Great Oxidation Research Articles

Technical comment on “Reexamination of 2.5-Ga ‘whiff’ of oxygen interval points to anoxic ocean before GOE”

Many lines of inorganic geochemical evidence suggest transient "whiffs" of environmental oxygenation before the Great Oxidation Event (GOE). Slotznick etal. assert that analyses of paleoredox proxies in the Mount McRae Shale, Western Australia, were misinterpreted and hence that environmental O2 levels were persistently negligible before the GOE. We find these arguments logically flawed and factually incomplete.

Response to comment on "Reexamination of 2.5-Ga 'whiff' of oxygen interval points to anoxic ocean before GOE".

Sedimentological, textural, and microscale analyses of the Mount McRae Shale revealed a complex postdepositional history, previously unrecognized in bulk geochemical studies. We found that metal enrichments in the shale do not reside with depositional organic carbon, as previously proposed by Anbar etal., but with late-stage pyrite, compromising claims for a "whiff" of oxygen ~50 million years before the Great Oxygenation Event.

Zinc enrichment and isotopic fractionation in a marine habitat of the c. 2.1 Ga Francevillian Group: A signature of zinc utilization by eukaryotes?

Constraining the timing of eukaryogenesis and the divergence of eukaryotic clades is a major challenge in evolutionary biology. Here, we present trace metal concentration and zinc isotope data for c. 2.1 billion-year-old Francevillian Group pyritized structures, previously described as putative remnants of the first colonial multicellular organisms, and their host black shales. Relative to the host rocks, pyritized structures are strongly enriched in zinc, cobalt and nickel, by at least one order of magnitude, with markedly lighter zinc isotope compositions. A metabolic demand for high concentrations of aqueous zinc, cobalt, and nickel combined with preferential uptake of lighter zinc isotopes may indicate metalloenzyme utilization by eukaryotes in marine habitats c. 2.1 billion years ago. Once confirmed, this would provide a critical calibration point for eukaryogenesis, suggesting that this major evolutionary innovation may have happened contemporaneously with elevated atmospheric oxygen levels during the latter part of the Great Oxidation Event, some 400 million years earlier than is currently widely accepted.

Redox-stratified seawater during the GOE: Evidences from rare earth elemental and C-O isotopic compositions of Paleoproterozoic BIF and carbonate rocks from the Taihua Group, North China Craton

The Paleoproterozoic Great Oxidation Event (GOE) is known for the dramatic change in atmospheric composition that led to oxygen becoming a persistent component of global surface processes. Drastic environmental changes greatly affected ocean and atmosphere chemistry. However, the distribution of dissolved oxygen in the ocean during the GOE is still unclear as rare contemporary sediment-records have been found. In order to identify the redox state of both shallow and deep water, and reveal the ocean redox structure during this time, we present new major and trace elemental and C-O isotopic data of bulk samples of the banded iron formation (BIF), dolomitic marble, and graphite-bearing marble of the early Paleoproterozoic upper Taihua Group in the Lushan area, southern margin of the North China Craton (NCC). The BIF samples exhibit typical major and trace element characteristics akin to very pure marine chemical sediments, such as the shale-normalized positive La, Ga, and Y anomalies, indicative of a marine depositional setting. In these BIF samples, both negative Ce anomalies and the lack of Ce anomalies reflect the presence of both oxic and suboxic/anoxic water in the ocean. Samples of the dolomitic marble are characterized by extremely low amounts of crustal material (such as Al, Ti, Zr, Hf) and high Y/Ho ratios (46–66), also implying a pure marine chemical origin. Excluding some contaminated samples, the rest of the graphite-bearing marble samples display similar features of the dolomitic marble. Significant positive Ce anomalies and high light to heavy REE (Pr/Yb(SN)) ratios in both dolomitic marble and graphite-bearing marble are essentially consistent with the 2.2–2.1 Ga carbonates from the Guanmenshan Formation of the Liaohe Group in the NE Sino-Korean Craton. Combined with the Ce anomalies in the BIF samples, we consider that the seawater when the upper Taihua Group deposited was redox-stratified from oxic shallow water to deeper anoxic water. Besides, the graphite-bearing marble record coeval surface water in the column that was enriched in nutritive materials and beneficial to microbiology and high productivity. Moreover, the early Paleoproterozoic IFs in the Songshan Group and the Lüliang Group in the NCC also exhibit significant both positive and negative Ce anomalies and enrichment of redox sensitive elements. These evidences, therefore, suggest that redox-stratified seawater occurred extensively during the GOE.

