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.
In this study, the He and Ar isotope compositions were measured for the Fe-Mn polymetallic crusts and nodules from the South China Sea (SCS), using the high temperature bulk melting method and noble gases isotope mass spectrometry. The He and Ar of the SCS crusts/nodules exist mainly in the Fe-Mn mineral crystal lattice and terrigenous clastic mineral particles. The results show that the 3 He concentrations and R/R A values of the SCS crusts are generally higher than those of the SCS nodules, while 4 He and 40 Ar concentrations of the SCS crusts are lower than those of the SCS nodules. Comparison with the Pacific crusts and nodules, the SCS Fe-Mn crusts/nodules have lower 3 He concentrations and 3 He/ 4 He ratios (R/R A , 0.19 to 1.08) than those of the Pacific Fe-Mn crusts/nodules, while the 40 Ar/ 36 Ar ratios of the SCS samples are significantly higher than those of the Pacific counterparts. The relatively low 3 He/ 4 He ratios and high 40 Ar concentrations in the SCS samples are likely caused by terrigenous detrital input with high radiogenic 4 He and 40 Ar contents. The SCS crusts and nodules have shorter growth periods, implying that in situ post-formation radiogenic 3 He, 4 He and 40 Ar produced by decay of U, Th and K have no effect on their isotope compositions. Thus, the SCS crusts/nodules inherited the noble gases characteristics of their sources. Helium and Ar isotope compositions in the SCS Fe-Mn crusts and nodules reflect the product of an equilibrium mixture between air-saturated seawater and radiogenic components during their growth, while the partial 3 He excess in some SCS samples may represent a little mantle-derived origin. The different He and Ar isotope compositions of the Fe-Mn crusts and nodules between the South China Sea and the Pacific Ocean are due to their different sources and genetic processes. The characteristics of He and Ar isotope compositions in the SCS polymetallic crusts and nodules are similar to the properties of hydrogenetic Fe-Mn oxide/hydroxide precipitates, which reflects mainly the product of an equilibrium mixture between air-saturated seawater and radiogenic components.isotopes provide important geological information for the research of modern ocean circulation, paleoceanography, seafloor hydrothermal and cold brine system and ocean/atmosphere gas exchange.Early studies of marine noble gases are mainly concentrated in solving geochemical problems, such as tracing the excess He in the seawater, which is likely produced by U-Th series radioactive decay in the marine sediments [1,2]. After the discovery of mantle-originated helium [3] and 3 He originated near the sediment surface (via 3 H decay in the sea) [4], people began to use noble gases to trace the source of submarine hydrothermal fluids, crust/mantle material cycle, constrain the formation process and thermodynamic mechanism of seamount systems [5][6][7][8][9][10][11] and to explore the formation and cycle of the ocean currents (e.g., [12][13][14]).Some studies have explored potential application of He isotopes...
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.
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