Gallium (Ga), one of the critical metal elements, is commonly refined as a by-product of sphalerite. Previous studies recognized that Ga is extremely enriched in the Fankou Zn-Pb deposit that is a world-class, carbonate-hosted Zn-Pb deposit, but the tempo-spatial distribution of Ga remains unclear. Its stratiform, stratabound orebodies are strictly hosted in Devonian to Carboniferous carbonate sequences along a series of thrust faults, analogous to a Mississippi Valley-type (MVT) deposit. Herein, we carried out an integrated petrographic, Electron microprobe analyses (EPMA), and Laser Ablation Inductively Coupled Plasma Mass Spectrometer (LA-ICP-MS) study on the sphalerite in the Fankou deposit, to clarify the concentration variations and occurrences of Ga and associated elements, as well as their substitution mechanism. Three types of sphalerites with different mineral associations and mineralogical characteristics were identified, that is, the earlier-crystalized, darker-colored Sp1a and Sp1b, and the later-crystalized, lighter-colored Sp2, respectively. Median values of Ga in the three sphalerite generations display an increasing trend, i.e., 12.76 ppm for Sp1a, 93.40 ppm for Sp1b, and 156.79 ppm for Sp2, respectively. Furthermore, trace elements mapping via LA-ICP-MS also shows that Sp1b in the grain rim is enriched in more Ga, Cu, and Ag contents. Further GGIMFis thermometers obtained a contrasting decreasing trend from early 203 °C to late 185 °C. Collectively, we conclude that Ga prefers to be enriched in the later-staged, light-colored, lower-temperatured sphalerite in the Fankou Zn-Pb deposit. This new study may shed light on the enrichment mechanism and exploration strategies of critical metal Ga in the global MVT Zn-Pb deposit.
The Fankou giant deposit (with exceeding 10 Mt Zn + Pb metals, grading at 15 wt%) is a carbonate-hosted, stratabound Zn-Pb deposit in the northern Quren Basin, South China. Lenticular, stratiform and wedge-shaped orebodies are strictly hosted in specific layers of Upper Devonian to Lower Carboniferous carbonate sequences along a series of NE and NNE trending faults. Previous ore geological and geochemical studies proposed that the Fankou can be analogous to a Mississippi Valley-type (MVT) deposit, but how the evolution of complex fault system controls ore-forming fluids migration, metals accumulation and orebodies localization remains unclear. To address this question, we conducted a deposit-scale structural analysis based on the geological mapping, underground works, and diamond drills logging. We identified three-order structures gradually growing in the Fankou deposit, including: 1) The first-order fault represented by F203 is a NW-striking thrust fault penetrating basement and acts as a major conduit for ultimate hydrothermal fluids migrations from depth; 2) The second-order faults include a spectrum of NNW-striking faults F2, F3, F4, F4, F5, F6, F7, F8 and F9. They are intersected with F203 in depth, and soon before and synchronous activities with Zn-Pb mineralization; 3) The third-order faults contain a series of NNE-striking F100, F101 and F102 with limited scale, which is subordinate to second-order faults and control the terminal localization of Zn-Pb orebodies. Collectively, we conclude that the evolutionary three groups of deposit-scale faults, derived from the regional NE-striking Wuchuan-Sihui Fault, jointly control the ore-forming fluids migrations from deep to shallow and from SE to NW in space. It is noteworthy that the second- to third-order faults act as the direct metal precipitation space when the upwards metalliferous fluids replaced with the favorable lithological layers. Therefore, we highlight that the southeast part of the mining area, where the metalliferous fluids came from, is a promising exploration target area in future.
