mid-Proterozoic Ocean Research Articles

Mineralogy of the 1.45 Ga Wafangzi manganese deposit in North China: Implications for pulsed Mesoproterozoic oxygenation events

Abstract Ancient manganese (Mn) deposits are primarily characterized by the presence of Mn(II) carbonates that likely formed by the diagenetic reduction of precursor Mn(IV) oxides. As such, Precambrian sedimentary Mn deposits have been used as a line of evidence for the evolution of oxygen in Earth’s surface environments. However, recent studies have shown that these Mn(II)-carbonates have the ability to directly accumulate within anoxic water columns, where free oxygen does not play a role in their formation. This alternative pathway casts uncertainty on the robustness of using ancient Mn deposits to constrain the redox fabric of the past marine water columns. Here, we investigate the Wafangzi Mn and Fe ore deposit from the 1.45 billion-year-old Tieling Formation, North China. The deposit contains Mn(II, III) mineral phases (hausmannite, braunite) as inclusions, or unreacted residues, trapped within Mn(II) carbonate (Ca-rhodochrosite). Some nodules and oolites of Mn(II) and Fe(II)-carbonate phases are also present and display a banded structure with concentric rings. Mn(III) oxide (manganite) is present in a paragenetic assemblage along with hematite and replacement textures with braunite. The negative carbon isotope composition (δ13C, –7‰ to –4‰) from Mn(II) carbonate samples in the Wafangzi Mn deposit which are distinct from that of contemporaneous seawater (~0‰), along with petrographic and speciation analyses, collectively suggest that the Mn(II, III)- and Fe(II)-bearing mineral phases formed through the diagenetic reduction of primary Mn(IV)/Fe(III) minerals coupled to the oxidation of organic matter. Therefore, the Wafangzi Mn deposit suggests the presence of sufficiently oxygenated marine waters, overlying anoxic ferruginous deeper waters with a transitional manganous water layer that could have driven the redox cycling of Mn, Fe, and C. Given the contemporaneous economic Mn deposits in the 1.45 Ga Ullawarra Formation in Western Australia, our findings imply the existence of a transient, and perhaps widespread, pulsed oxygenation event in the mid-Proterozoic oceans.

Coupled vanadium and thallium isotope constraints on Mesoproterozoic ocean oxygenation around 1.38-1.39 Ga

The oxygenation state of the Mid-Proterozoic (1.8 – 0.8 Ga) ocean and atmosphere is heavily debated and has implications for the relationship between environmental O2 and the emergence of complex life. While recent geochemical proxy studies of Mesoproterozoic marine sedimentary rocks inform a picture of deep water redox dominated by widespread ferruginous (iron-rich and anoxic) conditions, a growing number of datasets indicate that short-lived ocean oxygenation events were recurrent features of this time interval. The spatial extent of previously reported Mesoproterozoic oxygen pulses is often unclear as they are predominantly observed via localized environmental proxies. In this study, we use the vanadium (V) and thallium (Tl) isotope paleoredox proxies to provide a global marine redox perspective during a short interval of the Mesoproterozoic. We reconstructed seawater V (δ51VSW) and Tl (ε205TlSW) isotopic compositions from shales from Unit 2 of the 1.38-1.39 Ga Xiamaling Formation (North China craton) that show an up-section shift in average δ51VSW values from 0.02‰ to 0.15‰ and a short-lived perturbation in ε205TlSW from −2.5 to −4.2. Mass-balance models for both isotopic systems are consistent with these isotopic shifts representing an expansion of oxic water column and porewater conditions from a more anoxic (ferruginous) baseline ocean state. The short-lived nature of the ε205TlSW perturbation versus the shift in δ51VSW suggests that environments sufficiently oxygenated to support widespread Mn oxide burial were only established for a fraction of this overall oxic expansion. The ocean residence time of V and Tl requires that this oxygenation event was global in extent and may reflect either a purely oceanic phenomenon such as global deepening of the oxycline, or alternatively, global ocean-atmosphere equilibration during a short-lived episode of elevated atmospheric oxygenation.

