Seawater Sulfate Concentrations Research Articles

In Situ Analysis of Sulfur Isotopic Fractionation in Deep‐Sea Corals Using Secondary‐Ion Mass Spectrometry: Insights Into Vital Effects

AbstractCarbonate‐associated sulfate (CAS) δ34S values (δ34SCAS) are generally assumed to reflect S isotopic composition of paleo‐seawater and have been extensively used to reconstruct secular variations in seawater sulfate concentrations during the geological past. However, it has often been documented that δ34SCAS records are incompatible with seawater sulfur isotopes (20.9 ± 0.1%, 2σ) determined from other archives, such as sulfate evaporites and barite (both of which may also display inconsistencies). A possible explanation for this discrepancy is that δ34SCAS values can be easily altered by atmospheric sulfate and sulfide re‐oxidation. However, the specific influence of biological factors (vital effects, common in biogenic carbonates) on CAS S isotopic composition remains unresolved, particularly at microscale levels. To elucidate these effects on δ34SCAS, S isotopic profiles were analyzed across two skeletal transects of two modern deep‐sea corals (gorgonia) using a novel secondary‐ion mass spectrometry method. Strong S isotopic fractionation was observed in calcitic skeletons from the most 34S‐depleted center (δ34S = ∼19‰), increasing outward to a relatively constant 22.5‰ in gorgonia sp. coral and 21.6‰ in bamboo coral, suggesting that vital effects are much larger than previous estimated (∼±1‰ fractionation from seawater). Oxygen isotopic and Mg, S, O elemental compositions, and Raman spectral and crystal morphological features indicate that processes such as pH control, Rayleigh fractionation, and organic effects are precluded as causes of such fractionation. Instead, vital effects associated with kinetic processes related to surface entrapment seem plausible as controls on S isotopic fractionations in the coral. This novel method is significant for gaining insights into vital effects, assessing the reliability of biogenic carbonates as high‐resolution environmental archives of S isotopes, and understanding the fundamental mechanisms governing biomineralization.

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

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

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

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

Marine sulfate sulfur isotopic evidence for enhanced terrestrial weathering and expansion of oceanic anoxia during the Devonian-Carboniferous transition

The Hangenberg mass extinction during the Devonian-Carboniferous (D-C) transition represents one of the largest biodiversity losses of the Phanerozoic, while the underlying cause remains controversial. An improved understanding of the contemporaneous sulfur cycle can provide insights into the latest Devonian environmental changes that potentially affected marine biotas. Here, we report on a high-resolution chemostratigraphic study of the sulfur isotopic composition of carbonate-associated sulfate (CAS) through the D-C transition in the Long'an and Qilinzhai sections of South China. The δ34SCAS profiles exhibit a long-term (i.e., >105 yr) negative excursion from +19.0‰ in the upper Lower Si. praesulcata Zone to +13.0‰ in the middle Upper Si. praesulcata Zone, and terminated with a recovery to 20.3‰ in the lower Si. sulcata – Si. duplicata zones, representing a depositional interval of ∼0.9 Myr. In addition, this long-term negative excursion is punctuated by episodic sharp negative shifts. The negative δ34SCAS excursion coincided with the end-Devonian biotic crisis, a positive shift in carbonate δ13C, and negative shifts in bulk-sediment δ15N values and I/Ca ratios. Increasing organic carbon burial indicated by the positive shift in δ13C precludes decreased pyrite burial as an explanation for the negative shift of δ34SCAS, supported by intensified marine anoxia revealed by the negative shifts in δ15N and I/Ca. We attribute the long-term negative shift in δ34SCAS to enhanced inputs of 34S-depleted riverine sulfate in conjunction with low seawater sulfate concentrations within the semi-restricted Yangtze Sea, whereas the transient negative spikes in δ34SCAS were possibly caused by episodic upwelling and oxidation of H2S in expanded oceanic oxygen-minimum zones. In conjunction with the positive shift in δ13C, the negative shift in δ34SCAS supports a significant role for enhanced subaerial weathering in intensifying marine anoxia and triggering the biotic crises that occurred during the latest Devonian, the most likely driver of which was the spread of vascular (especially seed-bearing) land plants.

