Redox Proxies Research Articles

Do red marine carbonates represent oxic environments? New understanding from the Upper Ordovician marine limestone in Tarim Basin, China

Marine red beds (MRBs), typically colored by Fe- and Mn-rich minerals, are often interpreted as indicators of bottom water oxygenation. However, their continuous formation requires long-term input of aqueous derived Fe-Mn oxides and/or stable sources of Fe2+ and Mn2+ ions, challenging the traditional concept of “red equals oxic environment.” This study investigates two coeval Upper Ordovician Sandbian MRB carbonate intervals in the Tarim Basin. Previous studies attributed the pigment origin to hematite. Th/U values and total rare earth element and yttrium (REY) contents increased in the MRB interval, indicating a terrestrial source of iron. Hematite was observed within the intercrystal pores of calcite precipitating from porewater, consistent with high Nicarb abundance and MREE-enriched bulge pattern in the red intervals. Both sections exhibit high Fecarb and Mncarb, pointing to substantial reductive dissolution of Fe and Mn oxides. Simulation shows that isotopic discrimination (Δ13C) between carbonate and organic carbon could be biased by increasing benthic Fe-Mn flux, leading to decreased Δ13C values in MRB intervals. Ce/Ce∗ values in the high-Mncarb interval reflect the releasing of Ce by reductive dissolution of Mn oxides. The commonly used carbonate-based redox proxy I/(Ca + Mg) ratio is correlated positively with Mncarb in the shallower section and with TOC in the deeper section, while it is negatively correlated with TOC in the shallower horizon, suggesting that iodine behavior may be influenced by adsorption and releasing of Mn hydro-oxides and organic matter besides oxygen contents. This study links MRB coloring to Fe and Mn mineral cycling in pore water through reductive dissolution and oxidative precipitation, and highlights potential biases of carbonate-based redox proxies that might be susceptible to other electron acceptors/donors such as Fe-Mn oxides and organic matter, in addition to free oxygen in seawater.

Reconstructing the redox environment of the Cambrian Harkless Formation, Nevada, USA: Navigating the effects of iron-rich clay minerals on the iron speciation redox proxy

Understanding the oxygenation of ancient oceans is critical for contextualizing evolutionary events throughout Earth's history. While there are many geochemical proxies available for evaluating paleoredox state, iron speciation is one of the most robust and widely applied recorders of local bottom water redox. The proxy uses a series of sequential extractions which are operationally designed to target redox active iron in different mineral groups, including carbonates, oxides, magnetite, and sulfides. However, clay minerals that contain iron are not specifically targeted but can be important reservoirs of redox active iron. These clay minerals are abundant during many times in Earth's history, so it is critical to understand how they are extracted during iron speciation and their impact on paleoenvironmental interpretations.Here we apply the iron speciation proxy in combination with other geochemical proxies (FeT/Al, Mn enrichments) and mineralogical analyses to determine local bottom water redox conditions during deposition of the early Cambrian Harkless Formation exposed near Gold Point, Nevada, USA. The Harkless Formation contains one of the last occurrences of archaeocyathan reefs before their extinction, thus studying the underlying strata can provide information about the environmental conditions which led to reef development. Iron speciation results indicate oxic to potentially anoxic conditions in the water column. The presence of FeT/Al enrichments, Mn depletion, and the Fe-rich redox sensitive clay minerals chamosite and glauconite suggest intermittent anoxia in the water column and porewaters during some intervals of Harkless deposition. Further, by combining iron speciation extractions with petrographic and x-ray diffraction analyses, we demonstrate that glauconite and chamosite were likely formed at or below the sediment water interface and are also not consistently or fully removed by the standard sequential iron reagents, as noted by previous work.The presence of these authigenic Fe-bearing clay minerals overall results in an underestimation of the proportion of redox active iron during deposition and early sediment diagenesis that may lead to incorrect environmental characterization. We therefore advocate for caution and careful examination of the mineralogy of samples when applying the iron speciation proxy, particularly when authigenic and/or early diagenetic iron-bearing clay minerals are suspected to be present. Based upon these findings, we suggest that the Harkless Formation experienced variable local bottom water redox conditions ranging from oxic to anoxic during deposition. Changes in the relative abundances of chamosite and glauconite may also indicate an increase in oxygenation up section, suggesting that local water column oxygenation played a role in archaeocyathan reef development.