Organic molecular evidence in the ∼1.40 Ga Xiamaling Formation black shales in North China Craton for biological diversity and paleoenvironment of mid-Proterozoic ocean

Indigenous hydrocarbon biomarkers in the black shales of the 1.40 billion-year-old Xiamaling Formation (XML) from the North China Craton were systematically analyzed to reveal the redox condition and biological community. These black shales are not only rich in organic matter, but also undergone an unexpectedly low thermal evolution process, both of which contribute to well-preserved indigenous hydrocarbons and promote the convincing discovery of the Precambrian biology. The combination of the absence or low concentrations of gammacerane, dibenzothiophene series and aryl isoprenoids, abundant rearranged hopanes, the occurrence of micro-ripples, and low level of redox-sensitive trace elements suggested shallow, low salinity and suboxic to anoxic conditions during the deposition period of XML. The absence of aryl isoprenoids as diagnostic biomarkers for green/purple sulfur bacteria strongly argued against the pervasively euxinic (sulphidic) bottom water in mid-Proterozoic ocean. The scenario of large hump unresolved complex mixture and abundant monomethyl alkanes as well as absent steranes may be derived from benthic microbial reworking processes for biolipids. Here the absence of saturated and aromatic steroids in the XML sediments suggested that eukaryotic algae have little ecological contribution to primitive biomass and/or are the result of heterotrophic reworking from benthic microbial mats. Abundant presence of hopanoid, tricyclic terpane and n-alkane in these samples supported the predominant contribution of (cyano) bacteria.

Redbed formation in the redox-stratified mid-Proterozoic ocean

Deposition of iron-enriched redbeds occurred episodically on different continents throughout the mid-Proterozoic, but their origin remains unclear. Since these sediments host abundant Fe oxides, their occurrence potentially represents changes in ocean-redox state, a hypothesis having significant implications for the evolution of early aerobic eukaryotes. In the present study, we report Fe speciation and isotopes, major and trace elements, organic carbon contents, and mineralogy of the 1.6-Ga Cuizhuang and 1.4-Ga Xiamaling redbeds and intercalated non-redbeds in North China to investigate their depositional environments. As expected, the redbeds show significantly higher total Fe contents (FeT), FeT/Al, and FeHR/FeT ratios (FeHR: highly reactive Fe) than the adjacent non-redbeds (mean FeT: 5.0 % vs. 2.9 %), with 73–97 % of the FeHR in the form of Fe oxides (Feox), accounting for the difference in FeHR/FeT ratios. However, almost all other major (e.g., Al and Ti, typically associated with the detrital fraction) and trace elements show no obvious difference in concentrations between the redbeds and non-redbeds, supporting a single, shared detrital source. The FeT/Al and FeHR/FeT ratios of the redbeds are higher than their respective thresholds for anoxic conditions, whereas the non-redbeds show the opposite. We thus infer that the non-redbeds were deposited in a shallow oxic setting and the redbeds in a deep anoxic setting, separated by a pronounced Fe-redoxcline. The iron was mainly sourced from seafloor hydrothermal fluids and then partially oxidized and precipitated in shallow environments, resulting in positive Fe-isotope values (+0.24 to +0.57‰). Preservation of large amounts of Fe-(hydr)oxides within an anoxic setting can be explained through low-productivity conditions, as inferred from low TOC (mean 0.1 %) and P (mean 452 ppm) contents in both redbeds and non-redbeds. Based on this scenario, modeling indicates that the degree of fractionation of FeHR isotopes (+0.36 to +1.38‰) in the redbeds is consistent with oxidation of 66–98 % of the hydrothermally supplied Fe in waters with an average photic-zone O2 concentration of <0.1 μmol/L (equivalent to atmospheric pO2 < 0.1 % PAL), providing further evidence for extremely low O2 levels during the mid-Proterozoic.

