The Ediacaran Doushantuo Formation in South China is a prime target for geobiological investigation because it offers opportunities to integrate chemostratigraphic and paleobiological data. Previous studies were mostly focused on successions in shallow‐water shelf facies, but data from deep‐water successions are needed to fully understand basinal redox structures. Here, we report δ13Ccarb, δ13Corg, δ34Spyr, δ34
The Ediacaran Period (~635–539 Ma) is marked by the emergence and diversification of complex metazoans linked to ocean redox changes, but the processes and mechanism of the redox evolution in the Ediacaran ocean are intensely debated. Here we use mercury isotope compositions from multiple black shale sections of the Doushantuo Formation in South China to reconstruct Ediacaran oceanic redox conditions. Mercury isotopes show compelling evidence for recurrent and spatially dynamic photic zone euxinia (PZE) on the continental margin of South China during time intervals coincident with previously identified ocean oxygenation events. We suggest that PZE was driven by increased availability of sulfate and nutrients from a transiently oxygenated ocean, but PZE may have also initiated negative feedbacks that inhibited oxygen production by promoting anoxygenic photosynthesis and limiting the habitable space for eukaryotes, hence abating the long-term rise of oxygen and restricting the Ediacaran expansion of macroscopic oxygen-demanding animals.
more » « less- NSF-PAR ID:
- 10428736
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 14
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract SCAS , and δ15Nseddata from a drill core of the fossiliferous Lantian Formation, which is a deep‐water equivalent of the Doushantuo Formation. Our data confirm a large (>10‰) spatial gradient in δ13Ccarbin the lower Doushantuo/Lantian formations, but this gradient is probably due to the greater sensitivity of carbonate‐poor deep‐water sediments to isotopic mixing with13C‐depleted carbonate cements. A pronounced negative δ13Ccarbexcursion (EN 3) in the upper Doushantuo/Lantian formations, however, is spatially consistent and may be an equivalent of the Shuram excursion. δ34Spyris more negative in deeper‐water facies than in shallow‐water facies, particularly in the lower Doushantuo/Lantian formations, and this spatial pattern is interpreted as evidence for ocean redox stratification: Pyrite precipitated in euxinic deep waters has lower δ34Spyrthan that formed within shallow‐water sediments. The Lantian Formation was probably deposited in oscillating oxic and euxinic conditions. Euxinic black shales have higherTOC andTN contents, but lower δ34Spyrand δ15Nsedvalues. In euxinic environments, pyrite was predominantly formed in the water column and organic nitrogen was predominantly derived from nitrogen fixation orNH 4+assimilation because of quantitative denitrification, resulting in lower δ34Spyrand δ15Nsedvalues. Benthic macroalgae and putative animals occur exclusively in euxinic black shales. If preserved in situ, these organisms must have lived in brief oxic episodes punctuating largely euxinic intervals, only to be decimated and preserved when the local environment switched back to euxinia again. Thus, taphonomy and ecology were the primary factors controlling the stratigraphic distribution of macrofossils in the Lantian Formation. -
The Steptoean Positive Carbon Isotope Excursion (SPICE) event at ca. 497−494 Ma was a major carbon-cycle perturbation of the late Cambrian that coincided with rapid diversity changes among trilobites. Several scenarios (e.g., climatic/oceanic cooling and seawater anoxia) have been proposed to account for an extinction of trilobites at the onset of SPICE, but the exact mechanism remains unclear. Here, we present a chemostratigraphic study of carbonate carbon and carbonate-associated sulfate sulfur isotopes (δ13Ccarb and δ34SCAS) and elemental redox proxies (UEF, MoEF, and Corg/P), augmented by secular trilobite diversity data, from both upper slope (Wangcun) and lower slope (Duibian) successions from the Jiangnan Slope, South China, spanning the Drumian to lower Jiangshanian. Redox data indicate locally/regionally well-oxygenated conditions throughout the SPICE event in both study sections except for low-oxygen (hypoxic) conditions within the rising limb of the SPICE (early-middle Paibian) at Duibian. As in coeval sections globally, the reported δ13Ccarb and δ34SCAS profiles exhibit first-order coupling throughout the SPICE event, reflecting co-burial of organic matter and pyrite controlled by globally integrated marine productivity, organic preservation rates, and shelf hypoxia. Increasing δ34SCAS in the “Early SPICE” interval (late Guzhangian) suggests that significant environmental change (e.g., global-oceanic hypoxia) was under way before the global carbon cycle was markedly affected. Assessment of trilobite range data within a high-resolution biostratigraphic framework for the middle-late Cambrian facilitated re-evaluation of the relationship of the SPICE to contemporaneous biodiversity changes. Trilobite diversity in South China declined during the Early SPICE (corresponding to the End-Marjuman Biomere Extinction, or EMBE, of Laurentia) and at the termination of the SPICE (corresponding to the End-Steptoean Biomere Extinction, or ESBE, of Laurentia), consistent with biotic patterns from other cratons. We infer that oxygen minimum zone and/or shelf hypoxia expanded as a result of locally enhanced productivity due to intensified upwelling following climatic cooling, and that expanded hypoxia played a major role in the EMBE at the onset of SPICE. During the SPICE event, global-ocean ventilation promoted marine biotic recovery, but termination of SPICE-related cooling in the late Paibian may have reduced global-ocean circulation, triggering further redox changes that precipitated the ESBE. Major changes in both marine environmental conditions and trilobite diversity during the late Guzhangian demonstrate that the SPICE event began earlier than the Guzhangian-Paibian boundary, as previously proposed.more » « less
