LAUSR

Abstract The combination of authigenic chromium and cadmium stable isotopes in marine sedimentary archives enables reconstruction of the redox conditions and levels of primary productivity in past oceans and basins. The Ediacaran to Cambrian Nanhua Basin (Yangtze Platform, South China) and its sedimentary sequences have been studied intensively in the past with respect to investigating the effects of post-Snowball Earth glaciations on the oxygenation of Earth's atmosphere, and intimately related, on the consequences of climate changes on the evolution of the ocean environment and of life during the Precambrian-Cambrian transition. Following recent propositions of using cadmium isotopes as a novel proxy for reconstructing the extent of primary productivity in paleooceans, we here present results from a combined cadmium (Cd)‑chromium (Cr) isotope study on metalliferous black shale, black shale and phosphorite sediments deposited during the Early Cambrian Niutitang Formation at the Maoshi and Zhijin sections. Results point toward strongly oxidized and highly productive surface water layers in the Nanhua Basin during this period. The samples have strongly positively fractionated δ114Cd and δ53Cr values up to +0.6‰ and + 1.4‰, respectively, similar to such values from carbonaceous sediments in modern oceans. The association of Cd with sulfides in the sediments, together with high Cd/TOC ratios particularly in the metalliferous black shales, implies a sulfide-controlled enrichment of Cd under restricted euxinic conditions. The lower Cd/TOC values in phosphorites and barren black shales and negatively fractionated δ114Cd values down to −0.33‰ point to less effective precipitation of Cd under more suboxic conditions as likely prevailing in an open shallow shelf. The Cr content in the sediments is mostly close to average shale, and the δ53Cr values are little fractionated in the 0–0.2‰ range, corroborated by flat shale-like rare earth element + yttrium (REE + Y) patterns. However, some metal-rich shale samples have clearly authigenic Cr isotope signatures with up to +1.4‰ δ53Cr, and the authigenic Cr component in the phosphorite samples is around 1‰ δ53Cr, indicating oxic surface waters. The latter sediments also depict seawater-like, middle REE enriched REE + Y patterns with distinct negative Ce and positive Y anomalies indicative of an oxygenated surface water layer, and with positive Eu anomalies which they likely received during phosphatogenesis in the euxinic bottom water environment. In accord with previous studies reporting on extreme trace metal enrichments (Mo, Ni, V, Hg, etc.) in these Early Cambrian sediments, our Cd and Cr isotope signatures favor a scenario of a strongly stratified basin in which high primary productivity thrived in an oxidized surface water layer, potentially as a result of increased nutrient supply from a strongly weathering continental hinterland in the aftermath of the last Snowball Earth glaciations in the Ediacaran.