Xuelei Chu

Tracing the stepwise oxygenation of the Proterozoic ocean

Biogeochemical signatures preserved in ancient sedimentary rocks provide clues to the nature and timing of the oxygenation of the Earth’s atmosphere. Geochemical data suggest that oxygenation proceeded in two broad steps near the beginning and end of the Proterozoic eon (2,500 to 542 million years ago). The oxidation state of the Proterozoic ocean between these two steps and the timing of deep-ocean oxygenation have important implications for the evolutionary course of life on Earth but remain poorly known. Here we present a new perspective on ocean oxygenation based on the authigenic accumulation of the redox-sensitive transition element molybdenum in sulphidic black shales. Accumulation of authigenic molybdenum from sea water is already seen in shales by 2,650 Myr ago; however, the small magnitudes of these enrichments reflect weak or transient sources of dissolved molybdenum before about 2,200 Myr ago, consistent with minimal oxidative weathering of the continents. Enrichments indicative of persistent and vigorous oxidative weathering appear in shales deposited at roughly 2,150 Myr ago, more than 200 million years after the initial rise in atmospheric oxygen. Subsequent expansion of sulphidic conditions after about 1,800 Myr ago (refs 8, 9) maintained a mid-Proterozoic molybdenum reservoir below 20 per cent of the modern inventory, which in turn may have acted as a nutrient feedback limiting the spatiotemporal distribution of euxinic (sulphidic) bottom waters and perhaps the evolutionary and ecological expansion of eukaryotic organisms. By 551 Myr ago, molybdenum contents reflect a greatly expanded oceanic reservoir due to oxygenation of the deep ocean and corresponding decrease in sulphidic conditions in the sediments and water column.

Pulsed oxidation and biological evolution in the Ediacaran Doushantuo Formation

Recent geochemical data from Oman, Newfoundland, and the western United States suggest that long-term oxidation of Ediacaran oceans resulted in progressive depletion of a large dissolved organic carbon (DOC) reservoir and potentially triggered the radiation of acanthomorphic acritarchs, algae, macroscopic Ediacara organisms, and, subsequently, motile bilaterian animals. However, the hypothesized coupling between ocean oxidation and evolution is contingent on the reliability of continuous geochemical and paleontological data in individual sections and of intercontinental correlations. Here we report high-resolution geochemical data from the fossil-rich Doushantuo Formation (635–551 Ma) in South China that confirm trends from other broadly equivalent sections and highlight key features that have not been observed in most sections or have received little attention. First, samples from the lower Doushantuo Formation are characterized by remarkably stable δ13Corg (carbon isotope composition of organic carbon) values but variable δ34SCAS (sulfur isotope composition of carbonate-associated sulfate) values, which are consistent with a large isotopically buffered DOC reservoir and relatively low sulfate concentrations. Second, there are three profound negative δ13Ccarb (carbon isotope composition of carbonate) excursions in the Ediacaran Period. The negative δ13Ccarb excursions in the middle and upper Doushantuo Formation record pulsed oxidation of the deep oceanic DOC reservoir. The oxidation events appear to be coupled with eukaryote diversity in the Doushantuo basin. Comparison with other early Ediacaran basins suggests spatial heterogeneity of eukaryote distribution and redox conditions. We hypothesize that the distribution of early Ediacaran eukaryotes likely tracked redox conditions and that only after ≈551 Ma (when Ediacaran oceans were pervasively oxidized) did evolution of oxygen-requiring taxa reach global distribution.

A Stratified Redox Model for the Ediacaran Ocean

Oceans Before the Dawn Although the fossil record shows a clear explosion of animal diversity in the oceans at the beginning of the Cambrian period (∼542 million years ago), the evolutionary pressures driving this increase in diversity remain unclear. The likely scenario involves drastic changes in the distribution of oxygen in ocean basins, but global glaciations and poor preservation of rocks from this time often prevent a clear picture of global ecology before the dawn of animal life. Li et al. (p. 80, published online 11 February; see the Perspective by Narbonne) characterized the geochemical makeup of sedimentary rocks from south China that indicate alternating layers of sulfide- and iron-rich (i.e., sulfate-limited) anoxic waters in the several million years leading up to the Cambrian. These conditions may have set the stage for an eventual increase in productivity of photosynthetic life that oxygenated the oceans and allowed for rapid animal evolution. Geological records in China indicate that ocean chemistry may explain the delay in life’s biggest diversification period. The Ediacaran Period (635 to 542 million years ago) was a time of fundamental environmental and evolutionary change, culminating in the first appearance of macroscopic animals. Here, we present a detailed spatial and temporal record of Ediacaran ocean chemistry for the Doushantuo Formation in the Nanhua Basin, South China. We find evidence for a metastable zone of euxinic (anoxic and sulfidic) waters impinging on the continental shelf and sandwiched within ferruginous [Fe(II)-enriched] deep waters. A stratified ocean with coeval oxic, sulfidic, and ferruginous zones, favored by overall low oceanic sulfate concentrations, was maintained dynamically throughout the Ediacaran Period. Our model reconciles seemingly conflicting geochemical redox conditions proposed previously for Ediacaran deep oceans and helps to explain the patchy temporal record of early metazoan fossils.

