Ocean Redox Research Articles

Large igneous provinces played a major role in oceanic oxygenation events during the mid-Proterozoic

AbstractLow atmospheric oxygen levels during the mid-Proterozoic were occasionally interrupted by transient high oxygen levels. The cause of mid-Proterozoic ocean redox variability remains unclear. Here we investigate mercury chemostratigraphy across the Jixian section of North China Craton through two oxygenation intervals. Abnormal spikes in mercury concentration and excursions of mercury isotopes are observed in the Dahongyu and Hongshuizhuang formations, which occur just below the two oxygenation intervals, respectively. These mercury anomalies suggest that the two oxygenation events were preceded by subaerial volcanism. Furthermore, the two oxygenation intervals show increased nutrient concentrations and negative shifts in mercury isotopes, indicating that enhanced weathering and terrestrial nutrient influx occurred during oxygenation intervals. We infer that in the breakup setting of the Columbia supercontinent, large igneous province volcanism and its efficient low-latitude weathering could rapidly increase terrestrial nutrient influx into the ocean, promoting oceanic productivity and a pulsed rise in oxygen levels.

Ocean oxygenation and ecological restructuring caused by the late Paleozoic evolution of land plants

The dramatic increase in ocean-atmosphere oxygen levels during the Devonian and Mississippian is increasingly linked to the diversification of land plants, yet the timing and extent of this event remain uncertain. This study uses the redox-sensitive rare earth element cerium (cerium anomaly—Ce/Ce*) to investigate ocean redox conditions during the deposition of globally distributed Paleozoic carbonate strata. Our Paleozoic Ce/Ce* record suggests that Cambrian, Ordovician, and Silurian oceans had relatively low O2 levels (mean Ce/Ce* = 0.86 ± 0.10, 0.91 ± 0.14, and 0.91 ± 0.10 [±1σ], respectively). In contrast, short-lived ocean oxygenation events, possibly related to the diversification of small land plants, likely occurred throughout the Early and Middle Devonian (mean Ce/Ce* = 0.80 ± 0.07 and 0.58 ± 0.14, respectively). “Modern” Ce/Ce* values (<0.36) first occurred during the Late Devonian, suggesting that the main phase of Devonian and Mississippian oceanic oxygenation was related to the evolution of large vascular plants and the first forests. Despite this, the significant variability of Ce/Ce* values during this time suggests that shallow marine settings were susceptible to redox instability, possibly caused by upwelling of anoxic deep waters. This redox instability potentially provides evidence of a mechanism for contemporaneous mass extinction and metazoan reef collapse events. Development of strongly oxic conditions during the Late Devonian may have resulted in the demise of many Paleozoic-type organisms, facilitated the radiation of the modern evolutionary fauna, and established the modern oxygenated ocean-atmosphere system.

Re‐Evaluating Water Column Reoxygenation During the End Permian Mass Extinction

AbstractOcean anoxia is considered a key driver of the end‐Permian mass extinction (EPME). However, it is much debated whether there was an ocean reoxygenation phase during, and in the aftermath, of the EPME. Evidence for ocean reoxygenation is often inferred from the absence of framboidal pyrite in some boundary marine sediments (termed the “framboid gap”). To reconstruct ocean redox evolution across the EPME, we investigated the carbon isotopic, sedimentological, and redox records of the Ruichang and Ehtan sections in South China. These documents two negative δ13Ccarb excursions and the development of anoxia associated with deepening leading up to the Permian‐Triassic boundary. Above the level at which most siliceous organisms became extinct, pyrite framboid and iron proxies indicate that water column redox conditions were predominantly oxygenated but sporadically anoxic/ferruginous [non‐sulfidic, free Fe(II) in the water] at Ruichang, while ferruginous conditions were more widely developed at Ehtan. These contrasting redox states are characteristic of a dynamic ocean redox landscape in the extinction interval. The “framboid gap” is seen in strata deposited under both oxic and ferruginous conditions, suggesting that the availability of decomposable organic matter for sulfate reduction additionally controlled framboid genesis. Our data confirm that oxygenated conditions were developed in some deep water basins during the EPME.

