Oceanic Redox Conditions Research Articles

Fluctuation in redox conditions and the evolution of early Cambrian life constrained by nitrogen isotopes in the middle Yangtze Block, South China

AbstractThe Ediacaran–Cambrian (E-C) transition (∼542–517 Ma) witnessed the rapid evolution of Cambrian animals, which was accompanied by carbon cycling anomalies and a significant increase in the concentration of oxygen in Earth’s atmosphere. The mechanisms stimulating the evolution of complex eukaryotes, however, remain problematic, especially concerning the link between biological evolution and contemporaneous changes in the oceanic environment. In this study, integrated δ13Ccarb–δ13Corg–δ15N compositions were analysed from the YD-4 core samples to understand redox fluctuations and nitrogen cycling of the middle Yangtze Block across the E-C transition. Two negative δ13Ccarb excursions (N1 and N2) and a positive δ13Ccarb excursion (P1) are identified from the studied samples and are supposedly of primary origin. Constrained by of the U-Pb age, biolithology and pattern of isotopic variation, N1, P1 and N2 are comparable to the Basal Cambrian Carbon Isotope Excursion (BACE), Zhujiaqing Carbon Isotope Excursion (ZHUCE) and Shiyantou Carbon Isotope Excursion (SHICE). We interpreted the decreased δ15N values in this study as resulting from intensified atmospheric nitrogen fixation driven by enhanced denitrification associated with expanded marine anoxia, as well as partial ammonium assimilation, while increased δ15N values suggest weakened denitrification associated with an amplified oxic water mass. The temporal coincidence of N1 and N2, with two episodes of negative δ15N excursions, and of P1, with a positive δ15N excursion, suggests that variable oceanic redox conditions and nitrogen bioavailability may have influenced the evolution of the Cambrian eukaryote-dominated community.

Redox Conditions of the Late Ediacaran Ocean on the Southern Margin of the North China Craton

Previous studies have revealed dynamic and complex redox conditions of the late Ediacaran ocean. Integrated analyses of Ediacaran successions on different continents can help to better understand global ocean redox conditions. In this study, we used iron and redox-sensitive trace elements (RSTEs) geochemical analyses to present the detailed redox conditions of the late Ediacaran Dongpo Formation on the southern margin of the North China Craton (NCC). Paleoredox reconstruction reveals a dominantly anoxic late Ediacaran ocean punctuated by multiple transient oxygenation events across the southern margin of the NCC. These transient oxidation events in the NCC may have contributed to the appearance of the Ediacaran tubular fossil Shaanxilithes. Based on the assumption that local iron speciation data in a global framework can track the mean and variance of paleoredox conditions through time, we additionally analyzed about 3300 new and published iron speciation data from fine-grained clastic rocks to infer the global redox change in Ediacaran–Cambrian oceans. Our statistical analyses indicated dynamic Ediacaran marine redox conditions and stepwise early–middle Cambrian ocean oxygenation. The appearance and rise of the Ediacaran biota and the diversification of metazoans corresponded temporally with the middle Ediacaran global ocean oxygenation and the early–middle Cambrian stepwise oceanic oxygenation, respectively. Our results highlight the coevolutionary relationship between ocean redox conditions and early animals.

Constraining the elemental stoichiometry of early marine life

Abstract The relative proportions of carbon, nitrogen, and phosphorus, commonly referred to as the Redfield ratio (106:16:1), have likely varied dramatically through Earth’s history in response to changes in oceanic redox state and nutrient availability. However, there have been few attempts to track long-term secular patterns in the elemental stoichiometry of marine life. We use a sediment reactive-transport (diagenetic) modeling approach to provide new constraints on the elemental stoichiometry of marine ecosystems during Earth’s early history, by simulating environmental conditions associated with the formation and deposition of suites of Archean sedimentary iron and phosphorus-bearing minerals. Our results suggest that siderite formation in porewaters linked to dissimilatory iron reduction but limited formation of authigenic P phases can only be reproduced when C to P ratios in marine biomass are at least 500 (mol/mol), approximately five times higher than the values that characterize the modern ocean. This constraint indicates that Archean oceans were strongly nutrient-limited.

