Origin and preservation mechanisms of organic matter in carbonate concretions from Lower Cambrian black shales in South China

Abstract

Carbonate concretions are widely used in paleoclimate, paleoenvironmental, and paleontological studies, and even in the study of potential life on Mars. These petrological, elemental, isotopic, and lipid biomarker signals in Meso-Cenozoic carbonate concretions (relatively low thermal maturity) can effectively preserve details of seawater conditions and benthic ecosystems during the deposition of their host sediments/rocks. However, such research on Precambrian-Cambrian carbonate concretions under highly mature conditions remains scarce, and the ability of these ancient carbonate concretions to retain their original biogenic information remains uncertain. To achieve that, this study examines two Cambrian carbonate concretions, using samples from the center, transition, and rim of each, and their adjacent host black shales from the Lower Cambrian Qiongzhusi Formation in the Yangtze Block, South China. Organic and inorganic geochemical analyses were combined to elucidate the origin and preservation process of organic matter (OM) in these ancient Cambrian carbonate concretions. The results show that the thermal maturity of OM within these concretions (1.8 % EqVR_o) is relatively low compared to their adjacent host shales (2.9 % EqVR_o). Hopanes and steranes are detectable in both free and calcite-occluded hydrocarbons within these concretions, with concentrations of individual compounds ranging from 0.001 to 0.800 μg/g TOC, whereas kerogen-bound hydrocarbons lack detectable biomarkers. The results indicate that the two Cambrian carbonate concretions were formed mainly within the iron reduction and bacterial sulfate reduction zones, extending to depths of 10 to 38 m below the sediment-water interface. The OM within these concretions mainly inherited the initial unaltered signature of OM from the Qiongzhusi host shale. The carbonate concretions protected the internal OM from further thermal and secondary (e.g., biodegradation) alteration processes and might also prevent the formation of the conventional macromolecular skeletal kerogen manifested by the absence of bound biomarkers. The biomarkers, in both free and occluded forms, in the Cambrian carbonate concretions still retained their original source information, providing valuable insights into ancient biogeochemical processes during sediment burial and ancient seawater chemistry during the early Cambrian.