Orbital pacing and secular evolution of the Early Jurassic carbon cycle.

Global perturbations to the Early Jurassic environment (∼201 to ∼174 Ma), notably during the Triassic-Jurassic transition and Toarcian Oceanic Anoxic Event, are well studied and largely associated with volcanogenic greenhouse gas emissions released by large igneous provinces. The long-term secular evolution, timing, and pacing of changes in the Early Jurassic carbon cycle that provide context for these events are thus far poorly understood due to a lack of continuous high-resolution δ13C data. Here we present a δ13CTOC record for the uppermost Rhaetian (Triassic) to Pliensbachian (Lower Jurassic), derived from a calcareous mudstone succession of the exceptionally expanded Llanbedr (Mochras Farm) borehole, Cardigan Bay Basin, Wales, United Kingdom. Combined with existing δ13CTOC data from the Toarcian, the compilation covers the entire Lower Jurassic. The dataset reproduces large-amplitude δ13CTOC excursions (>3‰) recognized elsewhere, at the Sinemurian-Pliensbachian transition and in the lower Toarcian serpentinum zone, as well as several previously identified medium-amplitude (∼0.5 to 2‰) shifts in the Hettangian to Pliensbachian interval. In addition, multiple hitherto undiscovered isotope shifts of comparable amplitude and stratigraphic extent are recorded, demonstrating that those similar features described earlier from stratigraphically more limited sections are nonunique in a long-term context. These shifts are identified as long-eccentricity (∼405-ky) orbital cycles. Orbital tuning of the δ13CTOC record provides the basis for an astrochronological duration estimate for the Pliensbachian and Sinemurian, giving implications for the duration of the Hettangian Stage. Overall the chemostratigraphy illustrates particular sensitivity of the marine carbon cycle to long-eccentricity orbital forcing.

Uranium isotope evidence for two episodes of deoxygenation during Oceanic Anoxic Event 2.

Oceanic Anoxic Event 2 (OAE 2), occurring ∼94 million years ago, was one of the most extreme carbon cycle and climatic perturbations of the Phanerozoic Eon. It was typified by a rapid rise in atmospheric CO2, global warming, and marine anoxia, leading to the widespread devastation of marine ecosystems. However, the precise timing and extent to which oceanic anoxic conditions expanded during OAE 2 remains unresolved. We present a record of global ocean redox changes during OAE 2 using a combined geochemical and carbon cycle modeling approach. We utilize a continuous, high-resolution record of uranium isotopes in pelagic and platform carbonate sediments to quantify the global extent of seafloor anoxia during OAE 2. This dataset is then compared with a dynamic model of the coupled global carbon, phosphorus, and uranium cycles to test hypotheses for OAE 2 initiation. This unique approach highlights an intra-OAE complexity that has previously been underconstrained, characterized by two expansions of anoxia separated by an episode of globally significant reoxygenation coincident with the "Plenus Cold Event." Each anoxic expansion event was likely driven by rapid atmospheric CO2 injections from multiphase Large Igneous Province activity.

Mercury evidence for pulsed volcanism during the end-Triassic mass extinction.

The Central Atlantic Magmatic Province (CAMP) has long been proposed as having a causal relationship with the end-Triassic extinction event (∼201.5 Ma). In North America and northern Africa, CAMP is preserved as multiple basaltic units interbedded with uppermost Triassic to lowermost Jurassic sediments. However, it has been unclear whether this apparent pulsing was a local feature, or if pulses in the intensity of CAMP volcanism characterized the emplacement of the province as a whole. Here, six geographically widespread Triassic-Jurassic records, representing varied paleoenvironments, are analyzed for mercury (Hg) concentrations and Hg/total organic carbon (Hg/TOC) ratios. Volcanism is a major source of mercury to the modern environment. Clear increases in Hg and Hg/TOC are observed at the end-Triassic extinction horizon, confirming that a volcanically induced global Hg cycle perturbation occurred at that time. The established correlation between the extinction horizon and lowest CAMP basalts allows this sedimentary Hg excursion to be stratigraphically tied to a specific flood basalt unit, strengthening the case for volcanic Hg as the driver of sedimentary Hg/TOC spikes. Additional Hg/TOC peaks are also documented between the extinction horizon and the Triassic-Jurassic boundary (separated by ∼200 ky), supporting pulsatory intensity of CAMP volcanism across the entire province and providing direct evidence for episodic volatile release during the initial stages of CAMP emplacement. Pulsatory volcanism, and associated perturbations in the ocean-atmosphere system, likely had profound implications for the rate and magnitude of the end-Triassic mass extinction and subsequent biotic recovery.

Transient cooling episodes during Cretaceous Oceanic Anoxic Events with special reference to OAE 1a (Early Aptian).