Substantial incorporation of isotopically heavy reduced U species into marine carbonate sediments

The uranium (U) isotope ratio (238U/235U, reported as δ238U) in marine carbonates is an important proxy for reconstructing changes in past oceanic redox conditions, based on the essential assumption that U in carbonates originates from dissolved U(VI) in seawater. However, diagenetic processes may induce the addition of isotopically heavy U(IV) into the carbonates, complicating the application of the U isotope proxy. So far, the valence states of trace amounts of U and its relation with U isotope composition in marine carbonate sediments have not been directly studied. In this study, we have calibrated an ion-exchange chromatographic method to separate U(IV) from U(VI) in geological carbonate samples (e.g., modern and fossil corals, stalagmites, cold seep carbonates) and quantified their contents by mass spectrometry. Our study confirms that modern coral carbonates are faithful archives of U(VI) sourced from seawater. Surprisingly, drill core samples from a modern coral carbonate platform, which bear no sign of alteration inferred from conventional diagenetic proxies (e.g., Mn/Sr), show significant positive correlation between U(IV) fraction and bulk carbonate δ238U, suggesting U(IV) is present in the marine carbonates and drives δ238U toward higher values than that of seawater. We therefore suggest that coupled valence and isotope analyses of U in marine carbonates could provide critical constraints toward reliable reconstruction of marine redox evolution in the Earth’s history.

Constraining the major pathways of vanadium incorporation into sediments underlying natural sulfidic waters

Vanadium (V) is a redox-sensitive trace metal. Interconversion between different vanadium species (e.g., VIII, VIV, VV) occurs rapidly in association with changes in redox conditions in natural environments. Different vanadium species exhibit variable geochemical behavior that impacts if and how they are sequestered into sediments, which makes vanadium a useful proxy for ancient ocean redox conditions. However, we still lack constraints on how different dissolved vanadium sink pathways impact distributions of vanadium in water column, pore waters, and sediments, especially in natural sulfidic settings. In the present study, we combined field and experimental data to constrain the major scavenging processes that influence the partitioning of vanadium between aqueous and solid phases to provide an improved picture of vanadium geochemical cycling under anoxic-sulfidic conditions. We find that in the sulfidic bottom waters and sediment pore waters of the Chesapeake Bay, vanadium concentrations are correlated with manganese (Mn) concentrations in both aqueous and solid phases. Our experimental results support our interpretation that elevated concentrations of vanadium in anoxic-sulfidic waters result from the release of vanadium due to desorption from and/or dissolution of Mn oxides in anoxic/sulfidic waters. While sorption of vanadium results in strongly adsorbed complexes on both Mn oxides and pyrite surfaces, vanadium preferentially sorbs to Mn oxides rather than to pyrite. Thus, the impact of Mn oxides on vanadium geochemistry is greater than that imposed by scavenging via sorption on pyrite, although both processes should be considered. Mn oxides also have a greater impact on vanadium geochemistry than reductive formation of solid V(OH)3 by H2S. Sorption of vanadium is sensitive to pH conditions (especially in anoxic waters), moderately sensitive to ionic strength, and weakly sensitive to phosphate concentrations. In addition, our results show that as waters become more sulfidic, dissolved V/Mn molar ratios increase, whereas solid phase V/Mn molar ratios decrease, indicating that the V/Mn molar ratio can be used to trace redox changes. Finally, we investigate the V/Mn record of black shales that span the Proterozoic and Phanerozoic to show a framework of utilizing this proxy with applicability to identify changes in redox conditions associated with both oxygenation and anoxic events in ancient oceans.

Chromium isotopic compositions of a reef in the South China Sea: Biological effects and influence from early diagenetic Mn-oxides reduction

Global climate fluctuations have been inextricably linked with changes in the marine environment and ecosystems' evolution during the Cenozoic. The chromium isotopic compositions (δ53Cr) of marine carbonates have been used to study changes in ocean redox conditions. However, whether δ53Cr of carbonates faithfully reflect the information of ambient seawater at the time of deposition remains controversial. Here, we report major and trace element concentrations, as well as the Cr isotopic compositions for samples from a Neogene–Quaternary biogenic reef (Core NK-1) in the South China Sea. The samples exhibit highly variable Cr concentrations and δ53Cr values. The Cr concentrations range from 0.76 μg/g to 8.58 μg/g with an average of 3.96 μg/g, and the δ53Cr values vary from −0.54‰ to 0.68‰ with an average of 0.06‰, which are generally lower than the reported Cr isotopic compositions for global seawater. The fluctuation of δ53Cr values is unlikely to be controlled by changes in the redox conditions of seawater. Biogenic processes may have affected some samples with relatively low Cr concentrations and δ53Cr values. Other samples may have been affected by post-depositional addition of Cr from pore water. Early diagenetic reduction of ferromanganese oxides is likely another significant control factor for the variation of δ53Cr values. The results suggest that the factors influencing the Cr isotopic compositions of biogenic carbonate reefs are complex, and the variation of Cr isotopic compositions should not be directly linked to the redox state of the ocean. After evaluating the potential influences of multiple factors, the inferred Cr isotopic compositions of syn-depositional fluids of the carbonates from Core NK-1 are similar, which may suggest a relatively stable redox environment in the South China Sea during the Neogene to Quaternary period.

