Marine hydrogenetic Fe–Mn crusts on seamounts are known as potential mineral resources of rare earth elements plus yttrium (REY). In recent years, increasing numbers of deposits of Fe–Mn crusts and nodules were discovered in the South China Sea (SCS), yet the enrichment mechanism of REY is yet to be sufficiently addressed. In this study, hydrogenetic Fe–Mn crusts from the South China Sea (SCS) and the Western Pacific Ocean (WPO) were comparatively studied with mineralogy and geochemistry. In addition, we used an in situ REY distribution mapping method, implementing laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and a sequential leaching procedure to investigate the partitioning behavior of REY in the Fe–Mn crusts. The typical Fe–Mn crusts from SCS were mainly composed of quartz, calcite, vernadite (δ-MnO₂), and amorphous Fe oxides/hydroxides (FeOOH). The Fe–Mn crusts from the Central SCS Basin and the WPO contained quartz, δ-MnO₂, FeOOH, todorokite, and phillipsite. Furthermore, geochemical analysis indicated that the typical SCS crusts had a higher growth rate and lower REY concentrations. The LA-ICP-MS mapping results showed that the δ-MnO₂ and FeOOH dominated the occurrence phases of REY in the SCS crusts. Four mineral phases (i.e., easily exchangeable and carbonate, Mn-oxide, amorphous FeOOH, and residual aluminosilicates) in these Fe–Mn crusts were separated by a sequential leaching procedure. In the SCS and WPO crusts, the majority of total REY (ΣREY) was distributed in the Mn-oxide and amorphous FeOOH phases. The post-Archean Australian shale-normalized REY patterns showed that light REY (LREY) and heavy REY (HREY) were preferentially adsorbed onto δ-MnO₂ and FeOOH, respectively. It is noteworthy that ~27% of ΣREY was associated with the residual aluminosilicates phase of the WPO crusts. The La/Al ratios in the aluminosilicates phase of the typical SCS crusts were the values of the upper crust. We conclude that large amounts of terrigenous materials dilute the abundance of REY in the SCS crusts. In addition, the growth rates of Fe–Mn crusts have a negative correlation with the FeOOH-bound and aluminosilicate-bound REY. As a result of the fast growth rates, the SCS crusts contain relatively low concentrations of REY.

Fe-Mn polymetallic crusts and nodules from the South China Sea (SCS) consist of submarine ferromanganese (Fe-Mn) oxide precipitates, and represent important marine mineral resource with substantial economic and scientific research value. Previous studies on the SCS polymetallic crusts and nodules were mainly focused on their bulk mineralogy and geochemistry, whilst research on their nanomineralogy is still lacking. In this study, transmission electron microscopy (TEM), Raman spectroscopic mapping, and in-situ micro X-ray diffraction (XRD) analysis were conducted on the nano-mineralogy of the SCS polymetallic crusts and nodules. It is found that the SCS polymetallic crusts and nodules consist mainly of layered/columnar/mottled nano-phase Fe-Mn minerals and detritus such as quartz, feldspar, and clays. Also, an independent Ti mineral phase has been documented, and the mineralogical analysis reveals the transformation from vernadite to birnessite and todorokite. Titanium forms colloidal minerals in seawater and precipitates into the crusts and nodules with other colloids, such as FeOOH and Si-Al. Vernadite and birnessite can be transformed to todorokite with stable structure under sub-oxic conditions. Therefore, the SCS polymetallic crusts and nodules were formed in a short period of sub-oxic environment and diagenetic process, and the transformation can influence the enrichment of Ni and other metals during the crust/nodule growth.

In this study, we analyzed the clay mineralogy and geochemistry of surface and drill core samples from the northeastern Beibu Gulf in order to unravel the sediment provenance of, and factors controlling, the sedimentary environment. The main clay mineral assemblage in the surface sediment samples included kaolinite (27–72%), smectite (4–51%), illite (7–20%), and chlorite (8–17%). The study area comprises three major clay distribution zones (from the northeastern coastal area to central Beibu Gulf basin), i.e., the kaolinite-dominated, kaolinite–smectite, and smectite-dominated zones. The zoning of the clay mineralogy and major and trace elements indicated the mixing of coarse terrigenous sediments with distal fine sediments. Early Holocene sea level rise was documented in core B15-1, which had three sedimentary units (divided into Units 1–3 from top to bottom), as revealed by the changes in the dominant clay minerals and geochemical/oxide ratios (SiO₂/Al₂O₃, Rb/Sr, Sr/Ba, and Ti/Ca) in Unit 2. Unit 1 and Unit 3 were likely deposited in the continental and marine environments, respectively. The low sedimentation rate and hydrodynamic disturbance may have influenced the deposition process more than climatic fluctuations.

Ferromanganese (Fe-Mn) polymetallic nodules are significant marine mineral resources containing various metal elements of substantial economic and scientific research value. Previous studies have primarily focused on the mineralogy and geochemistry of the nodules, while research on their nano-mineralogy is still lacking. In this study, we conducted scanning electron microscopy (SEM), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR), Brunauer–Emmett–Teller (BET) porous structure gas adsorption/desorption, and specific surface area analysis to examine the nano-mineralogy and mineralization of the polymetallic nodules from the interbasin of seamounts in the western Pacific Ocean (IBSWP). The results indicate that the growth profiles of the IBSWP polymetallic nodules exhibit microstructural features such as laminated, stromatolithic, columnar, and mottled structures. The mineral compositions are primarily composed of Fe-Mn minerals and detritus, including quartz; minerals from the feldspar group; and minerals from the clay group. The Fe-Mn phase minerals are relatively poorly crystallized. The Mn-phase minerals contain vernadite and small amounts of todorokite, buserite, and birnessite, while the Fe-phase minerals are mainly comprised of amorphous FeOOH. The main ore-forming minerals consist of nano-minerals, and the nanostructures of the polymetallic nodules endow them with unusually large specific surface areas and pore volumes, resulting in strong adsorption properties. The unique nano-properties and surface/interface adsorption effects of Fe-Mn minerals play a crucial role in controlling the enrichment of ore-forming elements.