The two major oceanic anoxic events of the Cretaceous, those of the Early Aptian (OAE 1a) and the Cenomanian-Turonian boundary (OAE 2), registered some of the highest temperatures reconstructed for the Cretaceous Period, and are thought to be related to the input of volcanically derived carbon dioxide from one or more Large Igneous Provinces. Widely distributed deposition of marine organic matter, the hallmark of OAEs, and intensified silicate weathering in response to a globally accelerated hydrological cycle and/or reaction of seawater with freshly extruded basalt, are both potential mechanisms whereby the content of atmospheric carbon dioxide could have been drawn down to promote cooling, on the assumption that this potential effect was not offset by increased addition of this volcanically derived greenhouse gas. Reduction in the supply of such carbon dioxide, with deposition of organic matter and silicate weathering continuing at the same rate, could also have produced cooling. A transient fall in temperature and increase in marine dissolved oxygen levels is well documented for OAE 2, in the form of the so-called Plenus Cold Event or Benthic Oxic Event, associated with southward invasion of certain boreal faunas and an increase in many redox-sensitive and/or chalcophilic elements in seawater caused by temporary loss of anoxic-euxinic sinks as basalt-seawater interaction continued apace. High-resolution studies of OAE 1a show at least three cooling episodes of probable global distribution, one of which (recorded in the stratigraphy of the so-called C4 Segment) is documented at high enough resolution to show correlation with an increase in carbon-isotope values that was probably due to a rise in the quantities of organic matter being buried globally, with consequent potential drawdown of atmospheric CO2 and/or reduction in volcanic input of this greenhouse gas. Both calcium- and lithium-isotope records suggest an increase in silicate weathering over the OAE 1a interval but current relatively low-resolution records cannot at present be tied to any one cooling episode, although the lowest Li-isotope values do derive from the C4 Segment. Evidence for reoxygenation of the ocean during the transient cooling episodes of OAE 1a is meagre, due to the lack of suitable sedimentary archives, although a negative sulfur-isotope excursion in a Pacific shallow-water carbonate section, which can be interpreted as due to oxidation of pyrite and/or sulfur-rich organic matter in the global ocean, suggests that this phenomenon may also have been a feature of the C4 Segment. Further work is required to elucidate the similarities and differences between OAE 2 and OAE 1a, but both phenomena are demonstrably global in reach and represent major disturbances to the carbon cycle with attendant effects on marine temperatures.This article is part of a discussion meeting issue 'Hyperthermals: rapid and extreme global warming in our geological past'.

Sulfur isotopes track the global extent and dynamics of euxinia during Cretaceous Oceanic Anoxic Event 2.

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.

New age constraints on the Lower Jurassic Pliensbachian-Toarcian Boundary at Chacay Melehue (Neuquén Basin, Argentina).

The Pliensbachian-Toarcian boundary interval is characterized by a ~ 3‰ negative carbon-isotope excursion (CIE) in organic and inorganic marine and terrestrial archives from sections in Europe, such as Peniche (Portugal) and Hawsker Bottoms, Yorkshire (UK). A new high-resolution organic-carbon isotope record, illustrating the same chemostratigraphic feature, is presented from the Southern Hemisphere Arroyo Chacay Melehue section, Chos Malal, Argentina, corroborating the global significance of this disturbance to the carbon cycle. The negative carbon-isotope excursion, mercury and organic-matter enrichment are accompanied by high-resolution ammonite and nannofossil biostratigraphy together with U-Pb CA-ID-TIMS geochronology derived from intercalated volcanic ash beds. A new age of ~ 183.73 + 0.35/- 0.50 Ma for the Pliensbachian-Toarcian boundary, and 182.77 + 0.11/- 0.15 for the tenuicostatum-serpentinum zonal boundary, is assigned based on high-precision U-Pb zircon geochronology and a Bayesian Markov chain Monte Carlo (MCMC) stratigraphic age model.

Reduced plate motion controlled timing of Early Jurassic Karoo-Ferrar large igneous province volcanism.

Past large igneous province (LIP) emplacement is commonly associated with mantle plume upwelling and led to major carbon emissions. One of Earth's largest past environmental perturbations, the Toarcian oceanic anoxic event (T-OAE; ~183 Ma), has been linked to Karoo-Ferrar LIP emplacement. However, the role of mantle plumes in controlling the onset and timing of LIP magmatism is poorly understood. Using global plate reconstruction models and Lower Toarcian sedimentary mercury (Hg) concentrations, we demonstrate (i) that the T-OAE occurred coevally with Karoo-Ferrar emplacement and (ii) that timing and duration of LIP emplacement was governed by reduced Pangean plate motion, associated with a reversal in plate movement direction. This new model mechanistically links Earth's interior and surficial processes, and the mechanism is consistent with the timing of several of the largest LIP volcanic events throughout Earth history and, thus, the timing of many of Earth's past global climate change and mass extinction events.