A transient oxygen increase in the Mesoproterozoic ocean at ∼1.44 Ga: Geochemical evidence from the Tieling Formation, North China Platform

Oxygen availability is crucial for the evolution of eukaryotes in geological history, yet detailed Mesoproterozoic oceanic-atmospheric redox conditions remain enigmatic. In contrast to the generally accepted hypothesis of an anoxic mid-Proterozoic ocean and atmosphere, several transient oxygenation events may occur at the Earth’s surface during the Mesoproterozoic, especially for the period around 1.4 Ga. The North China Platform develops one of the most complete and continuous Mesoproterozoic stratigraphic successions globally, preserving key information on the redox state of the surface ocean–atmosphere system during the mid-Proterozoic. In this study, I/(Ca + Mg), rare earth elements (REE) plus Y (REY), and paired stable isotopes (δ34SCAS and δ13Ccarb) data are reported for the carbonate rocks of ∼1.44 Ga Tieling Formation in the Jixian section, North China Platform. The lower Tieling Formation (i.e., the Daizhuangzi Member) exhibits middle-REE-enriched patterns with several relatively high I/(Ca + Mg) values (0.56–0.83 μmol/mol) suggesting a possible oxic or suboxic seawater condition. The upper Tieling Formation (i.e., the Laohuding Member) is characterized by modern seawater-like REY patterns with negative Ce anomalies (0.67–0.91) and variable I/(Ca + Mg) values (0.02–1.77 μmol/mol). The peak I/(Ca + Mg) ratios (up to 1.77 μmol/mol), negative shifts in Ce/Ce* and δ13Ccarb, and previously reported positive Cr isotope fractionation in the middle Laohuding Member indicate a significant oxygen increase in both ocean and atmosphere. A long-term increasing trend in δ34SCAS below the middle Laohuding Member outlines roles of pyrite burial in contributions of rising oxygen levels during this period.

Mesoproterozoic seafloor authigenic glauconite-berthierine: Indicator of enhanced reverse weathering on early Earth

Abstract Sedimentary records suggest that the mid-Proterozoic (ca. 1.8–0.8 Ga) was persistently characterized by a greenhouse climate despite significantly lower solar luminosity compared to modern levels. To maintain greenhouse conditions, the partial pressure of carbon dioxide (pCO2) must have remained elevated, possibly indicative of key differences in the complexities of the carbon cycle compared to the modern. Modeling has suggested that high pCO2 was likely maintained by elevated rates of “reverse weathering:” marine authigenic clay formation, a process that consumes alkalinity and generates CO2. This process is kinetically slow in modern marine environments, yet is hypothesized to have been enhanced during the mid-Proterozoic due to the greater availability of important species for clay authigenesis such as silica and ferrous iron. This hypothesis is testable using the geological record, because enhanced reverse weathering would lead to the formation of abundant marine authigenic clays. However, the distribution of marine authigenic clays in the Proterozoic sedimentary record has not been paid sufficient attention. In this study, we report the presence of authigenic clays (glauconite and berthierine) from the Xiamaling Formation (ca. 1.4 Ga), North China. The glauconite-berthierine horizons occur as millimeter-to centimeter-thick laminae interbedded with muddy siltstone and feature detrital grains supported by the clay matrix. In places, these layers were partially reworked to form soft and cohesive intraclastic sands, suggesting a syndepositional origin. We hypothesize that marine iron cycling in the iron- and silica-rich mid-Proterozoic oceans may have facilitated the formation of authigenic iron-rich clay during the deposition of the Xiamaling Formation. The formation of iron-hydroxides on the seafloor—and the local increase in pH caused by subsequent dissimilatory iron reduction—could have resulted in the absorption of SiO2, Al(OH)3, and Fe(OH)2 to form soft, cohesive and noncrystalline Fe(OH)3-SiO2-Al(OH)3-Fe(OH)2 gels. These gels would have subsequently converted to glauconite/berthierine through aging. The transformation from glauconite-rich layers to berthierine-rich laminae was likely facilitated by a greater availability of Fe(II), and therefore higher Fe(II)/TFe and Fe/Si ratios. We suggest that the relatively rapid formation of syndepositional, seafloor berthierine and glauconite layers in the basal Xiamaling Formation is the result of enhanced reverse weathering during this time. This study provides an important geological support for carbon cycle models that invokes enhanced reverse weathering rates in the mid-Proterozoic ocean that may have helped to maintain a high-baseline pCO2 during this time.