Biogeochemical transformations after the emergence of oxygenic photosynthesis and conditions for the first rise of atmospheric oxygen.

The advent of oxygenic photosynthesis represents the most prominent biological innovation in the evolutionary history of the Earth. The exact timing of the evolution of oxygenic photoautotrophic bacteria remains elusive, yet these bacteria profoundly altered the redox state of the ocean-atmosphere-biosphere system, ultimately causing the first major rise in atmospheric oxygen (O2 )-the so-called Great Oxidation Event (GOE)-during the Paleoproterozoic (~2.5-2.2 Ga). However, it remains unclear how the coupled atmosphere-marine biosphere system behaved after the emergence of oxygenic photoautotrophs (OP), affected global biogeochemical cycles, and led to the GOE. Here, we employ a coupled atmospheric photochemistry and marine microbial ecosystem model to comprehensively explore the intimate links between the atmosphere and marine biosphere driven by the expansion of OP, and the biogeochemical conditions of the GOE. When the primary productivity of OP sufficiently increases in the ocean, OP suppresses the activity of the anaerobic microbial ecosystem by reducing the availability of electron donors (H2 and CO) in the biosphere and causes climate cooling by reducing the level of atmospheric methane (CH4 ). This can be attributed to the supply of OH radicals from biogenic O2 , which is a primary sink of biogenic CH4 and electron donors in the atmosphere. Our typical result also demonstrates that the GOE is triggered when the net primary production of OP exceeds >~5% of the present oceanic value. A globally frozen snowball Earth event could be triggered if the atmospheric CO2 level was sufficiently small (<~40 present atmospheric level; PAL) because the concentration of CH4 in the atmosphere would decrease faster than the climate mitigation by the carbonate-silicate geochemical cycle. These results support a prolonged anoxic atmosphere after the emergence of OP during the Archean and the occurrence of the GOE and snowball Earth event during the Paleoproterozoic.

SO2 Photodissociation at 193 nm Directly Forms S(3P) + O2(3Σg-): Implications for the Archean Atmosphere on Earth.

It is well-documented that photodissociation of SO2 at λ = 193 nm produces O(3Pj) + SO X(3Σ-). We provide experimental evidence of a new product channel from one-photon absorption producing S(3Pj) + O2 X(3Σg-) in 2-4% yield. We probe the reactant and all products with time-resolved photoelectron photoion coincidence spectroscopy. High-level ab initio calculations suggest that the new product channel can only occur on the ground-state potential energy surface through internal conversion from the excited state, followed by isomerization to a transient SOO intermediate. Classical trajectories on the ground-state potential energy surface with random initial conditions qualitatively reproduce the experimental yields. This unexpected photodissociation pathway may help reconcile discrepancies in sulfur mass-independent fractionation mechanisms in Earth's geologic history, which shape our understanding of the Archean atmosphere and the Great Oxygenation Event in Earth's evolution.