Mercury isotope evidence for Middle Ordovician photic-zone euxinia: Implications for termination of the Great Ordovician biodiversification event

The Darriwilian (Middle Ordovician) is marked by a striking peak of the Great Ordovician Biodiversification Event (GOBE) followed by an abrupt ∼50 % decline in invertebrate species. Understanding the ultimate driving mechanism behind this biotic turnover and its correlation with those proximate climatic-oceanic changes that directly result in elevated biotic mortality have garnered considerable attention. One hypothesis posits that oceanic redox evolution actively influenced biodiversification, and progressive expansion of marine anoxia caused the termination of this biotic event. In this study, we present sedimentological and geochemical profiles for three outcrops of different lithofacies across the Middle-Upper Ordovician transition, ranging from carbonate platform to deep-water slope-basinal facies of the Tarim and South China cratons. Mercury isotopes reveal that recurrent and spatially dynamic photic-zone euxinia (PZE) occurred in the slope-basinal facies while being absent in platform facies. Mass balance model results suggest that ∼23 % of local atmospheric Hg was sequestered in marine sediments due to elevated dissolved H2S in surface waters. This finding suggests that destabilized oceanic redox conditions developed during climatic cooling, particularly shoaling and upwelling of deep-marine euxinic waters into the photic zone, coupled with global carbon-cycle disturbances, resulted in biodiversity decline following the peak of the GOBE.

Seawater sulfate dynamics and a new tipping point in the Earth system

Seawater sulfate (SO42−) concentrations have changed by orders of magnitude in response to atmospheric and ocean redox dynamics throughout Earth’s history. A fundamental model that constrains seawater SO42− dynamics based on the principles of mass balance, however, is still lacking. Here, we used a dynamical systems approach to determine the effects of global source and sink strengths on seawater SO42− concentrations. Our stochastic analysis of the SO42− mass balance revealed two most probable seawater SO42− concentration ranges: one under widespread oceanic anoxic conditions with SO42− concentrations <1000 µM, and the other with SO42− concentrations around or above 10,000 µM under widely oxygenated ocean conditions. Swings between these two seawater SO42− concentration ranges are notably evident during the Phanerozoic Eon and developed in response to reoccurring oceanic anoxic events. We also identified a threshold for the extent of oceanic anoxia above which seawater SO42− concentrations collapse to <1000 µM, with corresponding impacts on global biogeochemical cycles, biology, and climate.

Climatic-hydrologic influence on redox condition in the Cryogenian interglacial Nanhua Basin: Insights from the Datangpo Formation in the northwestern Yangtze Block, South China

Tracking climatic and oceanic redox changes throughout the Neoproterozoic Cryogenian is crucial to a better understanding of the coevolution of life and environment in geological history. However, the processes and driven mechanisms of redox evolution in the Cryogenian interglacial ocean still remain uncertain. Here, we present a combined study of geochemical proxies, such as paleoclimatic proxies (CIA and Zr/Al) and paleosalinity proxies (B/Ga and Sr/Ba), from the interglacial Datangpo Formation in the shallow-water Zuojiawan section exposed in the northwestern Yangtze Block, to constrain climatic and hydrologic changes on redox conditions. Our data indicate that two apparently climatic cycles from warming to cooling occurred during the deposition of the Datangpo Formation, supplementing the monotonous climatic warming in previous research during the Cryogenian interglaciation. The low B/Ga and Sr/Ba ratios throughout Datangpo Formation suggest a continuous freshwater condition, which is in contrast to a transition of marine condition to brackish condition in relatively deep-water sections. Compiled salinity reconstructions at different paleo-depths imply the salinity gradient in the Nanhua Basin with a density stratification like modern Baltic Sea, at least during the early Cryogenian interglacial period. We find that the climate-driven local riverine freshwater input may be a significant driver for maintaining long-term freshwater condition in the Zuojiawan section. Accompanied by synchronously climatic warming, the progressive desalinization with declining B/Ga and Sr/Ba ratios in the middle to upper deposition of the Datangpo Formation are probably attributed to the persistent freshwater input to a nearshore shallow-water paleogeographic setting. Combined the improving oceanic oxygenation backdrop with the elevating seawater sulfate concentration in the Nanhua Basin in this period, we conclude that the continuous dilution of seawater in the restrict (semi-) Nanhua Basin could attenuate the density stratification and enhance the vertical mixing of watermass, favoring the ventilation of deepwater and penetration of sulfate. This contribution provides a new insight for the study of salinity changes on redox conditions in the Yangtze Block during the Cryogenian interglacial period, and provides new data for supporting a systematic understanding of the evolutional mechanism of oceanic redox state.

