Redox-sensitive Trace Metals Research Articles

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.

Terrestrial response to the Early Cretaceous Weissert Event: Insights from carbon isotope records of organic matter and leaf wax n-alkanes in an inland East Asian lake

The Weissert Event (WE), a significant Early Cretaceous environmental disruption, is recognized globally in marine carbonate records for its positive carbon isotope excursion (CIE), organic matter (OM) enrichment, and widespread anoxia. However, records of its terrestrial impact are sparse. This study examines carbon isotope compositions (δ13C) from the lacustrine facies of North China's Dabeigou Formation (Yushuxia section, Luanping Basin). The synchronous positive CIEs of total organic carbon (TOC) and C27–C31n-alkanes within Members 2 to 3 of the Dabeigou Formation corroborate the Weissert Event, marking its first terrestrial observation in North China. Ratios of the isoprenoids pristane and phytane (Pr/Ph), Corg/P ratios and enrichment factors (EFs) of redox-sensitive trace metals (Mo and U) indicate transient anoxic conditions within a mainly oxic-suboxic setting from the late Valanginian to early Hauterivian, which were unfavorable for OM preservation. This highlights that although a global positive CIE occurred during the Weissert Event, anoxia and/or high TOC deposition in inland lakes were not inherent features.

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.

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.

Sustained increases in atmospheric oxygen and marine productivity in the Neoproterozoic and Palaeozoic eras

A geologically rapid Neoproterozoic oxygenation event is commonly linked to the appearance of marine animal groups in the fossil record. However, there is still debate about what evidence from the sedimentary geochemical record—if any—provides strong support for a persistent shift in surface oxygen immediately preceding the rise of animals. We present statistical learning analyses of a large dataset of geochemical data and associated geological context from the Neoproterozoic and Palaeozoic sedimentary record and then use Earth system modelling to link trends in redox-sensitive trace metal and organic carbon concentrations to the oxygenation of Earth’s oceans and atmosphere. We do not find evidence for the wholesale oxygenation of Earth’s oceans in the late Neoproterozoic era. We do, however, reconstruct a moderate long-term increase in atmospheric oxygen and marine productivity. These changes to the Earth system would have increased dissolved oxygen and food supply in shallow-water habitats during the broad interval of geologic time in which the major animal groups first radiated. This approach provides some of the most direct evidence for potential physiological drivers of the Cambrian radiation, while highlighting the importance of later Palaeozoic oxygenation in the evolution of the modern Earth system.

C, N, Hg isotopes and elemental chemostratigraphy across the Ordovician–Silurian transition in the Argentine Precordillera: Implications for the link between volcanism and extinctions

Global geological processes that occurred during the Ordovician–Silurian transition (OST) were investigated exploring sections from the Argentine Precordillera (Cerro La Chilca, Baños de Talacasto and Villicum) which were deposited close to polar zones of Gondwana during the oldest Phanerozoic glaciation. C-N-Hg isotopes and redox-sensitive trace metal chemostratigraphy allowed to assess the relative importance of volcanism, glaciation, post-glacial sedimentation and extinction events during the OST. At Cerro La Chilca and Baños de Talacasto sections, Katian and early Hirnantian strata are missing. Hirnantian and Rhuddanian strata occur in the all three sections. At Cerro La Chilca, coeval positive δ13Corg shift, Hg spike and Δ199Hg ∼ 0 ‰ were recorded in the Sandbian Los Azules Formation, suggesting volcanic Hg loading. Coeval Hg/TOC spikes at the Baños de Talacasto and Villicum sections and Δ199Hg ∼ 0 ‰ in the late Hirnantian (M. persculptus Zone) recorded the second pulse of the Late Ordovician mass extinction (LOME 2), for which volcanism was postulated as the cause of warming and anoxia. Another Hg/TOC spike in the early Rhuddanian at Baños de Talacasto and Villicum is coeval with slightly positive Δ199Hg values, an enrichment related, perhaps, to an enhanced continental runoff that followed the Late Ordovician glacial cycle (LOGC-3). At the Cerro La Chilca, positive δ15N values in the Sandbian suggest less intense water-column denitrification while negative nitrogen isotope values in the LOME 2 period indicate denitrifying conditions. At the Baños de Talacasto and Villicum sections, sea-level fluctuations and nitrogen upwelling helped shaping the δ15N pathway within the LOME 2 and early Rhuddanian intervals, with negative δ15N values attesting that conditions became less reducing closer to the OST. The odd-MIF Hg isotope pattern within the LOME 2 time interval was probably induced by coeval volcanism, glaciation and sea-level fall, and in the early Rhuddanian by deglaciation and sea-level rise.