The Chinese Altay Orogen represents an accretionary collage with episodic subduction-related accretion from the Neoproterozoic to Permian, followed by Triassic continent–continent collision. Reddish gem-grade garnet grains are widespread in Au–Cu–Pb–Zn sulfide deposits of the Chinese Altay Orogen, and how their formation links to regional geological processes such as seafloor sedimentation, magmatic hydrothermal metasomatic, or orogenic metamorphism remains unclear. In this context, we present an integrated set of geological occurrences, mineral texture, and major trace elemental geochemistry of six garnet grains from the representative Tiemurt Cu–Pb–Zn(-Au) deposit. Two categories of garnets, Grt1 and Grt2, are identified in terms of distinct mineral assemblages, textures, and geochemistry. The sub- to euhedral biotite inclusion–rich Grt1 with fine grains of less than 0.3 cm in diameter is intergrown with amphibole, chlorite, and biotite. Comparatively, the euhedral mineral inclusion–poor Grt2 with coarse grains of 0.5–5 cm in diameter is paragenetic with quartz, calcite, chlorite, and biotite. Forty-one EMPA analyses show that Grt1 and Grt2 have similar major elemental compositions of SiO 2 (36.2–37.5 wt%), Al 2 O 3 (19.9–20.7 wt%), and CaO (5.3–7.8 wt%) but host variable contents of FeO (31.7–35.9 wt% for Grt1 and 23.0–30.0 wt% for Grt2) and MnO (0.8–3.7 wt% for Grt1 and 4.3–12.7 wt% for Grt2). Both Grt1 (with a chemical formula of Alm 49.3–54.6 Spe 19.7–24.6 Gro 14.6–18.4 Pyr 3.7–4.8 And 3.5–4.9 ) and Grt2 (Alm 57.4–64.4 Gro 15.5–18.3 Spe 9.62–19.8 Pyr 3.8–5.7 And 1.1–4.4 ) are plotted into the field close to the end-member of almandine (Fe-Al–garnet). Compared to Grt1, Grt2 displays a Fe-enriched and Mn-depleted trend. Additionally, Mn is enriched in the core but Fe is enriched in the rim on the major elemental profile of Grt1. Regarding the trends of trace elements and REEs, Grt2 is believed to be produced during the detriment and replacement of Grt1 by an intense external metal-rich fluid. In combination with previous fluid inclusion research, the garnet-related fluids are characterized by CO 2 -rich, mesothermal, mildly acidic, and reduced redox, analogous to metamorphic fluids generated during orogenesis. Collectively, we conclude that the reddish gem-grade garnet crystals in the Chinese Altay Orogen are of metamorphic origin.
The giant Fankou Zn-Pb deposit (more than 10 Mt Zn+Pb metals, grading at 15%), situated in northern margin of the Quren Basin, is one of the largest Zn-Pb deposits in China. The stratiform orebodies are jointly bounded by both the strata (in the specific layers of Middle to Upper Devonian Donggangling and Tianziling carbonate sequences) and the fault system (a three-order thrusting fault system). Ore textures of carbonate dissolution, replacement-infilling and cementation are widespread in Fankou, analogous to a MVT (Mississippi Valley-type) deposit. Owing to the poorly developed fluid inclusions, the nature of the Fankou ore fluids remains indeterminate. To address this problem, we herein utilize micro-petrography, carbon-oxygen (C-O) isotopes and quantitative isotopic exchange modelling to trace the ore-fluids and water-rock interaction process. A total of ninety-three (93) carbonate samples, covering the majorities of stratigraphic horizons, planar locations, and various alteration intensities, were systematically collected. Micro-petrography reveals the primitively sedimentary bioclastic limestone suffer from heterogeneous dolomitization and carbonatization followed by massive Zn-Pb precipitation. These carbonate samples display a widely-ranged, δ18O- and δ13C-depleted isotope signature (δ18O = 12.57 to 23.82‰, δ13C = -7.79 to -0.46‰), relative to normal marine carbonates (δ18O = 25‰, δ13C = 0‰). Further modelling of isotopic exchange indicates a low-temperature (100 to 250 °C), δ18O-depleted (-3 to 7‰) and δ13C-depleted (-10 to -7‰) ore fluid equilibrated with the host rock by a relatively low water-rock ratio (W/R = 1 to 10). In terms of space, we identified a relatively decreasing trend of δ18O and δ13C isotopic compositions of carbonates, from southeast to northwest, and from bottom to up. Based upon the previous structural analysis, we interpret that the δ18O and δ13C isotopic distribution patterns are caused by a northwestwards transfer pathway of ore-fluids along the thrusting fault system, and the metalliferous, δ18O- and δ13C-depleted fluids are sourced from the interior of the Quren Basin. Collectively, we clarify the deep southeastern part of the Fankou Zn-Pb deposit and the interiors of the Quren Basin is the favorable exploration target in future.
