Multiple sulfur isotope records at the end-Guadalupian (Permian) at Chaotian, China: Implications for a role of bioturbation in the Phanerozoic sulfur cycle

Abstract

A recent study on quadruple sulfur isotopes (32S, 33S, 34S, and 36S) of sedimentary pyrite suggested that the end-Guadalupian extinction was caused by shoaling of the sulfidic deep-water. This scenario is based on the assumption that sulfur isotopic compositions of pyrite from hosting sediments were controlled by benthos activities, thus by the redox conditions of the sedimentary environments. Nonetheless, the relationship between the sulfur isotope records and redox conditions, reconstructed from litho- and bio-facies, are poorly known. In order to examine the effect of bioturbation in sediments, quadruple sulfur isotopic compositions of sedimentary pyrite from the end-Guadalupian succession in Chaotian, South China, were analyzed. Black mudstones of deep-water facies immediately below the extinction horizon have consistently high Δ33S values of ca. +0.079‰, clearly suggesting a sulfate reduction in the anoxic water column. Our new data are consistent with the emergence of a sulfidic deep-water mass prior to the end-Guadalupian extinction; the upwelling of the toxic deep-water may have contributed to the extinction. In contrast, shallow-marine bioclastic limestones with burrows deposited under oxic conditions have negative Δ33S values. This anomalous isotopic signal indicates the mixing of two distinct types of pyrite; one generated during the sulfate reduction in an open system and the other in a closed system. We interpret that bioturbation supplied sulfate in the sediments and promoted sulfate reduction and in-situ sulfide precipitation within the sediments. The negative Δ33S values of oxic sediments in Chaotian are inconsistent with the previous model and demonstrate that the sedimentary sulfur cycle associated with bioturbation was more complicated than previously thought. Our study also implies that, more generally, the role of bioturbation in increasing seawater sulfate concentration in the Phanerozoic may have been overestimated in the previous studies, because bioturbation may have enhanced sulfide burial or sulfur output from the oceans.