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.

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

Impact of Chondrites on trace metal distribution in the sapropel S7 (ODP Site 966): Implications for paleoenvironmental and paleoceanographic reconstructions

Organic-rich deposits are valuable paleo-archives, recording significant paleoceanographic changes linked to past climate variations and marine deoxygenation events. The deposition of organic-rich sediments stops when bottom-water reventilation/oxygenation occurs. This impedes organic matter preservation, enabling macro and micro burrowing-organisms to recover and bioturbate the seafloor. In this sense, highly bioturbated sediments require particular attention when sampling is done for geochemical analyses, as sediments can be considerably mixed. While avoiding trace fossils during sampling for geochemical analyses is easy for large traces (e.g. Planolites, Thallasinoides, and Zoophycos), it becomes challenging for smaller and complex traces (< 0.5 cm), as is the case with Chondrites. Chondrites-producers have an opportunistic behavior, being one of the first organisms to colonize the seafloor after an anoxic event. As a result, Chondrites are commonly and sometimes abundantly found in the upper layers of organic-rich sediments, including sapropels and black shales.This study focuses on sapropel S7, which was deposited between ∼198.5 and 191.9 ka at the top of Eratosthenes Seamount and exhibits abundant Chondrites. For this sapropel, we demonstrated that Chondrites-producers can bioturbate significant volumes of organic-rich sediments (over 35%), introducing oxic/dysoxic material downward into anoxic sediments enriched in redox-sensitive trace metals and organic matter. This process can dilute up to 18% the original concentration of redox-sensitive trace metals (e.g. Mo, U and V). This dilution is especially important to consider when calculating trace metals and organic matter burial flux from bulk sediment data. Therefore, Chondrites-producers can play a crucial role in altering the sediment texture and distribution of minerals and organic matter at sub-cm scale, and may thus impact paleoenvironmental and paleoceanographic reconstructions based on geochemical signals. Furthermore, the subsequent redistribution of organic matter and redox-sensitive trace metals (including oligoelements) within the sediment can affect carbon and nutrient cycling, microbial activity, organic matter degradation in deep-marine sediments, and the overall sedimentary biogeochemistry.

Mediterranean-like “fall dump” events in the Baltic Sea

In the Mediterranean Sea, organic carbon-rich sapropels have been deposited periodically over the last fifteen million years. Some sapropels are characterized by high contents of the mat-forming, planktonic diatom Pseudosolenia calcar-avis and the planktonic diatom Thalassionema nitzschioides as a result of their mass sinking in autumn (the so-called “fall dump”). The present study shows that fall dump events also occurred in the brackish Baltic Sea around 6300–5800 calibrated years before present (cal yr BP; present = AD 1950). In sediments from the northern Baltic Sea these events are evidenced by high contents of a lipid specific for P. calcar-avis (a C25:2 highly branched isoprenoid alkene) and corroborated by fossil remains of both P. calcar-avis and T. nitzschioides. A biomarker index based on long-chain alkyl diol lipids indicates that mat-forming Proboscia diatoms were also present. High contents of calanoid resting eggs further suggest that the copepod population was stressed being unable to feed on such large diatoms. The fall dump events occurred during a complete stratification of the water column and euxinic conditions, as reflected by the redox-sensitive trace metal uranium, allowing upward diffusion of nutrients and the growth of rhizosolenid mat-forming diatoms in a deep chlorophyll maximum. Synchronous remains of P. calcar-avis in the central Baltic Sea further suggest that these events occurred on a basin-wide scale.