Evolution of the composition of hydrothermal mineral-forming fluid of ore deposits in early Precambrian of the Ukrainian Shield

The aim of the study, the results of which are presented in this article, is to study changes in the composition of hydrothermal fluid ore systems of the early Precambrian on the example of gold and uranium ore deposits of the Ukrainian shield in connection with the evolution of exo- and endogenous processes in the outer shells of the Earth. The method used is a complex isotope-geochemical study of the composition of gas-liquid inclusions of hydrothermal fluid of ore systems. Based on experimental isotope-geochemical studies of the fluid of gas-liquid inclusions in the minerals of Precambrian deposits of uranium and gold of the Serednoprydniprovsky and Ingul megablocks of the Ukrainian Shield, a consistent change in the quantitative and isotopic composition of hydrothermal fluids of mineral formation from Mesoarchean to Paleoproterozoic was established. The content of H2O and CO2 was investigated and the isotopic composition of carbon CO2 fluids in quartz, pyrite, and feldspar were studied. The age range of the studied deposits is 3200—1750 million years. A decrease in the carbon dioxide content in the hydrothermal mineral-forming fluid of the Precambrian occurred in the Neoarchean, that is, before the Great Oxygen Event (Great Oxidation Event) — an increase in the oxygen content in the atmosphere in the Paleoproterozoic and is probably associated with the processes of exogenous and endogenous hydration of ultramafic rocks during the formation of the protocontinental crust. Molar fraction of CO2 in the mineral-forming fluid, in the Precambrian correlates to some extent with atmospheric pressure. The increase in the content of the carbon-12 isotope in the Paleoproterozoic in the mineral-forming fluid occurred due to the oxidation of organic matter with an increase in the oxygen content in the atmosphere.

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.

Isotopic Constraints on the Nature of Primary Precipitates in Archean–Early Paleoproterozoic Iron Formations from Determinations of the Iron Phonon Density of States of Greenalite and 2L- and 6L-Ferrihydrite

Iron formations (IFs) are chemical sedimentary rocks that were widely deposited before the Great Oxidation Event (GOE) around 2.4–2.2 Ga. It is generally thought that IFs precipitated as hydrated Fe3+ oxides (HFOs) such as ferrihydrite following surface oxidation of Fe2+-rich, anoxic deep waters. This model often implicates biological oxidation and underpins reconstructions of marine nutrient concentrations. However, nanoscale petrography indicates that an Fe2+ silicate, greenalite, is a common primary mineral in well-preserved IFs, motivating an alternative depositional model of anoxic ferrous silicate precipitation. It is unclear, however, if Fe2+-rich silicates can produce the Fe isotopic variations in IFs that are well explained by Fe2+ oxidation. To address this question, we constrain the equilibrium Fe isotopic (56Fe/54Fe) fractionation of greenalite and ferrihydrite by determining the iron phonon densities of states for those minerals. We use ab initio density functional theory (DFT + U) calculations and nuclear resonant inelastic X-ray scattering spectroscopy to show that ferrous greenalite should be isotopically lighter than ferrihydrite by ∼1–1.2‰ at equilibrium, and fractionation should scale linearly with increasing Fe3+ content in greenalite. By anchoring ferrihydrite–greenalite mineral pair fractionations to published experimental Fe isotopic fractionations between HFOs and aqueous Fe2+, we show that ferrous greenalite may produce all but the heaviest pre-GOE Fe isotopic compositions and mixed valence greenalites can produce the entire record. Our results suggest that heavy Fe isotope enrichments alone are not diagnostic of primary IF mineralogies, and ferrihydrite and partially oxidized or even purely ferrous greenalite are all viable primary IF mineralogies.

An example of the Middle to Late Devonian marine nitrogen cycle from mudstones of the Horn River Group, Northwest Territories, Canada

