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Fossilized carotenoid hydrocarbons provide a window into the physiology and biochemistry of ancient microbial phototrophic communities for which only a sparse and incomplete fossil record exists. However, accurate interpretation of carotenoid-derived biomarkers requires detailed knowledge of the carotenoid inventories of contemporary phototrophs and their physiologies. Here we report two distinct patterns of fossilized C40 diaromatic carotenoids. Phanerozoic marine settings show distributions of diaromatic hydrocarbons dominated by isorenieratane, a biomarker derived from low-light-adapted phototrophic green sulfur bacteria. In contrast, isorenieratane is only a minor constituent within Neoproterozoic marine sediments and Phanerozoic lacustrine paleoenvironments, for which the major compounds detected are renierapurpurane and renieratane, together with some novel C39 and C38 carotenoid degradation products. This latter pattern can be traced to cyanobacteria as shown by analyses of cultured taxa and laboratory simulations of sedimentary diagenesis. The cyanobacterial carotenoid synechoxanthin, and its immediate biosynthetic precursors, contain thermally labile, aromatic carboxylic-acid functional groups, which upon hydrogenation and mild heating yield mixtures of products that closely resemble those found in the Proterozoic fossil record. The Neoproterozoic–Phanerozoic transition in fossil carotenoid patterns likely reflects a step change in the surface sulfur inventory that afforded opportunities for the expansion of phototropic sulfur bacteria in marine ecosystems. Furthermore, this expansionmight have also coincided with a major change in physiology. One possibility is that the green sulfur bacteria developed the capacity to oxidize sulfide fully to sulfate, an innovation which would have significantly increased their capacity for photosynthetic carbon fixation.

The partial pressure of oxygen in Earth’s atmosphere has increased dramatically through time, and this increase is thought to have occurred in two rapid steps at both ends of the Proterozoic Eon (∼2.5–0.543 Ga). However, the trajectory and mechanisms of Earth’s oxygenation are still poorly constrained, and little is known regarding attendant changes in ocean ventilation and seafloor redox. We have a particularly poor understanding of ocean chemistry during the mid-Proterozoic (∼1.8–0.8 Ga). Given the coupling between redox-sensitive trace element cycles and planktonic productivity, various models for mid-Proterozoic ocean chemistry imply different effects on the biogeochemical cycling of major and trace nutrients, with potential ecological constraints on emerging eukaryotic life. Here, we exploit the differing redox behavior of molybdenum and chromium to provide constraints on seafloor redox evolution by coupling a large database of sedimentary metal enrichments to a mass balance model that includes spatially variant metal burial rates. We find that the metal enrichment record implies a Proterozoic deep ocean characterized by pervasive anoxia relative to the Phanerozoic (at least ∼30–40% of modern seafloor area) but a relatively small extent of euxinic (anoxic and sulfidic) seafloor (less than ∼1–10% of modern seafloor area). Our model suggests that the oceanic Mo reservoir is extremely sensitive to perturbations in the extent of sulfidic seafloor and that the record of Mo and chromium enrichments through time is consistent with the possibility of a Mo–N colimited marine biosphere during many periods of Earth’s history.

Photic zone euxinia (PZE) is a condition where anoxic, H₂S-rich waters occur in the photic zone (PZ). PZE has been invoked as an impediment to the evolution of complex life on early Earth and as a kill mechanism for Phanerozoic mass extinctions. Here, we investigate the potential application of mercury (Hg) stable isotopes in marine sedimentary rocks as a proxy for PZE by measuring Hg isotope compositions in late Mesoproterozoic (∼1.1 Ga) shales that have independent evidence of PZE during discrete intervals. Strikingly, a significantly negative shift of Hg mass-independent isotope fractionation (MIF) was observed during euxinic intervals, suggesting changes in Hg sources or transformations in oceans coincident with the development of PZE. We propose that the negative shift of Hg MIF was most likely caused by (i) photoreduction of Hg(II) complexed by reduced sulfur ligands in a sulfide-rich PZ, and (ii) enhanced sequestration of atmospheric Hg(0) to the sediments by thiols and sulfide that were enriched in the surface ocean as a result of PZE. This study thus demonstrates that Hg isotope compositions in ancient marine sedimentary rocks can be a promising proxy for PZE and therefore may provide valuable insights into changes in ocean chemistry and its impact on the evolution of life.

The evolution of Earth’s biota is intimately linked to the oxygenation of the oceans and atmosphere. We use the isotopic composition and concentration of molybdenum (Mo) in sedimentary rocks to explore this relationship. Our results indicate two episodes of global ocean oxygenation. The first coincides with the emergence of the Ediacaran fauna, including large, motile bilaterian animals, ca. 550–560 million year ago (Ma), reinforcing previous geochemical indications that Earth surface oxygenation facilitated this radiation. The second, perhaps larger, oxygenation took place around 400 Ma, well after the initial rise of animals and, therefore, suggesting that early metazoans evolved in a relatively low oxygen environment. This later oxygenation correlates with the diversification of vascular plants, which likely contributed to increased oxygenation through the enhanced burial of organic carbon in sediments. It also correlates with a pronounced radiation of large predatory fish, animals with high oxygen demand. We thereby couple the redox history of the atmosphere and oceans to major events in animal evolution.