Assessment of bi-metal paleo-redox proxies in the Bakken Formation black shales, Williston Basin, North Dakota, USA

The influence of paleoredox conditions and water-mass restriction on trace metal (TM) accumulation in the lower (LBS) and upper black shales (UBS) of the Devonian–Mississippian (D–M) Bakken Formation was assessed utilizing V/Cr, V/(V + Ni), Ni/Co, U/Th, and enrichment factors (EF) for Mo vs. U. These assessments were compared to previously published estimates based on degree of pyritization (DOPT), sulfur‑iron and C–S–Fe relationships, and sedimentological data. Bi–metal ratios suggest >80 % of samples were deposited under suboxic to anoxic/euxinic conditions, whereas DOPT results suggest >60 % of samples were deposited under dysoxic (0.42–0.75 DOPT) bottom–water conditions. DOPT results are in good agreement with C–S–Fe and total S vs. Fe assessments of paleoredox conditions and sedimentological evidence. Good agreement is also seen between Mo/TOC and Mo EF/U EF that both suggest the Bakken shales were deposited under a relatively unrestricted water mass conditions resulting in consistent renewal of TMs into the basin. With TM resupply outpacing drawdown, the basin could support enhanced primary productivity as well as high concentrations of TMs. Trace metal concentrations for the Bakken Fm. show considerable range for Co (0–10,324 ppm), Mo (0–2018 ppm), Ni (0–1574 ppm), U (0–1604 ppm), and V (0–3194 ppm), and bi–metal ratios for the Bakken Fm. are up to 5× greater than those reported for other D–M black shale formations. Bivariate and principal component analysis indicate Mo, Ni, U, and V accumulation was more closely associated with the organic fraction than with reducing conditions, thus accumulation of organic matter during deposition and generation, migration, and biodegradation of hydrocarbons during diagenesis may have influenced the accumulation and distribution of these TMs. Furthermore, changes in biogeochemical processes during the D–M transition may have fundamentally altered marine chemistry, with the evolution of vascular land plants and enhanced terrestrial weathering leading to an increased influx of nutrients into marine waters resulting in the Annulata, Dasberg, and Hangenberg black shale events. Factors controlling TM accumulation during time of deposition (e.g., TM availability, bottom-water redox conditions, adsorption onto organic matter) and during diagenesis and catagenesis (e.g., alteration and break down of organic matter, movement of fluid hydrocarbons or other basinal fluids) likely contribute to the lack of agreement between redox proxies, and subsequently, the lack of applicability of bi–metal ratios in assessing bottom–water conditions for the Bakken shales. Therefore, it is suggested that these bi-metal redox proxies are not an effective means to describe bottom-water conditions during the deposition of the Bakken shales.

Hydrographic restriction conditions in the Middle and Upper Yangtze region during the Early Silurian post-glacial transgression: Constraints from major, trace elemental geochemistry and Mo-TOC relationship

Redox-sensitive trace metals have not only been widely used as the proxy for palaeoredox potential due to the strong enrichments under reducing conditions but also provide critical information into water-mass properties, such as the degree of basin restriction. In order to reveal the Early Silurian post-glacial transgression hydrographic restriction conditions throughout the Middle and Upper Yangtze region, trace metal concentrations and organic geochemical data of the lower Longmaxi Formation were analyzed by the Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Leco combustion techniques. We analyzed the hydrographic restriction conditions and redox conditions of different depocenters, including the Southern, Eastern, and Northern Sichuan Basin depocenters and the Western Hubei Region depocenter. The sedimentary Mo-TOC relationship, MoEF-UEF covariation, and upwelling intensity suggest that the Southern, Eastern Sichuan Basin depocenters and the Western Hubei Region depocenter were deep water areas with moderate hydrographic restriction, whereas the restriction conditions of Northern Sichuan Basin depocenter was relatively weak. In addition, due to the combined effect of geographical location, connectivity with the open Qinling Ocean, and estuarine circulation, restriction degrees varied in the same depocenter. The redox proxy (Corg/P) indicated that the lower Longmaxi Formation was deposited in an anoxic water column. There are significant spatial differences in redox conditions in different depocenters and different locations within the same depocenter, which may be controlled by relative sea level rise, hydrographic restriction, and upwelling intensity. Anoxic conditions were more likely to occur in areas where water column was relatively deep and restricted. In addition, the anoxic conditions in the Northern Sichuan Basin depocenter may also associated with the strong upwelling intensity and the behavior of P cycling back to water column, which can promote the primary productivity and further maintain persistent anoxic conditions. The correlation between Corg/P and Mo/TOC indicates that, in relatively weak restriction basin, the trace elements enrichment in sediments was controlled by trace elemental concentrations in seawater. In moderate restriction basin, the trace elements enrichment was mainly controlled by redox conditions. Whereas under more reducing conditions, hydrographic restriction may tend to become the dominant factor. The application of sediment Mo-TOC relationship, MoEF-UEF covariation, and upwelling can provide insights into hydrographic restriction conditions, but the Mo/TOC relationship is limited to anoxic facies, as little trace metal accumulation could also be the consequence of oxic conditions.