The Middle to Late Devonian was characterized by the widespread deposition of organic-rich mudstone units and successive biotic crises and anoxic events in the marine realm, the cause of which remains debated and requires constraints from associated marine conditions. This study provides an example of the marine nitrogen cycle throughout the late Eifelian to middle Frasnian anoxic pulses. We present new and previously published organic whole-rock N (δ15Nbulk) and carbon (δ13Corg) isotopic datasets from organic-rich mudstone units of the Horn River Group (Canol and Hare Indian Formations) and overlying Imperial Formation in the Central Mackenzie Valley, Northwest Territories, Canada. In the ConocoPhillips Mirror Lake N-20 core, δ13Corg ranges from −31.0 ‰ to −24.3 ‰ with δ15Nbulk from −3.8 ‰ to +1.9 ‰, whereas the Husky Little Bear N-09 core is characterized by δ13Corg from −31.0 ‰ to −27.2 ‰ and δ15Nbulk from −2.0 ‰ to +5.9 ‰. The N isotopic signatures near 0 ‰ and a lack of δ15Nbulk – δ13Corg relationship are characteristic of N2 fixation by primary producers. Regular oscillations in δ15Nbulk are interpreted as the product of episodic, mild oxygenation events. Together, our δ13Corg and δ15Nbulk results suggest that locally, N2 fixation was the dominant source of N for primary producers in the late Eifelian to middle Frasnian, despite fluctuations in δ13Corg and global marine paleoredox. These findings contribute to our understanding of the nitrogen speciation and bioavailability associated with anoxic events, biotic crises, and widespread organic carbon burial in the Eifelian to Frasnian oceans.

Did nutrient-rich oceans fuel Earth’s oxygenation?

Abstract Phosphorus (P) availability exerts a strong influence on primary productivity in global oceans. However, its abundance and role as a limiting nutrient prior to the start of the Great Oxygenation Event (GOE) 2.45–2.32 Ga is unclear. Low concentrations of seawater P have been proposed to explain the apparent delay between the early appearance of oxygen-producing Cyanobacteria and the onset of atmospheric oxygenation. We report evidence for seawater precipitation of Ca-phosphate nanoparticles in 2.46–2.40 Ga iron formations deposited on a marine shelf, including shallow-water facies, immediately prior to the onset of the GOE. Our modeling shows that the co-precipitation of Ca-phosphate and ferrous silicate (greenalite) required ferruginous seawater with dissolved P concentrations many orders of magnitude higher than in today’s photic zone. If correct, it follows that P availability is unlikely to have suppressed the expansion of Cyanobacteria prior to the GOE. A reservoir of P-rich surface water shortly before 2.40 Ga could ultimately have triggered a rapid rise in atmospheric oxygen by fueling a sharp increase in primary productivity and organic-carbon burial. We speculate that the enigmatic Lomagundi positive carbon-isotope excursion, recorded in 2.32–2.06 Ga shallow-water carbonates, may mark a key step in the transition toward a modern biosphere of high biological productivity controlled by nutrient availability.

Climate shapes the oxygenation of Earth's atmosphere across the Great Oxidation Event

We use a one-dimensional atmospheric photochemical model to investigate the effect of temperature and humidity variations on the evolution of O2 and O3 across the Great Oxidation Event (GOE), and find that changes to the atmospheric temperature profile can change O2 and O3 levels by up to three orders of magnitude. Cold temperatures (<280 K) result in stable low O2 levels (mixing ratio of 10−4), whereas temperate (280 K−310 K) and hot (>310 K) temperatures result in stable high O2 levels (mixing ratio of 10−2) after the GOE. Warm and wet climates lead to an increased atmospheric oxidation power through the increased production of hydrogen oxide (HOx) radicals, catalyzing the oxidation and depletion of the principal reduced species (CH4, CO and H2). Consequently, warmer temperatures lead to less O2 lost through the oxidation of reduced species, resulting in higher O2 and O3 levels relative to colder temperatures.The GOE occurred around the same period as the onset of the Snowball Earth Huronian glaciations. Cold climates during the glaciations were eventually terminated by the build-up of volcanic greenhouse gases in the atmosphere, leading to Hot-Moist Greenhouse climates. Temperature and humidity likely varied extensively from Snowball Earth climates during the glaciations to Hot-Moist Greenhouse climates. However, current photochemical models of the GOE do not consider the effect of this climate variability on the evolution of O2 and O3 across the GOE. Our results show that temperature and humidity exert a strong control on atmospheric chemistry through O2, O3, and HOx feedbacks, which has important implications for our understanding of the climate-redox evolution of the GOE.

