Inverse Mo versus U isotope correlation of Early Cambrian highly metalliferous black shales in South China indicates synsedimentary metal enrichment from a near-modern ocean

The basal unit of the Early Cambrian black shale sequence of South China hosts sulfide-rich polymetallic units, non-sulfidic vanadium-rich black shales, sapropelic alginite (combustible shale), barite, and phosphorite. This rock spectrum occurs in a paleoceanographic similar, and stratigraphically correlated, transgressive upwelling setting on the passive continental margin of the Neoproterozoic Yangtze Platform. Several centimeter-thick polymetallic sulfidic units (3–13 wt% Mo+Ni, 100–600 ppm U) have relatively light Mo (δ 98/95 Mo = 1.1 ± 0.2‰) and relatively heavy U isotope composition (δ 238/235 U = 0.2 ± 0.1‰). Several meter-thick V-rich shales with multiple ore-grade layers (0.1–0.8 wt% V, < 100 ppm U, Mo and Ni ~ 100 ppm) have isotopically lighter Mo (δ 98/95 Mo = 0.3 ± 0.4‰) and heavier U composition (δ 238/235 U = 0.4 ± 0.2‰ and up to 0.7‰). The inverse Mo versus U isotope correlation suggests that both metals were enriched by removal from anoxic to strongly euxinic bottom water in restricted basins along the rifted continental margin. Metal replenishment probably occurred via the cycling of Fe–Mn-oxyhydroxide particles across the redox boundary, with sorption/desorption of Mo (and likely Ni) in a stratified water column. In contrast, V enrichment with much lower Mo, Ni, and U contents, but more fractionated Mo and U isotope composition, reflects non-sulfidic anoxic depositional conditions in a partly open system with higher bottom water renewal rates. While Mo isotope fractionation likely occurred in the water column, U isotope fractionation may dominantly have occurred at the water-sediment interface, perhaps in a benthic organic flocculent layer. These findings indicate that local hydrodynamic control and stratified water column redox conditions may explain the observed variation of metal enrichment (Mo–Ni versus V) in the black shales. Furthermore, the high δ 98/95 Mo values up to 2.6‰ of the black shales studied and the correlated U and Mo isotope data suggest that Early Cambrian seawater was at least episodically broadly similar to modern seawater.