Marine Redox Conditions Research Articles

Redox dynamics of later Cambrian oceans

A growing body of evidence suggests that the deep oceans during the early Paleozoic Era were widely oxygen deficient, despite evidence for increased marine oxygenation during the Neoproterozoic. However, the temporal and geographic extents and dynamics of reducing marine conditions within these oceans are not well understood. Here, we investigate marine redox history during the Drumian through the earliest Jiangshanian International Stages of the Cambrian Period, using concentrations of redox-sensitive metals (vanadium, uranium, and molybdenum), iron speciation, and Mo isotope stratigraphy of the Alum Shale Formation of Scandinavia. These data suggest a major perturbation occurred in trace metal cycling during the later Cambrian Period that was linked to a transient change in marine redox conditions coincident with the well-known Steptoean Positive Isotope Excursion or SPICE. The δ98Mo measurements of the Alum shale show systematic variations during the interval that contains the SPICE which are broadly consistent with a transient expansion of sulfidic, reducing marine environments — indicating a significant exacerbation of an already-common condition during the Cambrian Period. Additionally, iron speciation data record a local transition from predominantly anoxic, ferruginous (Fe+2 containing) to anoxic, euxinic (sulfide containing) water column conditions near the initiation of the SPICE. Trace metal abundances, however, appear to decline well before the start of the SPICE, suggesting an earlier initiation of the global expansion of reducing environments. More broadly, our data and modeling support the notion that significant portions of the oceans remained oxygen deficient throughout the later portion of the Cambrian, and that these oceans were also prone to transient intervals of more reducing conditions similar to the Oceanic Anoxic Events of the Mesozoic.

A carbonate molybdenum isotope and cerium anomaly record across the end-GOE: Local records of global oxygenation

Earth’s Great Oxidation Event (GOE), ca. 2.5–2.0 Ga, was one of the most extreme environmental perturbations in the history of the planet. In addition to the first sustained accumulation of O2 in the atmosphere, the latter half of the GOE is associated with a very large positive carbon isotope excursion, both in terms of magnitude and inferred duration. The end of the GOE may have been associated with a decrease in atmospheric oxygen levels, although this transition remains poorly understood. We test if this suggested decline in atmospheric O2 is reflected in the molybdenum stable isotope compositions (δ98Mo) and Ce anomalies of a large number (N = 299) of carbonate sedimentary rocks collected from Finnish Lapland and the Canadian Labrador Trough and Belcher Group, which collectively span ca. 2.1–1.88 Ga. Clear evidence for a shift in redox conditions across the end-GOE is obscured by coupled stratigraphic variations in δ98Mo values, Ce anomalies, and Mn concentrations, suggesting local controls on these redox proxies as a function of depositional environment, likely as a result of particulate shuttling of Mo and Ce associated with Mn redox cycling across a chemocline. The most negative Ce anomalies recorded in the Belcher Group (<0.6) are among the lowest reported in literature from the mid-late Paleoproterozoic to early Neoproterozoic; however, the strong local controls on these proxies hinder direct evaluation of secular trends. These findings highlight the critical role of stratigraphic and paleobasinal context for the robust interpretation of δ98Mo values and Ce anomalies for the evolution of marine redox conditions.

Geochemistry of lower Ordovician microbialites on the Yangtze Platform, South China: Implications for oceanic oxygenation at the onset of the GOBE

The causes of the Great Ordovician Biodiversification Event (GOBE) remain a topic of debate. Recent studies indicate that global and regional oceanic oxygenation was a plausible trigger of the GOBE. The Ce anomaly of rare earth and yttrium (REY) elements in shallow marine carbonates is thought to be a powerful indicator of marine redox conditions of local waters. In this study, we analyzed REY, major and trace element compositions, and C and O isotopes of the Lower Ordovician microbial-dominant reefs on the Yangtze Platform, South China. We evaluate which carbonate components within the reefs most reliably record the seawater REY composition. The elemental correlations show that the REY elements of oncoids, stromatoporoids, sponges and carbonate infillings were affected by clastic influence, diagenetic processes, and the vital effects of carbonate secreting organisms; whereas the microbialites REY were partially modified by synsedimentary terrigenous and little diagenetic modification. Such introduction of synsedimentary terrigenous REY increased ΣREY and flattened the REY patterns of the microbialites, but the redox signals (Ce anomalies) of input source of the water column might still preserved in microbialites formed in situ. Although the magnitude of Ce anomalies is small, variation might still reflect authentic redox history of primary local seawater. In the middle Tremadocian, microbialites have positive Ce anomalies which were coeval to positive δ13Ccarb shifts. The positive δ13Ccarb shifts were documented from other sections of central Yangtze Platform, North American and Argentina, which might indicate global anoxic event. In the late Tremadocian to early Floian, microbialites have more visible negative Ce anomalies, which might indicate regional oceanic oxygenation event. The negative Ce anomalies provide direct local-geochemical evidence of oceanic oxygenation in the late Tremadocian-early Floian on the Yangtze Platform of South China, which might facilitate the first acme of biodiversification of local faunas predating the main pulse of the GOBE on the other palaeoplates.

