Isotope Excursion Research Articles

Recognition of a cryptic maximum flooding surface in shallow marine carbonate sequences using geochemical (Y/Ho) proxy data

ABSTRACTSince diagnostic primary depositional sedimentary structures and depth‐dependent grain‐size trends are rarely preserved, building a comprehensive sequence stratigraphic framework for the vast majority of the Phanerozoic carbonate platform sequences is pending. Among the two most important sequence stratigraphic surfaces, while the subaerial unconformity can be reliably identified by either karst development or the appearance of siliciclastic materials, the demarcation of the maximum flooding surface remains difficult in lithologically uniform shallow marine carbonate sequences. The present study attempts to identify the globally documented maximum flooding surface within the body of the negative carbon isotope excursion of the Palaeocene–Eocene Thermal Maximum recorded in the shallow marine carbonate platform sequences. The results show that, along with the carbonate microfacies, the yttrium to holmium ratio (Y/Ho ratio) of the carbonate fraction reliably records the sea‐level changes. A Y/Ho ratio between 70 and 80 demarcates the stratigraphic position of the maximum sea‐level state (the most open marine condition in the studied interval) and maximum flooding surface in the studied sections. Since the Y/Ho ratios remain relatively stable throughout diagenesis, they can be used for maximum flooding surface identification in shallow marine carbonate platform sequences. The possibility exists that the same method can also be applied to the mixed siliciclastic–carbonate systems.

Arctic Alaska deepwater organic carbon burial and environmental changes during the late Albian–early Campanian (103–82 Ma)

The middle Cretaceous greenhouse period experienced profound environmental change including episodes of enhanced global burial of organic carbon marked by carbon isotopic excursions (CIEs). However, the role and response of polar regions like the newly formed, partially enclosed Arctic Ocean Basin during middle Cretaceous carbon burial remains enigmatic. We present the first Arctic deepwater CIE record that characterizes conditions offshore of the Alaska margin north of 75°N paleolatitude. Organic carbon isotopes (δ13Corg) and 103–82 Ma ash zircon U-Pb dates from the distal Hue Shale record multiple Albian–Campanian CIEs during slow ∼3–15 m/Myr sediment accumulation rates. Average total organic carbon (TOC) increased substantially during large 2–3 ‰ CIEs of the ∼101 Ma Albian-Cenomanian boundary event (from 7 to 18 % TOC) and ∼94 Ma Cenomanian-Turonian boundary event (5 to 10 % TOC). Turonian TOC remained elevated (8–13 %) during high global sea levels and temperatures of the Cretaceous Thermal Maximum, followed by an increase from 7 to 11 % TOC during the ∼90 Ma late Turonian event 1.5 ‰ CIE. Average TOC subsequently decreased in the Coniacian–Campanian, but relative maxima occurred during subtle 0.5–1 ‰ CIEs interpreted as the ∼87 Ma late Coniacian event (increase from 4 to 7 % TOC), ∼85 Ma Horseshoe Bay event (3.5 to 4.5 % TOC), and ∼84 Ma Santonian-Campanian boundary event (3.5 to 5 % TOC). Increases in hydrogen index and productivity proxies (P, Ba, Nd) that accompanied each CIE episode with enhanced TOC suggest a strong link between marine productivity and organic carbon burial at short-term CIE timescales. However, long-term (>5–8 Myr) changes in trace metal redox (Mo, Fe, V) and salinity (B/Ga) proxies suggest shifts in prevailing environmental conditions at timescales longer than the CIEs. Late Albian–middle Turonian marine salinity occurred during euxinic (103–98 Ma) and suboxic (98–90 Ma) conditions with deposition interpreted to have occurred within and beneath an oxygen minimum zone, respectively. In contrast, late Turonian–early Campanian (90–82 Ma) freshening and restricted euxinic basin conditions may signal the start of widespread restriction known to characterize the Paleogene Arctic. Overall, these results highlight that middle Cretaceous Arctic deepwater remained a productive marine carbon sink coupled to the global carbon cycle despite evolving Arctic greenhouse conditions.

