Isotopic evidence for water-column denitrification and sulfate reduction at the end-Guadalupian (Middle Permian)

Abstract

The total nitrogen and pyrite sulfur isotopic compositions of the Guadalupian–Lopingian (Middle-Upper Permian) shelf carbonates are analyzed at Chaotian in northern Sichuan, South China, to clarify the environmental changes in the relatively deep disphotic zone (generally deeper than 150m) in the ocean at the end-Guadalupian, focusing on the possible relationships with the deep-sea oxygen depletion and the shallow-sea extinction. At Chaotian, the Guadalupian Maokou Formation and the Early Lopingian Wujiaping Formation are primarily composed of bioclastic limestone of shallow-water facies, although the topmost part of the Maokou Formation (ca. 11m thick) is composed of bedded black mudstone and chert that was deposited on the disphotic slope/basin under anoxic conditions. Substantially high δ15N values of total nitrogen (up to +14‰) in the topmost Maokou Formation of the deep-water facies indicate water-mass denitrification. In the same disphotic interval, the consistently low δ34S values of pyrite (ca. −37‰) suggest sulfate reduction in the sulfate-rich water column. The new nitrogen and sulfur isotopic records at Chaotian indicate the enhanced anaerobic respiration in the oxygen-depleted disphotic zone in the Late Guadalupian in northwestern South China. The active water-column sulfate reduction likely resulted in the emergence of a sulfidic deep-water mass on the disphotic slope/basin, which is supported by the high proportions of pyrite Fe to highly reactive Fe in the rocks shown using 57Fe Mössbauer spectroscopy. The anaerobic respiration in the disphotic zone at the end-Guadalupian may have been enhanced by an expansion of the oxygen minimum zone (OMZ) caused by the increased primary productivity in the surface oceans; the OMZ expansion may have corresponded to the onset of prolonged oxygen depletion in the deep sea. The clear stratigraphic relationship at Chaotian shows the emergence of the sulfidic deep-waters preceding the extinction, implying that the upwelling of the sulfidic deep-water from the previously overlooked disphotic zone to the shallow shelves along the continental margin may have acted as a stress to the shallow-marine biota.