Phosphorus burial in ferruginous SiO2-rich Mesoproterozoic sediments

Abstract Persistently low atmospheric oxygen requires that net organic carbon burial was muted through much of Earth’s middle age. In order to achieve global mass balance with respect to O2, recent models have suggested that redox-dependent mechanisms, such as Fe(II)-phosphate precipitation, limited phosphate availability in dominantly anoxic and ferruginous oceans, in turn limiting net primary production, and therefore organic carbon burial. Nevertheless, observational constraints on phosphorus cycling in ferruginous Proterozoic systems are rare, leaving these models largely untested. Here, we present high-resolution petrographic and mineralogical data showing that the 1.3 Ga Sherwin Ironstone (Roper Group, Australia) was dominated by syndepositional precipitation of the Fe(II)-silicate minerals greenalite and berthierine, interlaminated with abundant authigenic calcium fluorapatite (CFA). Set in a quantitative geochemical framework, these data reveal that elevated marine SiO2(aq) concentrations facilitated extensive Fe(II)-silicate production, leaving CFA, rather than Fe(II)-phosphate, as the principal inorganic phosphorous sink in shallow-water Roper Group sediments. More broadly, the physical and chemical factors that triggered Fe(II)-silicate and CFA burial in the Roper Seaway highlight semi-restricted basins as important loci of phosphorus removal from the mid-Proterozoic ocean.

A pulse of oxygen increase in the early Mesoproterozoic ocean at ca. 1.57–1.56 Ga

The relationship between oxygen and evolution of early eukaryotes including algae and primitive animals in geological history has been debated, partly due to the varying estimates of oxygen levels in the mid-Proterozoic (ca. 1.8–0.8 Ga) ocean and atmosphere. The upper part of the Gaoyuzhuang Formation (ca. 1.60–1.54 Ga) in North China hosts decimeter-scale multicellular eukaryotic fossils and is documented with a decrease in cerium anomaly indicative of ocean oxygenation. However, the atmospheric oxygen level across this interval and its subsequent oxidation state require further investigation using additional redox proxies. Here we report I/(Ca+Mg) ratios, carbonate/organic carbon isotopes (δ13Ccarb and δ13Corg), and phosphorous (P) contents across the ca. 1.57–1.56 Ga fossil-bearing interval in the North China Platform. High I/(Ca+Mg) ratios (≥2.6 μmol/mol; up to 3.8 μmol/mol) from shallow-water carbonates of the Gaoyuzhuang Formation suggest an episode of significant oxygen increase up to ≥4% PAL (present atmospheric level). The I/(Ca+Mg) ratios return back to ≤0.5 μmol/mol shortly after the peak values without evidence for increasing water depth or diagenetic alteration, implying a short-lived oxidation event. The increase of I/(Ca+Mg) ratios is associated with a −3.5‰ negative δ13Ccarb and δ13Corg anomaly and an increase in P/Al ratios that are best explained by oxidation of dissolved organic carbon (DOC) in the ocean. Oxygen consumption through oxidation of DOC may have quickly lowered marine and atmospheric O2 levels to the early mid-Proterozoic (1.8–1.4 Ga) background oxygen concentration of ≤0.1–1% PAL. Short-lived oxidation events in an overall anoxic mid-Proterozoic ocean and atmosphere best explain the existing geochemical data and evolutionary stasis of eukaryotes during the “Boring Billion”.