Indium (In), one of the strategic critical metal elements, is preferred to be enriched in the skarn system, but the enrichment regularity in terms of temporal and spatial distribution in a specific skarn Pb-Zn deposit remains unclear. To address the problem, we conducted a systematic geological, mineralogical, and trace element geochemical investigation on the Baoshan In-rich Pb-Zn polymetallic deposit, Hunan Province. This deposit is situated in the central part of the famous Nanling W-Sn-Pb-Zn polymetallic metallogeny belt, South China. Three ore districts in the Baoshan deposit with distinct economic element associations are divided, including the Central District (dominated by Cu-Mo), West District (dominated by Pb-Zn), and North District (dominated by Pb-Zn). They comprise a typical skarn system, including the outcropped granodiorite porphyry, typical skarn mineral assemblages, and Pb-Zn-hosting Carboniferous limestone. We systematically sampled the representative Pb-Zn ores in two ore districts (West and North) and three underground levels (-270 m, −230 m, and −190 m). Four types of sphalerites with different mineral associations and mineralogical characteristics were identified, that is, Sp1a and Sp1b (formed in the early sulfide stage), as well as Sp2a and Sp2b (formed in the late sulfide stage). Our EPMA (Electron Probe Micro-Analyzer) and LA-ICP-MS (Laser Ablation Inductively Coupled Plasma Mass Spectrometer) analyses reveal the four types of sphalerite have distinct chemical compositions. Such as, the mean value of indium is 3524 ppm for Sp1a, 142 ppm for Sp1b, 48.03 ppm for Sp2a, and 87.98 ppm for Sp2b in a decreasing order, and a similar trend of calculated temperatures ranging from 336 to 135 °C using GGIMFis thermometers can be obtained. Further LA-ICP-MS trace elements mapping show that the core of Sp1a is relatively enriched in more In, Cu, Sn, and Ag contents. Spatially, the sphalerites in the deep contain a higher indium content (mean = 1581 ppm) than those in the shallow (107.20 ppm) in the vertical profile. In the planar, indium is more enriched in the West District (mean = 1090 ppm) than in the North District (60.92 ppm). The indium distribution regularity reflects that the metals-carrying magmatic hydrothermal fluids flow from Central District, through the West District, to the North District. Collectively, we conclude that indium prefers to be enriched in the earlier stages, higher temperature, and deeper space during the sphalerite crystallization in the Baoshan skarn system, and therefore highlight the deep space of Baoshan West District is a promising target for indium exploration. This new finding maybe shed light on the scientific understanding on indium enrichment and associated exploration strategies in the similar skarn Pb-Zn metallogenic systems.
Metal endowment process of the clustered SEDEX (sedimentary exhalative) deposits in the Yunkai Domain (Cathaysia Block, South China) and their genetic connection with the regional tectonics is still open to debate. As a representative syngenetic deposit hosted in the black shale, the Yunfu iron-sulfide deposit (pyrite: 200 Mt @ 35%) has the potential to evaluate the missing linkage. Herein, pyrite Re–Os age and in-situ trace elements and sulfur isotope of principal ores were employed to constrain the metal accumulation process. The laminated pyrite (Py1), with the Re–Os isochron age of 303.4 ± 6.9 Ma (MSWD = 0.15), is enriched in heterogeneous distributed trace elements and highly negative heavy sulfur composition (δ34SV-CDT, mean = − 19.82‰, n = 29, standard deviation, s.d. = 0.67). This indicates the sulfur and metal precipitation was attributed for the bacterial sulfate reduction (BSR) during rapid deposition in the anoxic-seawater column of open sea at the Late Paleozoic time. The massive pyrite (Py2) hosts evenly distributed trace elements and slightly negative sulfur compositions (δ34SV-CDT, mean = − 2.00‰, n = 5, s.d. = 0.19), interpreted as further refinement and purification from Py1. To further trace its metallogenic tectonic, one hundred thirty-six (1 3 6) detrital zircon grains from ores and host rocks were selected for U–Pb and Lu–Hf isotopic analyses. Four samples of ores and ore-enveloping successions obtain the agreed youngest U–Pb ages of ∼ 430 Ma, also containing some inherited zircon grains of ca. 1200–800 Ma and ca. 2500 Ma. They possess a distinctive εHf(t) value of + 28.9 to + 40.5 for Archean, −15 to + 20 for Proterozoic and − 46.6 to − 0.2 for Paleozoic grains, respectively. This records that the episodic magmatism, including the Archean subduction, Proterozoic back-arc basin, and Paleozoic intra-continental orogeny prior to the eventual pyrite deposition, supply with substantial provenance. As a result, these collective data support that the Yunfu deposit was formed during the Late Paleozoic sedimentary exhalative deposition and hydrothermal activity in a local depression basin on the Yunkai passive continental margin without coeval magmatism.
