Marine Euxinia Research Articles

The dynamic ocean redox evolution during the late Cambrian SPICE: Evidence from the I/Ca proxy

The late Cambrian Steptoean positive carbon isotope excursion (SPICE) is a distinct chemostratigraphic feature of the Paleozoic, marked by a 4–5‰ shift in carbonate δ13C that has been recognized across the globe during the Paibian Stage. The SPICE may be related to enhanced burial of organic matter and pyrite during the expansion of marine euxinia, which as a source of O2 also results in a pulse of atmospheric oxygen. However, geochemical proxies have not clearly illustrated how the ocean redox evolved with atmospheric oxygen changes during the SPICE. This study presents new carbonate I/Ca data, a redox proxy for the upper ocean, from three basins. I/Ca values are low at Great Basin and South China from early into the peak of SPICE, indicating generally anoxic conditions in shallow waters. The overall increasing trend in I/Ca through the peak and recovery phase of the SPICE roughly correlates with the previously modeled rise in atmospheric oxygen. Spatially, the Georgina Basin (Mt. Whelan) might have recorded a relatively more oxic upper ocean compared to the Great Basin and South China. Earth system model simulations also demonstrate the importance of paleogeographic and oceanographic settings on local redox conditions, highlighting the redox heterogeneity during the SPICE.

Mass Extinction Coincided With Expanded Continental Margin Euxinia During the Cambrian Age 4

AbstractEarth's biosphere witnessed the first major extinction event in the Phanerozoic during the Cambrian Age 4, with a genera loss up to ∼45%. The traditional view suggested that marine anoxia was the main cause of the biotic crisis, yet recent geochemical investigations yielded highly debated opinions on marine redox states during the Cambrian Age 4. Herein, we supplement new geochemical evidence for expanded marine euxinia at the extinction intervals on the Yangtze Platform, South China. Most importantly, modern‐level sedimentary δ98Mo (∼+2.34‰) records were most parsimoniously explained by transitory expansion of continental margin euxinia and concomitant intensification of sedimentary Mo sequestration via Fe‒Mn shuttles in the global ocean. The results clarify global marine redox conditions during the Cambrian Age 4, and lend firm support to a causal link between expanded marine euxinia and the extinction event.

Widespread marine euxinia along the western Yangtze Platform caused by oxygen minimum zone expansion during the Capitanian mass extinction

The development of widespread marine anoxic and/or euxinic conditions has been proposed as a likely driver of the mid-Capitanian mass extinction. However, the driving mechanisms and spatiotemporal evolution of anoxia/euxinia remain poorly constrained. In order to decipher changes in marine redox conditions and their possible influence on the mid-Capitanian biotic crisis, we applied multiple geochemical indicators to three sections across a shelf-to-basin transect in the Middle Permian Kuhfeng and Lower Yinping formations of the Lower Yangtze Basin, South China. Our integrated Fe speciation and redox-sensitive trace element data suggest that euxinic waters dynamically coexisted at intermediate depths on the western margin of the Yangtze Platform, with oxygenated surface waters and ferruginous deeper waters providing compelling evidence for a redox structure similar to an oxygen minimum zone (OMZ). The synthesis of a five-stage spatiotemporal evolution of redox conditions, coupled with changes in upwelling and hydrographic restriction, indicates particularly intensified euxinia and an expanded OMZ across the shelf-basin transect during the middle Capitanian. Long-lasting anoxia-euxinia was likely maintained by enhanced phosphorus cycling, with sluggish ocean circulation due to collapsed upwelling and enhanced restriction under climate warming intensifying the euxinic conditions. Through a comparison of available global data, we infer that widespread anoxia-euxinia was prevalent in the middle Capitanian due to expanded OMZ conditions. Expanded anoxia and euxinia in shelf and slope environments occurred concurrently with an ongoing biotic crisis suggesting that these redox changes were a contributory factor.

Salinity variations of the inner Yangtze Sea during the Ordovician-Silurian transition and its influences on marginal marine euxinia

Salinity variations of the inner Yangtze Sea during the Ordovician-Silurian transition and its influences on marginal marine euxinia

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.