High temperatures in the Late Cretaceous Arctic Ocean.

To understand the climate dynamics of the warm, equable greenhouse world of the Late Cretaceous period, it is important to determine polar palaeotemperatures. The early palaeoceanographic history of the Arctic Ocean has, however, remained largely unknown, because the sea floor and underlying deposits are usually inaccessible beneath a cover of floating ice. A shallow piston core taken from a drifting ice island in 1970 fortuitously retrieved unconsolidated Upper Cretaceous organic-rich sediment from Alpha ridge, a submarine elevated feature of probable oceanic origin. A lack of carbonate in the sediments from this core has prevented the use of traditional oxygen-isotope palaeothermometry. Here we determine Arctic palaeotemperatures from these Upper Cretaceous deposits using TEX86, a new palaeothermometer that is based on the composition of membrane lipids derived from a ubiquitous component of marine plankton, Crenarchaeota. From these analyses we infer an average sea surface temperature of approximately 15 degrees C for the Arctic Ocean about 70 million years ago. This calibration point implies an Equator-to-pole gradient in sea surface temperatures of approximately 15 degrees C during this interval and, by extrapolation, we suggest that polar waters were generally warmer than 20 degrees C during the middle Cretaceous (approximately 90 million years ago).

Late inception of a resiliently oxygenated upper ocean.

Rising oceanic and atmospheric oxygen levels through time have been crucial to enhanced habitability of surface Earth environments. Few redox proxies can track secular variations in dissolved oxygen concentrations around threshold levels for metazoan survival in the upper ocean. We present an extensive compilation of iodine-to-calcium ratios (I/Ca) in marine carbonates. Our record supports a major rise in the partial pressure of oxygen in the atmosphere at ~400 million years (Ma) ago and reveals a step change in the oxygenation of the upper ocean to relatively sustainable near-modern conditions at ~200 Ma ago. An Earth system model demonstrates that a shift in organic matter remineralization to greater depths, which may have been due to increasing size and biomineralization of eukaryotic plankton, likely drove the I/Ca signals at ~200 Ma ago.

Evidence for rapid climate change in the Mesozoic-Palaeogene greenhouse world.

The best-documented example of rapid climate change that characterized the so-called 'greenhouse world' took place at the time of the Palaeocene-Eocene boundary: introduction of isotopically light carbon into the ocean-atmosphere system, accompanied by global warming of 5-8 degrees C across a range of latitudes, took place over a few thousand years. Dissociation, release and oxidation of gas hydrates from continental-margin sites and the consequent rapid global warming from the input of greenhouses gases are generally credited with causing the abrupt negative excursions in carbon- and oxygen-isotope ratios. The isotopic anomalies, as recorded in foraminifera, propagated downwards from the shallowest levels of the ocean, implying that considerable quantities of methane survived upward transit through the water column to oxidize in the atmosphere. In the Mesozoic Era, a number of similar events have been recognized, of which those at the Triassic-Jurassic boundary, in the early Toarcian (Jurassic) and in the early Aptian (Cretaceous) currently carry the best documentation for dramatic rises in temperature. In these three examples, and in other less well-documented cases, the lack of a definitive time-scale for the intervals in question hinders calculation of the rate of environmental change. However, comparison with the Palaeocene-Eocene thermal maximum (PETM) suggests that these older examples could have been similarly rapid. In both the early Toarcian and early Aptian cases, the negative carbon-isotope excursion precedes global excess carbon burial across a range of marine environments, a phenomenon that defines these intervals as oceanic anoxic events (OAEs). Osmium-isotope ratios ((187)Os/(188)Os) for both the early Toarcian OAE and the PETM show an excursion to more radiogenic values, demonstrating an increase in weathering and erosion of continental crust consonant with elevated temperatures. The more highly buffered strontium-isotope system ((87)Sr/(86)Sr) also shows relatively more radiogenic signatures during the early Toarcian OAE, but the early Aptian and Cenomanian-Turonian OAEs show the reverse effect, implying that increased rates of sea-floor spreading and hydrothermal activity dominated over continental weathering in governing sea-water chemistry. The Cretaceous climatic optimum (late Cenomanian to mid Turonian) also shows evidence for abrupt cooling episodes characterized by episodic invasion of boreal faunas into temperate and subtropical regions and changes in terrestrial vegetation; drawdown of CO(2) related to massive marine carbon burial (OAE) may be implicated here. The absence of a pronounced negative carbon-isotope excursion preceding the Cenomanian-Turonian OAE indicates that methane release is not necessarily connected to global deposition of marine organic carbon, but relative thermal maxima are common to all OAEs. 'Cold snaps' have also been identified from the Mesozoic record but their duration, causes and effects are poorly documented.