The Xiangzhong (XZ) Basin and its neighboring Xuefengshan (XFS) Mountain in South China, as one of the world-class antimony (Sb) producers, have provided appropriately 67% of globally exploited Sb metal (0.46 million tons) in human history. The associated gold (Au) with Sb in this region is also of significant economic values. In previous studies, these Sb-Au deposits were debated as a diversity of genetic types such as epithermal, magmatic-hydrothermal, sedimentary exhalative (SEDEX) and orogenic Sb-Au deposits. To evaluate these genesis hypotheses, we select the representative Longwangjiang-Jiangdongwan (LWJ-JDW) orefield to reveal the Sb-Au accumulation process and metal-fluid sources of these deposits. Our orefield-scale structural analysis shows that the localization of principal Sb-Au orebodies is controlled by a NE-striking sinistral shearing system composed by an integrated set of NE-striking and SE-dipping fractures in the pre-ore folded Neoproterozoic Wuqiangxi slate. Two chief ore periods were identified, including the marine sedimentation (SI, pyrite nodular) and tectonic-metamorphic hydrothermal period (SⅡ−SⅣ, Sb-Au veins). The second period is further subdivided into three stages of SⅡ (pre-tectonic deformed pyrite-milky quartz veins), Siii (syn-tectonic pyrite-arsenopyrite-stibnite-quartz veins) and SⅣ (post-tectonic stibnite-calcite veinlets). It is notable that gold precipitation is significantly prior to Sb ores at LWJ-JDW. Three sericite samples throughout SⅡ−SⅣ yield a group of well-defined 40Ar/39Ar plateau ages (253 ± 4, 234 ± 3 and 206 ± 2 Ma, respectively). This indicates the multistage Sb-Au mineralization initiated from Early Triassic and terminated at Late Triassic time. Further trace elements analyses show the earliest nodular PyI is enriched in a list of As, Ni, Sb, Cu, Se, Co, Pb, Zn and Ti that can be analogy to the diagenetic pyrite in the organic-rich marine sedimentary rocks. Extremely high Sb (median, 1107 ppm) and mediate Au (0.07 ppm) are monitored in PyI, indicative of the initial Sb and Au involvement from the Neoproterozoic sedimentation. Comparably, sulfides of the later SⅡ−SⅣ possess a similar spectrum of trace elements but with highly variable concentrations. All the sulfide generations host the wide range of in-situ δ34SV-CDT values (–23.9 to −3.7‰ for SⅠ, −7.6 to −2.9‰ for SⅡ−SⅣ, respectively), indicating sulfur originally sourced from bacterial sulfate reaction (BSR) of the Neoproterozoic seawater sulfates, and then gradually reduced by thermochemical sulfate reaction (TSR) during the subsequent Au-Sb-induced tectonic-metamorphic hydrothermal activity. The lead isotope compositions in accordance with the evolution lines of upper crust and orogen, implying that the Pb were chiefly sourced from host slate of the Wuqiangxi Formation and its underlying basement. Synthesis of these data, we proposed that the Sb-Au accumulation at LWJ-JDW was caused by the multistage mineralization from Neoproterozoic marine sedimentation to Triassic episodic deformation and metamorphic processes (253–206 Ma).
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