Oxygenation of the shallow ocean after the Great Oxidation Event: Geochemistry and Carbon isotopes of the Paleoproterozoic Hutuo Group in North China Craton

The Paleoproterozoic was known as a period of profound perturbations in marine environments and biogeochemical cycles due to the Great Oxidation Event (GOE), but the interconnections and consequences of these events remain poorly understood. We investigated the geochemistry and C isotopes of the 2.09-1.96 Ga Hutuo Group in the North China Craton (NCC) which provide evidence for the oxygenation of shallow oceans. The Hutuo Group is a >10-km-thick clastic and carbonate sequence with intercalated basalts and has undergone lower greenschist facies metamorphism. Diverse stromatolite morphotypes, ranging from small domical, conical, and columnar forms to bioherms with diameters up to 4 meters, as well as giant oncoids, are developed in the Hutuo carbonates. C isotopes of the Hutuo carbonates are characterized by a general decrease in δ¹³C_carb values upsection. It consists of a lower part with δ¹³C_carb ranging from 1.3 ‰ to 3.4 ‰, a middle part showing alternating positive and negative excursions of δ¹³C_carb from -3.6 ‰ to 2.7 ‰, and a upper part of exclusively negative excursions with δ¹³C_carb as light as -5.6 ‰. Most samples have δ¹⁸O_carb greater than -10 ‰ and show no correlation between δ¹⁸O_carb and δ¹³C_carb. This, along with relatively low Mn/Sr ratios (mostly < 10), exclude significant diagenetic modification of the C isotopes. δ¹³C_org of acid-insoluble residues of stromatolitic carbonates range between -30.9 ‰ and -22.3 ‰, consistent with C-fixation with the cyanobacterial RuBisCO enzymes. Therefore, the positive excursions are probably related to burial of organic matter produced by primary producers, consistent with the ending of the 2.22-2.06 Ga Lomagundi-Jatuli event. Similar positive C isotope excursions have also been reported from contemporaneous successions elsewhere in the NCC, including the Songshan Group in Henan and Liaohe Group in Liaoning. The following negative excursions, which is consistent with the excursions reported from the 2.1-2.0 Ga Zaonega Fm in the Fennoscandian Shield, thus correspond to pulsed oxidation of biomass in an oxygenated shallow ocean. The geochemical signatures of the carbonates which show minimal contamination by terrigenous materials provides constrains on the chemistry of the Paleoproterozoic ocean. PAAS-normalized REE patterns are flat or slightly LREE-depleted with variable but slightly negative to positive shale-normalized Ce anomaly and evident Eu anomaly. The carbonates have low concentrations of U, Mo, Co and Ni, and show upsection decrease in Mo, Co and Ni abundances, consistent with increasing redox states. Metapelites from the Hutuo Group show slightly positive Eu anomaly and low Mo concentrations and U/Th ratios (0.33 - 0.10), consistent with deposition in an oxygenated environment. Collectively, the data document the fluctuations of ocean redox states and final oxygenation of the Hutuo Basin in the aftermath of the GOE. Blooms of stromatolite-building cyanobacteria caused by high nutrient availability following the GOE might have played key roles in the final oxygenation of the atmosphere and shallow oceans.