Redox geochemical signatures in Mediterranean sapropels: Implications to constrain deoxygenation dynamics in deep-marine settings

Global warming and anthropogenic activity are boosting marine deoxygenation in many regions around the globe. Deoxygenation is a critical ocean stressor with profound implications for marine ecosystems and biogeochemical cycles. Understanding the dynamics and evolution of past deoxygenation events can enhance our knowledge of present-day and future impacts of climate change and anthropogenic pressure on marine environments. Many studies have reconstructed the evolution redox conditions of past deoxygenation events using geochemical proxies. In this regard, the present work focuses on understanding the paleoenvironmental significance of geochemical redox signals derived from the onset, evolution and termination of regional-scale deoxygenations in deep-marine settings, with a specific focus on sapropels in the Eastern Mediterranean (EM). Sapropels, rhythmic organic-rich sediments deposited in EM, offer a unique opportunity to investigate recent deoxygenation events linked to past climate changes. Sapropels serve as paleo-archives of past deoxygenation events and can provide insights into the potential impacts of ongoing climate change on marine ecosystems and biogeochemical cycles. By integrating previous sapropel geochemical studies with a detailed analysis of new geochemical data from five Quaternary sapropels (S1, S5, S6, S7 and S8) in three different EM deep-marine settings, this study enhances our understanding of the paleoenvironmental significance of geochemical redox signals produced by deoxygenation dynamics and postdepositional processes in different deep-marine settings. The study supports that certain trace elements, such as Mo, V, U, Co, and Ni, are identified as more reliable redox proxies compared to Cr, Cu, Pb, and Zn. Four recurrent geochemical intervals attributed to specific redox conditions and postdepositional processes have been identified. Moreover, internal calibration of redox proxies thresholds has been performed and demonstrates how local environmental conditions (e.g., productivity rate) and hydrogeographic features (e.g., water-depth, particulate-shuttling intensity, deep-water renewal and fluvial input) play crucial roles in controlling the authigenic uptake rates of redox-sensitive trace metals, and subsequently, redox thresholds values of geochemical redox proxies. The results also emphasize the importance of postdepositional processes to accurately interpret geochemical signals in paleoenvironmental studies. This research enhances our overall understanding of geochemical signals associated with regional-scale deoxygenation events in deep-marine settings, offering new insights into predicting biogeochemical changes in marine environments undergoing a transition towards anoxia. By comprehending the dynamics of past and present deoxygenation, we acquire valuable knowledge regarding the potential effects of climate variability in marine ecosystems.

Uranium isotopes in non-euxinic shale and carbonate reveal dynamic Katian marine redox conditions accompanying a decrease in biodiversity prior to the Late Ordovician Mass Extinction

The Late Ordovician mass extinction (LOME) is the first major mass extinction event in the Phanerozoic. However, global biodiversity started to decline during the Katian (prior to the LOME) and coeval global ocean redox conditions are not well understood. The deposition of Katian organic-rich sedimentary rocks, namely the calcareous Collingwood Member and overlying siliciclastic Rouge River Member, was triggered by the concurrent Taconic Orogeny in southern Ontario (Canada) near the interface between the epicratonic Appalachian and Michigan basins. In this study, we used geochemical elemental proxies and uranium isotope compositions (δ238U) to reconstruct local and global ocean redox states during deposition of both units at seven drill core localities throughout southern Ontario. Local redox conditions are revealed by several proxies (redox sensitive trace metals, Fe speciation, and Corg:P ratios). Collectively, these proxies suggest spatiotemporal redox variations for the Collingwood Member: O2-deficient conditions (non-euxinic) for the deep waters of the Appalachian and Michigan basins and mostly oxic-suboxic conditions for the shallow waters. In contrast, predominantly oxic-suboxic conditions are suggested for the Rouge River Member.Global ocean redox conditions are inferred from the δ238U of both units. The coeval seawater δ238U value during Collingwood Member deposition is estimated to be from ∼−0.87‰ to ∼−0.64‰, based on both carbonate δ238U (samples leached with 1 N HCl) and δ238Ubulk-non-detrital data (corrected from the bulk δ238U). Particularly, the δ238Ubulk-non-detrital data of the Collingwood Member from multiple cores (both shallow and deep waters) are positively correlated with elemental redox proxies, suggesting a local redox control on δ238U offsets between sediments and water columns. In contrast, the δ238Ubulk-non-detrital of the suboxic Rouge River Member (average = −0.32 ± 0.12‰) from several cores do not correlate with local redox proxies. The coeval seawater δ238U during Rouge River Member deposition is estimated between −0.62 ± 0.12‰ and −0.42 ± 0.12‰ assuming a δ238U offset of 0.1–0.3‰ as observed between modern suboxic sediments and seawater. For this range of seawater δ238U, a three-sink U isotope mass balance model suggests a contraction of global euxinic seafloor area from deposition of the Collingwood Member (0.5–31.6%; median = 1.0–14.2%) to the Rouge River Member (0.2–2.0%; median = 0.3–1.0%), which could have been associated with the concurrent Taconic Orogeny. Collectively, global marine redox proxy data (i.e., δ98Mo, δ238U) from this and previous studies imply dynamic Katian ocean redox conditions during the decrease of metazoan biodiversity prior to the LOME. As a similar extent of global ocean euxinia during the LOME2 also occurred episodically during the Katian but did not result in LOME2-like mass extinctions, it is suggested that other factors (e.g., climate), besides expanded ocean euxinia, could have contributed to the second phase of the LOME.