Redox changes in the Iapetus Ocean during the Late Ordovician extinction crises

The cause of the Late Ordovician mass extinction (LOME) is widely debated, with glaciation, volcanism and oceanic redox fluctuations being proposed as possible drivers. Here, we apply a multi-proxy approach to deep-water Iapetus Ocean samples from Dob's Linn, Scotland, to determine oceanic redox conditions and changes in chemical weathering intensity. We document major redox fluctuations between anoxic ferruginous and oxic conditions during the first, end-Katian extinction pulse, whereas the end-Hirnantian extinction phase witnessed more persistent anoxia. These two episodes were separated by oxic conditions and a major, short-lived decline in chemical weathering during the Hirnantian glaciation, suggesting that although global cooling may have placed stress on certain biota, it was unlikely to be the cause of the extinction crisis. Late Hirnantian anoxia persisted into the Silurian, with widespread euxinia resulting in global drawdown of redox-sensitive trace metals. Recent studies have identified a mid-Katian biotic crisis and recovery prior to the LOME, although the precise stratigraphic position is not yet defined. The mid-Katian record at Dob's Linn shows a major redox change, with dysoxic to anoxic ferruginous deep ocean waters giving way to well-oxygenated conditions at this time. However, links between the mid-Katian biotic crisis and these redox changes remain unclear.

Lateral redox variability in ca. 1.9 Ga marine environments indicated by organic carbon and nitrogen isotope compositions.

The stepwise oxygenation of Earth's surficial environment is thought to have shaped the evolutionary history of life. Microfossil records and molecular clocks suggest eukaryotes appeared during the Paleoproterozoic, perhaps shortly after the Great Oxidation Episode at ca. 2.43 Ga. The mildly oxygenated atmosphere and surface oceans likely contributed to the early evolution of eukaryotes. However, the principal trigger for the eukaryote appearance and a potential factor for their delayed expansion (i.e., intermediate ocean redox conditions until the Neoproterozoic) remain poorly understood, largely owing to a lack of constraints on marine and terrestrial nutrient cycling. Here, we analyzed redox-sensitive element contents and organic carbon and nitrogen isotope compositions of relatively low metamorphic-grade (greenschist facies) black shales preserved in the Flin Flon Belt of central Canada to examine open-marine redox conditions and biological activity around the ca. 1.9 Ga Flin Flon oceanic island arc. The black shale samples were collected from the Reed Lake area in the eastern part of the Flin Flon Belt, and the depositional site was likely distal from the Archean cratons. The black shales have low Al/Ti ratios and are slightly depleted in light rare-earth elements relative to the post-Archean average shale, which is consistent with a limited contribution from felsic igneous rocks in Archean upper continental crust. Redox conditions have likely varied between suboxic and euxinic at the depositional site of the studied section, as suggested by variable U/Al and Mo/Al ratios. Organic carbon and nitrogen isotope compositions of the black shales are approximately -23‰ and +13.7‰, respectively, and these values are systematically higher than those of broadly coeval continental margin deposits (approximately -30‰ for δ13Corg and +5‰ for δ15Nbulk). These elevated values are indicative of high productivity that led to enhanced denitrification (i.e., a high denitrification rate relative to nitrogen influx at the depositional site). Similar geochemical patterns have also been observed in the modern Peruvian oxygen minimum zone where dissolved nitrogen compounds are actively lost from the reservoir via denitrification and anammox, but the large nitrate reservoir of the deep ocean prevents exhaustion of the surface nitrate pool. Nitrogen must have been widely bioavailable in the ca. 1.9 Ga oceans, and its supply to upwelling zones must have supported habitable environments for eukaryotes, even in the middle of oceans around island arcs.