Seasonal euxinia in a coastal basin: Impact on sedimentary molybdenum enrichments and isotope signatures

Eutrophication and global warming are leading to increased deoxygenation of coastal waters worldwide. To predict future trajectories of oxygen loss, insight into the intensity and temporal dynamics of past coastal deoxygenation is essential. Here, we assess the use of sedimentary molybdenum (Mo) enrichments and isotopic signatures (δ98Mo) as redox proxies in sediments of a seasonally euxinic coastal basin (Scharendijke, Lake Grevelingen, the Netherlands). Strong drawdown of dissolved Mo (from ∼100 to ∼60 nmol L−1) was observed in the euxinic bottom waters from July to September in 2021, coinciding with sedimentary enrichment of Mo (with peak values up to 19 ppm). A mass balance for Mo indicates that both deposition of Mo in the form of particles and diffusion of dissolved Mo into the sediment account for this Mo enrichment. The δ98Mo composition of suspended matter in the euxinic waters (0.30 to −1.95 ‰) is in line with isotopic fractionation during formation of thiomolybdates, and removal of Mo by sulfur- and/or iron-rich particles. The δ98Mo composition of the bottom water increases from 2.42 to 3.16 ‰ throughout the euxinic period, thereby further supporting preferential uptake of light Mo isotopes during sulfidation in the water column and near the sediment-water interface. The exceptionally high sedimentation rate at this site (>13 cm yr−1) allows seasonal variations in sedimentary enrichments to be preserved in the sedimentary record. Notably, sediment δ98Mo values peak during the summer euxinic period, reaching 1.28 ‰ in 2021 and as high as 2.15 ‰ in 2020. The 2020 value is close to the mean ocean value of 2.3 ‰, implying that sediments overlain by seasonally and permanently euxinic bottom waters can record the same isotopic signatures for Mo. Further work is needed to determine the potential role of diagenesis in altering δ98Mo records on time scales of months to several years.

Zinc partitioning between mantle minerals and basaltic melts: Application to revisit the Zn/FeT redox proxy

Zn/FeT (FeT=Fe2+ + Fe3+) ratios in primitive melts have been proposed as a redox proxy to assess the redox states of the upper mantle. However, to effectively use the melt Zn/FeT ratio as a redox proxy, it is necessary to compare variations of melt Zn/FeT ratios induced by changes in oxygen fugacity (fO2) with variations due to changes in Zn-Fe contents and mineralogy of the sources. Here we show that the melt Zn/FeT ratio variation caused by fO2 change can be expressed as Δ(Znm/FemT) = (Znper/FeperT)* Δ(Fem2+/FemT)/(DZnper/m/DFe2+per/m). Zn/FeT ratios in most arc and MORB peridotites (Znper/FeperT) are 9.0 ± 1.0*10−4, and melt Fe2+/FeT ratio variation resulted from fO2 change [Δ(Fem2+/FemT)] can be easily obtained by the existing model. Hence, if the Zn and Fe2+ partition coefficients (DZnper/m and DFe2+per/m) between melt and peridotite are known, the melt Zn/FeT ratio variation resulting from fO2 change can be estimated. In this study, we determined DZn between olivine, orthopyroxene, clinopyroxene and basaltic melts at 0.75–2.5 GPa and 1250–1450 ℃. Our data show that melt composition (expressed as MgO content) dominantly controls the mineral-melt Zn partitioning under peridotite melting conditions. These data, along with published mineral-melt DFe2+ data, enable us to calculate appropriate DZnper/m/DFe2+per/m, which is 0.78 ± 0.02 under arc and MORB spinel peridotite melting conditions. Based on these parameters, the calculated average melt Zn/FeT ratio variation caused by per log unity fO2 change in typical fO2 span of arc and MORB mantles is only ∼ 0.69 ± 0.20*10−4. Alternatively, melt Zn/FeT ratio variations caused by changes in Zn-Fe contents and mineralogy of peridotites are ±1.10*10−4. These findings indicate that melt Zn/FeT ratio variation induced by one log units fO2 change is on the same order of magnitude as those caused by changes in Zn-Fe contents and mineralogy of peridotites. Therefore, unless the precise chemical and mineralogical compositions of the mantle sources can be determined independently, the melt Zn/FeT redox proxy is unsuitable for tracing the mantle fO2. Our study, combined with recent works on melt Cu and V/Sc redox proxies, suggests that these redox proxies, previously considered as the strongest evidence for a reduced arc mantle, might not support the idea of a reduced arc mantle.