Heterogeneous sulfide reoxidation buffered oxygen release in the Ediacaran Shuram ocean

Ediacaran (∼635–539 Ma) carbonate rocks record the largest negative carbonate-carbon isotope excursion in Earth history, termed the Shuram Excursion (SE). This event has been attributed to anaerobic oxidation of dissolved organic carbon as a result of enhanced weathering inputs of sulfate to the ocean during the amalgamation of Gondwana. However, the effect of carbon–sulfur cycle interplay on the net redox state of the ocean–atmosphere system remains unclear, impeding our understanding of the co-evolution of life and the environment during the Ediacaran. Here, we generate high-resolution records of paired sulfate sulfur and oxygen isotopes, in addition to phosphorus concentrations, for the SE interval in South Australia (Parachilna Gorge) and South China (Jiulongwan and Xiang’erwan sections, Three Gorges), and we evaluate these data in the context of COPSE biogeochemical model simulations to assess net long-term redox changes. Our results support widespread H2S reoxidation in shelf areas during the SE, which would have buffered the net release of oxygen sourced from the burial of organic carbon and pyrite. Varying degrees of H2S reoxidation on different cratons likely contributed significantly to high spatial heterogeneity in both local oceanic redox state and nutrient availability, which characterized local oxygen-deficient conditions in an overall oxygenated SE shelf ocean, and likely affected the distribution of the Ediacaran Biota. Our study highlights the important role of H2S reoxidation in the coevolution of marine redox conditions and complex life during the critical Ediacaran period.

Abrupt Northwest Atlantic deep-sea oxygenation decline preceded the Palaeocene-Eocene Thermal Maximum

Reconstruction of oceanic redox conditions across the Palaeocene-Eocene Thermal Maximum (PETM, ∼55.93 Ma) provides crucial information on potential PETM triggers and biotic turnover. Widespread oceanic deoxygenation has been documented to occur during the PETM, but the exact timing and regional variability is poorly understood. Here we document well-preserved magnetofossils with large variations in magnetic properties and crystal morphologies at International Ocean Discovery Program (IODP) Sites U1409 (∼2913 m palaeodepth) and U1403 (∼4374 m palaeodepth) across the PETM, and use these proxies to trace Northwest Atlantic palaeoredox changes. Our records suggest that deep-sea oxygenation at these sites decreased gradually, starting several hundred thousand years before the PETM, reaching a minimum ∼50 ky before the PETM, followed by a broad increase. This pattern in palaeoredox conditions likely reflects changes in deep-sea circulation and ocean temperature. We thus provide evidence for the existence of precursors to PETM warming, and suggest that ocean circulation changes might have played an important role in triggering carbon release to the ocean-atmosphere system at the PETM onset.

Expanded marine anoxia at the Cambrian-Ordovician transition: Evidence from lime mudstone I/Ca and δ238U signatures of the GSSP in western Newfoundland, Canada