Stable carbon isotope chemostratigraphy of the base of the Callovian in Greenland

D’Orbigny named the Callovian stage after Kellaways in Wiltshire, UK, in the 1850 s. However, agreement on its boundaries and, more recently, on the position and location of the Global Boundary Stratotype Section and Point (GSSP) for the base of the Callovian has proven difficult for the last 170 years. This is mainly due to the lack of agreement on the appropriate index fossil and its regional and global correlations, as well as the location of the stratotype section. Stable carbon isotope chemostratigraphy and event stratigraphy are now essential tools for aiding in the definition of GSSPs. In this study, stable carbon isotopic analysis of 91 samples from east Greenland’s Middle Jurassic shallow marine sandstones of the Pelion Formation (Store Koldewey and Hold with Hope) and correlative and well-dated offshore siltstones and mudstones of the Fossilbjerget Formation (Jameson Land) is used to discriminate several isotopic events previously observed in other European basins and propose the early Callovian (δ13CTOC) positive carbon isotopic excursion as a secondary marker for defining the Callovian GSSP. The early Callovian (δ13CTOC) positive carbon isotopic excursion is a fundamental tool for superregional correlation between candidate GSSPs and Standard Auxiliary Boundary Stratotypes. It can also help establish a chronological order (synchronous vs diachronous) of species occurrences between different locations.

Late Triassic carbon isotope anomalies in the Canadian Cordillera: Paleoenvironmental disturbances associated with the Norian/Rhaetian boundary and end-Triassic mass extinction event

The Late Triassic was a particularly turbulent interval of the geologic past, marked by repeated paleoenvironmental instability culminating in the end-Triassic mass extinction (ETME). These episodes of disturbance are associated with enhanced volcanism, harbinger of the eventual break-up of Pangea. As evidenced by geochemical signals in the marine carbon isotope record, these events were often significant enough to disrupt the global carbon cycle. However, the duration and extent of ETME-associated disturbances leading up to the Triassic/Jurassic boundary (TJB) remain contentious. The present study investigates eight stratigraphic sections from across British Columbia to create a comprehensive Panthalassan carbon isotope record spanning the Norian to early Hettangian. Three distinct negative excursions are observed: an excursion proximal to the Norian/Rhaetian boundary (NRB), another excursion within the Rhaetian, and a final excursion coinciding with the TJB. This is generally consistent with prior studies, but suggests there may be no clear distinction between the negative excursion associated with the NRB, and the oldest Rhaetian “precursor” excursion proposed to be associated with the TJB. Several of the excursions observed in the present study are too large in magnitude to plausibly reflect global ocean water chemistry (∼10 ‰ compared to the expected ∼3 ‰), indicating some local mechanism was amplifying these carbon isotope excursions. A potential explanation is increased organic carbon respiration in restricted marine environments, triggered during episodes of paleoenvironmental disturbance. Regardless, this evidence for repeated carbon isotope excursions supports paleontological data suggesting that the ETME is not a singular and geologically instantaneous event at the TJB, but is instead the amalgamation of several turnovers beginning as early as the NRB.

Pelsonian negative carbon isotope excursion (PENCIE): A Tethys-wide abnormal carbon cycle event in the Middle Triassic

After the highly perturbed, post-crisis environments of the Early Triassic, the Middle Triassic was characterized by stabilization of environmental and climatic conditions, as evidenced by geochemical profiles, including the carbon cycle. Here, we identify an unexpected new episode of global carbon cycle perturbation during the early Middle Triassic (∼244–243 Ma), indicated by the Pelsonian negative carbonate carbon isotope excursions (PENCIE) and mercury anomalies, which occurred widely across Tethys. These perturbations may have been driven by volcanic activity, as indicated by anomalous peaks in the Hg, Hg/TOC and Hg/TS signals. In addition, Sr isotope, gamma ray and other data suggest that the Hg anomalies were driven by increased terrestrial inputs. Environmental change during the Pelsonian was coupled with the emergence of diverse marine faunas that represented a fully recovered ecosystem. Nutrients brought in by volcanism or inputs from terrestrial sources during environmental perturbation may have contributed to biotic recovery.