Multiple ocean oxygenation events during the Ediacaran Period: Mo isotope evidence from the Nanhua Basin, South China

The Ediacaran Period (ca. 635–539 Ma) was an eventful interval in Earth history, during which a succession of biological and environmental changes, including episodic ocean oxygenation events (OOEs), paved the way for the Cambrian radiations of animal life. To better understand the evolution of ocean redox conditions and to estimate the extent of seafloor oxygenation during this period, we analysed molybdenum (Mo) isotope compositions and redox sensitive element (RSE) concentrations from a continuous, mid-slope section of the Doushantuo Formation (ca. 635–560 Ma) of the Nanhua Basin on the South China Craton. Alongside an updated compilation of published Mo isotope and RSE data, our new data show that three OOEs occurred within a generally anoxic Ediacaran ocean, with the last, particularly extensive event occurring during deposition of Doushantuo Member IV. Here we show how the global balance of redox-related Mo sinks shifted dynamically in response to these transient OOEs, which correlate well with the first appearance of Ediacaran fossil groups and so may have triggered or stimulated biotic innovations and radiations. Moreover, the spatial distribution of the Mo data from multiple sections supports episodic expansion of a euxinic wedge on the slopes of the Nanhua Basin, consistent with pyrite burial as a potential cause of the OOEs.

Manganese carbonate-bearing mudstone of the Witwatersrand-Mozaan succession in southern Africa as evidence for bacterial manganese respiration and availability of free molecular oxygen in Mesoarchaean oceans

AbstractThe Mesoarchaean (2.96 to 2.91 Ga) Witwatersrand-Mozaan succession of southern Africa contains multiple units that show evidence for the presence of free molecular oxygen in oceanic water columns approximately 500 million years prior to the Great Oxidation Event. The lithostratgraphically correlatable Thalu and Brixton formations of the Mozaan and West Rand groups, respectively, now yield further evidence for an oxygen-containing water column. The two formations contain multiple beds of manganese carbonate-bearing mudstone. This study documents these beds and their stratigraphy, mineralogy, petrography, whole rock geochemistry and stable carbon and oxygen isotopes from deep-level drill cores.The manganese carbonate-bearing beds occur towards the base of upward-coarsening units, indicating deposition during higher sea levels, followed by regressions. The mudstones show sharp contacts and compaction around manganiferous carbonate concretions, suggesting early diagenetic growth of the latter. The concretions are composed of either rhodochrosite cores and kutnahorite rims, or kutnahorite cores and ankerite rims, illustrating a decrease in manganese concentration from core to rim. Relative to the surrounding mudstone, the carbonate concretions are markedly enriched in manganese. The rare earth element and yttrium contents in the concretions, normalised to shale, show heavy over light rare earth element enrichment and positive europium and yttrium anomalies, indicating precipitation from mixed marine-hydrothermal water. The carbon and oxygen isotopes of concretionary carbonates are depleted in 13C (-12.2 to -21.30/00) and 18O (-14.9 to -23.90/00) relative to Pee Dee Belemnite, respectively.It is concluded that the main mode of deposition for iron and manganese was by precipitation likely facilitated by iron- and manganese-oxidising bacteria. The iron and manganese were sourced as dissolved Fe2+ and Mn2+ from a distal, high-temperature hydrothermal plume. The stratigraphic position of the studied units suggests that deposition occurred on the middle to outer shelf where iron oxidation and deposition proceeded far enough so that the environment could transition to manganese oxidation and deposition. These precipitates then reacted with organic carbon to form rhodochrosite that nucleated very locally to grow concretions. As the available manganese was all reduced and incorporated into the carbonates, Fe3+-oxyhydroxides were also reduced by any excess organic carbon and incorporated into the concretion rims during later stages of growth.The main implication of the proposed model for concretion formation is that free molecular oxygen was available in the water column of the shelf for manganese-oxidising microaerophyllic chemolithoautotrophs to function. The oxygen concentration was in excess of approximately 5 μM. This concentration, along with the depositional setting of the studied units, falls within the ranges and parameters of previous studies indicating conditions in “oxygen oases” of Archaean oceans.