A pilot study of upper Yangtze shallow-water carbonates of the Paibian global marine euxinia: Implications for the late Cambrian SPICE event

The SPICE (Steptoean Positive Carbon Isotope Excursion) is a significant event in the Late Cambrian, recording global carbon cycle perturbations. Its driving mechanism is still controversial, but mainly believed to be related to an increase of organic carbon burial caused by ocean anoxia. The shallow-water platform carbonates of the Upper Cambrian Loushanguan Formation of Yankong outcrop (Upper Yangtze) spans the event interval. Their primary geochemical proxy signatures (trace elements, carbon and strontium isotopes), have been utilized to better understand the driving mechanism of the SPICE event. The variations of paleoenvironmental proxies in the upper Loushanguan Formation exhibit a rapid transformation of redox conditions similar to those of deep-water regions, thus reflecting an expansion of anoxic seawater to shallow-water column. The increase of 87Sr/86Sr, Al, and ∑REE during the SPICE suggests an enhancement in nutrient inputs from continental weathering that might have promoted primary productivity, which preferentially consumed light 12CO2 of surface waters, resulting in 13C-enriched DIC. The occurrence of PGMEE (Paibian global marine euxinia event), immediately before the enhancement of continental weathering, suggests that it was the onset-driving mechanism of the SPICE event and the increase in continental weathering might have promoted primary productivity to further intensify carbon burial and play a superimposed effect on that of the SPICE event.

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.

A diverse Ediacara assemblage survived under low-oxygen conditions

The Ediacaran biota were soft-bodied organisms, many with enigmatic phylogenetic placement and ecology, living in marine environments between 574 and 539 million years ago. Some studies hypothesize a metazoan affinity and aerobic metabolism for these taxa, whereas others propose a fundamentally separate taxonomic grouping and a reliance on chemoautotrophy. To distinguish between these hypotheses and test the redox-sensitivity of Ediacaran organisms, here we present a high-resolution local and global redox dataset from carbonates that contain in situ Ediacaran fossils from Siberia. Cerium anomalies are consistently >1, indicating that local environments, where a diverse Ediacaran assemblage is preserved in situ as nodules and carbonaceous compressions, were pervasively anoxic. Additionally, δ238U values match other terminal Ediacaran sections, indicating widespread marine euxinia. These data suggest that some Ediacaran biotas were tolerant of at least intermittent anoxia, and thus had the capacity for a facultatively anaerobic lifestyle. Alternatively, these soft-bodied Ediacara organisms may have colonized the seafloor during brief oxygenation events not recorded by redox proxy data. Broad temporal correlations between carbon, sulfur, and uranium isotopes further highlight the dynamic redox landscape of Ediacaran-Cambrian evolutionary events.

A massive magmatic degassing event drove the Late Smithian Thermal Maximum and Smithian–Spathian boundary mass extinction

The role of volcanism as a driver of climate change remains widely debated. Following the end-Permian mass extinction, the protracted Early Triassic recovery interval was characterized by extreme climatic and environmental perturbations (hyperwarming, intense subaerial weathering, and extensive marine euxinia) and large carbon- and sulfur-cycle perturbations. Although a magmatic trigger is widely accepted, details regarding the timing and magnitude of degassing and its relationship to contemporaneous climate changes remain poorly understood. In this study, we present new paired carbonate δ13C and carbonate-associated-sulfate δ34S data from deep-water settings in the Lower Triassic of South China to evaluate these issues. Our dataset reveals large positive shifts of both proxies across the Smithian/Spathian boundary (SSB), recording globally synchronous changes in the C and S cycles linked to co-burial of large quantities of organic matter and pyrite. Biogeochemical modeling of the C-S cycles shows that massive carbon release linked to increased magmatic degassing can account for observations of concurrent positive shifts of δ34S and δ13C, enhanced weathering, expanded marine euxinia, and the Late Smithian Thermal Maximum (LSTM). Measured increases in δ13C (+3.2 ± 1.6‰) and δ34S (+7.3 ± 2.3‰) across the SSB relative to their baseline values are consistent with a major magmatic degassing event during the Early to Middle Smithian, whose magnitude and rate we estimate at ~78,000 ± 13,000 Gt C and 0.26 Gt C yr−1, respectively. Our results provide evidence that Early–Middle Smithian degassing was the primary trigger of the LSTM and concurrent biotic crisis.