Uranium isotope evidence for limited euxinia in mid-Proterozoic oceans

Reconstructing Earth's oxygenation history is key to deciphering environmental controls on early biospheric evolution. During the mid-Proterozoic Eon, low (but potentially variable) atmospheric pO2 led to highly heterogeneous marine redox conditions, with most studies indicating a relatively shallow depth of oxygen penetration. The relative proportion of oxic, anoxic and iron-rich (ferruginous), and anoxic and sulfide-rich (euxinic) conditions on the global seafloor is difficult to quantify, however, due to a general reliance on local redox proxies applied to the temporally discontinuous black shale record. It is particularly important to constrain the global prevalence of euxinic bottom waters because sulfide toxicity has been implicated as a primary constraint on evolution in mid-Proterozoic oceans and limits the solubility of bioessential trace metals such as copper, zinc, and molybdenum. Here, we present a suite of new uranium (U) isotope data from marine carbonate rocks that span the entire mid-Proterozoic interval (∼1.8 to 0.8 Ga). U-isotopes in well-preserved carbonate rocks represent a powerful new proxy that can be used to quantitatively constrain the global extent of marine euxinia. The median δ238U value for mid-Proterozoic carbonate samples is −0.43‰, which is lower than the median value for modern post-depositional carbonate sediments from the Bahamas, yet significantly higher than carbonate δ238U values recorded during other times of expanded anoxia in Earth history, such as during the end-Permian mass extinction. When paired with a three-sink isotope mass balance model, our data indicate that no more than 7% of the global seafloor was euxinic during the mid-Proterozoic Eon, although transient pulses of expanded euxinia are recorded. Although these results challenge early expectations of a sulfide-rich mid-Proterozoic ocean, they are consistent with more recent inferences from the black shale trace metal record. Evidence therefore indicates that euxinic bottom waters were relatively limited in their spatial extent in the mid-Proterozoic oceans.

Paleoenvironmental proxies and what the Xiamaling Formation tells us about the mid-Proterozoic ocean.

The Mesoproterozoic Era (1,600-1,000million years ago, Ma) geochemical record is sparse, but, nevertheless, critical in untangling relationships between the evolution of eukaryotic ecosystems and the evolution of Earth-surface chemistry. The ca. 1,400Ma Xiamaling Formation has experienced only very low-grade thermal maturity and has emerged as a promising geochemical archive informing on the interplay between climate, ecosystem organization, and the chemistry of the atmosphere and oceans. Indeed, the geochemical record of portions of the Xiamaling Formation has been used to place minimum constraints on concentrations of atmospheric oxygen as well as possible influences of climate and climate change on water chemistry and sedimentation dynamics. A recent study has argued, however, that some portions of the Xiamaling Formation deposited in a highly restricted environment with only limited value as a geochemical archive. In this contribution, we fully explore these arguments as well as the underlying assumptions surrounding the use of many proxies used for paleo-environmental reconstructions. In doing so, we pay particular attention to deep-water oxygen-minimum zone environments and show that these generate unique geochemical signals that have been underappreciated. These signals, however, are compatible with the geochemical record of those parts of the Xiamaling Formation interpreted as most restricted. Overall, we conclude that the Xiamaling Formation was most likely open to the global ocean throughout its depositional history. More broadly, we show that proper paleo-environmental reconstructions require an understanding of the biogeochemical signals generated in all relevant modern analogue depositional environments. We also evaluate new data on the δ98 Mo of Xiamaling Formation shales, revealing possible unknown pathways of molybdenum sequestration into sediments and concluding, finally, that seawater at that time likely had a δ98 Mo value of about 1.1‰.

1.1-billion-year-old porphyrins establish a marine ecosystem dominated by bacterial primary producers

The average cell size of marine phytoplankton is critical for the flow of energy and nutrients from the base of the food web to higher trophic levels. Thus, the evolutionary succession of primary producers through Earth's history is important for our understanding of the radiation of modern protists ∼800 million years ago and the emergence of eumetazoan animals ∼200 million years later. Currently, it is difficult to establish connections between primary production and the proliferation of large and complex organisms because the mid-Proterozoic (∼1,800-800 million years ago) rock record is nearly devoid of recognizable phytoplankton fossils. We report the discovery of intact porphyrins, the molecular fossils of chlorophylls, from 1,100-million-year-old marine black shales of the Taoudeni Basin (Mauritania), 600 million years older than previous findings. The porphyrin nitrogen isotopes (δ15Npor = 5.6-10.2‰) are heavier than in younger sedimentary sequences, and the isotopic offset between sedimentary bulk nitrogen and porphyrins (εpor = -5.1 to -0.5‰) points to cyanobacteria as dominant primary producers. Based on fossil carotenoids, anoxygenic green (Chlorobiacea) and purple sulfur bacteria (Chromatiaceae) also contributed to photosynthate. The low εpor values, in combination with a lack of diagnostic eukaryotic steranes in the time interval of 1,600-1,000 million years ago, demonstrate that algae played an insignificant role in mid-Proterozoic oceans. The paucity of algae and the small cell size of bacterial phytoplankton may have curtailed the flow of energy to higher trophic levels, potentially contributing to a diminished evolutionary pace toward complex eukaryotic ecosystems and large and active organisms.

