Marine Carbon-Sulfur Biogeochemical Cycles during the Steptoean Positive Carbon Isotope Excursion(SPICE) in the Jiangnan Basin, South China

Global occurrences of Steptoean Positive Carbon Isotope Excursion（SPICE） during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon（δ^（13）C） and organic carbon（δ^（13）C_（org）） isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate（CAS, δ^（34）S_（CAS）） and pyrite（δ^（34）S_（pyrite））, unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰ increase in δ^（13）C_（carb） of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions in δ^（34）S_（CAS） and δ^（34）S_（pyrite） have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound（VOSC, such as methanethiol and dimethyl sulfide） formation in sulfidic continental margins that were widespread during SPICE. Emission of 32S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of ^（32）S from continental margins to open oceans, elevating δ^（34）S of seawater sulfate in continental margins. A simple box model indicates that about 35% to 75% of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation.

2.0 Ga orogenic graphite deposits and associated 13C-enriched meta-carbonate rocks from South China Craton:Implications for global Lomagundi event

The Lomagundi(-Jatuli)event,characterized by extremely high positive global inorganic carbon isotope excursion at about 2.2 billion years ago,is pivotal in investigating the causes and consequences of great oxygenation event,inventory and sequestration of carbon on the Earth’s surface,evolution of life,and more profoundly tectonic control on Earth’s environment.However,the reasons that caused the isotopic excursion are not resolved yet.Herein,we report the discovery of meta-carbonate rocks with distinct positive carbon isotopic excursion from the Paleoproterozoic continental collision zone of the Kongling Complex,South China Craton.The δ^(13)C_(V-PDB) values for meta-carbonate rocks show positive values in the range from+5.5‰to+11.6‰,whereas the δ^(13)C_(V-PDB) values of associated graphite deposits range from-25.8‰to-9.5‰.Zircon U-Pb-Hf isotopes from zircon-bearing meta-carbonate sample yielded weighted average _(207)Pb/_(206)Pb age of 2001.3±9.5 Ma,with correspondingε_(Hf)(t)range from-7.05 to-3.16,comparable to the values of local 2.9–2.6 Ga basement rocks.Geochemical characteristics of meta-carbonate rocks,such as their rare earth element patterns and the trace element parameters of La,Ce,Eu,and Gd anomalies and Y/Ho ratio,suggest that the carbonate deposition took place in passive continental margin in association with large volumes of organic carbon.The extensive graphite deposits from Kongling Complex in South China Craton,their equivalents in the North China Craton and elsewhere across the globe prove that the burial of ^(12)C-enriched organic carbon has eventually resulted in the global enrichment of ^(13)C in the atmospheric CO_(2),which is recorded in the marine carbonate rocks.Isotopic mass balance estimates indicate that more than half of the organic carbon was buried during the oceanic closure.Hence,the observed global shift could be directly related to the continent collision event in greater China,thus resolving the long-standing paradox of the Lomagundi global positive carbon isotope excursion.Moreover,the present results suggest that orogenesis play a significant role in sequestration of carbon into the continental crust.