Marine Redox Research Articles

Episodic marine anoxia, primary production, and weathering controls on carbon‑sulfur cycling in the Early Cambrian Yangtze Block

The Early Cambrian Period has received significant attention for decades owing to its geological records of unprecedented skeletal fossils, suggesting a major bio-event known as “the Cambrian Explosion.” Notwithstanding, related primary production and marine redox variation with respect to evolution of biota remain elusive. These factors are intimately linked to marine carbon‑sulfur cycling, promoting an extensive use of related isotopes (e.g., δ13C and δ34S) as paleoenvironmental proxies. Nevertheless, bulk-rock δ34S and δ13C may reflect multigenerational 34S/32S and 13C/12C isotopic fractionations. Herein, we analyzed drill cores from continuous depth profiles in the recently discovered Qingchuan-Ziyang-Yibin intrashelf basin for δ34S of sedimentary sulfate (δ34Ssulf), δ13C of carbonates (δ13Ccarb), and bulk-rock elements. We find that highly positive (+23.60 ‰ to +29.90 ‰) and negative (as low as −12 ‰) δ34Ssulf V-CDT are associated with samples exhibiting low and high detrital inputs, respectively. In contrast, total sulfur and δ13Ccarb V-PDB show no relationship with terrigenous materials. Enrichment factors of molybdenum (MoEF) and uranium (UEF), biogenic contents of nickel (Nibio) and copper (Cubio), as well as total organic carbon (TOC), are all widely distributed among the samples. Integration of these findings with existing data from shallow to deep marine environments in the Yangtze Block, supports the following conclusions: (1) Five episodes of widespread marine anoxia coincide with extensive primary production. (2) Inputs of terrigenous materials promote 32S-enriched sulfate, which adds to subsequent biochemical fractionations, resulting in generally complex pathways for δ34S of pyrite. (3) Terrigenous nutrients were critical to extensive marine primary production.

Nitrogen cycling and marine redox evolution during the Ediacaran–Cambrian transition

Nitrogen cycling and marine redox evolution during the Ediacaran–Cambrian transition

Widespread upper-ocean deoxygenation in the Alpine-Mediterranean Tethys during the Toarcian Oceanic Anoxic Event

The early Toarcian (~183 Ma) was characterized by pronounced climate warming associated with massive release of 13C-depleted carbon to the exogenic system, as evidenced by globally recognized negative carbon-isotope excursions (N-CIE) in biospheric carbon reservoirs. Global warming during this interval triggered a variety of environmental perturbations, of which large-scale marine deoxygenation (as indicated by the presence of widespread organic carbon-rich deposits) is arguably diagnostic and led to the naming of the interval in question as the Toarcian Oceanic Anoxic Event (T-OAE). Nevertheless, the spatial variability of water-column redox during the T-OAE is unclear because most sedimentological and geochemical methods used to infer marine redox are likely reflective of bottom-water and/or pore-water conditions. Here we report new I/(Ca + Mg) and Cerium (Ce)-anomaly data from two carbonate successions from northern Italy that encompass the T-OAE interval. Both successions were deposited in the Alpine-Mediterranean Tethys; one in a shallow-water platform setting and the other within a pelagic environment. Both successions record an abrupt drop in I/(Ca + Mg) values, coupled with positive excursions in Ce-anomaly records at the onset of the T-OAE N-CIE. The synchronized changes in marine iodate depletion and Ce enrichment suggest widespread and significant upper-ocean deoxygenation in the Alpine-Mediterranean Tethys. This redox pattern is attributed to an expanded oxygen minimum zone (OMZ) formed as a result of sluggish oceanic circulation under climate warming, augmented by enhanced dissolved oxygen consumption due to increased nutrient availability and the consequent eutrophication in both proximal and distal settings. Because reduced seawater dissolved oxygen [O2] would increase the ecological stress and constrict any potentially hospitable habitats, the broad synchroneity between biotic turnovers and upper-ocean deoxygenation in the Alpine-Mediterranean Tethys is compatible with a potential causal link.