Millennial-scale sedimentary evolution of carbonate platforms during the Permian–Triassic boundary hyperthermal event

The millennial-scale response of shallow-water carbonate platforms to the climatic upheaval at the Permian–Triassic boundary (PTB) remains unclear. This study presents three carbonate platform sections across the Permian–Triassic (P–T) boundary in South China and the Lhasa terrane. A total of 14 types of carbonate microfacies were identified, which show that the Liangfengya and Taiping sections in South China were deposited in an inner ramp, and the Wenbudangsang section on the Lhasa terrane was deposited in an outer ramp. Bulk carbonate carbon isotope patterns through the sections are generally characterized by negative excursions (−2.2 to −3.5‰) during the PTB hyperthermal event. These excursions can be divided into four phases (NC1 to NC4), with NC1 before the negative carbon isotope excursion (NCIE) event, NC2 during the initiation phase of the NCIE, NC3 during the body of the NCIE, and the NC4 marking the recovery stage of the NCIE. The pattern of sedimentary changes in each section through the PTB hyperthermal event, and the relationship between these changes and the carbon isotope stages, was established. In the studied sections, the onset of the NCIEs (NC2 stage) preceded evidence for a carbonate production crisis, with the occurrence of anachronistic facies developed after this crisis but prior to the NC3 stage. In detail, our data show that the carbonate production crisis occurred 11 kyr after the onset of the NCIE, and 47 kyr before the first Permian–Triassic mass extinction (PTME), and that the carbonate production crisis may have been closely related to the environmental stresses associated with greenhouse gas emission from the Siberian Traps Large Igneous Province (STLIP).

Carbon isotope stratigraphy and biostratigraphy, and associated organic carbon deposition during the Late Cenomanian to Early Turonian in the Tarfaya Basin, Morocco

The Cenomanian-Turonian (C/T) boundary event, also known as Oceanic Anoxic Event 2 (OAE2), is characterised by significant organic carbon preservation and a positive carbon isotope excursion that is recorded globally in sedimentary strata. In this study of the Tarfaya Basin, Morocco, three outcrop sections were logged - at Lagguing East, Tazra, and En-Naila, dated from Late Cenomanian to Early Turonian. New dating, based on ammonites and planktic foraminifera, combined with high-resolution δ13C isotope stratigraphy, yields a more precise delineation of the C/T boundary in the studied section. A total of 99 samples were collected for combined sedimentological, mineralogical, and geochemical analyses to allow a better understand of the palaeoenvironments of deposition and interpret controlling factors on organic enrichment. Five lithofacies have been identified, all indicative of a relative deep marine setting. Variations in lithofacies can be correlated with relative sea level changes, which align with the global eustatic curve.The OAE2 interval comprises black mudstones that signal anoxic conditions, leading to significant organic matter (OM) preservation, even though they appear weathered in the studied section. Notably, organic matter-rich mudstones were evident during the post-OAE2 Early Turonian maximum marine transgression. Trace element enrichment in these organic-rick mudstones indicates that organic matter accumulation was accompanied with increased sea surface productivity and associated with oxygen-depleted bottom water conditions, which facilitated organic matter preservation and enrichment. Upwelling has also been previously described as a process to deliver nutrients to the shelf, enhancing productivity. Some units with depleted organic content are the result of dilution from continental derived clastics. Others may originally have had high TOC, but were influenced by weathering or diagenetic process, changing from the typical black mudstones to yellow in colour. The identified carbon isotopic values and organic carbon enrichment in the C/T strata of the Tarfaya Basin reflect signals of global perturbations in the carbon cycles.