Evidence for low sulfate and anoxic deep waters in early Cambrian

The role of environmental change as a significant force driving biological evolution during the Ediacaran–Cambrian transition remains a subject of extensive debate. In this study, we present high-resolution C-isotope data of organic matter (δ13Corg) and multiple S-isotope compositions of pyrite (δ34Spy and Δ33Spy) obtained from a continuous drill core (ZK1505) in South China, spanning the interval from the Ediacaran to Cambrian Stage 2. Our δ13Corg and δ34Spy data, combined with published data from four sections deposited across a shelf-to-basin transect, reveal substantial gradient from shallow to deep water in δ13Corg and sustained positive δ34Spy values in the early Cambrian. The vertical δ13Corg gradient suggests chemical stratification of the early Cambrian ocean, characterized by oxic shallow water and anoxic deep water. The sustained positive δ34Spy values in the same period suggest low seawater sulfate concentrations. Furthermore, we observed intermittent occurrences of negative Δ33Spy values coupled with positive δ34Spy, suggesting a dominant deep-water anoxia during early Cambrian in the Yangtze Block. We propose that protracted deep-water anoxia may have contributed to the extinction of the Ediacaran biota and played a significant role in the evolution of Cambrian animals.

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.

Modelling sulfate concentrations in the global ocean through Phanerozoic time

Understanding the long-term variations in seawater sulfate concentrations ([SO 4 2− ] sw ) is crucial to our understanding of the dynamic relationships between the sulfur, carbon, calcium and oxygen cycles, and their influence on the habitability of the Earth. Here, we explore how [SO 4 2− ] sw has changed throughout the Phanerozoic and its impact on other elemental cycles. We do this by utilizing the biogeochemical box model GEOCARBSULFOR. The model suggests that [SO 4 2− ] sw increased throughout the Paleozoic, decreased during the Mesozoic and then increased once more in the Cenozoic, generally matching geochemical proxies. Atmospheric oxygen mirrors [SO 4 2− ] sw changes during the Paleozoic and Mesozoic, but, intriguingly, decouples during the Cenozoic. We further explored the controls on [SO 4 2− ] sw by modifying the modelled gypsum fluxes via the incorporation of evaporite data from the geological record. We found that forcing gypsum burial with the observed evaporite deposition data causes the model to better match proxy records at some times, but worsens predictions at others. We also investigated the reliance of the model on a prescribed record of marine calcium concentrations, finding that it is a dominant control on modelled Phanerozoic [SO 4 2− ] sw and that removing this control seriously degrades the model predictions. We conclude that no model can yet simulate a reasonable evolution of both the calcium and sulfur cycles. Supplementary material: Figures S1–S5 are available at https://doi.org/10.6084/m9.figshare.c.7164928 Thematic collection: This article is part of the Sulfur in the Earth system collection available at: https://www.lyellcollection.org/topic/collections/sulfur-in-the-earth-system

Carbon and sulfur cycling across the Silurian-Devonian boundary in the Qujing Basin, South China

During the late Silurian – Early Devonian there were significant changes in the biosphere and environment. However, there are few integrated studies of carbon and sulfur cycling in the Qujing Basin, in South China, which has extremely well-preserved sarcopterygian fossils. Here we report C-isotopic data of organic carbon (δ13Corg) and multiple S-isotopes of pyrite (δ34S and Δ33S) from two sections in the Qujing Basin. Our δ13Corg data show an increase of ~4‰ near the Silurian-Devonian boundary which can be correlated globally. We suggest that this rise in δ13Corg near the Silurian-Devonian boundary may have resulted from the weathering of the 13C-enriched carbonate platform, rather than from oceanic anoxia. This interpretation may explain why there is little evidence of a mass extinction near the Silurian-Devonian boundary in the Qujing Basin. Our S-isotopic data show positive δ34S values with either positive or negative Δ33S values, and most of the δ34S and Δ33S data can be explained by microbial sulfate reduction and Rayleigh distillation processes. The S-isotopic data from both sections suggest that seawater sulfate concentrations were very low in the Qujing Basin during the late Silurian – Early Devonian.

