Early oceans(>520 Ma) were characterized by widespread water-column anoxia, stratification, and limited oxidant availability, which are comparable to the chemical characteristics of modern marine sedimentary pore-waters in productive continental margins. Based on this similarity and our current understanding of the formation mechanism of early Earth ocean chemistry, we propose an idealized chemical zonation model for early oceans that includes the following redox zones(from shallow nearshore to deep offshore regions): oxic, nitrogenous(NO3?-NO2?-enriched), manganous-ferruginous(Mn2+ or Fe2+-enriched), sulfidic(H2S-enriched), methanic(CH4-enriched), and ferruginous(Fe2+-enriched). These zones were dynamically maintained by a combination of processes including surface-water oxygenation by atmospheric free oxygen, nitrate reduction beneath the chemocline, nearshore manganese-iron reduction, sulfate reduction, methanogenesis, and hydrothermal Fe2+ inputs from the deep ocean. Our modified "euxinic wedge" model expands on previous versions of this model, providing a more complete theoretical framework for the chemical zonation of early Earth oceans that helps to explain observations of unusual Mo-S-C isotope patterns. This model may provide a useful foundation for future studies of ocean chemistry evolution and elemental biogeochemical cycles in early Earth history.
Following the Ediacaran metazoan radiation,the "Cambrian Explosion" set up the major framework of todays' animal phyla as well as modern marine ecosystem.Here,we present a preliminary investigation on the temporal and spatial(from shallow to deep waters) variations of the early Cambrian ocean chemistry in South China through analyzing a Fe-S-C systematic dataset integrated from literature.Our investigation indicates that the early Cambrian deep ocean in South China was still anoxic and Fe2+-enriched(i.e.,ferruginous) although its surface was oxic,and in between a metastable euxinic(anoxic and sulfidic) water zone may have dynamically developed in anoxic shelf waters with an increasing weathering sulfate supply.Furthermore,accompanying marine transgression and regression cycles in the early Cambrian,such a "sandwich" structure in ocean redox chemistry demonstrates five evolutional stages,which can be well correlated to the spatiotemporal patterns of fossil records in South China.The good correlation between metazoan fossil occurrences and water chemistry in South China suggests that early animals possibly possessed ability to inhabit anoxic but generally not euxinic environments as free H2S was fatal to most eukaryotes.This view can well explain why those small shell fauna and sponges disappeared from shelf to slope areas where sulfidic Ni-Mo-rich shales were widely deposited.Thus,we conclude that the spatiotemporal variations of ocean chemistry and its biological effects probably played a key role in the phased animal radiations and "extinctions" in the early Cambrian.
JIN ChengShengLI ChaoPENG XingFangCUI HaoSHI WeiZHANG ZiHuLUO GenMingXIE ShuCheng
The Ediacaran Doushantuo Formation（ca. 635–551 Ma） deposited immediately after the last Neoproterozoic glaciations and recorded the most prominent negative excursions of carbonate carbon isotopic composition（δ^（13）C（carb））. These excursions have been interpreted as a result of widespread remineralization of a large dissolved organic carbon（DOC） reservoir in the Ediacaran deep oceans. However, there is no direct evidence so far found in rocks for the proposed DOC reservoir, which devalues such an interpretation. Here, we conducted a detailed study on the glow-curves characteristics and signal origins of spurious thermoluminescence（TL） of the Doushantuo Formation at Jiulongwan in Yangtze Gorges area, South China, through sequential tests under CO2, N2 and air. Spurious TL intensities for test samples before and after removing soluble organic matter via accelerated solvent extraction（ASE） are nearly identical. Further, significant positive correlation between the spurious TL intensity and total inorganic carbon（TIC） content（R^2=0.7） indicate that the Doushantuo spurious TL with the characteristic peak at 393.5 °C from the sequential test is chemiluminescence（CL） which is derived from the oxidation of a type of non-volatile organic matter strongly associated with carbonate mineral lattice（termed as “X-OM”）. A most likely explanation is that the X-OM is a type of dissolved organic matter which co-precipitated with carbonate minerals into sediments in the Ediacaran Doushantuo Ocean. Furthermore, a significant exponential negative correlation（R^2=0.55） is observed between the CL data and the isotopic difference between carbonate and coexisting bulk organic matter（i.e., Δ^（13）C（carb-org）, a proxy for remineralization degree of DOC reservoir in proposed DOC hypothesis）, suggesting that the X-OM was derived from the oxidation of the DOC reservoir in the Ediacaran Ocean. We thus propose that the X-OM and its CL detected in our study may have recorded the e
Molybdenum(Mo) proxies, including bulk concentration and isotopic composition, have been increasingly used to reconstruct ancient ocean redox states. This study systematically reviews Mo cycles and their accompanying isotopic fractionations in modern ocean as well as their application in paleo-ocean redox reconstruction. Our review indicates that Mo enrichment in sediments mainly records the adsorption of Fe-Mn oxides/hydroxides and chemical bonding of H2 S. Thus, Mo enrichment in anoxic sediments generally reflects the presence of H2 S in the water column or pore waters. In addition to the effect of euxinia, sedimentary Mo enrichment is related to the size of the oceanic Mo reservoir. Given these primary mechanisms for oceanic Mo cycling, Mo abundance data and Mo/TOC ratios acquired from euxinic sediments in geological times show that fluctuations of the oceanic Mo reservoir are well correlated with oxygenation of the atmosphere and oceans and suggest that oxygenation occurred in phases. Mo proxies suggest that Mo isotopes in strongly euxinic sediments reflect the contemporaneous Mo isotopic composition of seawater, but other processes such as iron-manganese(Fe-Mn) adsorption and weak euxinia can result in different fractionations. Diagenesis may complicate Mo enrichment and its isotopic fractionation in sediments. With appropriate constraints on the Mo isotopic composition of seawater and various outputs, a Mo isotope mass-balance model can quantitatively reconstruct global redox conditions over geological history. In summary, Mo proxies can be effectively used to reconstruct oceanic redox conditions on various timescales due to their sensitivity to both local and global marine redox conditions. However, given the complexity of geochemical processes, particularly the effects of diagenesis, further work is required to apply Mo proxies to ancient oceans.