A long-term record of early to mid-Paleozoic marine redox change.

The extent to which Paleozoic oceans differed from Neoproterozoic oceans and the causal relationship between biological evolution and changing environmental conditions are heavily debated. Here, we report a nearly continuous record of seafloor redox change from the deep-water upper Cambrian to Middle Devonian Road River Group of Yukon, Canada. Bottom waters were largely anoxic in the Richardson trough during the entirety of Road River Group deposition, while independent evidence from iron speciation and Mo/U ratios show that the biogeochemical nature of anoxia changed through time. Both in Yukon and globally, Ordovician through Early Devonian anoxic waters were broadly ferruginous (nonsulfidic), with a transition toward more euxinic (sulfidic) conditions in the mid-Early Devonian (Pragian), coincident with the early diversification of vascular plants and disappearance of graptolites. This ~80-million-year interval of the Paleozoic characterized by widespread ferruginous bottom waters represents a persistence of Neoproterozoic-like marine redox conditions well into the Phanerozoic.

Constraining Shallow Seawater Oxygenation for the Yangtze Platform During the Early Cambrian

AbstractWhile atmospheric oxygenation occurred largely in two major steps, the oxygenation of Earth's oceans is assumed to be more complicated, shifting repeatedly between oxic and anoxic conditions. The exact timeline and causal drivers of these changes, which seemingly culminated in the well‐ventilated oceans we see today are not well understood. This study presents Cr isotope and rare earth element + yttrium (REE + Y) data combined with V/Cr ratios for the calcareous Yanjiahe and shaley Shuijingtuo Formations from the shelf of the Yangtze Block, South China, to improve our understanding of marine redox conditions during the early Cambrian. We measured authigenic δ53Cr values of up to 1.38‰ for the carbonates of the Yanjiahe Formation as well as Ce anomalies as low as 0.57 suggesting deposition under oxic conditions. The Shuijingtuo Formation is characterized by authigenic δ53Cr values as high as 1.27‰ at its base, but shows a strong increase in detrital content upwards, masking authigenic Cr isotope values and dissolved marine REE + Y profiles. The upper Shuijingtuo Formation is characterized by V/Cr ratios as high as 27, which indicate anoxic conditions. Hence, our data support a prevalence of oxic seawater conditions in the shallow seawater of the Yangtze Block during the Ediacaran‐Cambrian transition, which shifted repeatedly to anoxic during the early Cambrian likely as a result of sea level rise and a redox‐stratified ocean.

Stable W and Mo isotopic evidence for increasing redox-potentials from the Paleoarchean towards the Paleoproterozoic deep ocean

The scavenging of dissolved trace metals such as chromium (Cr), molybdenum (Mo) and tungsten (W) and their authigenic enrichment in sedimentary archives mainly occur by particle shuttling that cause resolvable isotope fractionation. Because their scavenging is also dependent on the local marine redox potential and the overall marine chemical environment, the stable isotope composition of these elements in Archean sediments is widely used as paleoredox proxy. Tungsten, a new element in this tool box, is dissolved as the oxyanion tungstate (WO42−) at extremely low marine redox potentials and can thus help to reconstruct the earliest changes in the marine redox state.We tested the applicability of stable W isotopes as a new paleoredox proxy of the atmosphere–ocean system. We analyzed the δ186/184W of Precambrian igneous rocks to investigate the detrital background δ186/184W signature. This Precambrian igneous inventory (PII) shows δ186/184W values between −0.007 and +0.097‰, identical to the range of modern igneous crustal rocks, which indicates that the average Earth’s crust δ186/184W remained constant over billions of years. Furthermore, we present δ186/184W values of euxinic sediments from the Black Sea as a modern sedimentary analog, which we then compare with δ186/184W data of Archean and Proterozoic black shales (3.47–2.3 Ga). Modern Black Sea sapropels reveal crustal-like δ186/184W values between +0.050 and +0.071‰ suggesting limited authigenic enrichment of W in euxinic environments. Similarly, post-Great Oxidation Event shales (2.3 Ga) show crustal- or PII-like δ186/184W values indicating the deposition in euxinic or oxic environment. However, the Archean shale sample suites show elevated W concentrations and fractionated δ186/184W values up to +0.246‰, which we attribute to authigenic enrichment of heavy seawater W in a ferruginous setting. Thus, black shales δ186/184W values can help to distinguish between anoxic-ferruginous and euxinic depositional environments.Furthermore, we combine previously published Cr and Mo isotope data with new Cr and W isotope data to quantify the evolution of the marine redox state during the Archean. By combining the Eh-pH stability fields of W and Mo with the δ186/184W and δ98/95Mo values of Precambrian sediments, we suggest a 3-step evolution of the Precambrian ocean. (1) From 3.47 to 3.0 Ga, the Eh of a dominantly ferruginous ocean was between −0.4 V and −0.25 V, enabling the persistence of soluble WO42− but not MoO42− and thus only the authigenic enrichment of isotopically fractionated W. (2) Starting from 3.0 Ga, the Eh of some shallow-marine environments increased above −0.25 V, as indicated by δ98/95Mo values above the detrital background in shallow-marine sediments, while the Eh of the deep ocean still remained below −0.25 V indicated by the lack of authigenic Mo enrichment and fractionated δ98/95Mo values in deep-sea shales. (3) After 2.7 Ga elevated δ98/95Mo and δ186/184W values in deep-marine sediments suggest that the Eh of the ferruginous open-ocean now also increased above −0.25 V. We therefore suggest that the combination of δ98/95Mo and δ186/184W values of shales is a very promising tool to investigate earliest changes in marine redox conditions during the Archean.