The early Paleozoic witnessed two spectacular radiations of marine organisms—the Cambrian (Є) Explosion and the Great Ordovician (O) Biodiversification Event. However, the period between them was characterized by a marine biodiversity plateau attributed to recurring biocrises. In the current study, we present the I/Ca records from slope lime mudstones of the Green Point Formation in western Newfoundland, along with a three-sink U-isotope mass balance model and previously reported limestone δ238Ucarb signals of the same interval, to further explore oceanic redox conditions at the Є-O boundary. The I/Ca ratios of the lime mudstones, deposited along the eastern Laurentian (western Iapetan) continental slope, exhibit a narrow range between 0.02 and 0.33 μmol/mol. Poor correlations between the I/Ca values and their [Sr], δ18O, Mn/Sr, Fe/Sr, Mg/Ca, and δ13Corg counterparts, together with near-micritic textures of the limestones, argue against significant influences of postdepositional alterations on the I/Ca signatures. The iodine-depleted lime mudstones, with I/Ca values well below the Proterozoic Eon baseline I/Ca ratios (∼0.5–1 μmol/mol), suggest the presence of shallow marine oxic-anoxic interfaces along the regional continental margin. Substantially low limestone I/Ca ratios (<0.5 μmol/mol) and dysoxic to anoxic depositional conditions have also been reported from several other age-equivalent sections deposited along the shelf and slope of ancient Iapetan and Laurentian continental margins. As a result, seawaters surrounding the Iapetan and Laurentian continental margins at the Є-O transition might have been commonly poorly oxygenated with shallow oxyclines or expanded oxygen minimum zones in the shelf and/or slope areas. This interpretation is further supported by our three-sink U-isotopemass balance modeling, which predicts widespread marine anoxia at the Є-O boundary with anoxic to euxinic water covering 1.0–21.1% of the ocean floor, significantly higher than the modern day (∼0.2%). Furthermore, the wide range of the oceanic δ238UOC (−1.22 to −0.25‰) values, estimated from the limestone δ238Ucarb signals, might reflect oceanic redox oscillations during this period. However, the δ238UOC fluctuations could also be attributed to variable accumulations of the 238U-enriched authigenic U phases during early diagenesis. Overall, evidence from the lime mudstone I/Ca ratios and the estimated extent of marine anoxia at the Є-O boundary in this study aligns with earlier viewpoints that the slowness of marine biodiversity accumulation during the late Cambrian and the Early Ordovician was linked to widespread oceanic anoxia.

Recurrent photic zone euxinia limited ocean oxygenation and animal evolution during the Ediacaran

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.

Uranium and molybdenum isotope evidence for globally extensive marine euxinia on continental margins and in epicontinental seas during the Devonian-Carboniferous Hangenberg Crisis

The end-Devonian Hangenberg Crisis was one of the biggest Phanerozoic mass extinctions. However, the mechanism(s) that triggered this event is still debated. In this study, multiple geochemical paleoredox proxies (redox-sensitive trace metals [e.g., Mo, U, Re, V] and isotope systems [Mo, U, S, C]) were applied to the Exshaw Formation black shales to infer ocean redox conditions during the Hangenberg Crisis. The measured δ13Corg values generally decrease upsection in the Exshaw Formation. The Exshaw black shales have increasing maturity levels from east to west in the Western Canada Sedimentary Basin. Large sulfur isotope fractionations (–15‰ to 65‰) between original seawater sulfate and pyrite is best explained by microbial sulfate reduction during deposition and early diagenesis rather than thermochemical sulfate reduction. Precise Re-Os ages previously reported for the Exshaw Formation suggest that metal geochemical signatures in these shales, including overmature shales, were minimally affected by hydrocarbon maturation and reflected depositional conditions. Both Sr/Ba and TS/TOC ratios (the latter only from immature shales affected minimally by hydrocarbon generation) suggest predominantly brackish and marine settings with significant water exchange between the basin and open ocean. The TOC contents, redox-sensitive trace metal concentrations (Mo, U, Re), and Fe speciation indicate local bottom waters ranged from suboxic (with sulfidic pore waters) to euxinic. The authigenic δ98Mo and δ238U values for the Exshaw shales range from 0.3‰ to 1.1‰, and from –0.23‰ to 0.39‰, respectively. The δ98Mo of the Exshaw Formation may have been offset to lower values than coeval seawater because of a local particulate Fe-Mn shuttle and/or local weakly euxinic bottom waters. Two different correlation patterns (positive correlation and no correlation) of δ238U and U enrichment factors (EF) were observed for Exshaw black shales deposited from locally euxinic bottom waters. The positive correlation group samples (−0.13‰ to 0.23‰) suggest U isotope fractionations (0.4‰ to 0.8‰) between sediments and seawater like those observed in modern euxinic basins. Higher δ238U values (>0.2‰) in the no correlation group suggest even larger U isotope offsets (0.8–1.2‰) from seawater, possibly associated with removal of U into organic floccule layers during deposition. Applying the above Mo and U isotope fractionations to the Exshaw shales, global seawater δ98Mo and δ238U at the Devonian-Carboniferous boundary (DCB) may have been in the range of 1.4‰ to 1.9‰ and −0.9‰ to −0.5‰, respectively. A Mo and U isotope mass balance model suggests a large areal extent of euxinic seafloor (6–10%) at the DCB, which could be pervasive along continental margins and in epicontinental seas during transgression. Therefore, our data support expanded ocean euxinia at the DCB as an important contributor to the Hangenberg Crisis.

