Cadmium-isotopic evidence for increasing primary productivity during the Late Permian anoxic event

Earth's most extreme extinction event near the end of the Late Permian decimated more than 90% of all extant marine species. Widespread and intensive oceanic anoxia almost certainly contributed to the catastrophe, though the driving mechanisms that sustained such conditions are still debated. Of particular interest is whether water column anoxia was a consequence of a 'stagnant ocean', or if it was controlled by increases in nutrient supply, primary productivity, and subsequent heterotrophic respiration. Testing these competing hypotheses requires deconvolving sedimentary/bottom water redox conditions from changes in surface water productivity in marine sediments. We address this issue by studying marine shales from East Greenland and the mid-Norwegian shelf and combining sedimentary redox proxies with cadmium-isotopic analyses. Sedimentary nitrogen-isotopic data, pyrite framboid analyses, and organic and inorganic shale geochemistry reveal sulfidic conditions with vigorous upwelling, and increasingly anoxic conditions with a strengthening upwelling in the Greenland and Norwegian sections, respectively. Detailed analysis of sedimentary metal budgets illustrates that Cd is primarily associated with organic carbon and records primary geochemical signatures, thus enabling reconstruction of surface water nutrient utilization. Cadmium-isotopic analyses of the authigenic shale fraction released by inverse aqua regia digestion yield an average delta(114)/(110) Cd of +0.15 +/- 0.01 parts per thousand (2 SE, n = 12; rel. NIST SRM 3108), indicative of incomplete surface water nutrient utilization up-section. The constant degree of nutrient utilization combined with strong upwelling requires increasing primary productivity - and not oceanic stagnation - to balance the larger nutrient fluxes to both study sites during the development of the Late Permian water column anoxia. Overall, our data illustrate that if bottom water redox and upwelling can be adequately constrained, Cd-isotopic analyses of organic-rich sediments can be used to provide valuable information on nutrient utilization and therefore past productivity. (C) 2014 Elsevier B.V. All rights reserved.