Redox-sensitive trace metal hyper-enrichment in Tremadocian Alum Shale (graptolite argillite) in northwestern Estonia, Baltic Palaeobasin

The Alum Shale Formation, a widespread metal-rich black shale in Baltoscandia, was deposited during the Cambrian–Ordovician transition. Given that it straddles a period of alternating extinction/recovery events following the Cambrian Explosion and prior to the Great Ordovician Biodiversification Event, the Alum Shale in Scandinavia has been extensively studied to assess the effect of oceanic redox variations on these biotic events. However, there is an on-going debate about the depositional environment and the prevailing redox state. An Early Ordovician (Tremadocian) equivalent of the Scandinavian Alum Shale, locally known as graptolite argillite, can be found in Estonia and NW Russia, in the easternmost extension of the ‘Alum Shale Sea’. In this contribution, we studied the redox-sensitive metal distribution and accumulation mechanisms in graptolite argillite successions in NW Estonia. Our aim was to provide better constraints on redox and depositional environments in the Baltic Palaeobasin. Our findings reveal that despite a consistent mineral and major elemental composition, V, Mo, Re and U contents vary systematically within the stratigraphy of the up to 7-m-thick black shale unit, with element contents reaching up to hyper-enrichment at the base (Mo > 200 mg/kg, U > 100 mg/kg and V > 1000 mg/kg) followed by a declining trend towards the upper part of the succession. This implies that temporal changes in redox conditions or sedimentation rates controlled trace element accumulation in the graptolite argillite. Although the redox-sensitive trace elements are hyper-enriched (particularly Mo), which has previously been interpreted to reflect euxinic depositional conditions, the V/Al vs. U/Al and V/Al vs. Mo/Al ratios indicate a non-euxinic anoxic depositional environment within a perennial oxygen minimum zone for the graptolite argillite. Further evidence of an unrestricted, relatively open marine depositional environment possibly influenced by upwelling is suggested by Cd/Mo and Co × Mn relationships. These results are supported by UEF and MoEF ratios that follow a seawater enrichment trend. The observed redox-sensitive element contents could be explained via diffusion-controlled uptake owing to the low sedimentation rates of the graptolite argillite (3–5 mm/kyr). These results highlight considerable redox variability within the Baltic Palaeobasin underscoring the need for a careful and critical reassessment of global redox interpretations based on Alum Shale data and emphasise the importance of using multiple independent redox and depositional environment proxies to determine palaeoredox conditions.

Geochemical Facets of the Inikan Formation as Indicators of Stratification and Hydrochemistry of the Cambrian Paleobasin

Abstract —Geochemical studies of Inikan Formation rocks from the coastal outcrops of the Yudoma River were carried out. All analyzed lithological varieties are characterized by significant enrichment in B, Ni, Mo, Ag, Sb, U (redox-sensitive trace metals and elements associated with biodeposition). The source of the elements was sea water that leached them from the eolian material. It was found that the deposits accumulated in anoxic environments with periods of both euxinic (probably, in the bottom water mass) and suboxic conditions. Such anoxic and euxinic conditions developed due to the stable stratification of the ocean that existed in the early–middle Cambrian in this part of the basin. In addition, the long-term accumulation of organic-rich sediment under conditions of anoxia, periodic euxinia, and stable stratification indicates the presence of a geomorphologically isolated depression in this part of the basin. CIA-Kcorr ranges from 68 to 95. The low values of the CIA may be related to the height of the relief in the sedimentary source area.