Widespread iron-rich conditions in the mid-Proterozoic ocean.

The chemical composition of the ocean changed markedly with the oxidation of the Earth’s surface, and this process has profoundly influenced the evolutionary and ecological history of life. The early Earth was characterized by a reducing ocean–atmosphere system, whereas the Phanerozoic eon (less than 542 million years ago) is known for a stable and oxygenated biosphere conducive to the radiation of animals. The redox characteristics of surface environments during Earth’s middle age (1.8–1 billion years ago) are less well known, but it is generally assumed that the mid-Proterozoic was home to a globally sulphidic (euxinic) deep ocean. Here we present iron data from a suite of mid-Proterozoic marine mudstones. Contrary to the popular model, our results indicate that ferruginous (anoxic and Fe2+-rich) conditions were both spatially and temporally extensive across diverse palaeogeographic settings in the mid-Proterozoic ocean, inviting new models for the temporal distribution of iron formations and the availability of bioessential trace elements during a critical window for eukaryotic evolution.

Hydrothermal origin of elevated iron, manganese and redox-sensitive trace elements in the c. 635 Ma Doushantuo cap carbonate

Abstract: Major and trace element, including REE, concentrations of the Doushantuo cap carbonate (c. 635 Ma) in South China show enrichment in Fe, Mn and redox-sensitive elements and slightly negative Ce anomalies, indicating anoxic environments during cap carbonate precipitation. High FeT/Al ratios but very low concentration of extractable pyrites suggest ferruginous rather than euxinic conditions. The REE + Y patterns of samples show enrichment of heavy REE (HREE), positive Eu anomalies and positive Y anomalies, implying a hydrothermal origin for elevated concentration of Fe, Mn and redox-sensitive elements. The results suggest that ferruginous Ediacaran oceans may have rooted from hydrothermally induced iron accumulation in severely glaciated Cryogenian oceans.

Chemical and isotopic evidence for secondary alteration of natural gases in the Hetianhe Field, Bachu Uplift of the Tarim Basin

H2S and CO2 are found in elevated concentrations in the reservoirs near the Carboniferous–Ordovician unconformity in the Hetianhe Field of the Tarim Basin, NW China. Chemical and isotopic analyses have been performed on produced gases, formation waters and reservoir rocks to determine the origin of CO2 and H2S and to explain the heterogeneous distribution of isotopic and geochemical characteristics of petroleum fluids. It is unlikely that H2S and CO2 had a mantle component since associated helium has an isotope ratio totally uncharacteristic of this source. Instead, H2S and CO2 are probably the result of sulphate reduction of the light hydrocarbon gases (LHG). Increasing H2S concentrations and CO2/(CO2+ΣC1–4) values to the west of the Hetianhe Field occur commensurately with increasingly heavy hydrocarbon gas δ13C values. However, thermochemical sulphate reduction is unlikely because the temperatures of the reservoirs are too low, no H2S or rare pyrite was detected in deeper reservoirs (where more TSR should have occurred) and inferred δ34S values of H2S (from late-stage pyrite in the Carboniferous and Ordovician reservoirs) are as low as −24.9‰. Such low δ34S values discount the decomposition of organic matter as a major source of H2S and CO2. Bacterial sulphate reduction of the light hydrocarbon gases in the reservoir, possibly coupled indirectly with the consumption of organic acids and anions is most likely. The result is the preferential oxidation of 12C-rich alkanes (due to the kinetic isotope effect) and decreasing concentration of organic acids and anions. Modern formation water stable isotope data reveal that it is possible that sulphate-reducing bacteria were introduced into the reservoir by an influx of meteoric water from the west by way of an inversion-related unconformity. This may account for the apparently stronger influence of bacterial sulphate reduction to the west of the Hetianhe Field, and the consequent greatest decrease of the δ13C-CO2 values and the greatest increase in δ13C values of the alkane gases.