Redox control on the tungsten isotope composition of seawater

Free oxygen represents an essential basis for the evolution of complex life forms on a habitable Earth. The isotope composition of redox-sensitive trace elements such as tungsten (W) can possibly trace the earliest rise of oceanic oxygen in Earth's history. However, the impact of redox changes on the W isotope composition of seawater is still unknown. Here, we report highly variable W isotope compositions in the water column of a redox-stratified basin (δ186/184W between +0.347 and +0.810 ‰) that contrast with the homogenous W isotope composition of the open ocean (refined δ186/184W of +0.543 ± 0.046 ‰). Consistent with experimental studies, the preferential scavenging of isotopically light W by Mn-oxides increases the δ186/184W of surrounding seawater, whereas the redissolution of Mn-oxides causes decreasing seawater δ186/184W. Overall, the distinctly heavy stable W isotopic signature of open ocean seawater mirrors predominantly fully oxic conditions in modern oceans. We expect, however, that the redox evolution from anoxic to hypoxic and finally oxic marine conditions in early Earth's history would have continuously increased the seawater δ186/184W. Stable W isotope compositions of chemical sediments that potentially preserve changing seawater W isotope signatures might therefore reflect global changes in marine redox conditions.

Spatial heterogeneity of redox-sensitive trace metal enrichments in upper Ediacaran anoxic black shales

The Ediacaran radiation of metazoans is widely thought to have been triggered by an increase in atmospheric and oceanic oxygen levels. Although supported by other proxies, rising oxygen levels were deduced to a significant degree from sedimentary enrichments of redox-sensitive trace elements (RSTEs). However, some organic-rich shales of this period show only minor enrichments in RSTEs, leaving the significance of RSTE data for palaeo-oxygenation interpretations in doubt. We measured and compiled proxies for marine redox conditions (Fe species, RSTEs), total organic carbon (TOC) and water mass restriction (Mo/TOC and Co × Mn v. Cd/Mo) in the intra-shelf Jiulongwan and basinal Sandu sections of the Nanhua Basin in South China. Compared with the same proxies from coeval sections in the Nanhua Basin and globally, our results document a strong spatial heterogeneity of RSTE enrichments in anoxic black shales during the late Ediacaran. We infer that RSTE enrichments were strongly influenced by local factors, such as basinal restriction, seawater RSTE concentrations, and differential elemental responses to redox conditions and other influences. The broader significance of our findings is that they highlight the difficulty of investigating global redox conditions based on an analysis of local RSTE proxies within a single depositional basin or a limited number of study sections. Thematic collection: This article is part of the Advances in the Cambrian Explosion collection available at: https://www.lyellcollection.org/cc/advances-cambrian-explosion Supplementary material : Tables S1–S3 are available at https://doi.org/10.6084/m9.figshare.c.5325047

Nitrogen geochemistry and abnormal mercury enrichment of shales from the lowermost Cambrian Niutitang Formation in South China: Implications for the marine redox conditions and hydrothermal activity

