The effect of Fe-Mn minerals and seawater interface and enrichment mechanism of ore-forming elements of polymetallic crusts and nodules from the South China Sea

Abstract

Ferromanganese crusts and nodules are important submarine mineral resources that contain various metal elements with significant economic value. In this study, polymetallic crusts and nodules obtained from the South China Sea (SCS) were determined by using X-ray power diffraction (XRD), Raman spectroscopy (RS), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) to systematically investigate and analyze the mineralogical and spectral characteristics of the Fe-Mn minerals. XRD measurements revealed that the SCS polymetallic crusts and nodules were composed of vernadite, quartz, and plagioclase. The nodules also contained todorokite. The Fe-phase minerals of the SCS crusts and nodules were composed of amorphous Fe oxide/hydroxide, and the Mn- and Fe-phases minerals exhibited relatively poor degrees of crystallization. FTIR results showed that the Fe-Mn minerals in the crusts and nodules included a large number of surface hydroxyl groups. These surface hydroxyl groups contained protons that could provide reactive sites for complexation of ore-forming elements in seawater. XPS results indicated that the surfaces of the Fe-Mn minerals mainly contained Fe, Mn, and O. Fe was present in the trivalent oxidation state, while Mn, which may contain several bivalent oxidation state, was present in the tetravalent and trivalent oxidation states. The SCS polymetallic crusts and nodules were compared with Pacific seamount crusts, and results showed that the surface hydroxyl (-OH) groups of the SCS crusts and nodules numbered more than the lattice oxygen (O2-). But the lattice oxygen of Pacific seamount crusts numbered more than the surface hydroxyl groups. This characteristic indicated that the degree of crystallization of Fe-Mn minerals from the Pacific Ocean was higher than that of minerals from the South China Sea. Comprehensive studies showed that ore-forming elements in the interface between seawater and the Fe-Mn minerals in the submarine ferromanganese crusts and nodules employed the following enrichment mechanisms: (1) the metal ion complexed with the surface hydroxyl of Fe-Mn minerals to form hydroxyl complexes, which were connected by coordination bonds or stable inner-sphere complexes that exchanged protons on the mineral surfaces; (2) the charged surfaces of the minerals and metal cations formed outer-sphere complexes, which made up the electrostatic double layer, through electrostatic adsorption; and (3) the metal cations isomorphously exchanged the Mn and Fe ions of the mineral lattice structure.