Calcium isotopes support spatial redox gradients on the Tethys European margin across the Triassic-Jurassic boundary

The end-Triassic mass extinction was among the most severe biotic crises of the Phanerozoic. It has been linked with the global expansion of marine anoxia, and the prolongation of these conditions within epeiric seas has been proposed as a cause for the suppression of biodiversity during the Hettangian. Testing this interpretation is complicated by spatially heterogeneous patterns of local marine redox conditions within the western Tethys European Epicontinental Shelf. In this study, we assess the redox state within this region by focusing on two carbonate successions in Italy, a peritidal platform at Mount Sparagio, Sicily, and an offshore ramp deposit at Val Adrara in the Southern Alps. Based on previously published I/Ca ratios, these locations record distinct local background redox conditions, with Val Adrara showing a notably lower pre-extinction oxygen saturation state than Mount Sparagio. Here, we measure δ13C and δ18O at Mount Sparagio and δ44Ca and trace element ratios at both sites to identify the roles of mineralogical and diagenetic effects on the preservation of primary redox signals. A numerical framework of multiple elemental (Sr, Mg, Mn, I) and isotopic (δ13C, δ18O, δ44Ca, δ238U, and δ34SCAS) ratios was constructed to recognize modes of carbonate diagenesis and source-mixing in the data. While diagenesis is impossible to completely rule out, our state-of-the-art approach provides robust evidence against common forms of diagenetic alteration as the main drivers of the overall paleoredox proxy trends.Where the redox signals are largely preserved, we interpret differences in pre-extinction I/Ca between the two sites to reflect distinct local oxygenation states. Drawing from published Community Earth System Model simulations, we propose that ocean circulation and hydrological regime could have been important drivers of spatial heterogeneity in paleo-redox conditions across the European Epicontinental Shelf.

Controls of paleogeomorphology on organic matter accumulation as recorded in Ordovician–Silurian marine black shales in the western South China Block

The Ordovician–Silurian transition represents a critical period marked by the formation of marine shale gas horizons within the South China Block. However, the mechanism for organic matter enrichment of Paleozoic marine shales in the western South China Block remain contentious, primarily due to insufficient understanding of paleogeomorphological evolution. In this paper, we describe the sedimentology of the Ordovician-Silurian succession composed of the Wufeng-Longmaxi Formation in the western South China Block and report new paleontological, and geochemical data for this succession to explore the relationship between basin paleogeomorphology and water mass environment. Nine graptolite zones are identified, spanning from the WF1 (Linxiang Formation) through WF2–WF4 (Wufeng Formation) to LM1–LM5 (Longmaxi Formation) in this well. Based on sedimentological and geochemical analyse results, three distinct stages of redox and paleoproductivity conditions in the water mass have been identified: (1) suboxic environments and low paleoproductivity in WF2–WF4; (2) euxinic and stagnant water conditions in LM1–LM3 accompanying with high paleoproductivity; and (3) anoxic water and low paleoproductivity in LM4–LM5. By integrating marine redox fluctuation, paleoproductivity conditions and regional hiatus (LM1-LM3) observed across multiple successions, we interpret thatthe western margin of the South China Block have been significantly affected by a collision between the South China Block and Yanbian terrane. The results of this study indicate that the accumulation of organic matter in the western margin of the South China Block was predominantly controlled by paleogeomorphology being caused by this collision event.

Redox-sensitive metals and δ238U in red and grey shales: Exploring a new archive for palaeo-redox studies

Reconstructions of past oceanic redox conditions, based on the measurement of metal distributions and their stable-isotope ratios in marine sediments, have now become more commonplace, providing new constraints on past environmental change. Almost all of these records, however, are based on organic-rich black-shale and carbonate sedimentary archives, which have formed primarily in low-latitude regions. This limitation leads to incomplete geographic coverage that complicates the global-scale interpretation of the results. In this study, the potential of oceanic ‘red beds’ and grey shales as new archives of past environmental conditions are explored to complement the datasets derived from other lithologies and extend reconstruction efforts to mid- to high-latitude regions. Our records originate from open-marine red and grey shales from two sedimentary sections spanning the Late Cretaceous Oceanic Anoxic Event 2 (OAE 2) in New Zealand, formerly deposited at high southern latitudes in the palaeo-Pacific Ocean at c. 94 Ma and where contemporaneous black-shale and/or carbonate successions do not exist. Access to the seawater-derived, authigenic fraction of the bulk sediment is essential for reconstructing past marine redox state at these mid- to high-latitude locations. Therefore, a series of leaching experiments using reagents of progressively increasing concentration were conducted to determine the best method for isolating the authigenic Fe- and Mn-(oxyhydr)oxide fraction from the red and grey shale lithologies. Chemostratigraphic records for the concentrations of a suite of redox-sensitive metals (Fe, Mn, Co, Ni, Mo, Cr, V and U), as well as the U-isotope palaeo-redox tracer (238U/235U; reformulated as δ238U), were obtained. These records imply that leaching with 6 M HCl at room temperature is the best of the tested methods for the selective extraction of the Fe- and Mn-(oxyhydr)oxide phase, whilst minimising the contribution from older inherited detrital material that potentially could confound the interpretation of the chemostratigraphic records. This method offers potential for reliably constraining the authigenic distributions of redox-sensitive elements in red and grey shales, provided Fe- and Mn-(oxyhydr)oxides are predominantly of authigenic origin and constitute at least 5 % of the mineralogy. By contrast, for the investigation of the U-isotope system, a larger Fe- and Mn-(oxyhydr)oxide proportion in the sediment for an ocean–atmosphere perturbation event recording more severe changes in ocean redox conditions and bigger U-isotope shifts than observed for OAE 2 are both necessary to obtain reliable results.