The Cambrian is an important period for life evolution during the geological history, and the basal Cambrian black shales with widespread occurrence worldwide record important paleoceanographic information during this critical period. The set of shales with stable distribution and thickness of about 200 m is also extensively developed in South China, which provides an important material for studying the marine redox environment, major geological events and biotic evolution. Here we conduct studies on the nitrogen cycle and mercury's abnormal enrichment based on mercury (Hg) concentrations and nitrogen (N) isotope compositions of the shales from the lower Cambrian Niutitang Formation in Tongren area of Guizhou Province, South China. The results show that both Hg and TOC exhibited abnormal enrichments at the bottom of the Niutitang Formation. Mo and U enrichment factors indicated a gradually oxidized redox evolution during the deposition of the Niutitang Formation, with two fluctuated redox cycles from reducing to oxic, and then from dysoxic to oxic conditions in the water column. And the abnormal enrichment of Hg during the early Cambrian may be related to the volcanic and hydrothermal activities. Nitrogen isotope (δ15N) has obvious negative shift at the bottom of the Niutitang Formation, which indicated that nitrogen fixation was enhanced under the anoxic condition in the water column, the organic carbon pool gradually reduced, and phosphorus (P) and other nutrient elements were available, leading to the enhancement of nitrogen fixation and an increase of bioavailable nitrogen in the water column. Nitrogen isotopes recorded the effects of early Cambrian biological evolution and marine redox environment on nutrient element circulation, with contemporaneous volcanic or hydrothermal fluid activities during this period.

Pulsed oxygenation events drove progressive oxygenation of the early Mesoproterozoic ocean

The Mesoproterozoic era has long been considered a time of relative environmental and biological stasis. However, emerging insight suggests that this period may have been more dynamic than previously considered, both in terms of oxygenation and potential consequences for biological evolution. Nevertheless, our understanding of this immense period of time remains limited. To provide more detailed constraints on oxygenation dynamics, we report a multiproxy geochemical study of an early Mesoproterozoic (∼1600–1540 million years ago, Ma) carbonate-dominated succession from the North China craton. We include inorganic carbon isotope (δ13Ccarb), iron-speciation, and major and trace element data, in addition to molybdenum isotopic compositions (δ98/95Mo). These geochemical data support previous inferences of persistent anoxic and ferruginous deeper water conditions in the earliest Mesoproterozoic ocean, with limited oxygenation of surface waters. However, the behaviour of these redox-sensitive geochemical proxies reveals pulsed oxygenation events, with each event increasing the maximum depth of oxygenation, leading to overall progressive oxygenation of the ocean. During these pulsed oxygenation events we find the lightest Mo isotope signatures ever measured in the rock record, which we attribute to initial drawdown of isotopically light Mo in association with extensive Mn and Fe (oxyhydr)oxide precipitation, followed by diagenetic recycling. However, shallower water sediments deposited after the pulses of deeper water oxygenation more faithfully record the Mo isotopic composition of coeval seawater. For these samples, we utilise a single reservoir Mo cycling model, constrained by an updated estimate of Mesoproterozoic seawater Mo concentration, and scaled using a function associated with differential organic carbon flux between the shelf and basin. When scaled to modern rates of Mo accumulation under variable marine redox conditions, our modelling estimates suggest a minimum oxic seafloor area of ∼30% of the total seafloor area at ∼1540 Ma. It remains unclear whether the oxygenation observed across this ∼60 million year interval represents a progressive transition to a more persistently oxygenated ocean, or whether oceanic oxygen levels fluctuated considerably through the later Mesoproterozoic.

Uranium Isotope Fractionation in Non‐sulfidic Anoxic Settings and the Global Uranium Isotope Mass Balance

AbstractUranium isotopes (238U/235U) have been used widely over the last decade as a global proxy for marine redox conditions. The largest isotopic fractionations in the system occur during U reduction, removal, and burial. Applying this basic framework, global U isotope mass balance models have been used to predict the extent of ocean floor anoxia during key intervals throughout Earth's history. However, there are currently minimal constraints on the isotopic fractionation that occurs during reduction and burial in anoxic and iron‐rich (ferruginous) aquatic systems, despite the consensus that ferruginous conditions are thought to have been widespread through the majority of our planet's history. Here we provide the first exploration of δ238U values in natural ferruginous settings. We measured δ238U in sediments from two modern ferruginous lakes (Brownie Lake and Lake Pavin), the water column of Brownie Lake, and sedimentary rocks from the Silurian‐Devonian boundary that were deposited under ferruginous conditions. Additionally, we provide new δ238U data from core top sediments from anoxic but nonsulfidic settings in the Peru Margin oxygen minimum zone. We find that δ238U values from sediments deposited in all of these localities are highly variable but on average are indistinguishable from adjacent oxic sediments. This forces a reevaluation of the global U isotope mass balance and how U isotope values are used to reconstruct the evolution of the marine redox landscape.