Re-appearance of precipitated aragonite crystal fans as evidence for expansion of oceanic dissolved inorganic carbon reservoir in the aftermath of the Lomagundi-Jatuli Event

The initial accumulation of atmospheric oxygen is marked by the unprecedented positive δ13Ccarb excursions of the Lomagundi-Jatuli Event (LJE) and records an interval of abnormal O2 production through elevated rates of organic carbon burial. Emerging evidence suggests that the post-LJE atmosphere-ocean system might have suffered a significant deoxygenation. These dynamic perturbations in the oceanic redox state and biogeochemical cycles would have led to fundamental changes in carbonate precipitation dynamics. Here, we report the discovery of centimeter-sized crystal fans in the post-LJE Huaiyincun Formation, Hutuo Supergroup in the North China Craton. The hexagonal cross-sections and square terminations suggest that these fan-like dolomitic structures were originally aragonite crystal fans (ACF). Variations of stromatolite morphology and frequent occurrences of storm-related deposits in the Huaiyincun Formation point to repeated cycles of sea level changes. The bedding-parallel distribution of the ACF and the homogeneous δ13C values of the ACF-bearing dolostones are consistent with a primary depositional origin for the ACF. An updated compilation of published records of ACF throughout geological history highlights a clear absence of ACF from the initiation of the Paleoproterozoic Great Oxidation Event until the end of the LJE, and a global reappearance of ACF in the post-LJE late Paleoproterozoic. We propose that the reappearance of ACF is in agreement with the expansion of the oceanic dissolved inorganic carbon reservoir. At the same time, consumption of dissolved oxygen during the oxidation of organic matter might have been stimulated by ferruginous deep seawater, facilitating the formation of Huiayincun ACF.

Microclimate of Grape Bunch and Sunburn of White Grape Berries: Effect on Wine Quality.

This research aimed to evaluate the composition of wines made with white grapes which are particularly susceptible to sunburn symptoms due to the absence of anthocyanin. Sunburn is a complex physiological dysfunction leading to browning or necrosis of berry tissues. In vintage 2021, the canopy of 'Verdeca' grapevines grown in Salento, South Italy, was differently managed by sun exposing or shading the bunches. Micrometeorological conditions were studied at different levels. Grapes were vinified, comparing the winemaking with and without skin maceration. The vegetative-productive balance of plants was not substantially modified. On the contrary, a significant effect was observed on the quality and quantity of grapes produced: smaller berries with sunburn symptoms were found on unshaded bunches. This influenced the percentage distribution among skin, pulp and seeds, causing a decrease in must yield of up to 30%. The pH was significantly higher in macerated wines made using shaded grapes, due to a lower titratable acidity and to significant impacts on the acid profile. Obviously, maceration produced a higher extraction of phenolics in wines, which reached their maximum in wines made with sunburned grapes. The absorbance at 420 nm, index of yellow color, was also significantly higher in sunburned grapes, indicating greater oxidation. Even though excessive grape sun-exposure could negatively affect the perception of white wines made without maceration (resulting in more oxidative character), the sensory quality of orange/amber wines was not significantly impacted by the presence of sunburned grapes. Thus, this winemaking technique could be particularly interesting to set up a production strategy adapted to viticultural regions strongly affected by climate change.

