Enrichment Characteristics and Mechanisms of Critical Metals in Marine Fe-Mn Crusts and Nodules: A Review

Marine Co-rich ferromanganese crusts and polymetallic nodules, which are widely distributed in oceanic environments, are salient potential mineral resources that are enriched with many critical metals. Many investigations have achieved essential progress and findings regarding critical metal enrichment in Fe-Mn crusts and nodules. This study systematically reviews the research findings of previous investigations and elaborates in detail on the enrichment characteristics, enrichment processes and mechanisms and the influencing factors of the critical metals enriched in Fe-Mn crusts and nodules. The influencing factors of critical metal enrichments in Fe-Mn crusts and nodules mainly include the growth rate, water depth, post-depositional phosphatization and structural uptake of adsorbents. The major enrichment pathways of critical metals in marine Fe-Mn (oxy)hydroxides are primarily as follows: direct substitution on the surface of delta-MnO2 for Ni, Cu, Zn and Li; oxidative substitution on the delta-MnO2 surface for Co, Ce and Tl; partition between Mn and Fe phases through surface complexation according to electro-species attractiveness for REY (except for Ce), Cd, Mo, W and V; combined Mn-Fe phases enrichment for seawater anionic Te, Pt, As and Sb, whose low-valence species are mostly oxidatively enriched on delta-MnO2, in addition to electro-chemical adsorption onto FeOOH, while high-valence species are likely structurally incorporated by amorphous FeOOH; and dominant sorption and incorporation by amorphous FeOOH for Ti and Se. The coordination preferences of critical metals in the layered and tunneled Mn oxides are primarily as follows: metal incorporations in the layer/tunnel-wall for Co, Ni and Cu; triple-corner-sharing configurations above the structural vacancy for Co, Ni, Cu, Zn and Tl; double-corner-sharing configurations for As, Sb, Mo, W, V and Te; edge-sharing configurations at the layer rims for corner-sharing metals when they are less competitive in taking up the corner-sharing position or under less oxidizing conditions when the metals are less feasible for reactions with layer vacancy; and hydrated interlayer or tunnel-center sorption for Ni, Cu, Zn, Cd, Tl and Li. The major ore-forming elements (e.g., Co, Ni, Cu and Zn), rare earth elements and yttrium, platinum-group elements, dispersed elements (e.g., Te, Tl, Se and Cd) and other enriched critical metals (e.g., Li, Ti and Mo) in polymetallic nodules and Co-rich Fe-Mn crusts of different geneses have unique and varied enrichment characteristics, metal occurrence states, enrichment processes and enrichment mechanisms. This review helps to deepen the understanding of the geochemical behaviors of critical metals in oceanic environments, and it also bears significance for understanding the extreme enrichment and mineralization of deep-sea critical metals.