Calibrating the coevolution of Ediacaran life and environment

The rise of animals occurred during an interval of Earth history that witnessed dynamic marine redox conditions, potentially rapid plate motions, and uniquely large perturbations to global biogeochemical cycles. The largest of these perturbations, the Shuram carbon isotope excursion, has been invoked as a driving mechanism for Ediacaran environmental change, possibly linked with evolutionary innovation or extinction. However, there are a number of controversies surrounding the Shuram, including its timing, duration, and role in the concomitant biological and biogeochemical upheavals. Here we present radioisotopic dates bracketing the Shuram on two separate paleocontinents; our results are consistent with a global and synchronous event between 574.0 ± 4.7 and 567.3 ± 3.0 Ma. These dates support the interpretation that the Shuram is a primary and synchronous event postdating the Gaskiers glaciation. In addition, our Re-Os ages suggest that the appearance of Ediacaran macrofossils in northwestern Canada is identical, within uncertainty, to similar macrofossils from the Conception Group of Newfoundland, highlighting the coeval appearance of macroscopic metazoans across two paleocontinents. Our temporal framework for the terminal Proterozoic is a critical step for testing hypotheses related to extreme carbon isotope excursions and their role in the evolution of complex life.

Biomarker evidence of algal-microbial community changes linked to redox and salinity variation, Upper Devonian Chattanooga Shale (Tennessee, USA)

AbstractLate Devonian marine systems were characterized by major environmental perturbations and associated biotic community changes linked to climate change and widespread oceanic anoxia. Here, we provide high-resolution lipid biomarker chemostratigraphic records from the Upper Devonian Chattanooga Shale (Tennessee, USA) to investigate algal-microbial community changes in the southern Illinois Basin that were related to contemporaneous shifts in marine redox (as proxied by trace metals, Fe-species, and Corg/P) and salinity conditions (as proxied by B/Ga, Sr/Ba, and S/total organic carbon). The Frasnian was characterized by dominantly bacterial lipids (high hopane/sterane), near-marine salinity, and a shift from oxic to increasingly reducing conditions in response to increasing organic carbon sinking fluxes. Aryl isoprenoids and aryl isoprenoid ratios reveal that the O2-H2S chemocline was unstable and intermittently shallow (i.e., within the photic zone). The Frasnian-Famennian boundary was marked by a shift in microalgal community composition toward green algal (e.g., prasinophyte) dominance (lower C27 and higher C28 and C29 steranes), a sharp reduction in watermass salinity, and a stable O2-H2S chemocline below the photic zone, conditions that persisted until nearly the end of the Famennian. We infer that changing watermass conditions, especially a sharp reduction in salinity to possibly low-brackish conditions (&amp;lt;10 psu), were the primary cause of concurrent changes in the microalgal community, reflecting tolerance of low-salinity conditions by green algae. Transient spikes in moretane/hopane (M/H) ratios may record enhanced terrestrial weathering at the Frasnian-Famennian and Devonian–Carboniferous boundaries, triggered by coeval glacio-eustatic falls and increased inputs of soil organic matter. High M/H and pristane/phytane, in combination with low chemical index of alteration and K/Al, record a decrease in chemical weathering intensity during the Famennian that may have been due to contemporaneous climatic cooling, and a concurrent reduction in silt content may reflect stabilization of land surfaces by vascular plants and resulting reduced sediment yields. This study demonstrates the effectiveness of combining organic and inorganic geochemical proxies (including novel paleosalinity indices) for determination of environmental controls on the composition and productivity of plankton communities in paleomarine systems.

Apatite-glaucony association in the Ediacaran Doushantuo Formation, South China and implications for marine redox conditions

Major phosphogenic events took place in the late Paleoproterozoic and the Ediacaran, both of which followed an episode of atmospheric oxygenation. These apparent coincidences have led to suggestions that the Precambrian phosphorus cycle was partly regulated by oceanic redox conditions, although direct evidence is lacking. In this paper, we report the discovery of glaucony in drill cores from the phosphorite-rich Ediacaran Doushantuo Formation at Weng'an, South China, which provides new insights into redox conditions and geochemical cycles during the deposition and early diagenesis of the lower Doushantuo Formation. The presence of flaser and lenticular bedding in the sandstones suggests deposition in a tidally-influenced shallow water environment. Apatite is present as millimeter-scale flasers in sandstones, but more commonly as intraclastic grains. Glaucony typically occurs as interstitial aggregates cementing and replacing detrital minerals and phosphatic grains, with an upsection decrease in abundance. The Doushantuo glauconies have consistently high K2O (7.5–9.6 wt%). In particular, phosphorite-hosted glaucony has generally higher total iron (TFe2O3) than sandstone-hosted glaucony, consistent with Al3+–Fe3+ substitution in the octahedral site, as supported by Raman peaks slightly shifted towards lower wavenumbers for higher Fe content. A decrease in detrital input probably resulted in limited Al availability during early diagenesis, which in turn led to the waning of glaucony upsection. The phosphate grains do not show any negative Ce anomalies, consistent with precipitation of authigenic apatite in suboxic environments with insignificant preferential remobilisation of Ce during deposition and early diagenesis. REE + Y features show variable diagenetic REE enrichment in phosphorites, but identical concave-down patterns. The wide occurrence of glaucony cement further documents the presence of a generally suboxic early diagenetic environment on the seafloor, which was in active exchange with bottom seawater. Slight fluctuations of redox states in the porewater and bottom water would have promoted the cycling of Fe, enrichment of phosphate and REE, and extensive glaucony authigenesis. Therefore, the glaucony-bearing phosphorites in the Doushantuo Formation are a direct result of Fe-redox driven diagenesis. Apatite-glaucony association likely forms in suboxic environments and is considered as a useful mineralogical proxy for paleoredox conditions on the Precambrian ocean floors.