Impact of seawater sulfate concentration on sulfur concentration and isotopic composition in calcite of two cultured benthic foraminifera

Abstract. Marine sediments can be used to reconstruct the evolution of seawater [SO42-] and δ34S over time, two key parameters that contribute to refine our understanding of the sulfur cycle and thus of Earth's redox state. δ34S evolution can be measured from carbonates, barites and sulfate evaporites. [SO42-] variations can be reconstructed using fluid inclusions in halites, a method that only allows a low-resolution record. Reconstruction of the past sulfur cycle could be improved if carbonates allowed the tracking of both seawater δ34S and [SO42-] variations in a sole, continuous sedimentary repository. However, most primary carbonates formed in the ocean are biogenic, and organisms tend to overprint the geochemical signatures of their carbonates through a combination of processes often collectively referred to as vital effects. Hence, calibrations are needed to allow seawater δ34S and [SO42-] reconstructions based on biogenic carbonates. Because foraminifera are important marine calcifiers, we opted to focus on calcite synthesized by individuals of rosalinid benthic foraminifera cultured in the laboratory under controlled conditions, with varying seawater [SO42-] (ranging from 0 to 180 mM). Our experimental design allowed us to obtain foraminiferal asexual reproduction over several generations. We measured bulk carbonate-associated sulfate (CAS) content and sulfur isotopic composition (δ34SCAS) on samples of tens to hundreds of specimens from a selection of culture media, where [SO42-] varied from 5 to 60 mM. Increasing or decreasing [SO42-] with respect to modern-day seawater concentration (28 mM) impacted foraminiferal population size dynamics and the total amount of bioprecipitated carbonate. Foraminiferal CAS concentration increased proportionally with [SO42-] concentration from 5 mM up to 28 mM and then showed a plateau from 28 to 60 mM. The existence of a threshold at 28 mM is interpreted as the result of a control on the precipitation fluid chemistry that foraminifera exert on the carbonate precipitation loci. However, at high seawater sulfate concentrations (> 40 mM) the formation of sulfate complexes with other cations may partially contribute to the non-linearity of the CAS concentration in foraminiferal tests at high increases in [SO42-]. Yet, despite the significant effect of seawater [SO42-] on foraminiferal reproduction and on CAS incorporation, the isotopic fractionation between CAS and seawater remains stable through varying seawater [SO42-]. Altogether, these results illustrate that CAS in biogenic calcite could constitute a good proxy for both seawater [SO42-] and δ34S and suggests that sulfate likely plays a role in foraminiferal biomineralization and biological activity.

Reconfiguring oxygenation at ∼1.4 Ga: New constraints as informed by the ancient oceanic sulfur cycle

The extent of atmospheric and oceanic oxygenation during the Mesoproterozoic remains an area of active debate. Here, we report major and trace elements, organic sulfur (OS) speciation, sulfur isotopes in multiple phases [pyrite (py), OS, and carbonate-associated sulfate (CAS)], and a numerical model of sulfate concentrations from one of the Mesoproterozoic's best-preserved geochemical archives, the Xiamaling Formation (ca. 1.4 Ga) in the Yanliao Basin. These data reveal a previously unrecognized ocean-atmosphere oxygenation process. Starting with Unit 3, intense sulfurization increased organic carbon burial and thus oxygen release, resulting in a deep-water oxidation event within the Yanliao Basin that could be regarded as a transient restricted oxygen oasis based on low pyrite content, elevated kerogen S:C ratios, higher δ34Spy than δ34SOS (Δδ34SOS-py < 0), and a low calculated sulfate concentration of ∼0.07–0.14 mM. During Unit 2, the basin was reconnected to the open ocean with the deposition of organic-rich shale across northern China and northern Australia, accompanied by a shift in Δδ34SOS-py to 5.0‰ and a calculated seawater sulfate concentration of ∼0.1–1.14 mM. Such large-scale burial of organic matter released oxygen into the atmosphere, accompanied by significant sulfate delivery to the basin and euxinic conditions characterized by Mo concentrations and 34S-depleted pyrite at the topmost of Unit 2. A subsequent globally synchronized atmospheric and deep ocean oxygenation event may have occurred during Unit 1. This event was recorded by a progressive increase in Δδ34SOS-py (up to +9.6‰), increased oxidized OS species, and positive Ce anomalies (attributed to the reductive dissolution of the Ce-enriched Mn oxides), all of which were caused by increased sulfate concentrations (calculated to be ∼1.15–2.31 mM) and a spatial descent of the redox interface. The combination of these lines of evidence illustrates the sensitivity of the oceanic sulfur cycle to the ocean-atmosphere system and provides novel constraints on oxygenation at ∼1.4 Ga.