Evidence for episodic oxygenation in a weakly redox-buffered deep mid-Proterozoic ocean

Over the last two decades, popular opinion about prevailing conditions in the mid-Proterozoic deep ocean has evolved from fully oxygenated to globally euxinic (sulfidic) to a more heterogeneous, stratified water column with localized pockets of euxinia existing in predominantly iron-rich (ferruginous) deep waters. The Animikie Basin in the Lake Superior region has been essential in shaping our view of marine redox evolution over this time period. In this study, we present a multi-proxy paleoredox investigation of previously unanalyzed strata of the late Paleoproterozoic Animikie Basin using drill cores through the ~1.85 Ga Stambaugh Formation (Paint River Group) in the Iron River-Crystal Falls district of the Upper Peninsula of Michigan, USA. Based on previous tectonic reconstructions and analysis of sedimentary regimes, the Iron River-Crystal Falls section captures strata from among the deepest-water facies of the Animikie Basin. In contrast to previous work on sedimentary rocks in this basin, we find evidence from iron speciation, trace metal, and Mo isotope data for episodes of at least local deep-water oxygenation within a basin otherwise dominated by ferruginous and euxinic conditions. While trace-metal enrichments and iron speciation data suggest predominantly anoxic conditions, the occurrence of Mn-rich intervals (up to 12.3 wt% MnO) containing abundant Mn-Fe carbonate, and a wide range of Mo isotope data with extremely negative values (δ98/95Mo = −1.0 to +1.1‰), record the shuttling of Mn-oxides from surface waters through oxic or suboxic waters to the sediment-water interface. We propose that such conditions are analogous to those of locally restricted modern and Holocene basins in the Baltic Sea, which receive episodic inflow of oxygenated water, producing similar geochemical signatures to those observed for the Animikie Basin. We argue that the mid-Proterozoic was characterized by a lack of a strong redox buffer (low sulfide, ferrous iron, and oxygen contents), and thus was vulnerable to dramatic, and at least local, redox shifts—including briefly oxygenated bottom waters. A refined view of the mid-Proterozoic ocean is emerging: one that was still predominantly anoxic, but marked by regional heterogeneities and short-term redox variability that may, in part, reflect a transitional state between prevailingly anoxic Archean and predominantly oxic Phanerozoic oceans.

A model for the oceanic mass balance of rhenium and implications for the extent of Proterozoic ocean anoxia

Emerging geochemical evidence suggests that the atmosphere-ocean system underwent a significant decrease in O2 content following the Great Oxidation Event (GOE), leading to a mid-Proterozoic ocean (ca. 2.0–0.8 Ga) with oxygenated surface waters and predominantly anoxic deep waters. The extent of mid-Proterozoic seafloor anoxia has been recently estimated using mass-balance models based on molybdenum (Mo), uranium (U), and chromium (Cr) enrichments in organic-rich mudrocks (ORM). Here, we use a temporal compilation of concentrations for the redox-sensitive trace metal rhenium (Re) in ORM to provide an independent constraint on the global extent of mid-Proterozoic ocean anoxia and as a tool for more generally exploring how the marine geochemical cycle of Re has changed through time. The compilation reveals that mid-Proterozoic ORM are dominated by low Re concentrations that overall are only mildly higher than those of Archean ORM and significantly lower than many ORM deposited during the ca. 2.22–2.06 Ga Lomagundi Event and during the Phanerozoic Eon. These temporal trends are consistent with a decrease in the oceanic Re inventory in response to an expansion of anoxia after an interval of increased oxygenation during the Lomagundi Event. Mass-balance modeling of the marine Re geochemical cycle indicates that the mid-Proterozoic ORM with low Re enrichments are consistent with extensive seafloor anoxia. Beyond this agreement, these new data bring added value because Re, like the other metals, responds generally to low-oxygen conditions but has its own distinct sensitivity to the varying environmental controls. Thus, we can broaden our capacity to infer nuanced spatiotemporal patterns in ancient redox landscapes. For example, despite the still small number of data, some mid-Proterozoic ORM units have higher Re enrichments that may reflect a larger oceanic Re inventory during transient episodes of ocean oxygenation. An improved understanding of the modern oceanic Re cycle and a higher temporal resolution for the Re compilation will enable further tests of these hypotheses regarding changes in the surficial Re geochemical cycle in response to variations in atmosphere-ocean oxygenation. Nevertheless, the existing Re compilation and model results are in agreement with previous Cr, Mo, and U evidence for pervasively anoxic and ferruginous conditions in mid-Proterozoic oceans.