The last episode of coral-stromatoporoid reef and faunal changes across a Devonian-Carboniferous Boundary section of South China

This study reports the final occurrence of coral-stromatoporoid biostromal reef and the faunal and facies change across the Devonian-Carboniferous Boundary (DCB) at Changtanzi section, Longmenshan area of South China. The biostrome occurred in the third member of the Changtanzi Formation and is uppermost Famennian in age, characterized by abundant and high diversity stromatoporoids and tabulate corals, which were subsequently greatly affected with the environmental fluctuations indicated by the end-Devonian carbon isotope excursion. Stromatoporoids and tabulate corals survived and thrived in the uppermost Famennian but their association was eventually terminated in the Lower Hangenberg Crisis (LHC) by extinction of Famennian stromatoporoids. Brachiopods and rugose corals are found to occur as early as in the Upper Hangenberg Crisis (UHC), represented by solitary rugose corals Hebukophyllum sp., Neozaphrentis sp. and Uralinia sp., as well as abundant brachiopods, gastropods, in general representing post-disaster fauna of low species level diversity. This study shows distinctive faunal and lithofacies changes during the Hangenberg Crisis, and examines the strong link between faunal and environmental changes. The result indicates that the environmental fluctuations in the Devonian-Carboniferous transitions caused sudden and significant impacts on marine ecosystems, leading to the disappearance of coral-stromatoporoid metazoan reefs.

Organic carbon isotope (δ13Corg) curve and extinction trends across the Triassic/Jurassic boundary at Mt. Sparagio (Italy): A tool for global correlations between peritidal and pelagic successions

The Triassic/Jurassic boundary (TJB, 201.3 Ma) is characterized by profound turnovers in both marine and terrestrial biota, known as end-Triassic mass Extinction event (ETE). During this severe event, distinct negative carbon isotope excursions (CIEs) have been globally observed, and they were linked to volcanogenic emissions or methane release by dissociation of clathrates. The triggering factor of the negative CIEs was attributed to the emplacement of the Central Atlantic Magmatic Province (CAMP) and the break-up of the Pangea. Specifically, three significant carbon-cycle disruptions named Precursor, Initial and Main CIE have been recorded in several stratigraphic successions deposited in terrestrial and pelagic environments. We investigated the organic carbon isotope curve from the subtidal facies of the Mount Sparagio section (Sicily, Italy), which is a continuous peritidal succession representing an Upper Triassic to Lower Jurassic carbonate platform edging the south-western side of the Tethys Ocean. For the first time, we achieved a complete profile of organic carbon stable isotopic composition (δ13Corg) during the end-Triassic mass Extinction event (ETE) in a carbonate shallow water environment. The δ13Corg profile highlights the 3 negative excursions that characterized the Triassic/Jurassic boundary time interval in pelagic and deep-water successions. The documented CIEs correspond to significant biotic turnovers recognized along the Mt. Sparagio section, suggesting that also the Upper Triassic-Lower Jurassic carbonate platforms were affected by the onset of the Central Atlantic Magmatic Province. Furthermore, although the Mt. Sparagio section has been studied in detail for microfacies associations and it is well biostratigraphically constrained with shallow marine macro- and microfossils, only the documented δ13Corg negative shifts allowed to correlate peritidal environments to pelagic successions, making the organic carbon curve (δ13Corg) a powerful tool for global correlations.

Transient micropaleontological turnover across a late Eocene (Priabonian) carbon and oxygen isotope shift on Blake Nose (NW Atlantic)

Abstract. The Gulf Stream, a western boundary current transporting warm water into the North Atlantic, plays a key role in climate regulation and oceanographic stability at a regional and global scale as part of the Atlantic Meridional Overturning Circulation (AMOC). Evidence suggests that an ancestral Gulf Stream has existed since the Mesozoic, and it has altered its course repeatedly over Cenozoic times. In this study, we focus on the upper Eocene (Priabonian, ca. 36 Ma) from Ocean Drilling Program Site 1053 on Blake Nose (subtropical North Atlantic). Bulk carbon and oxygen stable isotopes, as well as benthic foraminiferal and calcareous nannofossil assemblages, provide an integrated assessment of the palaeoceanographic changes impacting the area through the water column to the seafloor. Micropaleontological assemblages suggest changes in surface ocean stratification and nutrient supply to the seafloor coeval with a paired negative carbon and oxygen isotope excursion and the return to background conditions higher up in the study section. These transitory changes are compatible with the longitudinal displacement of the proto-Gulf Stream and its related eddies. Our results build on previous work and support the hypothesis that links palaeoceanographic changes in the Blake Nose area with shifts in the proto-Gulf Stream during the middle and late Eocene.