Oceanic Redox State During the Early Cambrian: Insights From Mo‐S Isotopes and Geochemistry of Himalayan Shales

AbstractThe Precambrian‐Cambrian (Pc‐C) boundary marks significant biological, atmospheric, and oceanic changes. These changes include extinction of the Ediacaran fauna, initiation of complex lifeforms, and oxygenation of the atmosphere and oceans. In this contribution, elemental and Mo‐S isotopic compositions of organic‐rich shales overlying the Pc‐C boundary from the Tal Formation, Lesser Himalaya, have been investigated. These datasets are used to reconstruct past oceanic redox state and sulfate concentrations. The principal component analysis of the elemental dataset identifies six major factors, with factors associated with organic matter and sulfide phases accounting for about half of the total variance. Iron speciation and Mo/U data suggest that the shales were deposited in anoxic and ferruginous deep water conditions. The δ98Mo data (1.5 ± 0.2‰) and their mass balance calculations indicate that the areal extent of sulfidic waters and pyrite burial rates were about 2–4 times higher during the Pc‐C transition than in the modern ocean. The pyrite‐δ34S values (3.6–8.3‰) for the Tal shales are isotopically heavier compared to modern‐day sedimentary pyrites (∼−21‰). Calculations involving earlier‐reported δ34S values for early Cambrian seawater and our measured pyrite‐δ34S data estimate the seawater sulfate concentration (8 ± 3 mM) during their deposition. This sulfate value for the Tal basin is higher than that reported for the late Neoproterozoic ocean (&lt;5 mM), attributable to increasing oxygen availability and continental supply during this time. The observed basinal conditions and high terrestrial input may have influenced metazoan diversification.

Spatially heterogenous seawater δ34S and global cessation of Ca-sulfate burial during the Toarcian oceanic anoxic event

The early Toarcian of the Early Jurassic saw a long-term positive carbon-isotope excursion (CIE) abruptly interrupted by a significant negative excursion (nCIE), associated with rapid global warming and an oceanic anoxic event (T-OAE, ∼183 Ma). However, the detailed processes and mechanisms behind widespread ocean deoxygenation are unclear. Here, we present high-resolution carbonate-associated sulfate sulfur-isotope (δ34SCAS) records spanning the late Pliensbachian–Toarcian (Pl–To) interval from the Tibetan Himalaya. We observe a large positive sulfur-isotope excursion (SIE) from ∼20‰ (around the Pl–To boundary) to ∼40‰ (around the end of the T-OAE nCIE), attributed to large-scale burial of reduced sulfur (pyrite and sulfurized organic matter) under widespread anoxic/euxinic conditions. Importantly, high δ34SCAS values were maintained into the mid–late Toarcian, even when global anoxic conditions diminished. The δ34S data confirm significant spatial heterogeneity in seawater δ34S compositions during the whole of the Toarcian, and provide strong evidence for a two-phase pattern of ocean deoxygenation. Upwelling of 34S-enriched equatorial deep water, affected by significant reduced-sulfur burial, likely caused the greatly amplified SIE in the formerly adjacent Tibetan area. By contrast, the dampened magnitude of the Toarcian SIE in Europe is attributed to a smaller, local reduced-sulfur sink. Box-modeling results indicate that the persistent post-T-OAE positive δ34S values were likely maintained because of a global reduction in Ca-sulfate (gypsum and anhydrite) burial driven by declining and continuously low seawater sulfate concentrations during and after the T-OAE. This geochemical pattern, albeit markedly reducing the total amount of global pyrite sequestration, increased the proportion of reduced to oxidized sulfur burial needed to generate the observed positive δ34S values.

Fluid Flow, Alteration, and Timing of Cu-Ag Mineralization at the White Pine Sediment-Hosted Copper Deposit, Michigan, USA