Integrated sedimentary, biotic, and paleoredox dynamics from multiple localities in southern Laurentia during the late Silurian (Ludfordian) extinction event

The Silurian was a time of major climatic transition punctuated by multiple biotic crises and global carbon cycle perturbations. The most severe of these biotic events was the late Silurian (Ludfordian) Lau/Kozlowskii extinction event (LKE) and the associated Lau carbon isotope excursion (CIE). Although the extinction event and Lau CIE are globally documented, the only records thus far of local and global marine paleoredox conditions through this interval are from a single region in Scandinavia. Here we examine four sections along a bathymetric transect of mixed carbonate-siliciclastic sediments from western Tennessee, USA. A novel approach using a multi-proxy dataset combining high-resolution geochemical data and microfacies analyses from multiple localities explores the possibilities of local/regional-scale redox heterogeneities during a time of widespread environmental upheaval on a global scale. Paired positive excursions recorded in carbonate carbon isotopes and carbonate-associated sulfate sulfur isotopes support recent work from carbonate and siliciclastic successions from Scandinavia, suggesting a global enhancement of organic carbon and pyrite burial driven by an expansion of euxinic (anoxic and sulfidic water column) conditions in the oceans during the mid-Ludfordian. Furthermore, positive excursions in organic carbon isotopes and pyrite sulfur isotopes reflect the global changes in redox. Stratigraphic trends in I/Ca ratios imply a local expansion of low-oxygen conditions, with low, but non-zero values during the rising limb and peak of the CIE. The fossil assemblages vary across the shelf and through the CIE interval. Stratigraphic changes in fossil assemblages and I/Ca are closely associated with local and global changes in oxygenation and sea level during the mid-Ludfordian. The collective data indicate significant biotic reorganization in response to changes in marine redox conditions and in conjunction with sea-level variation during the LKE interval, but detailed macroscopic biodiversity is currently unconstrained for this region.

Marine redox variability from Baltica during extinction events in the latest Ordovician–early Silurian

It is well documented that Upper Ordovician and Silurian successions record multiple marine turnover events – including the second-largest mass extinction in the Phanerozoic – widespread glaciation, and multiple global carbon cycle perturbations. Whereas causal mechanisms for the Late Ordovician major mass extinction event involving climate, paleoceanographic variation, and δ13C records have been published, similar records remain poorly constrained for subsequent extinction events in the early Silurian. Here, we present new organic matter carbon isotope (δ13Corg) chemostratigraphy and corresponding paleoredox proxies (Fe speciation, [Mn, V, Mo], and pyrite sulfur isotopes) from two organic-rich drill core sections in Sweden and Latvia that span the upper Katian through lower Wenlock stages (446–431 Ma). Pyritized Fe and bulk sedimentary Mn concentrations from Upper Ordovician strata in southern Sweden suggest a local redox shift to more reducing conditions in the late Hirnantian, possibly including euxinic (anoxic and sulfidic water column) conditions that coincide with the second mass extinction pulse. The new high-resolution δ13Corg and δ34Spyr datasets from the late Aeronian (early Silurian) interval within both drill cores show positive excursions that are broadly coincident with the associated Sandvika and sedgwickii extinction events. Independently, Fe speciation and bulk sedimentary trace metal data from this late Aeronian interval record locally euxinic conditions in both the deep basinal (Sweden) and distal shelf (Latvia) settings before and during the late Aeronian positive δ13C excursion. This multiproxy paleoredox dataset provides the first direct evidence for local to regional expansion of reducing marine conditions coincident with this early Silurian (late Aeronian) biotic event and positive δ13C excursion. Additionally, new δ34Spyr values spanning the Llandovery/Wenlock boundary interval in the Latvia core show a positive excursion coincident with Fe speciation and trace metal enrichments that imply a local redox perturbation with intermittently euxinic bottom waters during the rising limb of the Ireviken positive δ13C excursion. The combination of these geochemical data for local- to regional-scale (more data required for global interpretations) changes in marine redox conditions with paleobiological records and evidence for eustatic sea-level rise indicate that environmental stresses related to an expansion of anoxic to euxinic conditions were a probable driver for several extinction events during the latest Ordovician–early Silurian.

