Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements（REE） composition of the polymetallic crusts and nodules obtained from the South China Sea（SCS） were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances（∑REE） of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE（LREE）, the markedly positive Ce anomaly（δCe）, and the non-or weakly positive Eu anomaly（δEu）, suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event（sea-level change） during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.

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

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 （O^2-）. 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.

Enrichment of REEs in polymetallic nodules and crusts and its potential for exploitation

Polymetallic nodules and crusts are two of the most important mineral deposits in the ocean. They are rich in rare earth elements （REEs）, iron, manganese, copper, cobalt, nickel, and other useful metals. This paper discussed the analysis of 25 nodule and crust samples collected from the South China Sea, the Pacific, Atlantic, and Indian Oceans. The samples were analyzed for REE content by ICP-MS/AES. The average REE concentration was found to be 1096.96×10^-6 in the nodules and 1623.88×10^-6 in the crusts. Both of these values are much higher than those recorded in Earth＇s dry-land crust and sedimentary rocks. This REE enrichment is mainly controlled by the absorption of ferromanganese oxides and clay minerals in the nodules and crusts and the high levels of REEs in seawater and sediments. High cerium enrichment in the nodules and crusts may lead to more effective exploitation of REEs in the future.