The depositional redox conditions of Fe‐speciation reference materials (BHW and WHIT) using redox‐sensitive trace metal enrichment

Iron speciation has emerged as a robust proxy for discerning oceanic redox conditions; nonetheless, it is subject to certain limitations. Specifically, the applicability of the degree of pyritization is contingent upon the presence of unequivocal evidence of an anoxic water column and its discriminatory capacity is limited to distinguish between ferruginous (anoxic) and euxinic conditions. This study highlights that through the integration of redox‐sensitive trace metal enrichment data with Fe‐speciation data, the depositional redox conditions for marine sediments can be established with greater certainty. Recently, a set of dedicated geological reference materials (BHW and WHIT) have been developed for validating the Fe‐speciation analytical results for redox reconstruction studies; however, to the best of our knowledge, these reference materials are not characterized for trace and rare earth elements (REEs). In this connection, the BHW (oxic) and WHIT (anoxic) reference materials are measured for major, trace and REEs. After careful statistical considerations for these reference standards, a complete set of trace and REEs is reported. Furthermore, considering BHW and WHIT as oxic and anoxic end‐members, respectively, the utility of trace metal enrichment and Fe‐speciation data in combination has been discussed. The trace and REE concentrations of BHW and WHIT reported in this study will enhance their applicability as a reference material to understand ocean chemistry and the oxidation state of the ancient oceans.

Statistical estimation of the early to middle Ediacaran ocean redox architecture in the Yangtze block of South China

Early to middle Ediacaran organic-rich black shales host several famous fossil biotas and provide key evidence for understanding the coevolution of multicellular organisms and palaeoceanic environment. The water column redox states play critical roles in organic-rich shale deposition. Amongst multiple geochemical redox indexes, iron-speciation chemistry (FeHR/FeT, Fepy/FeHR) in shales constitutes a reliable proxy to reconstruct the first-order redox framework of the ocean basin. However, iron-speciation is a local marine redox proxy, and only compiled data collected from multiple different sedimentary facies record statistically significant changes of oxidation states within a depositional basin. Here we compiled the spatiotemporal distribution of iron-speciation data in early to middle Ediacaran black shales of the Yangtze block in South China. New high-resolution analysis on two outcrops and one drill-core reflects overall ferruginous condition and dominant euxinic condition locally interrupted by oxic states, respectively, generally indicating pervasive anoxic depositional environment for the Member II shales of the Ediacaran Doushantuo Formation in the Lower Yangtze block. Compilation of fourteen Ediacaran sections from shallow-, slope- and deep-water facies demonstrates frequent spatiotemporal oscillation of the redox conditions throughout the Yangtze block. Widespread ferruginous states, accompanied with euxinic zones mainly focusing in lower slope facies, are detected during the early Ediacaran period, in contrast with more widespread euxinic settings in the middle Ediacaran period. Statistical data including new high-resolution results from the Lower Yangtze block show generally low enrichment for redox sensitive elements (RSEs, e.g., Mo, V and U) in the Member II shales probably due to their contemporary low seawater concentrations. An increase of RSEs concentrations occurs in the Member IV shales, which probably reflects more oxidized Earth surface environment during middle Ediacaran period. The increasing Earth oxygenation documents the occurrence of widespread euxinic states during deposition of the Member IV shales. Compilation of spatial distribution of TOC contents in black shales demonstrates their apparent relevance to spatial distribution of the euxinic rather than ferruginous states, which is likely due to the favorable role of sulfurization process on burial and preservation of organic matters. The euxinic states may also facilitate the exceptional preservation of the soft-bodied Ediacaran fossils.