Abstract White Pine, located in Michigan’s Upper Peninsula, is an archetypal sediment-hosted stratiform copper deposit. The Midcontinent rift system is one of only seven basins globally that host a giant sediment-hosted stratiform copper deposit. Despite many similarities with other deposits of this type, White Pine displays some important differences, including the late Mesoproterozoic age, a thick basalt sequence, an apparent lack of evaporites, and a lacustrine depositional setting. This study analyzes paleofluid flow related to the formation of White Pine and places a particular emphasis on structural and diagenetic fluid pathways. Most of the ore is located in a 30-m-wide zone spanning the Copper Harbor Formation red beds and the overlying Nonesuch Formation shales. Sedimentation of these units was accompanied by subtle synsedimentary faulting. Premineralization phases include calcite concretions and nodules, illite and hematite grain coatings, isopachous chlorite rims, emplacement of liquid petroleum (now pyrobitumen), and bleaching. Mineralization introduced native copper into the footwall sandstones and a zoned suite of native copper and sulfur-poor copper sulfide minerals across a migrating redox front in the overlying shales where copper minerals nucleated on authigenic and detrital chlorite grains. Postmineralization phases include quartz cement, calcite cement, and calcite veins that partially overlapped inversion of synsedimentary faults. Contrary to previous studies, we identified evidence for only one phase of mineralization. An Re-Os chalcocite age of 1067 ± 11 Ma places mineralization 11 to 17 m.y. after host-rock deposition. Sulfide δ34S values of –14.0 to 29.9‰ suggest an important contribution from sour gas and thermochemical sulfate reduction of seawater. Carbon (δ13C) and oxygen (δ18O) isotope compositions of five calcite generations range from –15.1 to –1.3‰ and 10.4 to 41.3‰, respectively, and record early meteoric pore water displaced by later seawater. White Pine is both a sediment-hosted stratiform copper deposit and a paleo-oil field. Synsedimentary faults controlled the sedimentological character of the upper Copper Harbor Formation, and together these imparted a strong control on fluid flow and later diagenetic processes. Early oxidized meteoric fluids were displaced by liquid petroleum and sour gas, which were in turn succeeded by metal-rich but sulfate-poor oxidized seawater. Burial compaction during deposition of the overlying Freda Formation drove fluids through White Pine due to its situation on a paleotopographic high near the basin margin. Mineralization occurred at ~125°C at depths of ~2.0 km and spanned incipient basin inversion related to the distal effects of Grenvillian orogenesis. The hightenor copper mineral assemblage is the product of an abundant supply of metal from basaltic volcanic detritus in the Copper Harbor Formation and low seawater sulfate concentrations in late Mesoproterozoic oceans. This demonstrates that viable sediment-hosted stratiform copper systems can form when a readily leachable metal source rock is present, even if hypersaline and sulfate-rich brines are not.

Sulfur isotopic evidence for global marine anoxia and low seawater sulfate concentration during the Late Triassic

Sulfur isotopic evidence for global marine anoxia and low seawater sulfate concentration during the Late Triassic

Formation of molar tooth structures in low sulfate Precambrian oceans

Molar tooth structures (MTS) comprise calcite microspar-filled voids in fine-grained shallow-water carbonate, and were commonly formed in the Mesoproterozoic and early Neoproterozoic. However, the origin of MTS and links between the temporal distribution of MTS and contemporaneous seawater chemistry remains poorly understood. Here we report elemental and isotopic data for MTS and host rocks from the Mesoproterozoic Gaoyuzhuang Formation (∼1,600–1,550 Ma), North China Craton. The results reveal similar C, S and Sr isotope signatures between MTS and host rocks, which are close to the isotopic compositions of contemporaneous global seawater, suggesting an early diagenetic, seawater-buffered origin for MTS. A small sulfur isotopic fractionation between seawater sulfate and pyrite (Δ34SCAS-Py) of 4.1 ± 1.5‰ in host rocks is consistent with previously reported data, providing support for sub-millimolar sulfate concentrations in Mesoproterozoic seawater. Our observations suggest that the widespread occurrence of MTS through the Mesoproterozoic to early Neoproterozoic was broadly linked to sulfate scarcity in the ocean. We further propose that in Proterozoic oceans with sub-millimolar seawater sulfate concentrations, where aerobic and anaerobic methane oxidation was likely inhibited, methane produced via methanogenesis may have been more prone to accumulate in sediments, creating voids during escape. The absence of MTS across periods of higher sulfate concentrations during the Palaeoproterozoic and after the mid-Neoproterozoic, suggests that elevated sulfate concentrations promoted consumption of methane via anaerobic methane oxidation, thus preventing methane accumulation and the formation of sediment voids. Rapid lithification of the substrate as a result of elevated carbonate saturation may have also hindered the formation of MTS during these intervals. The link between MTS and changes in both oceanic sulfate levels and benthic methane fluxes gives a new perspective on temporal fluctuations in Earth’s redox state through time.