Synchrotron-based P K-edge XANES spectroscopy reveals the transition of phosphorus cycling in the early Cambrian ocean

Phosphorus, as a long-term limiting nutrient, is essential for the rapid animal diversification in the early Cambrian ocean. However, the widespread occurrence of phosphorites during this period indicates anomalous phosphorus cycling mechanisms that remain inadequately explored. To investigate the interplay between marine redox conditions and phosphorus cycling, we used geochemical proxies and synchrotron-based P K-edge X-ray Absorption Near Edge Structure (XANES) spectroscopy to analyze the Cambrian Terreneuvian Yurtus Formation (Fortunian to Stage 2) from the Tarim Block. Redox-sensitive elements, iron speciation and nitrogen isotopes reveal an expansion of the surface oxygenated waters, despite persistent ferruginous bottom waters. Moreover, a shift of phosphorus speciation was observed in bedded cherts via P K-edge XANES, suggesting a transition of phosphorus cycling. Specifically, the samples exhibit low total phosphorus contents with a high rate of carbonate-fluorapatite authigenesis in the lower Yurtus Formation. This is followed by an increase in the proportion of terrestrial-derived fluorapatite and iron-bound phosphorus, corresponding to the expansion of surface oxygenated waters. Our findings reveal a significant shift in dominant phosphorus speciation in the early Cambrian marine sediments, which is intricately linked to the coupled phosphorus‑iron‑carbon‑oxygen cycles in the Cambrian ocean.

Isotopically light Mo in sediments of methane seepage controlled by the benthic Fe–Mn redox shuttle process

Methane seepage has been extensively observed in various continental margin settings. It has profound effects on the marine redox environment and the molybdenum (Mo) cycles in marine sediments. Therefore, there has been much recent attention on the redox-sensitive behavior of Mo in methane seepage environments. However, the characteristics of the Mo isotope composition in the cold-seep system remain poorly understood. In this study, we performed geochemical analyses, including Mo content and isotope composition, on sediment samples (core QDN-MS6) from the “Haima” cold-seep deposit area in the South China Sea. The analysis reveals a significant concentration of authigenic pyrite in the mid-section of QDN-MS6 core (373–403 cm). Moreover, the δ34S value in this interval is notably elevated with high total sulfur/total organic carbon ratio. Additionally, the sediments in the mid-section exhibits substantial enrichment in Mo (enrichment factors of Mo ranging from 5.29 to 39.32). This implies that the sediments in the mid-section are influenced by sulfate-driven anaerobic oxidation of methane. Most notably, the sediments in the mid-section displayed distinct low δ98Mo values (with an average of −0.7‰). After careful consideration, we ruled out the influence of organic matter, an oxic environment, a weakly sulfidic environment, and incomplete removal of thiopolybdate as contributing factors. Based on δ56Fe-Fe/Al ratios, (Mo–U) enrichment factors, and As enrichment factors, we propose that the “benthic Fe-Mn redox shuttle process” is the primary cause of the observed light δ98Mo signatures in sediments. This newly identified mechanism sheds light on Mo isotope cycling in methane seepage environments and enhances our understanding of the Mo isotope cycling process.

Acceleration of phosphorus weathering under warm climates.