Links between hydrographic restriction, redox conditions, and organic matter accumulation in the Early Cambrian intrashelf basin, South China

There was a strong relationship between paleo-oceanic conditions and organic matter accumulation during the critical period of the Early Cambrian. The Yangtze Platform in South China provides an opportunity to study this relationship, but the basin architecture and paleo-hydrographic dynamics remain poorly understood, which hinders one’s understanding of the evolution in oceanic redox state and its relationship to organic matter accumulation. To fill the knowledge gap, a newly obtained data set from the Lower Cambrian Niutitang Formation shales (Late Cambrian Stage 2-Stage 3) of the intrashelf basin is used. Results show that the molybdenum–uranium covariation, along with the abnormally low Mo contents and Mo/TOC ratios in the anoxic (ferruginous and euxinic) Niutitang shales of the intrashelf basin, indicate a hydrographic circulation that is moderately to strongly restricted. The hydrographic evolution at different stages, influencing redox conditions to a certain extent, in conjunction with variations in primary productivity, controls the enrichment of organic matter. In particular, the relatively low sea level during Interval I (Late Stage 2) resulted in weak connectivity between the intrashelf basin and open ocean; this, coupled with high primary productivity and enhanced chemical weathering, formed stable stratified water (euxinic bottom-water) conditions that were favorable for organic matter enrichment. In contrast, Interval II (Early–Middle Stage 3) and Interval III (Late Stage 3) involved less organic matter enrichment due to weakened restricted hydrographic circulation (Interval II) and oxic bottom-water conditions (Interval III). This study highlights how hydrodynamic processes affected the marine environment during the Early Cambrian and reveals that sluggish oceanic circulation combined with high primary productivity led to anomalous enrichment of organic matter. This may be a common feature of basins with restricted hydrographic circulation in deep time.

Oceanic euxinia and seafloor oxygenation linked to continental weathering and influxes during the Late Devonian Frasnian–Famennian bio-crisis and Annulata bio-event

Oceanic anoxia is regarded as the immediate cause of the Late Devonian Frasnian–Famennian (F–F) bio-crisis and Annulata bio-event. The oceanic anoxia has been linked to continental weathering and input. However, some previous findings indicate oxic marine environments during the F–F bio-crisis. Moreover, the relative impact of terrestrial input on the Late Devonian oceanic redox conditions, when comparing a bio-crisis and a bio-event, remains unknown . Here, we present a decoupled oceanic redox model suggesting the redox conditions were different between shallow and deep water columns during the F–F bio-crisis, i.e., intensified euxinia in the photic zone and a more oxygenated condition at the seafloor. Geochemical (biomarker and trace metal) and sedimentologic evidence from the Late Devonian Seaway, eastern U.S., indicate that the shallow-deep decoupled oceanic redox conditions were regulated by terrestrial weathering and input. During the F–F bio-crisis, land nutrient input intensified photic zone euxinia through eutrophication, while hyperpycnal flows oxygenated seafloors. After the F–F bio-crisis, the seafloor redox conditions shifted from oxygenation to silled euxinia, and the watermass became hydrographically restricted. During this post-F–F interval, the euxinia at the seafloor intensified due to land nutrient runoff during the Annulata bio-event. Importantly, the land weathering and input during the F–F bio-crisis were more prominent than during the Annulata bio-event. This resulted in widespread and intense photic zone euxinia during the F–F bio-crisis, relative to the seafloor euxinia that developed in restricted areas during the Annulata bio-event. Our decoupled oceanic redox model may explain the preferential decimation of shallow-water organisms during the F–F bio-crisis. The seafloor euxinia during the Annulata bio-event may provide a niche for the turnover of benthic faunas adapting to low oxygen levels. This study suggests that continental weathering and influxes played an important role in regulating oceanic oxygen evolution and impacting life evolution and bio-diversity.