Significance of pH and iron-sulfur chemistry for molybdenum sequestration under sulfidic conditions

Molybdenum (Mo), a redox-sensitive trace metal, plays an important role in recording ancient oxygenation and deoxygenation events as a paleoredox proxy. The mobility and reactivity of Mo in aqueous conditions are closely tied to the chemistry of reduced sulfur and iron species. However, our current knowledge on the formation, structure, stability, and condensation pathways of FeMoS clusters in aqueous settings remains limited, which has driven the current study. In this study, we conducted systematic experiments investigating the interactions between dissolved Mo (initially introduced as molybdate, MoO42−, or tetrathiomolybdate, MoS42−), ferrous iron (Fe2+), and sulfide (ΣH2Saq) in variously defined abiotic sulfidic systems to determine the external conditions (i.e., pH, and reactant concentrations and ratios) necessary for the formation of solid-phase Fe-Mo sulfides. Solution samples of each system were monitored using ultraviolet-visible spectroscopy (UV–vis) to track the degree of thiolation of dissolved Mo species. Precipitates were analyzed using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) to determine their elemental compositions and valences, and structure (i.e., crystalline or amorphous), respectively. All FeMoS precipitates were amorphous and contained 76–90% Mo(IV) and 10–24% Mo(V) with a trend toward lower Mo(IV):Mo(V) ratios with increasing pH. The degree of Mo thiolation, which was strongly dependent on solution pH and Fe2+ concentrations, greatly affected the amount of Mo sequestered (i.e., an increased degree of Mo thiolation in solution led to an increased amount of Mo in the final FeMoS precipitate). These findings suggest that changes in pH and Fe2+ concentrations may be responsible for the sulfide-independent variations in Mo behavior observed in euxinic basins.

Sedimentary molybdenum and uranium cycling under seasonally contrasting redox conditions on the Namibian Shelf

Sedimentary molybdenum (Mo) and uranium (U) enrichments have been widely used as a proxy for redox conditions in oxygen-depleted marine paleo-environments. However, in a dynamic upwelling system the seasonal fluctuations from oxic to completely anoxic-sulfidic bottom waters and lateral sediment transport can modify the primary Mo and U signal of the sediment, which in turn may impact paleo-redox interpretations. In this study we present pore water and solid phase data collected at two cross shelf transects during the ‘more oxygenated’ austral winter and ‘anoxic’ austral summer to study the influence of spatially and seasonally contrasting redox conditions on the formation of authigenic Mo and U enrichments in organic carbon (TOC) rich mud belt sediments on the Namibian shelf. A mass balance was established for each element based on diffusive fluxes and element mass accumulation rates to evaluate the respective mechanisms of trace metal delivery, accumulation and recycling.Mo is delivered to the sediment in its dissolved form via diffusion across the sediment–water interface, especially during austral summer when bottom waters are anoxic and surface sediments are highly sulfidic. In the center of the inner shelf mud belt, the benthic Mo fluxes of up to 37 nmol cm−2 yr−1 into sulfidic surface sediments are the highest ever reported for reducing sulfidic systems and agree with the rate of Mo accumulation in the solid phase. Concurrently, high sedimentation rates and low terrigenous input limit solid phase Mo accumulation on the Namibian shelf. In ancient marine sediments, this mode of Mo cycling can be identified by low Mo/TOC ratios of ∼2 similar to those found in sediments deposited below the perennial oxygen minimum zone on the Peruvian shelf and to those found in deposits of the Cretaceous Oceanic Anoxic Event 2. Diffusive U fluxes into the sediment are generally too low to account for the sedimentary enrichment leading to the conclusion that U is delivered mainly in particulate form. In areas with anoxic bottom water, shallow dissolved U maxima directly below the sediment water interface and rather low sedimentary U content indicate that particulate U is recycled and largely released back into the bottom water. At sites where bottom water oxygen concentrations vary from anoxic to completely oxic on seasonal timescales, the depth at which Mo and U are removed from pore waters moves vertically within the sediment column thus defining a layer between the sediment surface and ∼20 cm depth, in which Mo and U accumulate in the solid phase. Our results emphasize the importance of short-term redox fluctuations in the bottom waters and underlying sediments, as well as lateral sediment transport for the authigenic enrichment of redox-sensitive trace metals in reducing shelf sediments. The relative enrichment patterns identified might be useful for the reconstruction of open marine anoxia in the geological past.