The release of phosphorous (P) via chemical weathering is a vital process that regulates the global cycling of numerous key elements and shapes the size of the Earth's biosphere. It has long been postulated that global climate should theoretically play a prominent role in governing P weathering rates. Yet, there is currently a lack of direct evidence for this relationship based on empirical data at the global scale. Here, using a compilation of temperature and P content data of global surface soils (0 to 30 cm), we demonstrate that P release does enhance at high mean annual surface temperatures. We propose that this amplification of nutrient supply with warming is a critical component of Earth's natural thermostat, and that this relationship likely caused expanded oceanic anoxia during past climate warming events. The potential acceleration of phosphorus loss from soils due to anthropogenic climate warming may pose threats to agricultural production, terrestrial and marine ecosystems, and alter marine redox landscapes.

Marine redox and nutrient dynamics linked to the Cambrian radiation of animals

Abstract The early Cambrian witnessed an increase in metazoan ecosystem complexity, likely linked to enhanced oxygen and nutrient availability. However, while improved stratigraphic and geochemical records suggest that the Cambrian explosion occurred under highly dynamic redox conditions, mechanistic links to nutrient availability and early Cambrian evolutionary innovations are poorly constrained. Here, we report paleoredox and nutrient data for two drill cores documenting late Cambrian Stage 2 to Stage 3 (ca. 522–514 Ma) strata from the Yangtze block, South China. The development of water-column euxinia during Cambrian Stage 2 led to extensive recycling of P, fueling elevated primary production and hence an increase in atmospheric and shallow-marine oxygen concentrations. The resulting expansion of oxygenated shelf area promoted sedimentary P retention and, in combination with a diminished supply of P from upwelling, drove a transition to oligotrophic shallow-marine conditions during Cambrian Stage 3. Reduced primary production and limited water-column oxygen consumption allowed for the stabilization of oxygenated continental shelf habitats that supported a burgeoning biotic complexity.

Enrichment pattern of tungsten in sediments under methane seepage environments: Applicability as a proxy for tracing and reconstructing (paleo-)methane seepage

The release of hydrogen sulfide by sulfate-driven anaerobic oxidation of methane (SD-AOM) during methane seepage activities has a strong impact on the evolution of marine redox conditions and the cycles of redox-sensitive elements (e.g. Mo and U). Consequently, the sedimentary enrichment or depletion of these elements is often used to trace and reconstruct (paleo-)methane seepage activity. In recent years, tungsten (W) has shown promise as an indicator of marine redox changes, but its applicability to trace methane seepage activity is unknown. This study identified significant differences in the W content of sediments in methane seepage environments compared to suboxic environments not influenced by methane seepage and oxic environments in the South China Sea. The sediments subjected to methane seepage were characterized by low W contents, similar to those of euxinic Black Sea sapropels. It is believed that the sulfidic environment resulting from SD-AOM is the primary cause of W depletion in sediments subjected to methane seepage. By examining W's interaction with its twin element, Mo, we present WMo enrichment patterns in various environments. In methane seepage environment (sulfidic environments), sediments had high MoEF (> 10) and low WEF (< 2) with a high Mo/W molar ratio (> 10); in suboxic environments not influenced by methane seepage, sediments exhibited a WMo enrichment pattern similar to the UCC (the MoEF and WEF values are predominantly below 1 and 2, respectively, with a low Mo/W molar ratio, <1.5); in oxic environments (enrichment of FeMn (oxy)hydroxides), sediments exhibited high MoEF (2 < MoEF < 10) and high WEF (> 2), with a medium Mo/W molar ratio (1.5–10). This further indicates that the Mo/W molar ratio has great potential in tracing and reconstructing (paleo-)methane seepage activities.

Shallow-water redox changes and nitrogen cycles in the early Cambrian Nanhua Basin, South China

Widespread oceanic anoxia has been frequently invoked for metazoan extinctions during the Cambrian. However, this hypothesis remains to be debated. In this study, we measured total organic carbon (TOC), total bulk nitrogen (TNbulk), iron speciation, major and trace elements, and isotopic compositions of sedimentary bulk nitrogen (δ15Nbulk) for the Shiyantou Formation in the Meishucun section. Our results suggest ferruginous conditions and high productivity in the lower member (LM: 0–16.0 m), dominantly suboxic conditions and low productivity in the middle member (MM: 16.0–23.7 m), and oxic conditions and low productivity in the upper member (UM: 23.7–28.0 m). Low δ15Nbulk values (average 1.0 ‰) in the LM suggest quantitative assimilation of NH4+ and strong nitrogen fixation as a consequence of high primary productivity and widespread water-column reducing conditions in the Nanhua Basin. δ15Nbulk values close to 0 ‰ in the MM suggest intense nitrogen fixation owing to quantitative denitrification and anammox in an oligotrophic environment. Low δ15Nbulk values (average 1.2 ‰) in the UM are indicative of marine nitrogen limitations in an oligotrophic environment. These findings suggest a similar range of low δ15Nbulk values might result from different environments. In comparison with marine redox conditions and δ15Nbulk data from the other coeval sections in the Nanhua Basin, we propose that widespread anoxic conditions might cause the extinction of small shelly faunas. More importantly, the oligotrophic environment and anoxic conditions might delay the recovery of small shelly faunas in the shallow and deep waters of the Nanhua Basin, respectively.