Mobilization and enrichment of high-field strength elements during late- and post-magmatic processes in the Shuiquangou syenitic complex, Northern China

Abstract The Shuiquangou syenitic complex consists of melasyenite and leucosyenite. In the northeastern part, there is a small area where the leucosyenite was affected by alteration. The altered leucosyenite contains much higher concentrations of high-field strength elements (HFSE), especially Nb, Zr, REE and Y compared to fresh leucosyenite. REE patterns of the altered leucosyenite show moderate negative Eu anomaly, in contrast to the slightly positive to non-anomalous Eu signature of the fresh syenitic rocks. Allanite from the hydrothermal mineral assemblage in the altered leucosyenite also contains much higher concentrations of REE and Ti than the euhedral magmatic allanites in unaltered leucosyenite. The enrichment of HFSE in altered leucosyenite was interpreted to be caused by the hydrothermal fluids based on mineral chemistry and whole-rock data. Within the fresh leucosyenite, allanite occurs in two habits, euhedral ones indicating a primary magmatic origin and anhedral ones suggesting a late-magmatic origin. The latter has higher concentrations of REE and Ti than the former. The anhedral allanite was presumed to be formed coeval with the alteration of the euhedral allanite as a result of residual magmatic fluid derived directly from the syenitic magma. The alteration of magmatic euhedral allanite and the enrichment of REE and Ti in the anhedral late-magmatic allanite suggest that these elements were mobilized by the residual magmatic fluid. Both residual late-magmatic and hydrothermal fluids have an inferred composition characterized by high alkalic and F contents, suggesting that F may be the most ligand that complexed the high-valence cations.

Sulfur and carbon isotopic variations in Neoproterozoic sedimentary rocks from southern China

Abstract A new set of δ34Ssulfide δ34Ssulfate and δ13Ccarbonate values has been reported from Neoproterozoic sedimentary rocks in southern China. The interglacial blackshales of the Datangpo Fm. display higher δ34Ssulfied values with > + 20‰. average, but the postglacial black shales from the Doushantuo Fm. show negative δ34Ccarbonate values. However, the Jinjiadong Fm., the same post-glaciation 3 as the Doushantuo Fm., has positive δ34Ssulfide values, implying that the δ34S value of sedimentary sulfides wouldbe controlled by lithofacies and paleogeographic environments. The δ34Ssulfate values relative to δ13Ccarbonate were obtained by extraction of trace sulfate from the successive carbonate sequences in the Yangtze Gorges sections. A preliminary interpretation suggests that the oceanic environment may fluctuate dramatically at the post-glacial Doushantuo stage and, then, recover its stability at the Dengying stage on the basis of the high resolution δ34S and δ13C corves of seawater.

Variations of sulfur and carbon isotopes in seawater during the Doushantuo stage in late Neoproterozoic

Successive analyses of sulfur and carbon isotopic compositions of carbonates strata in the Doushantuo Formation in the Yangtze area were accomplished through a method of extracting trace sulfate from carbonates. Sulfur and carbon isotopic compositions of coeval seawater were estimated from the samples that show the least diagenetic alteration. A high-resolution age curve of sulfur isotopes in seawater sulfates was obtained in the Doushantuo stage, which reflects the trend of variation in seawater sulfur isotopes after the Neoproterozoic snowball Earth event. Similar characteristics of variation in carbon isotopes were observed in the coeval carbonates. A large positive δ34S excursion over +20‰ occurs in ancient seawater sulfates in the early Doushantuo stage. Simultaneously, the δ13 C values in ancient seawater carbonates exhibit a positive excursion up to 10‰ The maximum δ34S and δ13C values are +46.4‰ and +6.9‰, respectively. In the middle Doushantuo stage, the range of variation in δ34 S values of seawater is relatively narrow, but δ13C values are quite high. Then, δ34S values of seawater become oscillating, and the same occurs in δ13C values. Negative excursions in δ34 S and δ13 C values occur simultaneously at the end of the Doushantuo stage, and the minimum δ34S and δ13C values dropped down to −10.1‰ and –5.7‰, respectively. The characteristics of variations in the sulfur and carbon isotopes of ancient seawater imply strong changes in oceanic environment that became beneficial to inhabitation and propagation of organism. The organic productivity and burial rate of organic carbon once reached a quite high level during the Doushantuo stage. However, the state of environment became unstable after the global glaciation. The global climate and environment possibly were fluctuating and reiterating. The negative excursions in δ34S and δ13C values occurring at the end of the Doushantuo stage may represent a global event, which might be related to oxidation of deep seawater.

Stratigraphic architecture of the Neoproterozoic glacial rocks in the “Xiang-Qian-Gui” region of the central Yangtze Block, South China

Abstract The Yangtze Block in South China is one of the important regions where Neoproterozoic glacial rocks are well developed and studied. However, the classification and correlation of the Neoproterozoic glacial sequences in the central Yangtze Block stillremain controversial among Chinese geologists. The original Sinian sections around the Yangtze Gorges Region became an official standard for classification and correlation since the 1950s. Subsequent regional geologic studies, however, resulted in different classification and correlation, because of its incompleteness. We select one of the complete sections in the bordering areas of Xiang (Hunan). Qian (Guizhou) and Gui (Guangxi). as a standard of classification and correlation. The temporal and spatial distribution, i.e. the stratigraphic architecture, of the glacial rocks in the central Yangtze Block is suggested. Our results indicate that the glacial sequence on the Yangtze Block was deposited during the Nantuo Ice-age, the Datangpo Interglacial-ag...