Marine Fe cycling linked to dynamic redox variability, biological activity and post-depositional mineralization in the 1.1 Ga Mesoproterozoic Taoudeni Basin, Mauritania

The concentration of redox sensitive trace metals (RSTEs) and their isotopic composition preserved in Precambrian marine sediments, are critical for the reconstruction of ocean–atmosphere oxygenation history. Particularly, the concentration of Fe, its redox speciation, and isotopic distribution, have gained widespread use for inferring the biogeochemical processes that controlled Fe cycling in Precambrian oceans linked to the reconstruction of Earth surface redox budget. However, questions remain about the biotic and abiotic processes involved in Fe cycling in these ancient oceans, including the impact of post-depositional alterative processes on the reliability of the Fe redox proxy. Here we present a multi-proxy mineralogical and geochemical study of the ∼1.1 Ga Atar and El Mreiti strata of the Taoudeni Basin in Mauritania, to better constrain pathways involved in Fe cycling, linked to Fe mineralogy, redox speciation, isotopic ratios during this time and metamorphism. We compare unmetamorphosed sedimentary deposits with facies metamorphosed by dolerite sill intrusion. The results reveal the occurrence of diagenetic Fe minerals in the basal unmetamorphosed samples associated with light δ56Fe signatures, reflecting dominant anoxic conditions that promoted microbial dissimilatory Fe reduction. Notably, δ56Fe composition of these rocks reveal several fluctuations in evolving seawater redox state from oxic to anoxic/sulfidic conditions associated with changes in sea level stand and periods of full bottom water oxygenation and redox stratification. Overall, Ce anomalies suggest a general up sequence increase in seawater oxygen content. Metamorphosed rocks display heterogeneous δ56Fe distribution, consisting of light and heavy signatures associated with secondary Fe-bearing minerals produced by metamorphic and metasomatic overprinting of carbonated rocks by hot circulating fluids. The results thus indicate metamorphic overprinting of primary seawater δ56Fe promoted by increased mobility of reactive Fe during post-depositional metamorphic transformation. They show that post-depositional metamorphic/metasomatic overprinting complicates direct reconstruction of seawater biogeochemical Fe cycling and redox state using δ56Fe systematics.

Effects of a landslide on the geochemistry of dissolved major and trace elements in a granite-gneiss forest catchment of Southeast Brazil

This study investigated the hydrogeochemical variations in a scenario following a landslide event in the Soberbo pristine rainforest small catchment (13 km2). The selected catchment is underlain by granite gneiss and located at the Serra dos Órgãos a mountainous region in the Rio de Janeiro, Brazil, that faces frequent high-intensity rainfall events. Stream water sampling, water discharge, and pH and electrical conductivity measurements were conducted monthly from May 2018 to October 2019. In January 2019, a landslide occurred upstream. Concentrations of dissolved organic carbon (DOC), HCO3−, major elements (Ca, K, Mg, Na, and Si), and trace elements (Al, Ba, Ce, Fe, Mn, Nd, Sr, Rb, La, Pr and Sm) were determined. The Spearman correlation and the multivariate analysis (PCA) indicated that during baseflow, rock weathering hydrolysis reactions are the main source of Si, Na, Mg, Ba and Sr. On the other hand, the forest plays a significant role during the rainy months by remobilizing colloidal litter material (represented by the DOC concentration) closely associated with colloidal Al. The landslide promoted a change in local redox conditions, resulting in the early release of Mn-scavenged elements, and about a month later, Fe and LREE, following a deepening in reduced conditions. The Ce/La molar ratio appeared to be a reliable hydrogeochemical redox proxy. The landslide effects persisted for at least nine months. In this case, the traceability of natural geochemical impacts of landslides was achieved through the river hydrogeochemistry in a mountainous small catchment model area.

Elemental Geochemical Characteristics of Shales from Wufeng-Longmaxi Formations in the Southern Margin of the Qinling Orogenic Belt, China: Implications for Depositional Controls on Organic Matter.