Regional and global proxies for varying ocean redox conditions at ∼1.57 Ga: A causal connection with volcanism-induced weathering

Regional and global proxies for varying ocean redox conditions at ∼1.57 Ga: A causal connection with volcanism-induced weathering

Oceanic redox conditions during the terminal Cambrian extinction event

Marine animal diversity during the late Cambrian was reduced by a series of extinctions that have generally been attributed to oceanic anoxic events associated with positive carbon isotope excursions. Here we present carbon and uranium isotope ratios (δ13C and δ238U values) as proxies for global carbon cycle and oceanic redox conditions, respectively, from carbonate rocks of the Wa'ergang section, South China. The dataset spans an interval that includes the last major negative δ13C excursion (TOCE) of the Cambrian Period. The TOCE is a globally documented event, recovery from which corresponds to the terminal Cambrian extinction event. The δ13C and δ238U values covary through the section, shifting initially to lower values, with δ238U falling below the modern open-ocean seawater value from the start to the middle of the profile, followed by a shift to higher values towards the end of the Cambrian. Neither the co-occurrence of δ13C and δ238U negative excursions, nor the association of rising δ238U with extinction have been commonly reported. Here we argue that robust positive coupling of δ13C and δ238U relates to the existence of extensive intermediate reducing settings (from low-O2 suboxia to intermittent anoxia) during the late Cambrian alongside low atmospheric pO2 and a greenhouse climate. Similarly, a stepwise increase in the δ238U baseline in carbonates across the Ediacaran−Cambrian boundary is consistent with the growing importance of an intermediate reducing sink through that interval. We propose further that divergent trends in lower and upper ocean redox conditions could have driven the parallel isotope excursions. An expansion of intermediate reducing conditions, rather than persistent anoxic euxinia, is consistent with the recovery of δ13C and δ238U to higher values, as well as the presence of benthic fauna and shoreward extension of deeper-water fauna that may have had a greater tolerance against hypoxia.

Coupling of the recovery of earliest Silurian sponges and ocean redox conditions: Evidence from South China

Many aspects of the Late Ordovician Mass Extinction (LOME) aftermath and recovery have been puzzling due to heterogeneities in tempo and triggering mechanisms. Benthic fossil groups, which are the most severely affected by oxidative stress, offer the best opportunities for understanding both biological and ecological recovery after the LOME. In recent studies, deep-water sponge assemblages (which may have had high physiological tolerance to oxygen deviations) have been reported widely across South China in the immediate aftermath of the extinction interval. In order to further explore the lateral and temporal distributions of sponges, and ecological effects of benthic recovery during this critical interval, this study presents new Llandovery sponge assemblages recovered from two sections in Hunan Province, South China, accompanied by geochemical analyses. The sponge communities are preserved by pyritic spicule replacements and shows a relatively deep-water affinity (estimated around 60–150 m in depth) comparable to several previously reported assemblages in South China, and consistent with the observed graptolite ecology. Geochemical analysis of total organic carbon (TOC) and major and trace element composition in both sections show similar trends, indicating a shift in redox state of the bottom-water from persistent anoxia or intermittent euxinia in the earliest Rhuddanian, becoming oxygenated in the early Aeronian. Based on the present study and previous biological and geochemical data from South China, the distribution of early Silurian sponge assemblages in South China demonstrates a gradual expansion towards deeper regions when ocean redox conditions ameliorated. This study confirms the continuity of the end-Ordovician sponge faunas and taxa, both laterally across South China, and temporally through the early Silurian. The pioneering colonization of sponges in low-oxygen environments after the LOME may have set the stage for the subsequent recovery of other benthic organisms.

Regional conditions cause contrasting behaviour in U-isotope fractionation in black shales: Constraints for global ocean palaeo-redox reconstructions

The U-isotope system is a well-established palaeo-redox proxy that potentially constrains the global extent of marine anoxia during average as well as extreme redox events throughout Earth's history. A typical archive that forms underneath a reducing water column and acts as an intense U sink is organic-rich black shale. However, the degree to which black shale archives reflect the marine U-isotope signature is not well understood because U-isotope fractionation between U(VI)-bearing seawater and U(IV)-bearing black shales may vary as a function of local environmental conditions. Here, we present a combination of U-isotope and elemental concentration datasets, supported by a complementary Mo-isotope record, for the Furlo sedimentary section in Marche–Umbria, Italy and interrogate the combined systematics to unravel the mechanisms controlling the U-isotope fractionation factor between black shales and ambient seawater. We examine black shales deposited before and during Oceanic Anoxic Event 2 (OAE 2), which was one of the most extreme climatic perturbations of the Mesozoic Era that took place around the Cenomanian–Turonian boundary (Late Cretaceous, c. 94 Ma). The results of this study show that the U-isotope signature in the black shales deposited before OAE 2 was controlled by different mechanisms than the U-isotope ratios recorded in black shales deposited during OAE 2, with both stratigraphic intervals likely influenced by local environmental conditions. Probable local environmental changes include increased U reduction associated with biomass at or above the sediment–water interface and varying dissolved hydrogen sulphide concentrations in the water column and sediment. The overall results of this study confirm that black shales are a highly complex archive for U-isotope studies of past oceanic redox conditions, due to the sensitivity of the U-isotope fractionation mechanism to local environmental conditions, which are difficult to constrain. We propose the application of a ∆238Ushale-seawater of 0.6 ± 0.1 ‰ to black shale records deposited under locally constant euxinic conditions at non-restricted settings.