Extensive marine anoxia in the European epicontinental sea during the end-Triassic mass extinction

Warming-induced marine anoxia has been hypothesized as an environmental stressor for the end-Triassic mass extinction (ETME), but links between the spread of marine anoxia and the two phases of extinction are poorly constrained. Here, we report iron speciation and trace metal data from the Bristol Channel Basin and Larne Basin of the NW European epicontinental sea (EES), spanning the Triassic–Jurassic (T–J) transition (~ 202–200 Ma). Results show frequent development of anoxic-ferruginous conditions, interspersed with ephemeral euxinic episodes in the Bristol Channel Basin during the latest Rhaetian, whereas the contemporaneous Larne Basin remained largely oxygenated, suggesting heterogeneous redox conditions between basins. Subsequently, more persistent euxinic conditions prevailed across the T–J boundary in both basins, coinciding precisely with the second phase of the ETME. We propose that this later phase of benthic faunal loss in the NW EES was directly driven by the bottom-water oxygen crisis. Conversely, although anoxic conditions persisted into the early Hettangian, the benthos diversified at this time in nearshore areas. Post-extinction conditions were poised at a fluctuating redox state, but anoxia did not extend into the shallowest areas where benthic marine ecosystem recovery was occurring. • Water column anoxia was common in the European epicontinental sea through the Triassic–Jurassic transition. • Intensified marine euxinia developed at the second phase of the end-Triassic mass extinction. • A low oxygen ocean persisted post-extinction, but with a fluctuating redox state and limited ecological influence.

The Upper Yangtze Shallow-Water Carbonates Unveiling the Broadly Paibian Global Marine Euxinia Event: Implications for the Late Cambrian Spice

The Upper Yangtze Shallow-Water Carbonates Unveiling the Broadly Paibian Global Marine Euxinia Event: Implications for the Late Cambrian Spice

Spatiotemporal Evolution and Genesis of the Late Ordovician—Early Silurian Marine Euxinia in Northeastern Upper Yangtze Basin, South China

Marine redox conditions and their dynamic changes were a major factor that controlled the formation of black shale and caused the late Ordovician marine extinction in the Upper Yangtze Basin (South China). However, the spatiotemporal variation and potential controlling factors of marine redox conditions in this area remain unclear. We analyzed whole-rock geochemistry and pyrite sulfur isotopes (δ34Spy) of 47 shale samples from the Late Katian to Rhuddanian in a shelf-to-slope (Qianjiang Shaba section and Wc-1 well) region of northeastern Upper Yangtze Basin, and reconstructed water column redox conditions during the Late Ordovician–Early Silurian Transition. The geochemical characteristics of shale, including the ratio of elements, discriminant function and ternary diagram location in the study area suggest a passive continental margin sedimentary environment, wherein the terrigenous detritus is mainly derived from felsic igneous rocks in the upper crust, showing characteristics of near-source deposition. The redox indices (Fe speciation, Corg/P, UEF, and MoEF) showed that the development of anoxic water, especially euxinia, has obvious spatiotemporal heterogeneity. Under conditions of high availability of active organic carbon and limited sulfate supply, high active Fe input and strong biological irrigation in the shallow water area may effectively remove H2S produced by microbial sulfate reduction, conducive to the prevalence of ferruginous water columns. However, for this deep water area, the rapid accumulation rate of organic matter, decrease in dissolved Fe (caused by upwelling in the open sea), and seawater stratification (caused by the rising of sea level) promoted the development of a euxinic water column. This inference is supported by the covariant relationship between organic carbon accumulation rate, chemical index of alteration, Co × Mn, and δ34Spy. Our study highlights the potential control effects of sea level change, continental weathering and upwelling on the development of euxinic water columns.