The paleoredox context of early eukaryotic evolution: insights from the Tonian Mackenzie Mountains Supergroup, Canada.

Tonian (ca. 1000-720 Ma) marine environments are hypothesised to have experienced major redox changes coinciding with the evolution and diversification of multicellular eukaryotes. In particular, the earliest Tonian stratigraphic record features the colonisation of benthic habitats by multicellular macroscopic algae, which would have been powerful ecosystem engineers that contributed to the oxygenation of the oceans and the reorganisation of biogeochemical cycles. However, the paleoredox context of this expansion of macroalgal habitats in Tonian nearshore marine environments remains uncertain due to limited well-preserved fossils and stratigraphy. As such, the interdependent relationship between early complex life and ocean redox state is unclear. An assemblage of macrofossils including the chlorophyte macroalga Archaeochaeta guncho was recently discovered in the lower Mackenzie Mountains Supergroup in Yukon (Canada), which archives marine sedimentation from ca. 950-775 Ma, permitting investigation into environmental evolution coincident with eukaryotic ecosystem evolution and expansion. Here we present multi-proxy geochemical data from the lower Mackenzie Mountains Supergroup to constrain the paleoredox environment within which these large benthic macroalgae thrived. Two transects show evidence for basin-wide anoxic (ferruginous) oceanic conditions (i.e., high FeHR/FeT, low Fepy/FeHR), with muted redox-sensitive trace metal enrichments and possible seasonal variability. However, the weathering of sulfide minerals in the studied samples may obscure geochemical signatures of euxinic conditions. These results suggest that macroalgae colonized shallow environments in an ocean that remained dominantly anoxic with limited evidence for oxygenation until ca. 850 Ma. Collectively, these geochemical results provide novel insights into the environmental conditions surrounding the evolution and expansion of benthic macroalgae and the eventual dominance of oxygenated oceanic conditions required for the later emergence of animals.

Shifts in magnetic mineral assemblages support ocean deoxygenation before the end-Permian mass extinction

Expansion of oceanic anoxia is a prevailing hypothesis for driving the marine end-Permian mass extinction and is mainly based on isotopic geochemical proxies. However, long-term oceanic redox conditions before the end-Permian mass extinction remain unresolved. Here we report a secular redox trend based on rock magnetic experiments and cerium anomalies through the Changhsingian and across the Permian-Triassic boundary at the Meishan section, China. Magnetic mineral assemblages changed dramatically at ca. 252.8 million years age (Ma), which indicates that oceanic deoxygenation started about 0.9 million years earlier than the end-Permian mass extinction. The magnetite-dominant post end-Permian mass extinction interval suggests a ferruginous dysoxic conditions with enhanced weathering in the earliest Triassic. Also, a gradual magnetite abundance decrease to pre-extinction levels is observed at ca. 251.5 Ma, coinciding temporally with the waning of Siberian Trap and arc volcanism. All of these observations demonstrate that environmental deterioration began much earlier than the end-Permian mass extinction and finally collapsed in the end-Permian.

Oceanic and atmospheric oxygenation during the late Ediacaran based on multiple isotope records from South China