The tectonic background and sedimentary environment during the transition period from the Ordovician to Silurian have been widely studied by many scholars. This study focuses on the Upper Ordovician Wufeng Formation and Lower Silurian Longmaxi Formation in the Bajiaokou profile at the southern margin of the Qinling Orogenic Belt in southern China. In order to study the aggregation mechanism of organic matter, geochemical proxies were proposed, including redox proxies (V, V/Al, U, U/Al, Mo, and Mo/Al), paleoproductivity proxies (P, P/Ti, Ba, Ba/Al, and SiXS), paleoclimate proxies (CIA), and terrigenous flux proxies (Al, Zr, and Zr/Al). In addition, Al-Co[EF] × Mn[EF] is used to provide information on paleoenvironmental parameters such as watermass restriction conditions. The redox proxies show that the Wufeng-Longmaxi shale is mainly accumulated under oxic-dysoxic conditions. During the shale deposition period of Wufeng-Longmaxi formations, the marine surface primary productivity in the southern Qinling area is generally low to moderate. The paleoclimate proxies show that from the Late Ordovician to the Early Silurian the southern Qinling area generally had a warm and humid climate. The upwelling current is widely developed in the northern margin of the Sichuan Basin and the southern margin of the Qinling area. Although the upwelling current was highly developed during the deposition of the Wufeng Formation in the Bajiaokou profile, the concentrated accumulation of a large amount of volcanic ash resulted in the low primary productivity of the ocean. During the sedimentary period of the Longmaxi Formation in the Bajiaokou profile, the development of seasonal upwelling currents and a small amount of volcanic ash supply increased the primary productivity to moderate, which provided a good material basis for the enrichment of organic matter, but the high detritus flux and the water body condition of oxic-dysoxic resulted in the slight enrichment of organic matter.

Weathering-induced organic matter enrichment in marine-continental transitional shale: A case study on the early Permian Taiyuan Formation in the Ordos Basin, China

A comparative analysis of the factors controlling organic matter (OM) enrichment between marine-continental transitional (transitional hereafter) and marine or lacustrine shales is lacking. The early Permian Taiyuan Formation in the Ordos Basin, deposited during a shift from marine to continental settings in northern China, provides a unique opportunity to unravel the differences in OM enrichment mechanisms among these shales. The Taiyuan Formation is characterized by high TOC content (average 4.50%) and kerogen type II2-III. Most samples are thermally mature with a few high to post-mature samples relating to the Late Jurassic–Early Cretaceous Yanshanian magmatism. Rare earth elements and yttrium (REY) are dominated by light- and medium-types enrichments, with distinctly positive Gd anomaly, likely due to seawater incursion. A warm and humid climate prevailed during deposition of the Taiyuan Formation, consistent with the tropical-subtropical location of the North China Plate in the early Permian. The climatic conditions promoted intense continental weathering as reflected by high Th/Sc ratios, chemical index of alteration values, and feldspar alteration to scaly kaolinite. The V/(V + Ni) ratio is inconsistent with the other redox proxies, presumably due to variations in the redox buffer supply in the transitional facies (e.g., OM and pyrite), varying burial rates and dissimilar redox potential of different elements. Hence, this proxy should be interpreted with caution in such settings. Most redox proxies indicate oxic bottom water during deposition of the Taiyuan Formation transitional shale, in contrast to typical OM enriched marine and lacustrine shales where redox stratification or euxinic conditions are common. Instead, the dominant factor for OM enrichment in transitional shales appears to have been a high influx of terrestrial weathering products, including abundant higher-plants OM, associated with preservation of OM due to rapid burial. This process minimizes the detrimental effects of oxic conditions on OM accumulation in the transitional shale facies. This mechanism may hold relevance for analogous basins elsewhere.

Weathering, redox proxies and carbon isotope data from the Maokou Formation, Upper Yangtze, South China: Implications for the Guadalupian P3 glaciation of the Late Paleozoic Ice Age

Late Paleozoic Ice Age (LPIA) was a key climate event of the deep-time earth evolution system. Although the sedimentary successions from eastern Australia have well constrained the timeframe of the glacial-nonglacial intervals, the link between these glaciations and coeval geological events is still being explored. The Guadalupian (Middle Permian) P3 glaciation was the prelude to the upcoming end of LPIA, which is a key window to examine the uncertainty of the climatic transition from icehouse to greenhouse and linkages with the geological and biological events. This study focuses on the marine sedimentary succession of the Shangsi outcrop located in the low-latitude Yangtze block, investigating the carbon/strontium isotopes, redox proxy, and chemical index of alteration (CIA). Multiple weathering indices revealed climatic fluctuations during the Guadalupian, corresponding to the onset and demise of the high-latitude P3 glaciation. The high level of CIA following the Kungurian-age Large Igneous Provinces (LIPs) event indicates that the weathering of basic rocks caused the positive 13C drift, which was the main factor for the onset of the P3 glaciation. Then the breakup of Pangea, enhanced ocean oxidation, and a series of volcanic activities including Emeishan LIP could contribute to the accumulation of CO2 and consequently cause the demise of the P3 glaciation in middle Capitanian. Enhanced continental weathering was synchronous with the eruption surge of the volcanic activities, indicating a following global warming event, which may play a crucial role in triggering the Mid-Capitanian extinction event.

