LAUSR

Abstract The intrinsic link between atmospheric oxygenation, surface seawater redox and bioproductivity in the upper water column of oceans offers to combine cadmium with chromium isotopes in marine archives to deduce information on past controls of biological metal and nutrient cycling. We here use a novel approach in combining chromium and cadmium isotope signatures in metalliferous and organic matter (OM) rich shales from the Early Cambrian Niutitang formation (south China) to reconstruct the surface water redox and cycling of bioessential metals, in a period directly following the Cambrian animal evolution. The inventory of authigenic Cd in the black shales is controlled by their sulfide abundance, whereas authigenic Cr is dominantly controlled by iron(oxy-)hydroxides and OM. Cadmium isotopes measured on bulk sediments and 3 N HNO3 leachates exhibit e114Cd values from −1.5 to +4.5, with Mo Ni rich sulfidic shales revealing elevated values > + 2.5. Chromium isotopes define δ53Cr values from +0.4 to +1.7‰, with V-rich non-sulfidic shales yielding more positively fractionated signatures than Mo Ni rich sulfidic shales. The negative δ53Cr-e114Cd correlation trend recorded in the black shales suggests a high-e114Cd sulfide endmember of authigenic Cd preserved in anoxic bottom conditions. The other endmember is constituted by OM with the isotopically heavy Cr and light Cd signals reflecting efficient phytoplankton uptake in the photic zone. The endmembers constrain the Cd and Cr isotope signatures of surface waters in the Early Cambrian Nanhua Basin to e114Cd of ~ +7 to +17, and to δ53Cr of ~ + 0.7 to +1.9‰. These values are compatible with those of modern ocean surface waters and attest to a Cambrian surface ocean water sustaining elevated primary bioproductivity in the aftermath of late Ediacaran snowball Earth glaciations. Our study emphasizes the potential of the Cr Cd double tracer in studies aimed at the reconstruction of paleoproductivity and (bio)geochemical metal cycling in marine paleo-basins.