A mid-Cretaceous carbon isotope reference curve for the SE Neo-Tethys region (Zagros, W Iran)

Stable carbon isotope chemostratigraphy and the associated reference curves have proved to be valuable tools for stratigraphic calibration and long-distance correlations. Nonetheless, the reference curves covering the Cretaceous have mostly been produced from localities located within the W Neo-Tethys. In order to establish a reference curve for the SE Neo-Tethys margin, an Aptian–Albian hemipelagic carbonate-rich succession deposited along the Zagros Basin (SW Iran) was examined for planktic foraminifera biostratigraphy, carbon isotope stratigraphy, and sedimentological characteristics. Eight biozones including Globigerinelloides ferreolensis, Globigerinelloides algerianus, Hedbergella trocoidea, Paraticinella bejaouaensis, Muricohedbergella planispira, Ticinella (T.) primula, Biticinella breggiensis, and Pseudothalmanninella (P.)ticinensis as well as two subzones enclosing T. praeticinensis and P. subticinensis assign the strata to the early late Aptian–late Albian age. A carbon isotope record constrained by the planktic foraminifera zonation scheme shows good concordance with existing composite reference curves from the W Neo-Tethys region. Several carbon isotope excursions (CIEs) characterizing global marine events including Oceanic Anoxic Event (OAE) 1a, OAE1b, OAE1c and associated sub-events can be identified in the studied section. Deoxygenated bottom waters associated with the formation of OAE1a and OAE1b are indicated by distinct lithological signatures including enrichment in pyrite and glauconite, nodular and stratiform chert beds, as well as enhanced organic matter contents. We integrate the here-studied interval with a previously published upper Albian−Turonian succession from the same outcrop section, forming a composite, stratigraphically well-constrained section. This results in a high-resolution carbon isotope record for the SE Neo-Tethys margin, considered to represent an expedient reference Aptian–Turonian curve for this region. Correlation of this new curve with previously published records from the Middle East has helped to address ambiguities regarding the stratigraphic positions of the early/late Aptian and Aptian/Albian boundaries identified by previous studies.

Identification of carbonates with high positive carbon isotope excursion from the Liaohe Group in the northeastern North China Craton and implications for the Lomagundi-Jatuli Event

Identification of carbonates with high positive carbon isotope excursion from the Liaohe Group in the northeastern North China Craton and implications for the Lomagundi-Jatuli Event

Volcanogenic mercury and plant mutagenesis during the end-Permian mass extinction: Palaeoecological perturbation in northern Pangaea

The end-Permian extinction (EPE) (∼251.9 Ma) is considered the most severe biotic crisis in Earth’s history. Rapid climatic change and oceanic acidification triggered by Siberian Traps volcanism culminated in a widely documented mass extinction in the marine realm, but the event’s impact on terrestrial ecosystems, particularly plant communities, is less well understood. While the existence of a floral mass extinction at the Permian-Triassic Boundary (PTB) is still debated, there is mounting evidence for pervasive mutagenesis among various plant lineages, as expressed by the high incidence of aberrant spores and pollen grains. Previous studies have proposed a causal relationship between increased UV-B flux and plant mutagenesis across the PTB, yet the role of volcanically derived heavy metals as a contributing factor has received considerably less attention. Here we present the results of a high-resolution palynological, sedimentological, and geochemical analysis of a continuous and previously unstudied PTB section from the Norwegian Arctic. The study reveals an abrupt increase in the levels of heavy metals across the EPE negative carbon isotope excursion (CIE). Palynological analysis indicates disruption, and a phased transition of plant communities at the PTB, without a significant turnover in species or decrease in diversity. However, the abrupt appearance and elevated abundance of aberrant palynomorphs coincides with increased concentrations of As, Co, Hg, and Ni, which is interpreted as compelling evidence for heavy metal-induced stress and genetic disturbance in plant communities during the EPE. We hypothesise that biomagnification of these elements may have been a significant driver for the end-Permian biotic crisis. Our findings are correlated via biostratigraphy and chemostratigraphy with other circum-Arctic PTB sections described in the literature, demonstrating the isochroneity and facies independence of these widespread palaeoecological changes.