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.

Zinc isotopic evidence for enhanced continental weathering and organic carbon burial in the Early Silurian

The Late Ordovician and Early Silurian periods experienced glaciation and mass extinctions. However, debates exist regarding the factors that initiated the glaciation and the subsequent delay in biotic recovery. To uncover the relationships between paleoclimate, marine redox states, and biotic recovery in the Early Silurian, temporal variations in Zinc (Zn) isotopic compositions along with other multi-geochemical proxies were analyzed for a carbonate-dominated section in South China. A stratigraphic δ66Zn trend was found in studied section, indicating a widespread disturbance to the marine Zn cycle. A significant negative shift in δ66Zn by up to ∼0.7 ‰ was observed immediately following the Hirnantian Glaciation and HICE, which can be attributed to a combination of reduced burial efficiency of organic carbon, fast weathering of large igneous provinces and increased riverine Zn input. This was followed by a ∼ 0.4 ‰ rise in δ66Zn values, alongside a sharp decrease in δ13C values, indicating an increase in sulfide precipitation (e.g., ZnS, FeS) due to expansions of euxinia. Subsequently, a notable rise in δ66Zn values by up to ∼1.1 ‰ is interpreted as an increase in organic carbon burial, given the concurrent variation of δ66Zn and δ13C during this period. The findings suggest that the increase in organic carbon burial, a reduction in reverse weathering, or a combination of them contributed to the glaciation in Silurian. Furthermore, the weathering-induced high primary productivity led to anoxic water conditions in the latest Hirnantian and Rhuddanian. This prolonged marine anoxia in seawater thus caused the deposition of organic-rich sediments and hindered biotic recovery in the Rhuddanian.

Phosphate-associated sulfate in Lingula shells represents a potential archive for seawater sulfate composition

The marine sulfur cycle is highly sensitive to redox environments at the Earth's surface. Fluctuations in atmospheric pO2 level or marine redox environments are commonly associated with changes in seawater sulfate concentration, sulfate sulfur (S) and oxygen (O) isotopes. Thus, the marine S cycle through the Earth's ancient past provides a first-order constraint on the redox evolution of the Earth's surface. Reconstructions of the marine S cycle have been approached through analyses of various sulfate-bearing geological materials, such as sedimentary barite, evaporitic sulfate (e.g., gypsum), carbonate associated sulfate (CAS), and phosphate-associated sulfate (PAS) in phosphatic ores. These geological materials have their own pros and cons. In this study, we focus on PAS in Lingula brachiopods, which possess phosphatic shells and have a long evolutionary history since Cambrian times. Biogenic phosphate typically has a higher sulfate concentration than carbonate and phosphate ores, and is less vulnerable to diagenetic alteration. Here, we analyzed modern Lingula shells from the South China Sea and fossil Lingula shells collected from the Late Devonian Xiejingsi Formation of South China. Living and fossil Lingula shells have similar P/S ratios (PO43−/SO42−) of ∼76, and S and O isotopes of PAS (δ34SPAS and δ18OPAS) in each group show limited variations. For living Lingula shells, the mean values of δ34SPAS and δ18OPAS are +15.0 ± 1.5‰ and + 9.8 ± 0.4‰, respectively, which are ∼6‰ lower and comparable to those of modern seawater sulfate compositions (δ34SSW and δ18OSW-SO4), probably due to vital effects. For fossil Lingula shells, δ18OPAS (14.1 ± 0.9‰) is identical to coeval evaporite. The range of δ34SPAS is encompassed by the values of both coeval evaporite and CAS, but the mean value of δ34SPAS (29.5 ± 0.9‰) is higher. Thus, fossil Lingula shells show a good potential for reconstructing δ34SSW and δ18OSW-SO4 values.

