Multiple sources of metals of mineralization in Lower Cambrian black shales of South China: Evidence from geochemical and petrographic study

Black shales of the Lower Cambrian Niutitang Formation in southern China (Huangjiawan mine, Zunyi region, northern part of the Guizhou Province) host regionally distributed stratiform polymetallic Ni-Mo-platinum group elements (PGE)-Au phosphate- and sulfide-rich ores. These are confined to a >= 0.2-m thick ore horizon composed of mineralized bodies of algal onkolites, phosphate nodules, and sulfide and shale clasts in a mineralized phosphate- and organic matter-rich matrix. Compared to footwall and hanging wall shales, the ore bed is strongly enriched in Ni (up to 100-fold), As (up to 97-fold), Mo (up to 95-fold), Sb (up to 67-fold), Rh (up to 49-fold), Cu (up to 37-fold), Pd (up to 33-fold), Ru (up to 24-fold), Zn (up to 23-fold), Pt (up to 21-fold), Ir (up to 15-fold), Co (up to 14-fold), and Pb (up to 13-fold). Even footwall and hanging wall black shales are significantly enriched by Mo (21-fold) and Ni (12-fold) but depleted in Cr in comparison to average Cambrian black shale. Organic matter is represented by separate accumulations dispersed in the rock matrix or as biotic bitumen droplets and veinlets in ore clasts. Similar organic carbon (C-org) values in an ore bed and enclosing footwall and hanging wall shales of little mineralization indicate that metal accumulation was not controlled only by biogenic productivity and organic matter accumulation rate. Evaporitic conditions during sedimentation of the basal part of the Niutitang Formation were documented by an occurrence of preserved Ni-, V-, Cr-, and Cu-enriched phosphate-rich hardground with halite and anhydrite pseudomorphs on the paleosurface of the underlying Neoproterozoic carbonates. Neoproterozoic black shales of the Doushantuo Formation are characterized by increased metal concentrations. Comparison of metal abundances in both hardground and Doushantuo black shales indicate that black shales could have become a source of metal-rich hardground during weathering. The polymetallic Ni-Mo-PGE sulfide-rich ore bed is interpreted to represent a remnant of shallow-water hardground horizon rich in metals, which originated in a sediment-starved, semi-restricted, seawater environment. During the Early Cambrian transgression an influx of fresh seawater and intensive evaporation, together with the hydrothermal enrichment of seawater in a semi-restricted basin, resulted in the formation of dense metalliferous brines; co-precipitation of metals together with phosphates and sulfides occurred at or above the oxic-anoxic sediment interface. Metal-enriched hardground was disintegrated by the action of waves or bottom currents and deposited in a deeper part of the anoxic basin. Contemporaneously with the formation of a polymetallic Ni-Mo-PGE-Au sulfide ore bed, economic sedimentary exhalative (SEDEX)-type barite deposits were forming in a stratigraphically and geotectonically similar setting. The results of geochemical study at the Shang Gongtang SEDEX-type Ba deposit indicate that concentrations of Ag, As, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, Zn and other metals decrease from top of the barite body toward the hanging wall black shale. Lower Cambrian black shales of the Niutitang Formation above the barite body also display similar element abundances as Neoproterozoic black shales of the Doushantuo Formation, developed in the footwall of the barite body. But the geochemical composition of the sulfide layer is different from the Ni-Mo ore bed, showing only elevated Pb, Cu, Ni and Mo values. It is suggested that hydrothermal brines at Shang Gongtang might have leached metals from foowall Neoproterozoic sequences and became, after mixing with normal seawater, an additional source of Ag, Cr, Cu, Pb, Sb, Zn, Ni, PGE, V and other metals.