Extremely low oxygen concentration in mid-Proterozoic shallow seawaters

The mid-Proterozoic (1.8–0.8Ga) witnessed the first appearance but unusually low diversification of eukaryotes. The stagnant biotic evolution during this billion-year-long period (commonly referred to as the “Boring Billion”) was arguably ascribed to low oxygen levels in atmosphere and ocean. However, evidence supporting low oxygen in shallow-marine environments where early eukaryotes first evolved is generally lacking or insufficient. Here we report Rare Earth Element and yttrium (REE+Y) data, particularly cerium (Ce) anomalies, from a suite of mid-Proterozoic sedimentary rocks of the North China platform. The new data from North China, in combination with available Ce anomaly data from other Proterozoic successions, demonstrate that during mid-Proterozoic, negative Ce anomalies did not occur until ∼1.54Ga and after ∼1.54Ga, only episodic negative Ce anomalies were present in shallow-water carbonates. Trace element enrichments (UEF, VEF, and MoEF) remained at the average continental crust level before ∼1.54Ga but showed a sudden increase at ∼1.54Ga. The data suggest that oxygen concentration in shallow-marine environments of the mid-Proterozoic ocean was extremely low, probably <0.2μM prior to ∼1.54Ga (based on minimal oxygen concentration requirement for Ce(III) oxidation) and fluctuating around 0.2μM afterwards. The low oxygen concentration (∼0.2μM) in shallow waters of the mid-Proterozoic ocean accounts for only ∼0.1% of the modern surface ocean oxygen level (∼280μM) and may help explain the evolutionary stasis of eukaryotes during the mid-Proterozoic.

Statistical analysis of iron geochemical data suggests limited late Proterozoic oxygenation.

Sedimentary rocks deposited across the Proterozoic-Phanerozoic transition record extreme climate fluctuations, a potential rise in atmospheric oxygen or re-organization of the seafloor redox landscape, and the initial diversification of animals. It is widely assumed that the inferred redox change facilitated the observed trends in biodiversity. Establishing this palaeoenvironmental context, however, requires that changes in marine redox structure be tracked by means of geochemical proxies and translated into estimates of atmospheric oxygen. Iron-based proxies are among the most effective tools for tracking the redox chemistry of ancient oceans. These proxies are inherently local, but have global implications when analysed collectively and statistically. Here we analyse about 4,700 iron-speciation measurements from shales 2,300 to 360 million years old. Our statistical analyses suggest that subsurface water masses in mid-Proterozoic oceans were predominantly anoxic and ferruginous (depleted in dissolved oxygen and iron-bearing), but with a tendency towards euxinia (sulfide-bearing) that is not observed in the Neoproterozoic era. Analyses further indicate that early animals did not experience appreciable benthic sulfide stress. Finally, unlike proxies based on redox-sensitive trace-metal abundances, iron geochemical data do not show a statistically significant change in oxygen content through the Ediacaran and Cambrian periods, sharply constraining the magnitude of the end-Proterozoic oxygen increase. Indeed, this re-analysis of trace-metal data is consistent with oxygenation continuing well into the Palaeozoic era. Therefore, if changing redox conditions facilitated animal diversification, it did so through a limited rise in oxygen past critical functional and ecological thresholds, as is seen in modern oxygen minimum zone benthic animal communities.