Methane Index: Towards a quantitative archaeal lipid biomarker proxy for reconstructing marine sedimentary methane fluxes

In marine sediments, anaerobic methane oxidation (AOM) carried out by consortia of methanotrophic archaea (ANME groups) and sulfate reducing bacteria (SRB) represents a major sink for methane (40–290 Tg of C yr−1). The variability of seafloor methane seepage and AOM is crucial to sedimentary biogeochemistry and global carbon/sulfur cycling, yet poorly constrained for Earth’s history. Based on the rationale that a major group of ANME preferentially synthesizes certain tetraether lipids, Methane Index (MI) measured from sedimentary archaeal lipid biomarkers called GDGTs (glycerol dialkyl glycerol tetraethers) has been widely used as a qualitative indicator for methane-impact on sediments. However, it was unclear whether small amounts of diagenetic methane in porewater could cause high MI values or that high methane flux associated with, for example cold seeps, is required. Since not all ANME groups synthesize GDGTs, another contested issue is whether this index is broadly representative of AOM. Here, we use modern porewater and sedimentary lipid profiles from the world’s ocean to further explore MI’s potential to address these questions. The new data show that MI is quantitatively linked to sedimentary methane diffusive flux and the depth of sulfate-methane transition zone (SMTZ) which is the diagenetic front where AOM activity is mostly concentrated. In particular, high MI values (>0.3–0.5) are strongly associated with high methane fluxes (>∼0.1 mmol m−2 d−1) and shallow SMTZ depths (<1–3 m) commonly linked to gas hydrate dissociations. Sensitivity analyses suggest that when the variability of several key parameters (e.g., seawater sulfate concentration, geothermal gradient, and sediment porosity) is small, modern MI – methane flux and MI – SMTZ depth relationships can be applied to reconstruct methane history and diagenetic zonation of the geological past. Although only Group I of ANME archaea synthesizes GDGTs, the co-occurrence of AOM biomarkers (e.g., crocetane, PMI, and hydroxyarchaeol) that are attributed to ANME-2 or ANME-3 and high MI values suggest that MI is broadly representative of AOM. Lastly, we applied MI to probe the methane venting history by using new data from a Cascadia Margin site (Hydrate Ridge, IODP U1328) since the penultimate interglacial, and reinterpreted recently reported MI data from three Southern Ocean sites (ODP 1168, 1170, and IODP U1356) during the late Oligocene – early Miocene. Overall, these applications demonstrate that MI can serve as a sensitive and quantitative proxy to help broadly establish Cenozoic and Mesozoic history of marine methane biogeochemical cycling.

Marine redox variation and hydrographic restriction in the early Cambrian Nanhua Basin, South China

The early Cambrian Nanhua Basin is an important archive of information related to contemporaneous marine redox evolution and its relationship to the radiation of early animals. However, the nature of watermass conditions in the Nanhua Basin remains uncertain owing to conflicting redox signals. Here, we generated a redox proxy dataset comprising Fe speciation, redox-sensitive element (RSE), pyrite framboid size distributions, and molybdenum isotopic data (δ98Mo), in combination with proxies for hydrographic restriction (i.e., Co × Mn, Cd/Mo, and Mo/TOC), in order to evaluate environmental conditions in the basinal Yuanjia section. We then compared these data with previous results for outer-shelf (Jinsha, Zhongnancun, and Yangjiaping), slope (Daotuo, Songtao, and Longbizui), and basinal facies (Silikou) to develop an integrated picture of environmental (especially redox) changes in the early Cambrian Nanhua Basin. At Yuanjia, the lower member (LM, 0–28 m) is characterized by weakly euxinic conditions and an intense Fe-Mn shuttle, and the upper member (UM, 28–65 m) by moderately euxinic conditions and a weak Fe-Mn shuttle. Our integrated analysis demonstrates co-existence of oxic surface waters, euxinic mid-depth waters, and ferruginous deep waters in the Nanhua Basin, with euxinic conditions prevailing in shelf-slope facies of the Yangtze Block and basinal facies of the Cathaysia Block but declining in intensity from the LM to the UM. The Nanhua Basin changed from being moderately restricted with strong upwelling during the LM to relatively more restricted with weak upwelling during the UM. We infer that redox fluctuations in the early Cambrian Nanhua Basin were linked to hydrographic restriction, although global factors such as low seawater sulfate concentrations may have played a role also. Our study highlights the need for caution in assuming that redox variation in the early Cambrian Nanhua Basin was representative of contemporaneous global-ocean redox states.

