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Bauxite deposits are an important source of Al and also host a variety of critical metals, including rare earth elements (REEs). However, the parent rocks of bauxite deposits generally have low REE contents, leading to uncertainty over the REE sources and enrichment mechanisms. In this study, we report high REE (2095 ppm; Ce = 1340 ppm) contents in the Lijiatian bauxite deposit in Luxi County, western Hunan Province, South China. The Lijiatian bauxite deposit is the largest deposit in Hunan Province, with a total Al resources exceeding 7 × 106 tons. The ore-bearing strata in the lower Permian Liangshan Formation (ca. 275 Ma) are comprised a 3–5-m-thick bauxite layer (bauxite ore/clay) and an underlying 4–8-m-thick Fe layer (Fe ore/Fe-rich clay). The high REE contents in the bauxites can be attributed to the widespread presence of bastnäsite. The bastnäsite commonly coexists with authigenic chlorite, which formed at temperatures of 221–285 °C, indicative of a hydrothermal origin. Uranium–Pb dating of the bastnäsite yielded an age of 141.4 ± 7.0 Ma, indicating a hydrothermal overprint occurred during the Early Cretaceous, which resulted in the enrichment of REEs in the bauxites. The high contents of REEs, Ba, and P in the Cambrian Niutitang Formation black shales indicate it was a potential source of these elements for bastnäsite and coexisting barite and apatite. The deep-seated hydrothermal fluids (enriched in HF, CO 2 , and H 2 S) associated with the late Yanshanian extensional tectonic event in South China (155–123 Ma) ascended along fractures. The ascending fluids interacted with the black shales, extracting REEs, Ba, and P. When the fluids reached a certain depth, they mixed with the infiltrating basinal waters to form a mineralising fluid. The fluid then migrated towards the bauxite layers, underwent cooling and depressurisation, and precipitated bastnäsite, barite, apatite, and chlorite. We propose that a hydrothermal event led to the enrichment of REEs in the bauxites in Hunan Province. Considering the scarcity of REEs in the parent rocks of bauxites worldwide, hydrothermal activity likely has a key role in REE enrichment in bauxites. [Display omitted] • The main mineral hosting REE (Ce) in Permian bauxite from southern China is Bastnäsite. • The bastnäsite formed during the Cretaceous period due to hydrothermal fluid activity. • The REEs are source from the basement black shale. [ABSTRACT FROM AUTHOR]

• Cobalt is enriched (up to 962 ppm) in the paleo-karstic bauxite deposit at Yunfeng. • Cobalt is positively correlated with sulfur. • Cobalt occurs mainly as Co-bearing pyrites and Co-rich sulfides/sulfoarsenides. Cobalt can be enriched in a variety of different geologic settings, while it is mainly produced as a by-product of sediment-hosted stratiform Cu deposits and magmatic Ni-Cu deposits associated with mafic and ultramafic rocks. In this study, we report elevated Co concentrations in a paleo-karstic bauxite deposit at Yunfeng, Guizhou Province. Whole-rock chemical analyses indicate that Co is concentrated in carbonaceous ferruginous clay layers (167–962 ppm, average 383 ppm, n = 5) and siderite layers (47–439 ppm, average 213 ppm, n = 7) within the bauxite deposit. The positive correlation between Co and S, together with petrographic and EPMA analyses, suggests that Co occurs primarily as Co-rich/bearing sulfides/sulfoarsenides rather than cobaltiferous oxides/hydroxides as in most lateritic Ni-Co deposits. Many of the Co concentrations measured in this study are higher than the minimum grade (300 ppm) or cut-off grade (200 ppm) for economic exploitation of Co from sulfides or arsenides. Basing on these results, we put forward the scientific significance of Co enrichment in paleo-karstic environments and the potential importance of Co resources (as by-products of aluminum production) in bauxite deposits. [ABSTRACT FROM AUTHOR]

Many paleo-karstic bauxite deposits contain elevated concentrations of Ni and Co. It has been known that Co and Ni are dominantly hosted in sulfides, but it remains unclear how Ni and Co were incorporated into sulfides and what kind of physiochemical conditions were involved. The Maochang bauxite deposit, as one of the large Ni- and Co-bearing paleo-karstic bauxite deposits in Guizhou Province, southwest China, was selected to tackle these questions. Detailed mineralogical and sulfur isotopic analyses using integrated EBSD, EPMA, LA-ICPMS, and LA-MC-ICPMS methods revealed three stages of sulfide mineralization: stage I with pyrite (PyI), stage II with pyrite (PyII), millerite, sphalerite, chalcopyrite and violarite, and stage III with pyrite (PyIII), chalcopyrite and galena. The fine-grained, euhedral PyI has up to 0.79 wt% Ni and up to 0.53 wt% Co. In contrast, PyII, which replaced or overgrew PyI, exhibits high but variable Ni, Co and As contents, and is further divided into three sub-types: Ni-rich PyII-a (up to 16.54 wt% Ni, 0.94 wt% Co, and 0.38 wt% As) and PyII-b (up to 3.30 wt% Ni, 1.41 wt% Co, and 0.36 wt% As), and Co-rich PyII-c (up to 0.99 wt% Ni, 7.57 wt% Co, and 1.81 wt% As). PyIII is Ni- and Co-poor. Ni increases from PyI to PyIIa and PyIIb, and then decreases to PyIIc and PyIII, whereas Co remains at similar levels for PyI, PyIIa and PyIIb, significantly increases to PyIIc, and then drops abruptly to PyIII. δ34S V-CDT values vary dramatically from negative values for PyI (−6.9 to −16.6‰) to positive values for PyII-b (+19.4 to +22.8‰), sphalerite (+17.2 to +19.7‰), and PyIII (+25.3 to +32.3‰). Based on these results, and considering that the protoliths of the bauxites were likely Ni- and Co-rich black shales according to previous studies, a four-step model is proposed to explain the enrichment of Ni and Co in the bauxites: 1) during weathering and bauxite formation on the surface, Ni and Co were leached from the black shale together with sulfate; the metals were dissolved in the solution and partly adsorbed by Fe-oxides/hydroxides under moderate to high f O2 ; 2) during early diagenesis, the sulfate was partially reduced to sulfide via the bacterial sulfate reduction (BSR) process and formed PyI; much of the Ni and Co, together with sulfate, remained in the solution; 3) with increasing burial, temperature increased and f O2 decreased, and the remaining sulfate (with elevated δ34S V-CDT) was reduced to sulfide via the same BSR process and formed PyII; Ni was largely consumed and incorporated into PyIIa and PyIIb, whereas Co remained in the solution until precipitation of PyIIc; 4) by the time of PyIII precipitation, both Ni and Co had been taken by PyII, leaving a Ni- and Co-poor solution and PyIII. Step 1 occurred in a relatively open system, whereas steps 2–4 likely occurred in a closed system. [Display omitted] [ABSTRACT FROM AUTHOR]