Reductive sorption of vanadium by green rust in seawater

Vanadium (V) is a redox-sensitive trace metal that typically exists in one of three oxidation states (+3, +4 and +5) in natural waters; a feature increasingly used in paleoredox studies of ancient marine sediments. However, our knowledge of V geochemistry in low-oxygen marine environments is still limited, especially regarding interactions of V with reduced iron minerals such as green rust. Carbonate green rusts (GRCO3) are mixed FeII/FeIII-phases found in some modern ferruginous settings, such as Lake Matano (Indonesia), and were likely abundant in ancient ferruginous marine systems where they may have played an essential role in authigenic V enrichments in sediments. Here, we present an abiotic pathway of V removal from seawater via reduction and adsorption onto amorphous GRCO3. Suspensions of the freshly precipitated GRCO3 (1 g L−1) were added to vanadate (1 mg VV L−1 initial concentration) in anoxic synthetic seawater solutions. Vanadium removal by GRCO3 was rapid and efficient, with 92 – 99% of V removed in under 20 seconds. Synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy showed that VV adsorbed by GRCO3 was partially reduced to a mixture of VV and VIV, with the average oxidation state of adsorbed V increasing (+4.3 to +4.7) with increasing solution pH (7.5 to 8.5). Upon subsequent exposure to aerated seawater, V-bearing GRCO3 oxidized to lepidocrocite [γ–FeO(OH)] within 24 h, with concomitant reduction of all solid-phase VV to VIV. During oxidation, V was not released back into solution; rather, extended X-ray absorption fine structure (EXAFS) modeling revealed that VIV was structurally incorporated into lepidocrocite as octahedral vanadyl (VO2+). Our work further constrains the aqueous geochemistry of V, which has implications for understanding V cycling and removal mechanisms in both modern and ancient marine systems.

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

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

Evidence of postdepositional remobilization of redox-sensitive metals across sapropel boundaries: New insights from LA-ICP-MS and EDX mapping analyses

Deoxygenation in marine systems is globally increasing due to anthropogenic pressures and climate change impacts, leading to significant ecological and environmental consequences. Understanding past deoxygenation events is crucial for assessing the response of ocean stressors to climate variability and for predicting and managing the impacts of current and future changes. Deep-marine basins with organic-rich deposits serve as valuable palaeo-archives, preserving evidence of profound palaeoceanographic changes involving deoxygenation events. Such events have been broadly studied and reconstructed using redox-sensitive trace metals (RSTMs) as proxies for oxygenation conditions. Assessing these proxies is therefore crucial for further understanding deoxygenation events. To do so, this study focuses on RSTMs distribution across the most recent sapropel, S1, which is a well-preserved organic-rich sediment layer that represents the most recent large-scale deoxygenation event in the Eastern Mediterranean. High-resolution geochemical microanalyses, including Laser Ablation ICP-MS and SEM-EDX, were conducted to investigate sub-mm scale geochemical signals and post-depositional remobilization of RSTMs within S1 and surrounding sediments. Statistical analyses have also helped to identify the geochemical fractions within S1, including detritic, carbonate, and authigenic, enriched in RSTMs and organic matter. The study revealed distinct specific geochemical intervals, such as the marker bed, oxidized interval, unoxidized interval, and synsapropel interval. These intervals provided insights into the diagenetic processes and post-depositional reactions occurring within and across sapropel S1 boundaries. The enrichment of RSTMs within pyrite aggregates in the synsapropel interval was primarily attributed to post-depositional processes rather than the initial syndepositional conditions of S1. Large pyrite surfaces below S1 and the precipitation of Mn-oxyhydroxides over S1 played a significant role in the fixation and absorption of dissolved RSTMs derived from postdepositional oxidation. Furthermore, the sub-mm scale analysis revealed spatial heterogeneities in mineralogical composition and elemental distribution, providing valuable information on the complexity of post-depositional reactions and processes. The findings highlight the importance of microscale geochemical analyses for understanding the dynamics of RSTM fixation and enrichment processes in marine sediments. By differentiating between syndepositional and post-depositional geochemical signals, this study contributes to the interpretation of palaeoenvironmental conditions and enhances our understanding of the spatial complexity of deoxygenation processes. Such insights are crucial for accurately assessing the impacts of deoxygenation on biogeochemical cycling and ecosystem functioning in marine environments.

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.