Marine redox dynamics and biotic response to the mid-Silurian Ireviken Extinction Event in a mid-shelf setting

The early Silurian Llandovery–Wenlock boundary interval is marked by significant marine perturbations and biotic turnover, culminating in the Ireviken Extinction Event and the Early Sheinwoodian Carbon Isotope Excursion. Here, we apply multiple independent redox proxies to the early Wenlock Buttington section, which was deposited in a mid-shelf location in the Welsh Basin, UK. To account for the regional geochemical variability in marine sediments due to factors such as sediment provenance, we first define oxic baseline values for the Welsh Basin, utilizing deeper water, well-oxygenated intervals of late Llandovery age. Our approach documents unstable, oscillating redox conditions on the mid-shelf at Buttington. We suggest that these dynamic redox fluctuations are likely to relate to changes in the position of the chemocline or a migrating oxygen minimum zone. Benthic biota, such as trilobites, brachiopods, bivalves and gastropods, appear to have been relatively unaffected by fluctuating oxic-ferruginous conditions, but were more severely impacted by the development of euxinia, highlighting the inhibiting role of toxic sulfides. By contrast, the redox perturbations appear to have placed extreme stress on graptolites, causing many extinction losses regardless of the specific development of euxinia. Supplementary material: The geochemical data for the Buttington section is available at https://doi.org/10.6084/m9.figshare.c.7165009 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

Local depositional and diagenetic conditions control the positive δ34S excursion during the Ordovician-Silurian transition: Evidence from the Wufeng-Longmaxi formations in Sichuan Basin

The Ordovician-Silurian (OS) transition was characterized by significant changes in global climate, marine redox conditions, and biological evolution, which include global seawater euxinia, the onset of the Hirnantian glaciation, and large-scale extinctions. During this time, the marine sulfur cycle was disrupted, and the pyrite sulfur isotope (δ34Spy) showed a large positive excursion. This excursion is closely tied to the Hirnantian glaciation, with δ34Spy increasing at the start of and decreasing at the end of the glaciation. Although it is thought that variations in marine sulfate concentration and primary productivity are responsible for the positive excursion in δ34Spy, contemporary marine sediment δ34Spy data suggest that sedimentary processes can also lead to significant fluctuations in δ34Spy. To assess the impact of local changes in sedimentary conditions on this positive δ34Spy excursion event, we conducted detailed depositional and geochemical analyses of sedimentary pyrite found in black shales from the Wufeng-Longmaxi formations in the Weiyuan area of the Sichuan Basin, China. These sedimentary pyrites include three types: framboidal, euhedral, and laminated pyrite. Bulk sample sulfur isotope analyses revealed that δ34Spy values vary from −16.2‰ to 15.8‰ (mean = −3.8‰, n = 22). In situ analyses of δ34Spy show that different pyrite crystals exhibit a range of intragranular δ34Spy values that are likely indicators of diagenesis. Variations in bulk sample δ34Spy are strongly and negatively correlated with the proportion of framboidal pyrite, i.e., lower levels of framboidal pyrite content resulted in a higher bulk sample δ34Spy value, suggesting diagenetic alteration controls on δ34Spy. In addition, the δ34Spy excursion in the Wufeng-Longmaxi formations also appears to be compatible with lithological changes related to sedimentation rate. The δ34Spy values from the Guanyinqiao Bed, which consists of calcareous shales, are higher than those from black shales with a relatively low sedimentation rate. Our results suggest that the positive δ34Spy excursion during the OS transition during the Hirnantian glaciation is controlled not only by diagenetic alterations but also by local sedimentation rate.

Formation conditions of Jixian System cherts in the Qishan area, Ordos Basin: Implications for marine redox conditions and paleoecology