The Paleoproterozoic Zhaigou banded iron formation in the Fuping Complex, North China Craton: Geochemistry, geochronology and implications for genesis and tectonic setting

Precambrian Banded iron formations (BIFs) provide important insights on the chemical composition of ancient seawater, as well as the tectonic setting of their formation. The Precambrian BIFs deposits in the North China Craton are widely distributed in the Archean greenstone belts and are composed predominantly of Neoarchean Algoma-type including those in the Anshan-Benxi and eastern Hebei areas of the Eastern Block, together with minor Paleoproterozoic Superior-type BIFs in the southern segment of the trans-North China Orogen. The Zhaigou BIF deposit is associated with Paleoproterozoic Wanzi supracrustal sequence and amphibolite in the Fuping Complex in central North China Craton. Here, we present petrological, geochronological and geochemical data of the meta-sedimentary rocks, BIF ores and amphibolites from the Zhaigou BIF deposit in the Fuping Complex for the first time to constrain the formation age, source characteristics and depositional setting, and evaluate the redox states of the Paleoproterozoic seawater. Whole-rock geochemical data show that the BIF ores are enriched in HREE with low (La/Yb)PAAS values (0.037–0.073), and exhibit positive Eu (3.34–6.21) and Pr (1.05–1.10) anomalies. The PAAS-normalized REY patterns resemble 1:100 mixture of high-temperature hydrothermal fluid and seawater, indicating the involvement of the two end members. In combination with whole-rock geochemical data of BIF ores, trace elements of magnetite and U-Pb ages of detrital zircons from the meta-sedimentary rocks, we propose that crustal components from the Fuping TTG gneiss also contributed to the BIFs. The geochemical features suggest that the protolith of amphibolite is basalt formed in island arc setting. The negative Ce anomaly (Ce/Ce* = 0.81 ∼ 0.90) indicates the deposition of the Zhaigou BIF ore in an oxidizing environment. Zircon U-Pb data on the BIF ore yield weighted mean 207Pb/206Pb ages of 2028 ± 33 Ma and 1874 ± 52 Ma, representing the formation age of the Zhaigou BIF deposit and the subsequent metamorphic event, respectively. The Zhaigou BIF deposit belongs to the Algoma-type which shows close association with the Paleoproterozoic sedimentary sequence and basaltic magmatism in oceanic island arc setting. The Paleoproterozoic seawater forming the Zhaigou deposit was oxidized after the Great Oxygenation Event (GOE) during the terrane assembly in the trans-North China Orogen.

Reconciling discrepant minor sulfur isotope records of the Great Oxidation Event

Understanding the timing and trajectory of atmospheric oxygenation remains fundamental to deciphering its causes and consequences. Given its origin in oxygen-free photochemistry, mass-independent sulfur isotope fractionation (S-MIF) is widely accepted as a geochemical fingerprint of an anoxic atmosphere. Nevertheless, S-MIF recycling through oxidative sulfide weathering—commonly termed the crustal memory effect (CME)—potentially decouples the multiple sulfur isotope (MSI) record from coeval atmospheric chemistry. Herein, however, after accounting for unrecognised temporal and spatial biases within the Archaean–early-Palaeoproterozoic MSI record, we demonstrate that the global expression of the CME is barely resolvable; thereby validating S-MIF as a tracer of contemporaneous atmospheric chemistry during Earth’s incipient oxygenation. Next, utilising statistical approaches, supported by new MSI data, we show that the reconciliation of adjacent, yet seemingly discrepant, South African MSI records requires that the rare instances of post-2.3-billion-year-old S-MIF are stratigraphically restricted. Accepting others’ primary photochemical interpretation, our approach demands that these implied atmospheric dynamics were ephemeral, operating on sub-hundred-thousand-year timescales. Importantly, these apparent atmospheric relapses were fundamentally different from older putative oxygenation episodes, implicating an intermediate, and potentially uniquely feedback-sensitive, Earth system state in the wake of the Great Oxidation Event.

Control of Cell Size by c-di-GMP Requires a Two-Component Signaling System in the Cyanobacterium Anabaena sp. Strain PCC 7120.