The Neoproterozoic–Cambrian transition was a key period in Earth's history, particularly because changes in the oceanic redox environment were crucial to the Cambrian explosion of life. However, the redox state of the ocean during this transition is unclear. In this study, the carbonate strata of the Dengying Formation in Yunnan Province, South China, were subjected to δ98/95Mo, δ13C, 87Sr/86Sr, and trace element analyses. The low δ98/95Mo results (0‰ ∼ +2‰) of most samples indicate that a shallow-marine sedimentary environment dominated by low-O2 conditions during the late Ediacaran period (Dengying Formation), but a brief period of marine oxidation existed at this time, reflected by elevated δ98/95Mo values (+2.07‰ ∼ +2.43‰). At this time, δ13C values were increasing, which possibly indicate an increase in primary productivity and photosynthesis in shallow waters, causing oxidation of the shallow seawater. However, two anomalously high δ98/95Mo values (>2.65‰) could have resulted from additional isotope fractionation due to the upwelling of euxinic bottom waters abruptly. In addition, an increase in 87Sr/86Sr ratios lagged the δ13C and δ98/95Mo changes, suggesting that atmospheric changes appear to have lagged oceanic oxidation, but more evidence are needed to prove the relationship. The dynamic changes in the redox conditions of the shallow sea during deposition of the Dengying Formation provided favorable conditions for changes in the atmosphere and the Ediacaran biota.

Marine eutrophication within the Tarim Platform in sync with Middle to Late Ordovician climatic cooling

Previous work has proposed climatic cooling and atmosphere–ocean oxygenation as potential triggers for the Great Ordovician Biodiversification Event, with the suggestion of better oxygenated oceans during the Middle to Late Ordovician. However, recent studies have argued for spatial and temporal heterogeneity in marine redox state on several continents. Here we investigate a black-shale succession accumulated within the Tarim Platform via a combination of geochemical proxies to address these debates. Negative shifts in bulk nitrogen isotopes and synchronous increases in excess phosphorus suggest moderate-high marine primary production coinciding with the development of bottom-water anoxia, as indicated by enrichments in highly reactive iron and modest concentrations of redox-sensitive trace metals (Mo, U). Moreover, the occurrence of black shale correlates well with equivalent successions formed in deep-water marginal basins along several continents, including South China, North China, Laurentia and Baltica. This may suggest an expansion of marine anoxia in low-latitude zones of the late Darriwilian to early Sandbian oceans, probably as a result of enhanced upwelling in sync with climatic cooling. The extent and ultimate cause of marine anoxia requires further quantifying constraints at a global scale, which will enable potential links between global oceanic redox conditions and concurrent biotic changes to be evaluated in more detail. Supplementary material: Geochemical dataset for the Dawangou section (Table S1) is available at https://doi.org/10.6084/m9.figshare.c.7036552 Thematic collection: This article is part of the Chemical Evolution of the Mid-Paleozoic Earth System and Biotic Response collection available at: https://www.lyellcollection.org/topic/collections/chemical-evolution-of-the-mid-paleozoic-earth-system

Marine redox fluctuations during the Marinoan glaciation

The proliferation of eukaryotes preceding the Cryogenian Marinoan glaciation (650–635 Ma) and the subsequent radiation of early animals imply a conceivable linkage between global glaciation and complex life evolution. However, the marine redox condition remains enigmatic during the Cryogenian, impeding our understanding of the role of O2 on this biological innovation. To fill this gap, we comprehensively reported mineralogy, iron isotope (δ56Fe), and iron speciation in the Cryogenian Nantuo Formation at Liulongshan, South China. This section encompasses glacial marine and non-glacial deposits, where the redbeds situated in the middle of the section, in conjunction with the diamictites adjacent to them, divide the Nantuo Formation into three distinct glacial sedimentary cycles. Micro-particle hematite within the Nantuo Formation indicates that the primary Fe-oxide was authigenic and trapped in water column. Furthermore, the Fe isotopic compositions of these authigenic components (δ56FeHR) calculated by mass balance equation reveal the redox state of the ocean coinciding with dynamic glaciation. The lower diamictite shows an increasing trend of δ56FeHR, Fe/Al, and FeHR/FeT, indicative of gradually more anoxic seawater conditions coupled with ice advance. Although redbeds intervals exhibit higher FeHR/FeT ratios (∼ 0.51), traditionally indicative of anoxic environments, our integration of mineralogical evidence suggested that the increased Feox content in redbeds might represent increased oxidation of Fe(II) at the redox chemocline, rather than the redox conditions of the bottom waters. This interpretation is consistent with the observed decreasing trend in our Fe isotope data, as well as the sedimentological evolution. Subsequently, the positive and increasing δ56FeHR values suggest that the oceanic redox conditions shifted to anoxic as the second glacial episode re-emerged. These findings suggest dynamic fluctuations in the redox condition of the ocean during the Marinoan Ice Age. Specifically, the formation of the redbeds may reflect a locally oxic environment. A modern analogy resembling this situation is blood falls, where the oxidation of iron-rich brine plumes under the Antarctic ice sheets. Such subglacial environments could have potentially provided a habitable “refuge” for early life to survive during the Neoproterozoic glaciation.