Abundant chert bands and nodules are discovered throughout the Mesoproterozoic Jixian System in the Ordos Basin. These cherts faithfully record the Jixian period oceanic conditions and paleoecology. However, the diagenetic mechanism of the cherts remains unclear and controversial. To understand the origin of these cherts, we performed a multitracer study by combining field reconnaissance, petrological analyses, Si isotope analysis, and major and trace element analysis of chert samples from the Qishan section. The results show that Jixian cherts had a high Al/(Al + Fe + Mn) value (~0.48), showed a flat distribution of rare earth elements in seawater, and most of the Fe/Ti values are <20. A weak negative Ce anomaly (~0.97) indicates the contribution of REY to weakly oxygenated seawater. The high isotopic composition of silicon (δ30Si = 0.74 ‰-1.35 ‰) and the average Siex value of 37.52 indicate that there is a source of biological silica, and the relationship between Eu/Eu* and Y/Ho and δ30Si shows that the hydrothermal and volcanic influences were less and correlated with seawater. The chert bands were closely related to biological activities. The chert nodules were influenced by hydrothermal activity. Secondary cherts were related to diagenesis, but the nature of siliceous fluids remains unchanged, still characterized by biogenic activity origins. The sea oxygen concentration in the Jixian period had increased, with periodic variations in the intensity of biological activities affecting the pH of the water body, or biological photosynthesis binding SiO2 colloid in water, affecting chert sediments, leading to frequent interlayering between dolomite and chert bands. Episodic hydrothermal fluids and late-stage diagenetic processes jointly influenced the formation of cherts. This study bears significant significance in enhancing our understanding of the sedimentary environment and the origin of cherts during the Jixian period in the Ordos Basin.

Synglacial carbonate records of snowball Earth ocean composition—Evidence from the Nantuo Formation, South China

Abstract The Cryogenian (ca. 717–635 Ma) snowball Earth glaciations ended with the precipitation of “cap” carbonate successions with negative carbon isotope (δ13Ccarb) values, which have been explained by the addition of various 13C-depleted carbon sources in the deglacial process. These arguments assumed that marine dissolved inorganic carbon (DIC) was enriched in 13C in the synglacial ocean. However, this assumption has not yet been tested, because the synglacial ocean chemistry is unknown. In this study, we carried out detailed analyses of the petrology, carbonate carbon (δ13Ccarb) and oxygen (δ18Ocarb) isotopes, organic carbon (δ13Corg) isotopes, major and minor elemental compositions (Ca, Mg, Mn, Fe, Sr), and iron speciation (total Fe, highly reactive Fe, pyrite Fe) of the carbonate layers (also called synglacial carbonate layers) from the Nantuo Formation (ca. 650–635 Ma) on the Yangtze block, South China. Petrographic observations indicated that the synglacial carbonate comprises dolomicrite, mud-crystal powder dolomite, lime dolomite, and dolomitic limestone, supporting an authigenic carbonate origin, and thus, it potentially recorded the ocean chemistry during the Marinoan ice age. The synglacial carbonate is characterized by extreme Mn enrichment, low Fe/Mn ratios, and low δ13Ccarb (−7‰) values. High Mn contents and low Fe/Mn ratios imply marine redox conditions favoring Mn2+ accumulation and Fe2+ oxidation, while low δ13Ccarb values might be attributed to CO2 degassing of submarine volcanoes as well as low primary burial during the glaciation. Since the δ13CDIC value of the synglacial ocean was lower than the δ13Ccarb values of most cap carbonates, we infer the addition of 13C-enriched DIC or removal of 12C during cap carbonate precipitation, such as through carbonate weathering or organic carbon burial. These findings provide new insights into the nature of Cryogenian glaciation, the origin of cap carbonates, and the aftermath of global glaciation.

Molybdenum Isotope Fingerprinting of Microbial Sulfate Reduction in Seep Carbonate Rocks

AbstractUnderstanding the interaction between molybdenum (Mo) and organic matter during microbial sulfate reduction is critical for the use of Mo to reconstruct marine redox conditions throughout Earth's history. However, little is known about Mo isotope fractionation and how it relates to organic matter remineralization during microbial sulfate reduction. Here, we report Mo abundances and isotopic (δ98Mo) compositions for bulk‐rock, non‐lithogenic and sequentially extracted fractions, including carbonate (carb), pyrite, and organic matter (OM), of seep carbonate rocks. Our data indicate that the difference between δ98Mocarb and δ98MoOM (Δ98Mocarb‐OM) displays significant variability in the studied samples, ranging between 0.72 and 1.01‰. Remarkably, the obtained Δ98Mocarb‐OM values indicate correlative trends with stable carbon isotope ratios and bulk abundances of (a) total organic carbon, (b) Mo, and (c) pyrite in seep carbonates, which we interpret as reflecting sustained adsorption of isotopically light Mo onto organic matter during enhanced sulfate reduction. On this basis, we put forward the concept that Δ98Mocarb‐OM of authigenic carbonate rocks can be used as a measure of the intensity of sulfate reduction and for reconstructing past interactions between Mo and organic matter in marine sediments.