Active methanogenesis during the melting of Marinoan snowball Earth

Geological evidence indicates that the deglaciation of Marinoan snowball Earth ice age (~635 Myr ago) was associated with intense continental weathering, recovery of primary productivity, transient marine euxinia, and potentially extensive CH4 emission. It is proposed that the deglacial CH4 emissions may have provided positive feedbacks for ice melting and global warming. However, the origin of CH4 remains unclear. Here we report Ni isotopes (δ60Ni) and Yttrium-rare earth element (YREE) compositions of syndepositional pyrites from the upper most Nantuo Formation (equivalent deposits of the Marinoan glaciation), South China. The Nantuo pyrite displays anti-correlations between Ni concentration and δ60Ni, and between Ni concentration and Sm/Yb ratio, suggesting mixing between Ni in seawater and Ni from methanogens. Our study indicates active methanogenesis during the termination of Marinoan snowball Earth. This suggests that methanogenesis was fueled by methyl sulfides produced in sulfidic seawater during the deglacial recovery of marine primary productivity.

Persistent global marine euxinia in the early Silurian

The second pulse of the Late Ordovician mass extinction occurred around the Hirnantian-Rhuddanian boundary (~444 Ma) and has been correlated with expanded marine anoxia lasting into the earliest Silurian. Characterization of the Hirnantian ocean anoxic event has focused on the onset of anoxia, with global reconstructions based on carbonate δ238U modeling. However, there have been limited attempts to quantify uncertainty in metal isotope mass balance approaches. Here, we probabilistically evaluate coupled metal isotopes and sedimentary archives to increase constraint. We present iron speciation, metal concentration, δ98Mo and δ238U measurements of Rhuddanian black shales from the Murzuq Basin, Libya. We evaluate these data (and published carbonate δ238U data) with a coupled stochastic mass balance model. Combined statistical analysis of metal isotopes and sedimentary sinks provides uncertainty-bounded constraints on the intensity of Hirnantian-Rhuddanian euxinia. This work extends the duration of anoxia to >3 Myrs – notably longer than well-studied Mesozoic ocean anoxic events.

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.

Sulfate-controlled marine euxinia in the semi-restricted inner Yangtze Sea (South China) during the Ordovician-Silurian transition

Conflicting published interpretations of marine redox conditions during the Ordovician-Silurian transition (OST) may have been linked to spatial redox heterogeneity during this interval. However, details of the pattern of redox heterogeneity and its underlying causes remain unclear. Here, we present a high-resolution geochemical study of a drillcore section (Pengye #1) from Pengshui County (Chongqing municipality, southwestern China) that was located in the semi-restricted inner Yangtze Sea during the OST. We analyzed Fe-speciation, redox-sensitive trace elements, major elements, and pyrite δ34S compositions (δ34Spy) and then compared these data with published results from coeval sections at Datianba and Shuanghe in the same basin. The integrated dataset demonstrates pronounced spatiotemporal heterogeneity of redox conditions—especially the local development of euxinic conditions in the inner Yangtze Sea during the OST. Integrated data further suggest that high primary productivity and ample Fe fluxes in the inner Yangtze Sea may have depleted dissolved sulfate through microbial sulfate reduction (MSR) and subsequent pyrite formation, except in areas with enhanced sulfate supply from continental weathering or open-ocean exchange, which varied as a function of both tectonic (i.e., the regional Kwangsian Orogeny) and eustatic changes (i.e., the global Hirnantian glaciation). Limited sulfate availability thus likely prevented the development of euxinic conditions in some regions of the inner Yangtze Sea, as reflected in spatial variation of δ34Spy. Our study highlights the potential role of sulfate availability on the development of watermass euxinia in semi-restricted marginal-marine basins during the OST.