The Ediacaran Period (635 to 542 million years ago) was a time of fundamental environmental and evolutionary change, culminating in the first appearance of macroscopic animals. Here, we present a detailed spatial and temporal record of Ediacaran ocean chemistry for the Doushantuo Formation in the Nanhua Basin, South China. We find evidence for a metastable zone of euxinic (anoxic and sulfidic) waters impinging on the continental shelf and sandwiched within ferruginous [Fe(II)-enriched] deep waters. A stratified ocean with coeval oxic, sulfidic, and ferruginous zones, favored by overall low oceanic sulfate concentrations, was maintained dynamically throughout the Ediacaran Period. Our model reconciles seemingly conflicting geochemical redox conditions proposed previously for Ediacaran deep oceans and helps to explain the patchy temporal record of early metazoan fossils.

Biological nitrogen fixation constitutes the main input of fixed nitrogen to Earth’s ecosystems, and its isotope effect is a key parameter in isotope-based interpretations of the N cycle. The nitrogen isotopic composition (δ ¹⁵N) of newly fixed N is currently believed to be ∼–1‰, based on measurements of organic matter from diazotrophs using molybdenum (Mo)-nitrogenases. We show that the vanadium (V)- and iron (Fe)-only “alternative” nitrogenases produce fixed N with significantly lower δ ¹⁵N (–6 to –7‰). An important contribution of alternative nitrogenases to N ₂ fixation provides a simple explanation for the anomalously low δ ¹⁵N (<–2‰) in sediments from the Cretaceous Oceanic Anoxic Events and the Archean Eon. A significant role for the alternative nitrogenases over Mo-nitrogenase is also consistent with evidence of Mo scarcity during these geologic periods, suggesting an additional dimension to the coupling between the global cycles of trace elements and nitrogen.

Continental interiors were flooded by epeiric seas during many intervals of the geologic past. Few modern analogs exist for these environments, however, and basic variables such as redox, salinity, and restriction are difficult to reconstruct in deep time. Despite these challenges, constraining epeiric watermass properties is critical because much of our preserved and accessible sedimentary record was deposited in such settings. Here, we present a four‐dimensional reconstruction of watermass evolution in the Late Devonian Appalachian Seaway of North America. We use combined proxies for sediment supply, paleosalinity, paleoredox, and basin hydrography in six cores through the Upper Devonian Cleveland Shale deposited across a paleo‐depth transect. Cyclic, coupled changes in sedimentation, redox, and salinity are recorded in environments near the Catskill Delta. Additionally, a pronounced salinity gradient was present from low‐brackish conditions near the delta to fully marine conditions in the basin interior, with a lower‐salinity mixing zone recorded across the Cumberland Sill. We also identified two broad sequences—the lower and upper Cleveland Shale—each of which shows distinct watermass signatures. The lower Cleveland Shale records a redox gradient with euxinia only present along the Cumberland Sill, whereas the upper Cleveland Shale records intensification of euxinia (potentially in the photic zone) at all six sites, which may be coincident with the Hangenberg extinction event. Ultimately, this study identifies pronounced epeiric watermass gradients over short timescales (millennia) and distances (hundreds of km or less), highlighting the need for interpreting the geochemistry of epicontinental deposits in the context of basin hydrography and paleosalinity. Plain Language Summary The interiors of continents were flooded by shallow seas during many intervals of Earth history; however, little is known about the basic watermass properties of ancient inland seas and how they differed from the open ocean. Here, we provide an example of watermass reconstruction in an ancient inland sea by investigating the Cleveland Shale, which was deposited in a flooded region west of the Appalachian Mountains during the Late Devonian (∼383–359 million years ago). We use geochemical proxies for oxygen concentrations (redox) and salinity in six rock cores located across a gradient of ancient water depth. Our data reveal a pronounced salinity gradient and two discrete stages in the sea's chemical evolution, with the first stage recording a strong redox gradient across the sea and the second stage characterized by oxygen deficiency and toxic hydrogen sulfide at all sites investigated. This expansion of shallow‐water hydrogen sulfide occurred at the same time as the Hangenberg mass extinction event that killed many inhabitants of the shallow oceans. Ultimately, this study is among the first to identify pronounced chemical gradients in an ancient inland sea and link spatiotemporal watermass properties to ocean habitability and extinction during a critical time in Earth history. Key Points Four‐dimensional paleoredox, paleosalinity, and hydrographic reconstruction of the Late Devonian Appalachian Seaway Pronounced watermass heterogeneity over short timescales and distances, including large vertical and lateral salinity gradient Basin‐wide intensification of water column (and potentially photic zone) euxinia during the Hangenberg extinction event

