs occur as carbonate complexes; preferably, the light rare earth elements (LREEs) form REECO3 +(aq) and the heavy Rare Earth Elements (HREEs) REE(CO3)2 (aq) complexes. The REEs are transition metals, their 6s orbital of the outermost shell is filled before the filling of lower 4f electron shells is completed, thus the configuration of the valence electrons is similar in all the REEs, and all REEs exhibit similar chemical behavior and exist, dominantly, as 3+ cations. The ionic radius decreases progressively from La3+ (1.18 Å) to Lu3+ (0.97 Å), this phenomenon is called "lanthanide contraction". Due to the fact that REEs in seawater form cationic and anionic carbonate complexes, the two main hydrogenetic constituents, hydrous !-MnO2 and Fe-oxyhydroxide, fractionate the group of REEs by surface absorption processes. According to the pHZPC-concept the ?- MnO2 phase has an electronegative surface, and Fe-oxyhydroxide a slightly positive surface charge at seawater pH. These relationships are the main reason for the observed REEs fractionation."