Uranium isotope evidence for limited euxinia in mid-Proterozoic oceans

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

Geochemical evidence for expansion of marine euxinia during an early Silurian (Llandovery–Wenlock boundary) mass extinction

Repeated biotic crises have become the hallmark for the Silurian with the three most significant marine turnover events being related to dramatic global environmental perturbations. Causal mechanisms linking these marine extinction events with positive carbon isotope (δ13C) excursions, paleoceanographic change, and climate remain poorly constrained. Here, we examine the positive δ13C excursion across the Llandovery/Wenlock boundary, and the associated Ireviken extinction event. This positive δ13C excursion has been interpreted to reflect a major change in global oceanographic-climate state and enhanced organic carbon burial. New geochemical data from two paleocean basins have been analyzed to determine local and global redox conditions using carbon- and sulfur-isotopes (δ34S), and iodine (I/Ca+Mg) proxies. The high-resolution δ13C and δ34S data from both sections show positive excursions indicative of global perturbations to each of these elemental cycles, with minimal temporal offsets between the two systems. Numerical box modeling of δ13C and δ34S data indicates that these isotopic shifts can be generated by significant increases in the burial of organic carbon and pyrite, which are most likely due to enhanced burial under euxinic (anoxic and sulfidic) conditions. Independently, I/(Ca+Mg) values point to locally anoxic bottom waters in the distal and deeper basinal setting in Nevada before, during, and after the Ireviken positive δ13C excursion. I/(Ca+Mg) values in the proximal shelf setting in Tennessee show relatively oxic waters during the onset of peak δ13C values, after which bottom-water oxygen concentrations dropped throughout the remainder of the excursion. This multiproxy paleoredox dataset provides the first direct evidence for local and global expansion of reducing marine conditions coincident with the Silurian biotic event and positive δ13C excursion. Integration of these geochemical data for local- and global-scale changes in marine redox conditions with the paleontological data and evidence for eustatic sea-level rise points toward a shoaling of anoxic and/or euxinic waters onto the shelf as a driver for the Ireviken extinction event.

Transient marine euxinia at the end of the terminal Cryogenian glaciation

Termination of the terminal Cryogenian Marinoan snowball Earth glaciation (~650–635 Ma) is associated with the worldwide deposition of a cap carbonate. Modeling studies suggest that, during and immediately following deglaciation, the ocean may have experienced a rapid rise in pH and physical stratification followed by oceanic overturn. Testing these predictions requires the establishment of a high-resolution sequence of events within sedimentary records. Here we report the conspicuous occurrence of pyrite concretions in the topmost Nantuo Formation (South China) that was deposited in the Marinoan glacial deposits. Sedimentary facies and sulfur isotope data indicate pyrite precipitation in the sediments with H2S diffusing from the overlying sulfidic/euxinic seawater and Fe (II) from diamictite sediments. These observations suggest a transient but widespread presence of marine euxinia in an ocean characterized by redox stratification, high bioproductivity, and high-fluxes of sulfate from chemical weathering before the deposition of the cap carbonate.

Conodont size reduction and diversity losses during the Carnian Humid Episode in SW China

The enigmatic biotic and environmental changes during the Carnian Humid Episode (CHE) have been investigated in South China. The body size of conodonts, assessed as length of P1 elements, and their diversity show substantial changes in the mid-Carnian. The well-dated Long Chang, Yongyue and Caizitang sections in southwestern China record a change of palaeoenvironments from shallow-marine carbonate platforms to deeper, euxinic basins. All sections show a major loss of conodont diversity and abundance late in the Julian 1 at a time of rapid warming and marine anoxia. Conodont size saw a reduction in maximum, mean and minimum size during the Julian 2 to Tuvalian 2 interval caused by the short-lived appearance of small species and a size decrease of the survivors. Conodont mean size reduction coincided with marine euxinia or anoxia and temperature fluctuations during the Julian 2 to Tuvalian 2 interval. Carnian conodonts thus follow Bergmann's Rule: element size is inversely correlated to the temperature. Climate warming with the consequential development of marine anoxia or euxinia is probably directly responsible for biotic changes at this time. Supplementary material: Conodont length data from the Long Chang (LC), Yongyue (NR) and Caizitang (CZ) sections and data for the cross plot between estimated temperature and conodont mean size in the Long Chang section are available at https://doi.org/10.6084/m9.figshare.c.4114424