Euxinia, a crucial geological condition, usually signifies more severe extinction events attributed to deoxygenation in Earth's history. Despite extensive exploration of various proxies in paleoredox studies, most are primarily utilized to reconstruct atmospheric pO2, the proportion of anoxic water relative to the entire basin, and broader trends in redox states. Few, however, hold the capacity to precisely delineate local euxinia within confined areas. To address this gap and gain insights into the temporal and spatial extent of benthic euxinia, we propose leveraging the synergistic analysis of total nitrogen isotopes (δ15NTN) and pyrite sulfur isotopes (δ34Spy). Our study focuses on the Triassic Chang 7 Member from the Yanchang Formation, Ordos Basin, North China. Through coupling the δ15NTN and δ34Spy systematics on 11 drill cores within the Ordos Basin, we reconstruct the temporal and spatial distribution of the benthic euxinia zone during the Chang‐7 period. Our results suggest strong spatial heterogeneity of benthic redox conditions, with the euxinia boundary shifting from the central lake to the southwestern sections. Moreover, we identify redox‐controlling factors, including organic carbon loading, water depth, and potential water circulation, and evaluate their interplay with benthic euxinia. Furthermore, the discernment of water circulation patterns may provide an innovative approach to restore the paleowind direction. These findings highlight the effectiveness of coupling δ15NTN and δ34Spy in reconstructing the local benthic redox landscape of benthic environments, and enrich our understanding of biogeochemical processes. Plain Language Summary Understanding past oxygen levels in Earth's waters is crucial for tracing its evolution and habitability. Euxinia, marked by severe deoxygenation, is a key indicator of environmental conditions. While a series of proxies have been used, only a handful of them are applicable to local euxinia identification, especially for lake systems that may possess unique thresholds, complicating the investigation of their biogeochemical processes. The coupling of nitrogen‐sulfur isotopes is innovatively raised to distinguish local bottom euxinia from more oxic (i.e., non‐euxinic) settings. The reconstructed redox landscape of the Triassic Ordos Basin exhibits strong spatiotemporal diversity. The temporal evolution is mainly controlled by water depth, while the spatial heterogeneous euxinia distribution is probably dominated by water circulation, mainly influenced by paleowinds at the surface of lake water. These deductions align with geochemical, tectonic, and sedimentological observations, such as ancient topography of the basin and thickness distribution of tuff layers. These findings put forward a unique window for identifying local euxinia and investigating paleowind orientation. Key Points Systematic analyses of C‐N‐S‐Fe geochemistry of the Triassic Ordos Basin were conducted The spatiotemporal paleoredox landscape was reconstructed by the coupling of nitrogen‐sulfur isotopes The temporal and spatial heterogeneity of euxinia was controlled by water depth and water circulation/ventilation, respectively

The Mesozoic Era is characterized by numerous oceanic anoxic events (OAEs) that are diagnostically expressed by widespread marine organic-carbon burial and coeval carbon-isotope excursions. Here we present coupled high-resolution carbon- and sulfur-isotope data from four European OAE 2 sections spanning the Cenomanian–Turonian boundary that show roughly parallel positive excursions. Significantly, however, the interval of peak magnitude for carbon isotopes precedes that of sulfur isotopes with an estimated offset of a few hundred thousand years. Based on geochemical box modeling of organic-carbon and pyrite burial, the sulfur-isotope excursion can be generated by transiently increasing the marine burial rate of pyrite precipitated under euxinic (i.e., anoxic and sulfidic) water-column conditions. To replicate the observed isotopic offset, the model requires that enhanced levels of organic-carbon and pyrite burial continued a few hundred thousand years after peak organic-carbon burial, but that their isotope records responded differently due to dramatically different residence times for dissolved inorganic carbon and sulfate in seawater. The significant inference is that euxinia persisted post-OAE, but with its global extent dwindling over this time period. The model further suggests that only ∼5% of the global seafloor area was overlain by euxinic bottom waters during OAE 2. Although this figure is ∼30× greater than the small euxinic fraction present today (∼0.15%), the result challenges previous suggestions that one of the best-documented OAEs was defined by globally pervasive euxinic deep waters. Our results place important controls instead on local conditions and point to the difficulty in sustaining whole-ocean euxinia.

The oxygen content of Earth’s atmosphere has varied greatly through time, progressing from exceptionally low levels before about 2.3 billion years ago, to much higher levels afterward. In the absence of better information, we usually view the progress in Earth’s oxygenation as a series of steps followed by periods of relative stasis. In contrast to this view, and as reported here, a dynamic evolution of Earth’s oxygenation is recorded in ancient sediments from the Republic of Gabon from between about 2,150 and 2,080 million years ago. The oldest sediments in this sequence were deposited in well-oxygenated deep waters whereas the youngest were deposited in euxinic waters, which were globally extensive. These fluctuations in oxygenation were likely driven by the comings and goings of the Lomagundi carbon isotope excursion, the longest–lived positive δ ¹³C excursion in Earth history, generating a huge oxygen source to the atmosphere. As the Lomagundi event waned, the oxygen source became a net oxygen sink as Lomagundi organic matter became oxidized, driving oxygen to low levels; this state may have persisted for 200 million years.