Seasonal euxinia in a coastal basin: Impact on sedimentary molybdenum enrichments and isotope signatures

Eutrophication and global warming are leading to increased deoxygenation of coastal waters worldwide. To predict future trajectories of oxygen loss, insight into the intensity and temporal dynamics of past coastal deoxygenation is essential. Here, we assess the use of sedimentary molybdenum (Mo) enrichments and isotopic signatures (δ98Mo) as redox proxies in sediments of a seasonally euxinic coastal basin (Scharendijke, Lake Grevelingen, the Netherlands). Strong drawdown of dissolved Mo (from ~100 to ~60 nmol L−1) was observed in the euxinic bottom waters from July to September in 2021, coinciding with sedimentary enrichment of Mo (with peak values up to 19 ppm). A mass balance for Mo indicates that both deposition of Mo in the form of particles and diffusion of dissolved Mo into the sediment account for this Mo enrichment. The δ98Mo composition of suspended matter in the euxinic waters (0.30 to −1.95 ‰) is in line with isotopic fractionation during formation of thiomolybdates, and removal of Mo by sulfur- and/or iron-rich particles. The δ98Mo composition of the bottom water increases from 2.42 to 3.16 ‰ throughout the euxinic period, thereby further supporting preferential uptake of light Mo isotopes during sulfidation in the water column and near the sediment-water interface. The high sedimentation rate at this site (>13 cm yr−1) allows seasonal variations in sedimentary enrichments to be preserved in the sedimentary record. Notably, sediment δ98Mo values peak during the summer euxinic period, reaching 1.28 ‰ in 2021 and as high as 2.15 ‰ in 2020. The 2020 value is close to the mean ocean value of 2.3 ‰, implying that sediments overlain by seasonal and permanently euxinic bottom waters can record the same isotopic signatures for Mo. Further work is needed to determine the potential role of diagenesis in altering δ98Mo records on time scales of months to several years.

Uranium enrichment driven by paleomarine condition and event deposition: Insights from the lower Cambrian Niutitang Formation organic-rich shales in northeastern Guizhou, South China

Organic-rich shale related uranium (U) mineralization has attracted widespread attention as a strategic and clean alternative to fossil energy and a paleoceanic redox proxy. A comprehensive study of mineralogy, organic geochemistry and elemental geochemistry of the lower Cambrian Niutitang Formation organic-rich shales in northeastern Guizhou, South China was conducted to address this issue. SEM-EDS results showed that the U occurrence state in the Niutitang Formation shales is dominated by nanoscale U minerals, mainly including coffinite, brannerite, U-bearing apatite and U-bearing xenotime. Various states of U are closely associated with organic matter, apatite, pyrite and clay minerals. Based on geochemical indexes, paleomarine condition and event deposition jointly drove the U enrichment in the Niutitang shales, in which hydrothermal activities and/or volcanic eruptions increased U fluxes in seawater and euxinic environment with high primary productivity provided a favorable condition for U reduction. The adsorption, complexation and reduction of UO22+ by organic matter and the formation of uranyl phosphate complexes by the combination of phosphate and UO22+ accelerated U immobilization and enrichment from bottom water to sediments. The microbial activities (e.g., BSR) in this process created favorable euxinic conditions and released inorganic-phase P to provide available ligands for UO22+. The U enrichment models of the lower Cambrian Niutitang shales in northeastern Guizhou were established. This paper provides a new insight into the U enrichment mechanism in organic-rich shales, and may also have implications for the applicability of U as redox proxy and the exploration of organic-rich shale related U deposits.

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.

Redox indication potential of isoprenoid tetraether lipids in marine environments: Insights from the East China Sea

The response of marine ammonia-oxidizing archaea (AOA) to environmental stress is reflected in changes in their membrane lipid composition, particularly the unique isoprenoid glycerol dialkyl glycerol tetraethers (iGDGTs). However, the influence of dissolved oxygen (DO) on the composition of iGDGTs in the ocean remains unclear. This study aims to investigate the link between DO levels and the fractional abundances of iGDGTs in the East China Sea (ECS) to establish a redox proxy. Results suggested that the absolute abundances of iGDGTs were influenced by Thaumarchaeota biomass when DO concentrations exceeded 2 mg/L. Vertical distributions of iGDGTs through the water column suggested their transport from bottom waters to sediments. Increasing proportions of iGDGT-0 and the sum of iGDGT-1, iGDGT-2 and iGDGT-3 from suspended particulate matters to surface sediments indicated their preferential preservation. DO concentrations (2–6 mg/L) in the water column showed a significant positive correlation with the relative abundance of crenarchaeol (cren%) but a negative correlation with iGDGT-0%, suggesting insufficient DO levels to promote AOA cyclization. However, bottom DO concentrations exhibited significant negative correlations with both cren% and iGDGT-0% in surface sediments, attributed to enhanced cyclization of iGDGTs and Euryarchaeota abundance within more reducing sediments, respectively. The consistent relationship between iGDGT-0% and DO in both water column and sediments enabled iGDGT-0% to be a potential redox proxy. Temporal variations in iGDGT-0% in the ECS in recent decades aligned well with in-situ DO monitoring data, further validating iGDGT-0% as a promising redox proxy.