Oxygen increase and the pacing of early animal evolution

While it is widely accepted that early animals originated and primarily evolved during the Neoproterozoic to Cambrian period, there remains ongoing debate over how fluctuations in marine-atmospheric oxygen levels influenced their evolution and diversification. To investigate this, we analyzed pristane/phytane ratios—a redox-proxy based on organic geochemistry—in surface sediments from the Cryogenian to Cambrian successions in South China, Oman, and Australia. The temporal changes in this proxy exhibited consistent patterns across all sites, revealing five cycles of anoxic to oxic conditions in the ocean between 660 and 510 Ma. By examining the average pristane/phytane ratios, we identified three events when oxygen levels increased. This represents a transition from anoxic conditions to anoxic-dysoxic boundary at 630–600 Ma, followed by a shift to dysoxic conditions at 570 Ma (Shuram event), and finally reaching oxic conditions at 520 Ma (Cambrian explosion). Significantly, these oxygenation events align with eumetazoan evolution. An inverse relationship was observed between oceanic redox events and positive/negative shifts of δ13Ccarb, occurring between the first and second oxygenation events, suggesting an increase in atmospheric oxygen levels. Based on these findings, we propose that there were global increases in oceanic and atmospheric oxygen levels, at least during the early Ediacaran period. These shifts in oxygen levels likely played a role in influencing the rate of evolution among early animals.

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.

Speciation and cycling of iodine in the subtropical North Pacific Ocean

Iodine intersects with the marine biogeochemical cycles of several major elements and can influence air quality through reactions with tropospheric ozone. Iodine is also an element of interest in paleoclimatology, whereby iodine-to-calcium ratios in marine carbonates are widely used as a proxy for past ocean redox state. While inorganic iodine in seawater is found predominantly in its reduced and oxidized anionic forms, iodide (I−) and iodate (IO3−), the rates, mechanisms and intermediate species by which iodine cycles between these inorganic pools are poorly understood. Here, we address these issues by characterizing the speciation, composition and cycling of iodine in the upper 1,000 m of the water column at Station ALOHA in the subtropical North Pacific Ocean. We first obtained high-precision profiles of iodine speciation using isotope dilution and anion exchange chromatography, with measurements performed using inductively coupled plasma mass spectrometry (ICP-MS). These profiles indicate an apparent iodine deficit in surface waters approaching 8% of the predicted total, which we ascribe partly to the existence of dissolved organic iodine that is not resolved during chromatography. To test this, we passed large volumes of seawater through solid phase extraction columns and analyzed the eluent using high-performance liquid chromatography ICP-MS. These analyses reveal a significant pool of dissolved organic iodine in open ocean seawater, the concentration and complexity of which diminish with increasing water depth. Finally, we analyzed the rates of IO3− formation using shipboard incubations of surface seawater amended with 129I−. These experiments suggest that intermediate iodine species oxidize to IO3− much faster than I− does, and that rates of IO3− formation are dependent on the presence of particles, but not light levels. Our study documents the dynamics of iodine cycling in the subtropical ocean, highlighting the critical role of intermediates in mediating redox transformations between the major inorganic iodine species.