Spatiotemporal evolution and causes of marine euxinia in the early Cambrian Nanhua Basin (South China)

Marine redox conditions and their dynamic variations in the early Cambrian are thought to have strongly influenced the evolution of early animals. However, the patterns and mechanisms of contemporaneous marine redox variation remain poorly understood. The Nanhua Basin (South China) was a failed rift basin located between the Yangtze Block (NW margin) and Cathaysia Block (SE margin) in the early Cambrian. In this study, we conducted a comprehensive study of marine redox conditions, sulfur cycling, and chemical weathering intensity of source areas for the lower Cambrian shales of the Qingxi Formation in the basinal Shimensuidao section, which was geographically close to the Cathaysia Block. We integrated these results with previously published data from the nearby Silikou section as well as the coeval inner-shelf Xiaotan, upper-slope Daotuo, lower-slope Longbizui, and basinal Zhalagou sections, where were closer to the Yangtze Block. At Shimensuidao, iron species and redox-sensitive trace element data suggest dominantly euxinic conditions for the organic-rich black shale interval (lower member; LM) and variable redox conditions (oxic-ferruginous-euxinic) for the overlying organic-lean shales (upper member; UM) of the Qingxi Formation. Integrated redox results show a similar lessening of euxinic conditions from LM to UM across the entire basin and that euxinia developed along both the Yangtze and Cathaysia basin margins, but it was mainly in upper-slope areas (e.g., Daotuo) on the Yangtze margin and reached basinal areas (e.g., Silikou and Shimensuidao) on the Cathaysia margin. A decline of δ34Spy from LM to UM was observed at Shimensuidao and other sections, which can be explained by decreasing microbial sulfate reduction rates due to decreasing organic availability and increasing riverine sulfate flux at study sections. Lower δ34Spy values in shallow-marine relative to deep-marine areas suggest increased terrestrial sulfate availability to the shallower sites. Chemical index of alteration (CIA) values at Shimensuidao are uniformly high for both the LM (CIAcorr1: 82.5 ± 0.4, CIAcorr2: 88.6 ± 0.5) and UM (CIAcorr1: 80.2 ± 2.3, CIAcorr2: 86.2 ± 2.5) compared with the low-to moderate values at Daotuo (CIAcorr2: 61.9 ± 3.9 for LM, 71.3 ± 4.8 for UM). This pattern is consistent with intense chemical weathering of source areas on the Cathaysia Block and weaker chemical weathering of source areas on the Yangtze Block. Based on these observations, we propose that strong chemical weathering of the Cathaysia Block led to regionally high terrigenous sulfate fluxes, resulting in expansion of mid-depth euxinia into deep basinal areas on the Cathaysia margin of the Nanhua Basin. In contrast, weak chemical weathering of the Yangtze Block yielded lower terrigenous sulfate fluxes, limiting euxinia to upper slope areas on the Yangtze margin of the basin. Weaker euxinia during UM deposition may have been due to its decreasing organic availability and/or small seawater sulfate reservoir caused by persistent euxinic consumption during LM deposition. Our results highlight the complex controls and the key role of continental weathering and resulting terrigenous sulfate fluxes in marine euxinic variations in early Cambrian marginal seas, providing new insights into the co-evolution of continents, oceans, and early animals.

Regional nutrient decrease drove redox stabilisation and metazoan diversification in the late Ediacaran Nama Group, Namibia

The late Ediacaran witnessed an increase in metazoan diversity and ecological complexity, marking the inception of the Cambrian Explosion. To constrain the drivers of this diversification, we combine redox and nutrient data for two shelf transects, with an inventory of biotic diversity and distribution from the Nama Group, Namibia (~550 to ~538 Million years ago; Ma). Unstable marine redox conditions characterised all water depths in inner to outer ramp settings from ~550 to 547 Ma, when the first skeletal metazoans appeared. However, a marked deepening of the redoxcline and a reduced frequency of anoxic incursions onto the inner to mid-ramp is recorded from ~547 Ma onwards, with full ventilation of the outer ramp by ~542 Ma. Phosphorus speciation data show that, whilst anoxic ferruginous conditions were initially conducive to the drawdown of bioavailable phosphorus, they also permitted a limited degree of phosphorus recycling back to the water column. A long-term decrease in nutrient delivery from continental weathering, coupled with a possible decrease in upwelling, led to the gradual ventilation of the Nama Group basins. This, in turn, further decreased anoxic recycling of bioavailable phosphorus to the water column, promoting the development of stable oxic conditions and the radiation of new mobile taxa.