Watermass architecture of the Ordovician–Silurian Yangtze Sea (South China) and its palaeogeographical implications

The South China Craton experienced large changes in climate, eustasy and environmental conditions during the Late Ordovician Hirnantian Ice Age, but their impact on the watermass architecture of the Yangtze Sea has not yet been thoroughly evaluated. Here, we reconstruct the salinity–redox structure of the Yangtze Sea based on five Upper Ordovician–Lower Silurian shale successions representing a lateral transect from a deep-water area of the Inner Yangtze Sea (IYS; Shuanghe section) across the shallow Hunan–Hubei Arch (Pengye, Jiaoye and Qiliao sections) to the relatively deep-water Outer Yangtze Sea (OYS; Wangjiawan section). Carbon isotope ( δ 13 C org ) profiles show that the Guanyinqiao Bed (recording the peak Hirnantian glaciation) thins and is less completely preserved at sites on the flanks of the Hunan–Hubei Arch than in deeper water areas to the SW and NE, reflecting bathymetric influences. Watermass salinities were mainly marine at Shuanghe and brackish at the other four study sites, with little variation among Interval I (pre-glaciation), Interval II (Hirnantian glaciation) and Interval III (post-glaciation). Redox proxies document mainly euxinia at Shuanghe and Wangjiawan and suboxia at the other sites during Interval I, with shifts towards more reducing (mostly euxinic) conditions at most sites during Intervals II and III, which shows that all the study sections were deep enough to remain below the redoxcline during the glacio-eustatic lowstand. Two features of the Shuanghe section mark it as being unusual: it alone exhibits fully marine salinities, implying greater proximity to the open ocean than the other four sites, and it exhibits an especially large shift towards more reducing conditions during Interval III (i.e. the post-Hirnantian transgression), implying greater water depths. These features are difficult to reconcile with the standard palaeogeographical model for the Ordovician–Silurian South China Craton, which is characterized by a geographically enclosed and restricted IYS and a more open OYS, arguing instead for the SW end of the IYS to have been connected to the global ocean and the OYS to have been a restricted oceanic cul-de-sac. A review of sedimentological and facies data for the IYS region suggests that our re-interpretation of the Ordovician–Silurian palaeogeography of the South China Craton is viable, although further vetting of this hypothesis is needed. Supplementary material: The dataset and the full crossplot of Sr/Ba v. CaO for this study are available at https://doi.org/10.6084/m9.figshare.c.7170648 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

The relationship between total organic carbon and bottom water redox state in North American black shales

It is clear from modern analogue studies that O2-deficient conditions favor preservation of organic matter (OM) in fine-grained sedimentary rocks (black shales). It is also clear that appreciable productivity and OM flux to the sediment are required to establish and maintain these conditions. However, debates regarding redox controls on OM accumulation in black shales have mainly focused on oxic versus anoxic conditions, and the implications of different anoxic redox states remain unexplored. Here, we present detailed multi-proxy sedimentary geochemical studies of major Paleozoic and Mesozoic North American black shale units to elucidate their depositional redox conditions. This is the first broad-scale study to use a consistent geochemical methodology and to incorporate data from Fe-speciation – presently the only redox proxy able to clearly distinguish anoxic depositional conditions as ferruginous (H2S-limited) or euxinic (H2S-replete, Fe-limited). These data are coupled with total organic carbon (TOC), programmed pyrolysis, and redox-sensitive trace element proxies, with almost all measurements analyzed using the same geochemical methodology. Consistent with expectations based on previous geochemical and paleontological/ichnological studies, these analyses demonstrate that the study units were almost exclusively deposited under anoxic bottom waters. These analyses also demonstrate that there is wide variance in the prevalence of euxinic versus ferruginous conditions, with many North American black shale units deposited under predominantly ferruginous or oscillatory conditions. TOC is significantly higher under euxinic bottom waters in analyses of both preserved (present day) TOC and reconstructed initial TOC values, although sediments deposited under both redox states do have economically viable TOC content. While this correlation does not reveal the mechanism behind higher organic enrichment in euxinic environments, which may be different in different basins, it does open new research avenues regarding resource exploration and the biogeochemistry of ancient reducing environments.