Biotic and abiotic processes in Ediacaran spheroid formation

Organic-rich shales from the uppermost Doushantuo Fm. (South China) record one of the most negative carbonate carbon isotopic excursions in Earth’s history, known as the Shuram excursion, and contain meter to micro-size spheroids. In this study, we use Raman and energy dispersive spectroscopy to identify and describe the most common diagenetic spheroids to refine our understanding of the profound perturbations of the carbon cycle and the evolution of pore fluid chemistry imprinted in the sedimentary Precambrian record, especially in the late Ediacaran. The presence of 13C-depleted carbonate concretions or organic matter (OM) enclosed by lenticular dolomitic structures within the host shale unit suggests OM remineralisation and anaerobic oxidation, resulting in authigenic carbonate precipitation during the earliest stages of sediment diagenesis. Other mineralogical features, however, point to high levels of primary production, such as apatite bands that host spheroidal microfossils with highly fluorescent quartz and OM within abiotic concretions. These observations highlight the importance of considering co-occurring biotic and abiotic processes in explaining the formation of diagenetic spheroids in ancient sedimentary environments. From an astrobiology perspective, the interplay of biotic and abiotic processes reflects the complexity of early life systems and the environments that may exist on other terrestrial planets. Understanding the signatures of biotic and abiotic interactions in the Doushantuo Fm. is crucial for identifying potential biosignatures in extraterrestrial materials, thereby enhancing our understanding of life’s universality and adaptability in diverse and extreme environments.

A protracted Mesoproterozoic carbon cycle perturbation in response to volcanism at ∼ 1.39 Ga

The Earth's carbon cycle throughout the Mesoproterozoic Eon remains a long-standing problem in geology. Recent studies have reported vigorous tectonic and volcanic activities and co-appearances of multiple black shale depositions and large igneous provinces (LIPs) events of this time. These events might have greatly affected the Mesoproterozoic carbon cycle. Additionally, compared with the Phanerozoic, the Mesoproterozoic Eon frequently recorded peculiarly long-lasting carbon isotope disruptions, suggesting specific driven systems behind them. Yet, the internal links between carbon isotope perturbations, black shale depositions and magmatism during this period are poorly understood. Here we identify a ∼ 5.7‰, lengthy (10.6 Myr) negative carbon isotope excursion event recorded in the Mesoproterozoic Xiamaling Formation of North China Craton (XML-NCIE). Laboratory and modeling work indicate that, dissimilar to most Phanerozoic NCIEs, this event is a two-stepped, multi-factor-controlled case. Step 1-NCIE is caused by massive light carbon injection (125,000 Gt, -30‰) from the coexisting strong volcanism (LIPs) and methanogenesis. After step 1, although the volcanism is terminated, it probably sparks some follow-up activities and brings about another episode of carbon input (30,000 Gt, -37‰). In summary, volcanism is the primary triggering factor of XML-NCIE and further acts to motivate successive reactions. Meanwhile, the Mesoproterozoic less forceful volcanism is conducive to the particularly long XML-NCIE duration. This finding may also bring fresh perspectives on the Mesoproterozoic black shale depositions, suggesting that both volcanism and microbial reworking processes might have remarkably affected the Mesoproterozoic carbon cycle and promoted organic carbon burial at that time.