Anoxygenic photosynthesis controls oxygenic photosynthesis in a cyanobacterium from a sulfidic spring.

Before the Earth's complete oxygenation (0.58 to 0.55 billion years [Ga] ago), the photic zone of the Proterozoic oceans was probably redox stratified, with a slightly aerobic, nutrient-limited upper layer above a light-limited layer that tended toward euxinia. In such oceans, cyanobacteria capable of both oxygenic and sulfide-driven anoxygenic photosynthesis played a fundamental role in the global carbon, oxygen, and sulfur cycle. We have isolated a cyanobacterium, Pseudanabaena strain FS39, in which this versatility is still conserved, and we show that the transition between the two photosynthetic modes follows a surprisingly simple kinetic regulation controlled by this organism's affinity for H2S. Specifically, oxygenic photosynthesis is performed in addition to anoxygenic photosynthesis only when H2S becomes limiting and its concentration decreases below a threshold that increases predictably with the available ambient light. The carbon-based growth rates during oxygenic and anoxygenic photosynthesis were similar. However, Pseudanabaena FS39 additionally assimilated NO3 (-) during anoxygenic photosynthesis. Thus, the transition between anoxygenic and oxygenic photosynthesis was accompanied by a shift of the C/N ratio of the total bulk biomass. These mechanisms offer new insights into the way in which, despite nutrient limitation in the oxic photic zone in the mid-Proterozoic oceans, versatile cyanobacteria might have promoted oxygenic photosynthesis and total primary productivity, a key step that enabled the complete oxygenation of our planet and the subsequent diversification of life.

Nitrogen cycle feedbacks as a control on euxinia in the mid-Proterozoic ocean

Geochemical evidence invokes anoxic deep oceans until the terminal Neoproterozoic ~0.55 Ma, despite oxygenation of Earth's atmosphere nearly 2 Gyr earlier. Marine sediments from the intervening period suggest predominantly ferruginous (anoxic Fe(II)-rich) waters, interspersed with euxinia (anoxic H(2)S-rich conditions) along productive continental margins. Today, sustained biotic H(2)S production requires NO(3)(-) depletion because denitrifiers outcompete sulphate reducers. Thus, euxinia is rare, only occurring concurrently with (steady state) organic carbon availability when N(2)-fixers dominate the production in the photic zone. Here we use a simple box model of a generic Proterozoic coastal upwelling zone to show how these feedbacks caused the mid-Proterozoic ocean to exhibit a spatial/temporal separation between two states: photic zone NO(3)(-) with denitrification in lower anoxic waters, and N(2)-fixation-driven production overlying euxinia. Interchange between these states likely explains the varying H(2)S concentration implied by existing data, which persisted until the Neoproterozoic oxygenation event gave rise to modern marine biogeochemistry.

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 Fe(2+)-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.

Response to Comment on "Molybdenum Isotope Evidence for Widespread Anoxia in Mid-Proterozoic Oceans"

Relating changes in Mo isotope signatures preserved in the geologic record to changes in the extent of seafloor anoxia is not a trivial exercise. We previously presented and interpreted new Mo isotope data as indicating expanded anoxia in mid-Proterozoic oceans, potentially reaching global extent. Ling et al. challenge our conclusions, arguing that the data are not consistent with widespread anoxia. We stand by our original interpretation but welcome the opportunity to clarify and expand on those conclusions, particularly in view of the potential importance of ocean redox change for biological evolution.

Comment on "Molybdenum Isotope Evidence for Widespread Anoxia in Mid-Proterozoic Oceans"

Arnold et al . ([ 1 ][1]) reported Mo isotope compositions of mid-Proterozoic black shale, which were different from those of euxinic sediments in the Black Sea. On the basis of a mass balance model calculation, they claimed that “the area of oxic sedimentation in the mid-Proterozoic oceans was