Low-salinity conditions in the “marine” Late Triassic-Early Jurassic Neuquén Basin of Argentina: Challenges in paleosalinity interpretation

Salinity, a key property of watermasses, is difficult to reconstruct in paleodepositional systems, and errors in assigning salinity facies to epicratonic and marginal-marine deposits may be common. In this study, we evaluate the salinity conditions of mudstones of the Arroyo Malo Formation (AMF), spanning the Triassic-Jurassic transition (TJT) of the Neuquén Basin, Argentina. Although the AMF has long been considered marine based on its fossil fauna, we find that three elemental salinity proxies (B/Ga, Sr/Ba, S/TOC) are consistent in indicating dominantly freshwater influence, with occasional excursions to low-brackish conditions. In this context, the sparse, fragmented, and poorly preserved assemblage of bioclasts in the AMF do not accurately represent its salinity facies. We infer that, during the TJT, the Neuquén Basin was largely isolated from the Panthalassic Ocean, or perhaps intermittently weakly connected to it. The same elemental salinity proxies indicate low-brackish conditions in a Lower Jurassic unit previously assumed to be marine and fully marine conditions in Lower Cretaceous mudstone formations of the Neuquén Basin. This trend documents the gradual establishment of open communication with the Panthalassic Ocean, with fully marine conditions prevailing by the Middle to Late Jurassic. Standard redox proxies show that the AMF watermass was not markedly reducing, demonstrating that the impoverishment of the fossil biota was not due to unfavorable redox conditions. These findings demonstrate that inferences of marine conditions based on fossil content are potentially erroneous, and they emphasize the general need to make use of salinity proxies in analysis of deep-time depositional systems.

Late Paleozoic oxygenation of marine environments supported by dolomite U-Pb dating

Understanding causal relationships between evolution and ocean oxygenation hinges on reliable reconstructions of marine oxygen levels, typically from redox-sensitive geochemical proxies. Here, we develop a proxy, using dolomite U–Pb geochronology, to reconstruct seawater U/Pb ratios. Dolomite samples consistently give U–Pb dates and initial 207Pb/206Pb ratios lower than expected from their stratigraphic ages. These observations are explained by resetting of the U–Pb system long after deposition; the magnitude of deviations from expected initial 207Pb/206Pb are a function of the redox-sensitive U/Pb ratios during deposition. Reconstructed initial U/Pb ratios increased notably in the late-Paleozoic, reflecting an increase in oxygenation of marine environments at that time. This timeline is consistent with documented shifts in some other redox proxies and supports evolution-driven mechanisms for the oxygenation of late-Paleozoic marine environments, as well as suggestions that early animals thrived in oceans that on long time scales were oxygen-limited compared to today.

Large Igneous Province Control on Ocean Anoxia and Eutrophication in the North Sea at the Paleocene–Eocene Thermal Maximum

AbstractThe Paleocene–Eocene Thermal Maximum (PETM) was a global hyperthermal event ∼56 Ma characterized by massive input of carbon into the ocean–atmosphere system and global warming. A leading hypothesis for its trigger is the emplacement of the North Atlantic Igneous Province (NAIP), with extensive extrusion/intrusion of igneous material into nearby sedimentary basins, forcing local uplift and warming‐inducing carbon emissions. It remains unclear if oceanographic changes in the North Sea–Norwegian Sea–Arctic basins, such as anoxia and productivity, were causally linked to local NAIP uplift/activity, and at what time scales these perturbations occurred. To test mechanisms and time scales, we present geochemical proxies (XRF analysis, clay mineralogy, molybdenum isotopes, and pyrite framboid size distribution) in undisrupted marine sediment core E−8X located in the central North Sea. We find evidence for a rapid onset of anoxia/euxinia at the negative carbon isotope excursion from redox proxies, followed by a gradual drawdown of molybdenum/total organic carbon (Mo/TOC) during the PETM main phase indicative of tectonically‐restricted basin likely from NAIP uplift. A short‐lived increase in Mo, pyrite and TOC occurred during a precursor event associated with a sedimentary mercury pulse indicative of volcanic activity. We suggest thermal uplift and flood basalt volcanism tectonically restricted the North Sea and tipped it into an euxinic state via volcanic emission–oceanographic feedbacks inducing eutrophication. This fine temporal separation of tectonic versus climatic geochemical proxies, combined with pulsed NAIP volcanism, demonstrates that Large Igneous Province emplacements can, at least locally, result in ocean biogeochemical feedbacks operating on relatively short timescales.