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.

Low-phosphorus concentrations and important ferric hydroxide scavenging in Archean seawater.

The availability of nutrients in seawater, such as dissolved phosphorus (P), is thought to have regulated the evolution and activity of microbial life in Earth's early oceans. Marine concentrations of bioavailable phosphorus spanning the Archean Eon remain a topic of debate, with variable estimates indicating either low (0.04 to 0.13 μM P) or high (10 to 100 μM P) dissolved P in seawater. The large uncertainty on these estimates reflects in part a lack of clear proxy signals recorded in sedimentary rocks. Contrary to some recent views, we show here that iron formations (IFs) are reliable recorders of past phosphorus concentrations and preserved a primary seawater signature. Using measured P and iron (Fe) contents in Neoarchean IF from Carajás (Brazil), we demonstrate for the first time a clear partitioning coefficient relationship in the P-Fe systematics of this IF, which, in combination with experimental and Archean literature data, permits us to constrain Archean seawater to a mean value of 0.063 ± 0.05 μM dissolved phosphorus. Our data set suggests that low-phosphorus conditions prevailed throughout the first half of Earth's history, likely as the result of limited continental emergence and marine P removal by iron oxyhydroxide precipitation, supporting prior suggestions that changes in ancient marine P availability at the end of the Archean modulated marine productivity, and ultimately, the redox state of Earth's early oceans and atmosphere. Classification: Physical Sciences, Earth, Atmospheric and Planetary Sciences.

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.

Dynamic oceanic redox conditions across the late Cambrian SPICE event constrained by molybdenum and uranium isotopes

The Steptoean Positive Carbon Isotope Excursion Event (SPICE) represents one of the largest carbon cycle perturbations in the Cambrian, which coincided with climatic changes and dramatic extinction of shallow-shelf faunas. This carbon perturbation has been linked to a global expansion of marine euxinia (SPICE-OAE), but the precise timing, duration and extent of changing redox conditions across the SPICE event, as well as its influences on the coeval biotic evolution, remain unclear. Here, we report paired δ98Mo–δ238U data across this event, constrained by a radioisotopically anchored astrochronology, based on Alum Shale samples from the Albjära-1 and Billegrav-2 drill-cores in Scandinavia. The δ98Mo profiles are largely invariant around 1.08±0.21‰ with short-term fluctuations parallelling changes in pyritization of iron, possibly as a result of locally varying [H2S]aq in the water column and/or fluctuating reactive iron delivery. The bottom water is interpreted to have been primarily anoxic, but with frequent local variations between oxic and sulfidic conditions in a moderately restricted basin. A novel analytic method based on variation of Mo concentrations at millimeter scale stratigraphic resolution was applied to distinguish between local and global redox signatures, revealing that cyclic redox changes are recorded in the Alum Shale sea with periods of ∼0.3 Myr, ∼0.9 Myr and ∼0.15 Myr before, during and after the SPICE-OAE, respectively. Stratigraphic profiles of Mo, U, Mo/TOC ratios and δ238U in the two cores show comparable trends, facilitating recognition of three chemically distinct stages across the SPICE event: 1) global expansion of marine euxinia (SPICE-OAE; 497.9–496.6 Ma), 2) global contraction of euxinia accompanied by enhanced carbonate weathering inputs (496.6–495.8 Ma) and 3) general global oxygenation (495.8–494.4 Ma). The first in situ correlation between the onset of the SPICE-OAE and the end-Miaolingian extinctions in Baltica corroborates that expansive anoxic and sulfidic water masses likely contributed to the biotic crisis. The time gap between the start of the extinction and the appearance of the new fauna in Baltoscandia is estimated to be ∼600 kyr.

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.