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Abstract 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 δ13C of seawater dissolved inorganic carbon. Here, we present carbonate and organic carbon isotope (δ13Ccarband δ13Corg) 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 theSE . Contrary to expectations, our results show that the magnitude and morphology of this excursion and its relationship with coexisting δ13Corgare highly heterogeneous across the platform. Integrated geochemical, mineralogical, petrographic, and stratigraphic evidence indicates that theSE is a primary marine signature. Data compilations demonstrate that theSE was also accompanied globally by parallel negative shifts of δ34S of carbonate‐associated sulfate (CAS ) and increased87Sr/86Sr ratio and coastalCAS concentration, suggesting elevated continental weathering and coastal marine sulfate concentration during theSE . In light of these observations, we propose a heterogeneous oxidation model to explain the high spatial heterogeneity of theSE and coexisting δ13Corgrecords of the Doushantuo, with likely relevance to theSE in other regions. In this model, we infer continued marine redox stratification through theSE but with increased availability of oxidants (e.g., O2and 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 theSE , future models must consider the evidence for spatial heterogeneity in δ13C presented in this study. -
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Abstract. Mercury (Hg) is emitted to the atmosphere mainly as volatile elemental Hg0. Oxidation to water-soluble HgII plays a major role in Hg deposition to ecosystems. Here, we implement a new mechanism for atmospheric Hg0∕HgII redox chemistry in the GEOS-Chem global model and examine the implications for the global atmospheric Hg budget and deposition patterns. Our simulation includes a new coupling of GEOS-Chem to an ocean general circulation model (MITgcm), enabling a global 3-D representation of atmosphere–ocean Hg0∕HgII cycling. We find that atomic bromine (Br) of marine organobromine origin is the main atmospheric Hg0 oxidant and that second-stage HgBr oxidation is mainly by the NO2 and HO2 radicals. The resulting chemical lifetime of tropospheric Hg0 against oxidation is 2.7 months, shorter than in previous models. Fast HgII atmospheric reduction must occur in order to match the ∼ 6-month lifetime of Hg against deposition implied by the observed atmospheric variability of total gaseous mercury (TGM ≡ Hg0+HgII(g)). We implement this reduction in GEOS-Chem as photolysis of aqueous-phase HgII–organic complexes in aerosols and clouds, resulting in a TGM lifetime of 5.2 months against deposition and matching both mean observed TGM and its variability. Model sensitivity analysis shows that the interhemispheric gradient of TGM, previously used to infer a longer Hg lifetime against deposition, is misleading because Southern Hemisphere Hg mainly originates from oceanic emissions rather than transport from the Northern Hemisphere. The model reproduces the observed seasonal TGM variation at northern midlatitudes (maximum in February, minimum in September) driven by chemistry and oceanic evasion, but it does not reproduce the lack of seasonality observed at southern hemispheric marine sites. Aircraft observations in the lowermost stratosphere show a strong TGM–ozone relationship indicative of fast Hg0 oxidation, but we show that this relationship provides only a weak test of Hg chemistry because it is also influenced by mixing. The model reproduces observed Hg wet deposition fluxes over North America, Europe, and China with little bias (0–30%). It reproduces qualitatively the observed maximum in US deposition around the Gulf of Mexico, reflecting a combination of deep convection and availability of NO2 and HO2 radicals for second-stage HgBr oxidation. However, the magnitude of this maximum is underestimated. The relatively low observed Hg wet deposition over rural China is attributed to fast HgII reduction in the presence of high organic aerosol concentrations. We find that 80% of HgII deposition is to the global oceans, reflecting the marine origin of Br and low concentrations of organic aerosols for HgII reduction. Most of that deposition takes place to the tropical oceans due to the availability of HO2 and NO2 for second-stage HgBr oxidation.
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Photic zone euxinia (PZE) is a condition where anoxic, H2S-rich waters occur in the photic zone (PZ). PZE has been invoked as an impediment to the evolution of complex life on early Earth and as a kill mechanism for Phanerozoic mass extinctions. Here, we investigate the potential application of mercury (Hg) stable isotopes in marine sedimentary rocks as a proxy for PZE by measuring Hg isotope compositions in late Mesoproterozoic (∼1.1 Ga) shales that have independent evidence of PZE during discrete intervals. Strikingly, a significantly negative shift of Hg mass-independent isotope fractionation (MIF) was observed during euxinic intervals, suggesting changes in Hg sources or transformations in oceans coincident with the development of PZE. We propose that the negative shift of Hg MIF was most likely caused by (
i ) photoreduction of Hg(II) complexed by reduced sulfur ligands in a sulfide-rich PZ, and (ii ) enhanced sequestration of atmospheric Hg(0) to the sediments by thiols and sulfide that were enriched in the surface ocean as a result of PZE. This study thus demonstrates that Hg isotope compositions in ancient marine sedimentary rocks can be a promising proxy for PZE and therefore may provide valuable insights into changes in ocean chemistry and its impact on the evolution of life.