Significant fluctuation in the global sulfate reservoir and oceanic redox state during the Late Devonian event.

Ocean sulfate concentration might have fluctuated greatly throughout the Earth's history and may serve as a window into perturbations in the ocean-atmosphere system. Coupling high-resolution experimental results with an inverse modeling approach, we, here, show an unprecedented dynamic in the global sulfate reservoir during the Frasnian-Famennian (F-F) boundary event, as one of the "Big five" Phanerozoic biotic crises. Notably, our results indicate that, in a relatively short-time scale (∼200 thousand years), seawater sulfate concentration would have dropped from several mM before the Upper Kellwasser Horizon (UKH) to an average of 235±172 μM at the end of the UKH (more than 100 times lower than the modern level) as the result of evaporite deposition and euxinia, and returned to around mM range after the event. Our findings indicate that the instability in the global sulfate reservoir and nutrient-poor oceans may have played a major role in driving the Phanerozoic biological crises.

Low marine sulfate levels during the initiation of the Cryogenian Marinoan glaciation

The microbial sulfate reduction plays a significant role in regulating marine organic matter degradation. Thus the variation of ancient marine sulfate levels is closely coupled with the changes in global organic carbon burials and Earth’s surface redox evolution in geological time. It is widely assumed that seawater sulfate concentration was deficient during the anoxic Cryogenian Marinoan glaciation (ca.650–635 Ma) which represents the most extreme icehouse condition in Earth’s history. However, such a low seawater sulfate level has not been explicitly confirmed. To address this, here we carried out pyrite content and sulfur isotope (δ34Spy) analysis of the Cryogenian non-glacial (the Datangpo Formation) and the Marinoan glacial successions (the Nantuo Formation) in South China. The Datangpo and Nantuo Formation show relatively high values of δ34Spy, ranging from +19.9 ‰ to +32.9 ‰, and low values of pyrite content (mean = 0.72 wt%). These pyrites are dominated by euhedral crystals with a rare occurrence of framboids, indicating an early diagenetic origin, i.e., pyrite formed in sediments with sulfate supplied from seawater. Using and a one-dimensional diffusion–advection-reaction (DAR) model, we calculate marine sulfate levels. The modeling results show that the seawater sulfate concentration is <1 mM during the transition from the top Datangpo to the basal Nantuo Formation, suggesting a shrink of the marine sulfate reservoir at the onset of Marinoan glaciation. We propose that the low marine sulfate concentration was resulted from a decrease in continental chemical weathering. This study provides a quantitative constraint on marine sulfate levels during the Cryogenian snowball Earth event, and it may shed new light on our understanding of the marine biogeochemical changes in the Neoproterozoic.

Marine anoxia as a trigger for the largest Phanerozoic positive carbon isotope excursion: Evidence from carbonate barium isotope record

The mid-Ludfordian Lau carbon isotope excursion (Lau CIE) represents the largest positive carbon isotope excursion in the Phanerozoic (∼9‰), coincident with the biodiversity loss of many marine animal clades. Two main explanations for the Lau CIE are enhanced organic carbon burial via increased marine productivity and preservation-driven expansion of anoxia. While these two explanations are not mutually exclusive, the main driver of Lau CIE is yet to be constrained. Here, we resolve this longstanding debate using barium isotopes (δ138Ba) of marine carbonates deposited across the Lau CIE. Our δ138Ba data from the Kosov section (Czech Republic) record a large negative excursion in correlation to the positive shift in δ13Ccarb. We suggest that the observed negative shift in δ138Ba to values as low as −0.33‰ can be best interpreted as upwelling of isotopically light Ba from deeper waters due to pelagic barite dissolution under euxinic conditions. This hypothesis is consistent with results from barium concentration data as well as the results from the sulfate mass balance modeling that indicates a contraction in the seawater sulfate reservoir, with seawater sulfate concentrations decreasing from several mM ranges before the Lau CIE to less than 100 μM during Lau CIE. Taken together, evidence for a strong negative correlation between δ138Ba and δ13Ccarb suggests that shallow water anoxia, rather than enhanced marine productivity, was a primary driver of the Lau CIE that resulted in a notable decrease in the size of seawater sulfate reservoir.