Meng Cheng

A theoretical prediction of chemical zonation in early oceans (>520 Ma)

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.

Coupled oceanic oxygenation and metazoan diversification during the early–middle Cambrian?

The early–middle Cambrian (Fortunian to Age 4) is characterized by a significant increase in metazoan diversification. Furthermore, this interval is marked by a prominent environmental and ecological expansion of arthropod- and echinoderm-rich biotas. Recent redox work has suggested that this shift occurred during stable or decreasing marine oxygen levels, suggesting that these paleobiological and paleoecological transformations were decoupled from a redox control. We tested this idea by conducting new paleoredox analyses on Age 2–Age 4 Cambrian outer shelf (Jiuqunao-Wangjiaping), slope (Wuhe-Geyi), and basinal (Zhalagou) sections of the South China Craton. Multiple sections indicate that mid-depth waters transitioned from anoxic conditions during Cambrian Age 2 to stable oxic conditions during Cambrian Age 4. These findings suggest a stepwise expansion of oxic waters from shallow to deep settings during the early–middle Cambrian, consistent with a redox control of metazoan diversification and ecological expansion. More broadly, despite the surge in redox work over the past decade, this study highlights the need for continued coupled redox and paleontological studies to directly test models about the links between the evolution of animals, ecosystems, and marine redox conditions.

Uncovering the spatial heterogeneity of Ediacaran carbon cycling

Records of the Ediacaran carbon cycle (635-541 million years ago) include the Shuram excursion (SE), the largest negative carbonate carbon isotope excursion in Earth history (down to -12‰). The nature of this excursion remains enigmatic given the difficulties of interpreting a perceived extreme global decrease in the δ13 C of seawater dissolved inorganic carbon. Here, we present carbonate and organic carbon isotope (δ13 Ccarb and δ13 Corg ) records from the Ediacaran Doushantuo Formation along a proximal-to-distal transect across the Yangtze Platform of South China as a test of the spatial variation of the SE. Contrary to expectations, our results show that the magnitude and morphology of this excursion and its relationship with coexisting δ13 Corg are highly heterogeneous across the platform. Integrated geochemical, mineralogical, petrographic, and stratigraphic evidence indicates that the SE is a primary marine signature. Data compilations demonstrate that the SE was also accompanied globally by parallel negative shifts of δ34 S of carbonate-associated sulfate (CAS) and increased 87 Sr/86 Sr ratio and coastal CAS concentration, suggesting elevated continental weathering and coastal marine sulfate concentration during the SE. In light of these observations, we propose a heterogeneous oxidation model to explain the high spatial heterogeneity of the SE and coexisting δ13 Corg records of the Doushantuo, with likely relevance to the SE in other regions. In this model, we infer continued marine redox stratification through the SE but with increased availability of oxidants (e.g., O2 and sulfate) limited to marginal near-surface marine environments. Oxidation of limited spatiotemporal extent provides a mechanism to drive heterogeneous oxidation of subsurface reduced carbon mostly in shelf areas. Regardless of the mechanism driving the SE, future models must consider the evidence for spatial heterogeneity in δ13 C presented in this study.

Evidence for marine redox control on spatial colonization of early animals during Cambrian Age 3 (c. 521–514 Ma) in South China

The early Cambrian Period was a key interval in Earth history with regard to changes in both ocean chemistry and animal evolution. Although increasing ocean ventilation has been widely assumed to have played a key role in the rapid appearance, diversification and spatial colonization of early animals, this relationship is in fact not firmly established. Here, we report a high-resolution Fe-C-S-Al-Ti geochemical study of the lower Cambrian Wangjiaping section from an outer-shelf setting of the Yangtze Sea of South China. Iron speciation data document a redox transition from dominantly euxinic to ferruginous conditions during Cambrian Age 3 ( c. 521–514 Ma). Interpretation of coexisting pyrite sulphur isotope (δ 34 S py ) records from Wangjiaping reveals relatively high marine sulphate availability at Wangjiaping. Furthermore, Wangjiaping section shows lower δ 34 S py (‒2.1±5.3‰) and lower TOC (2.4±1.1%) values but higher positive correlation ( R 2 = 0.66, p < 0.01) between TOC and Fe py /Fe HR relative to deeper sections reported previously, suggesting that euxinia developed at Wangjiaping in response to increasing marine productivity and organic matter-sinking fluxes. Our reconstructed redox conditions and fossils at Wangjiaping in comparison with previously well-studied strata in the inner-shelf Xiaotan and Shatan sections suggest that planktonic and benthic planktonic trilobites with bioturbation appeared in the oxic water columns, whereas only planktonic trilobites without bioturbation occurred within the anoxic (even euxinic) water columns during Cambrian Age 3. This finding indicates that spatial heterogeneity of redox conditions in the shelves had an important effect on early animal distribution in the Yangtze Block.

Mo marine geochemistry and reconstruction of ancient ocean redox states

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 H2S. Thus, Mo enrichment in anoxic sediments generally reflects the presence of H2S 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.

Heterogeneous and dynamic marine shelf oxygenation and coupled early animal evolution

It is generally agreed that early diversification of animals and significant rise of atmospheric and oceanic oxygen (O2) levels occurred in the Ediacaran (635-541 million years ago, Ma) and early Cambrian (ca. 541-509 Ma). The strength and nature of their relationship, however, remain unclear and debated. A recent wave of paleoredox research - with a particular focus on the fossiliferous sections in South China - demonstrates high spatial heterogeneity of oceanic O2 (redox) conditions and dynamic marine shelf oxygenation in a dominantly anoxic ocean during the Ediacaran and early Cambrian. This pattern shows a general spatiotemporal coupling to early animal evolution. We attribute dynamic shelf oxygenation to a complex interplay among the evolving atmosphere, continents, oceans, and biosphere during a critical period in Earth history. Our review supports the idea of a complex coevolution between increasing O2 levels and early diversification of animals, although additional work is required to fully delineate the timing and patterns of this coevolution and the mechanistic underpinnings.