Abstract

The transgressive basal unit of the Early Cambrian black-shale sequence along the rifted margin of the southeastern Yangtze platform hosts a wide spectrum of marine sedimentary rocks distributed over more than a length of 1,000 km. A few-centimeter-thick sulfide-rich black shale units have spectacular metal tenors (Mo and Ni in the percent range, PGE + Au around 1 ppm) and consist of submillimeter-scale laminated sulfide and carbonaceous material and centimeter-sized pebble-like rip-up clasts of Mo-S-C compounds, pyrite, and Ni-rich polymetallic sulfides in carbonaceous and phosphate-rich matrix.

The δ53/52Crauthigenic values of Mo-Ni sulfide-rich black shale samples from the Zunyi mining district (Guizhou province), as well as from the Sancha district (Hunan province), 400 km northeast, have a mean of 0.96 ± 0.22‰ (n = 8), while V-rich black shale from both districts has a mean of 1.34 ± 0.46‰ (n = 5). These data indicate significantly positively fractionated values compared to igneous silicate Earth. The Cr isotope values of the studied shales compare with recent findings of positively fractionated δ53/52Cr values in Late Neoproterozoic-Phanerozoic marine carbonates and shale/mudstones and attest for the operation of an intensified oxidative surface Cr cycle from at least around ~0.75 Gyr ago. We propose that the major change in Cr cycling around the Precambrian-Cambrian boundary was caused by a significant rise of atmospheric oxygen levels.

The Cr isotope data confirm earlier conclusions from Mo and Os isotopes, which indicate a seawater metal source with ultimate metal supply by oxidative weathering of continental crust. In particular, covariation trends of Re-Os and of platinum-group elements display a distinct seawater signature, and a degree of metal enrichment which is an extension of the normal black shale pattern.

The Mo-Ni sulfide-rich black shale units are probably produced by winnowing of subaquatic hardground deposited under euxinic conditions. The same stratigraphic level also hosts anoxic/suboxic V-rich black shale (V in illite) and huge phosphorite deposits in oxic/suboxic settings, bedded barite, as well as 10s of meter-thick sapropelic alginite (combustible shale). We show that the extreme metal enrichment of the Mo-Ni sulfide-rich black shale can be understood as a combination of redox cycling and bottom-water/sediment-interface scavenging under euxinic conditions (Mo, noble metals), and of oxidation (remineralization) of organic matter settling from the photic zone, with sulfide fixation of Ni and other biophile elements under denitrifying and sulfate-reducing conditions.

High biological activity (as in coastal upwelling settings with high nutrient supply), very low clastic accumulation rate (as in protected basins), and low organic matter deposition (high rate of remineralization) in stratified oxic-suboxic-euxinic basins are requirements for advanced metal enrichment in black shales. A special bathymetric condition of slope deposition with intrabasinal olistostrome-like mass movement and gravitational winnowing explains both the peculiar ore textures and the further metal enrichment to ore grade in the Early Cambrian rock units on the Yangtze platform. The Mo-Ni sulfide-rich sediments can be regarded as the euxinic variant of the marine hydrogenous ore deposit spectrum, where ferromanganese nodules/crusts represent the oxic variant of extreme fractionation from seawater.

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