Each bacterial species possesses a specific cell size and morphology, which constitute important and recognizable physical traits. How bacteria maintain their particular cell size and morphology remains an essential question in microbiology. Cyanobacteria are oxygen-evolving photosynthetic prokaryotes. Although monophyletic, these organisms are highly diverse in their cell morphology and cell size. How these physical traits of cyanobacteria are controlled is poorly understood. Here, we report the identification of a two-component signaling system, composed of a histidine kinase CdgK and a response regulator CdgS, involved in cell size regulation in the filamentous, heterocyst-forming cyanobacterium Anabaena sp. PCC 7120. Inactivation of cdgK or cdgS led to reduction of cell length and width with little effect on cell growth capacity. CdgS has a GGDEF domain responsible for the synthesis of the second messenger c-di-GMP. Based on genetic and biochemical studies, we proposed a signaling pathway initiated by CdgK, leading to the phosphorylation of CdgS, and thereby an enhanced enzymatic activity for c-di-GMP synthesis of the latter. The GGDEF domain of CdgS was essential in cell size control, and the reduction of cell size observed in various mutants could be rescued by the expression of a c-di-GMP synthetase from E. coli. These results provided evidence that a minimal threshold of c-di-GMP level was required for maintaining cell size in Anabaena. IMPORTANCE Cyanobacteria are considered the first organisms to produce oxygen on Earth, and their activities shaped the evolution of our ecosystems. Cell size is an important trait fixed early in evolution, with the diversification of micro- and macrocyanobacterial species during the Great Oxidation Event. However, the genetic basis underlying cell size control in cyanobacteria was not understood. Our studies demonstrated that the CdgK-CdgS signaling pathway participates in the control of cell size, and their absence did not affect cell growth. CdgK has multiple domains susceptible to signal input, which are necessary for cell size regulation. This observation suggests that cell size in Anabaena could respond to environmental signals. These studies paved the way for genetic dissection of cell size regulation in cyanobacteria.

Dynamic seawater redox status in the early Mesoproterozoic: Evidence from trace elements and sulfur isotopic compositions of carbonate associated sulfate in multiple sections

The early Mesoproterozoic (1.6–1.4 Ga) is a critical stage for oxygenation of Earth’s surface and early eukaryote evolution. However, the relationship between both remains uncertain. Here, we provide new carbonate associated sulfate (CAS) sulfur isotopic compositions (δ34SCAS) and trace elements from the 1.6 to 1.55 billion-year-old Gaoyuzhuang Formation in multiple sections within the Yanshan Basin, North China, to investigate the temporal and spatial variation of ocean redox conditions. New and collected δ34SCAS data from five sections (Pingquan, Kuancheng, Qianxi, Jixian and Gan'gou sections) reveal similar sulfur isotopic excursions, but the differences in absolute values indicate spatial heterogeneity of sulfur isotopic compositions, which may reflect marine low-sulfate concentrations and oceanic redox stratification. The most elevated δ34SCAS values appeared at the top of the Second Member of the Gaoyuzhuang Formation, followed by distinct negative excursions at the bottom of the Third Member, suggesting a dynamic sulfur cycle and seawater redox status during this period. Combined with previous reported carbon and sulfur isotopes and some redox proxies (e.g., Ce anomalies, manganese-rich deposit, I/(Mg + Ca) and Fe speciation), we suggest that at least two possible oxygenation events may have occurred in the Gaoyuzhuang Formation: (1) the bottom of the Second Member and (2) the bottom or middle part of the Third Member. Different sections show asynchronous timing of these events, indicating that the redox status was spatial heterogenous within the Yanshan Basin. The spatial heterogeneity may be controlled by facies and paleogeographic locations. Considering that decimeter‐scale multicellular eukaryotes are preserved in the middle part of the Third Member, we argue that oxic bottom water condition may be a critical factor for early eukaryote evolution.