Two distinct episodes of marine anoxia during the Permian-Triassic crisis evidenced by uranium isotopes in marine dolostones

The end-Permian mass extinction (EPME; ca. 251.94 Ma) is the most severe mass extinction in the geological record. Detailed paleobiological investigations show a very rapid EPME event, and recently published δ238U data show a large negative excursion and thus a massive shift to globally expanded anoxia at the main extinction phase in the latest Permian. The negative shift in δ238U is in correlation with a globally characterized negative δ13C excursion near the Permian-Triassic boundary (PTB). In some highly expanded PTB carbonate sections, however, there are two distinct negative δ13C excursions whereas uranium isotopes (δ238U) from such sections have not yet been examined, leaving a gap in the understanding of the global perturbations of marine redox conditions immediately following the EPME. Here, we present a new δ238U study of syn-depositional dolostones from a well-characterized and highly expanded drill core, which recorded two pronounced negative δ13C excursions across the PTB, from the Carnic Alps, Austria. This drill core extends 331-meters across the PTB and provides a unique opportunity to explore the detailed timing, duration, and extent of marine redox chemistry changes before, during, and immediately after the EPME. Our new δ238U record shows two negative shifts, which are correlated with the two negative δ13C excursions. The first negative δ238U excursion preceding the EPME confirms the recently published δ238U records from across the EPME and support that syndepositional marine dolostones can record δ238U trends of seawater similar to that of limestones. Modeling of uranium isotope cycling in the latest Permian and earliest Triassic oceans suggests two distinct stages of expanded marine anoxia separated by a brief interval (∼100 kyr) of reoxygenation across the PTB. The first anoxic episode lasted for ∼ 60 kyr while anoxic seafloor area expanded to cover >18% of the entire seafloor, coeval with the main EPME horizon, agreeing with marine anoxia as a proximate kill mechanism for the EPME. The second anoxic event was less intense compared to the first anoxic pulse but sustained for a longer duration. A global modeling of coupled C, P, and U cycles show that two pulses of volcanic carbon injection that drives global warming and increased phosphorus weathering rate can reasonably reproduce our data to match two phases of anoxia. The model also demonstrates that the loss of terrestrial vegetation in the EPME is crucial to generating an intervening interval of oxygenated ocean. Our new study adds to a growing body of evidence that the global marine redox conditions underwent rapid oscillations during the EPME event and continued afterward, which may have played a central role in delaying the marine ecosystem recovery in the Early Triassic.

Uranium reduction and isotopic fractionation in reducing sediments: Insights from reactive transport modeling

Uranium concentrations and isotopic ratios (238U/235U, denoted as δ238U) have been used to provide quantitative information about the degree of oxygenation and de-oxygenation of past oceans. The potential to constrain changes in global redox conditions, in contrast to many other proxies that reflect local conditions, is a particular strength of the uranium isotope approach. Because uranium reduction primarily occurs in sediments underlying anoxic water columns rather than in the anoxic water column itself, the removal of uranium in organic-rich shales is the largest lever on seawater δ238U. Accordingly, accumulation and isotopic fractionation are modulated by local variations in productivity, basin connectivity, sedimentation rate, and bottom-water redox conditions. To isolate the processes at the sediment-water interface that control δ238U and uranium accumulation in reducing sediments, we constructed a reactive transport model that couples biogeochemical reactions to diffusive transport and the burial of solutes and minerals.Using the model framework, we test the sensitivity of authigenic uranium isotopic fractionation and accumulation to oxygenation, permeability, sedimentation rate, organic carbon delivery, and basin restriction. Our results demonstrate that these external forcings produce diagnostic patterns in isotopic fractionation. Specifically, the model predicts that authigenic δ238U is sensitive to productivity because of the associated organic carbon burial rate. Moreover, our results suggest that the isotopic offset does not vary significantly due to changing bottom-water O2 concentrations, but the amount of accumulation does—a result that differs from previous estimates. Water column uranium reduction adds additional complexity to the ultimate δ238U value. The predictive patterns derived from model results can offer insight into local depositional conditions, such as sedimentation patterns. Collectively, these effects—including bottom-water redox conditions and related reducing sediments—alter the isotopic signature of the overlying water column according to the authigenic δ238U value and the diffusive fluxes arising from porewater concentration gradients. More broadly, this work provides important new constraints on the major controls on the δ238U of sediments while also supporting its use as a proxy for global marine redox conditions.