Carbon isotope chemostratigraphy of the Yucca Formation from the Solitario, Big Bend Ranch State Park, Texas

Introduction: The Yucca Formation is a Lower Cretaceous sedimentary unit present in West Texas. Based on its relative stratigraphic position in the Cretaceous succession of West Texas, it is expected that the Yucca Formation is of Albian and/or Aptian age. It is also expected that the carbon isotope excursions associated with OAE 1a and OAE 1b should be identified in the Yucca Formation. The goals of this project are to 1. construct a carbon isotope chemostratigraphic record of the Yucca Formation, and 2. correlate the Yucca Formation with strata of similar age using chemostratigraphy.Methods: 163 samples were collected from Big Bend Ranch State Park (BBRSP) to determine the δ13C value of bulk sedimentary organic matter.Results: C-isotope values range from −27.02‰ to −18.42‰.Discussion: Carbon isotope excursions (CIEs) that are associated with the Aptian-Albian Boundary are identified as well as CIEs associated with Oceanic Anoxic Events (1a and 1b). This allows us to conclude that the Aptian-Albian boundary is recorded within the Yucca Formation strata at about 71 m above the base of the section exposed in the Lower Shutup of the Solitario in Big Bend Ranch State Park. Regional correlation of the Yucca Formation to other chemostratigraphic records from other Cretaceous strata suggests that the Yucca Formation in BBRSP is time equivalent to the Sligo, Pine Island, James, Bexar, and a portion of the lower Glen Rose Formation on the Comanche Platform and to a portion of the lower Glen Rose Formation in Big Bend National Park.

Mercury isotope profiles against the massive dissolved organic carbon remineralization for the largest Ediacaran carbonate-carbon isotope excursion

The Doushantuo negative carbon isotope excursion (DOUNCE), which corresponds to the worldwide mid-Ediacaran Shuram-Wonoka anomaly (567∼574 Ma), is characterized by a significant shift in carbonate-carbon isotopic values (δ13Ccarb) from ∼ 5‰ down to ∼ -12‰. It has been proposed to result from remineralizing a giant dissolved organic carbon (DOC) pool within the Ediacaran Ocean. However, direct geological proof confirming the existence and oxidation of such a large DOC reservoir is still scarce. The strong affinity of Hg for organic carbon in the surface environment could provide helpful information on the potential contribution of Hg-associated DOC to the DOUNCE. Here, Hg content and isotope values of marine sediments from the slope (Songtao) and basin (Fengtan) settings were measured and discussed with the previously published data from the shelf environment (Jiulongwan) in South China. The generally low Hg concentration and the absence of Hg/TOC (total organic carbon) anomaly within the DOUNCE carbonate from the proximal to distal sections argue against the massive contribution of DOC to the DOUCE. The gradually decreasing Δ199Hg but increasing δ202Hg in the proximal depositions would be indeed ascribed to the enhanced terrestrial input and the photic zone euxinia (PZE), which might hinder the development and expansion of macroscopic multicelluar eukaryotes via H2S poisoning. Our new Hg isotope data casts doubt on the DOC oxidation model, and contributions from other 12C-enriched reservoirs (e.g. recycled carbonatites) could be the cause of the most significant negative δ13Ccarb excursion in Ediacaran.

Carbonate uranium isotopes record global expansion of marine anoxia during the Toarcian Oceanic Anoxic Event

The Toarcian Oceanic Anoxic Event (T-OAE; ~183 Mya) was a globally significant carbon-cycle perturbation linked to widespread deposition of organic-rich sediments, massive volcanic CO2 release, marine faunal extinction, sea-level rise, a crisis in carbonate production related to ocean acidification, and elevated seawater temperatures. Despite recognition of the T-OAE as a potential analog for future ocean deoxygenation, current knowledge on the severity of global ocean anoxia is limited largely to studies of the trace element and isotopic composition of black shales, which are commonly affected by local processes. Here, we present the first carbonate-based uranium isotope (δ238U) record of the T-OAE from open marine platform limestones of the southeastern Tethys Ocean as a proxy for global seawater redox conditions. A significant negative δ238U excursion (~0.4‰) is recorded just prior to the onset of the negative carbon isotope excursion comprised within the T-OAE, followed by a long-lived recovery of δ238U values, thus confirming that the T-OAE represents a global expansion of marine anoxia. Using a Bayesian inverse isotopic mass balance model, we estimate that anoxic waters covered ~6 to 8% of the global seafloor during the peak of the T-OAE, which represents 28 to 38 times the extent of anoxia in the modern ocean. These data, combined with δ238U-based estimates of seafloor anoxic area for other CO2-driven Phanerozoic OAEs, suggest a common response of ocean anoxia to carbon release, thus improving prediction of future anthropogenically induced ocean deoxygenation.

Oxygenation of Earth's atmosphere induced metabolic and ecologic transformations recorded in the Lomagundi-Jatuli carbon isotopic excursion.

The oxygenation of Earth's atmosphere represents the quintessential transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution; molecular clock models indicate the diversification and ecological expansion of respiratory metabolisms in the several hundred million years following atmospheric oxygenation. Across this same interval, the geological record preserves 13C enrichment in some carbonate rocks, called the Lomagundi-Jatuli excursion (LJE). By combining data from geologic and genomic records, a self-consistent metabolic evolution model emerges for the LJE. First, fermentation and methanogenesis were major processes remineralizing organic carbon before atmospheric oxygenation. Once an ozone layer formed, shallow water and exposed environments were shielded from UVB/C radiation, allowing the expansion of cyanobacterial primary productivity. High primary productivity and methanogenesis led to preferential removal of 12C into organic carbon and CH4. Extreme and variable 13C enrichments in carbonates were caused by 13C-depleted CH4 loss to the atmosphere. Through time, aerobic respiration diversified and became ecologically widespread, as did other new metabolisms. Respiration displaced fermentation and methanogenesis as the dominant organic matter remineralization processes. As CH4 loss slowed, dissolved inorganic carbon in shallow environments was no longer highly 13C enriched. Thus, the loss of extreme 13C enrichments in carbonates marks the establishment of a new microbial mat ecosystem structure, one dominated by respiratory processes distributed along steep redox gradients. These gradients allowed the exchange of metabolic by-products among metabolically diverse organisms, providing novel metabolic opportunities. Thus, the microbially induced oxygenation of Earth's atmosphere led to the transformation of microbial ecosystems, an archetypal example of planetary microbiology.IMPORTANCEThe oxygenation of Earth's atmosphere represents the most extensive known chemical transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution by providing oxidants independent of the sites of photosynthesis. Thus, the evolutionary changes during this interval and their effects on planetary-scale biogeochemical cycles are fundamental to our understanding of the interdependencies among genomes, organisms, ecosystems, elemental cycles, and Earth's surface chemistry through time.

Shallow ocean deoxygenation drove trilobite turnover during the late Cambrian SPICE event

The spread of marine anoxia is believed to have played a key role in the development of the SPICE (Steptoean Positive Carbon Isotope Excursion) event and the end-Marjuman extinction in the late Cambrian (∼497.5 m.y. ago), but their cause-and-effect relationship is poorly constrained. Here we present an integrated analysis of carbonate δ13C, cerium anomalies (Ce/Ce*), and genus-level diversity data of trilobites from the North China Platform. Our results show tightly coupled changes between the SPICE, an increase in Ce/Ce*, and a trilobite turnover event, which we interpret as indicating enhanced productivity and organic remineralization, leading to the development of low-oxygen conditions in shallow-water settings. This study therefore establishes a direct link between local ecological stress and trilobite turnover during the global SPICE event. Furthermore, the presence of low-oxygen rather than fully anoxic conditions during the peak of the SPICE event could explain the nature of the end-Marjuman crisis, which was characterized by the replacement of shallow-water fauna by deeper-water counterparts that were potentially more tolerant of hypoxia.