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Ocean acidification (OA) during the Paleocene-Eocene thermal maximum (PETM) likely caused a biocalcification crisis. The calcium isotope composition (δ44/40Ca) of primary carbonate producers may be sensitive to OA. To test this hypothesis, we constructed the first high-resolution, high-precision planktic foraminiferal δ44/40Ca records before and across the PETM. The records employ specimens of Morozovella spp. collected from Ocean Drilling Program Sites 1209 (Shatsky Rise, Pacific Ocean) and 1263 (Walvis Ridge, Atlantic Ocean). At Site 1209, δ44/40Ca values start at −1.33‰ during the Upper Paleocene and increase to a peak of −1.15‰ immediately before the negative carbon isotope excursion (CIE) that marks the PETM onset. Values remain elevated through the PETM interval and decrease into the earliest Eocene. A shorter-term record for Site 1263 shows a similar trend, although δ44/40Ca values are on average 0.22‰ lower and decrease shortly after the CIE onset. The trends support neither diagenetic overprinting, authigenic carbonate additions, nor changes in the δ44/40Ca value of seawater. Rather, they are consistent with a kinetic isotope effect, whereby calcite δ44/40Ca values inversely correlate with precipitation rate. Geologically rapid Ca isotope shifts appear to reflect the response of Morozovella to globally forced changes in the local carbonate geochemistry of seawater. All data combined suggest that the PETM-OA event occurred near the peak of a gradual reduction in seawater carbonate ion concentrations during a time of elevated atmospheric pCO2, potentially driven by North Atlantic igneous province emplacement.

Large igneous province (LIP) eruptions are hypothesized to trigger biocalcification crises. The Aptian nannoconid crisis, which correlates with emplacement of the Ontong Java Plateau and Oceanic Anoxic Event 1a (OAE 1a, ca. 120 Ma), represents one such example. The Ca isotope (δ44/40Ca) system offers potential to detect biocalcification fluctuations in the rock record because Ca isotope fractionation is sensitive to precipitation rate. However, other primary and secondary processes, such as input-output flux perturbations and early diagenesis, can produce similar signals. Here, we exploit emergent properties of the stable Sr isotope (δ88/86Sr) system to resolve the origin of δ44/40Ca variability during OAE 1a. This study reports high-precision thermal ionization mass spectrometry (TIMS) δ44/40Ca, δ88/86Sr, and 87Sr/86Sr records for Hole 866A of Ocean Drilling Program Leg 143 drilled in Resolution Guyot, mid-Pacific Ocean. The samples span ∼27 m.y. from the Barremian (ca. 127 Ma) to the Albian (ca. 100 Ma). The δ44/40Ca and δ88/86Sr secular trends differ from the 87Sr/86Sr record but mimic each other. δ44/40Ca and [Sr], as well as δ44/40Ca and δ88/86Sr, strongly correlate and yield slopes predicted for kinetic control, which demonstrates that variable mass-dependent fractionation rather than end-member mixing dominated the isotopic relationship between carbonates and seawater. Positive δ44/40Ca and δ88/86Sr shifts that begin before OAE 1a and peak within the interval are consistent with reduced precipitation rates. All results combined point to a cascade of effects on rate-dependent Ca and Sr isotope fractionation, which derive from the dynamic interplay between LIP eruptions and biocalcification feedbacks.

Paleoclimate during the Cenomanian-Turonian Oceanic Anoxic Event 2 (OAE 2, 94.5–93.9 Ma) was characterized by elevated atmospheric CO2 concentrations and peak global temperatures. In this study, we employ δ66Zn measured on samples spanning OAE 2 in an expanded hemipelagic section in Tibet to trace changes in the major fluxes that influence biogeochemical cycles. The prominent feature of the δ66Zn record in the studied section is a continuous decrease from ∼1‰ at the onset of OAE 2 to a minimum of ∼0.2‰ within the Plenus Cold Event (ca. 94.3 Ma), followed by a stepwise recovery through the upper part of OAE 2. The negative shift in δ66Zn corresponds with higher terrigenous inputs, as revealed by previously published detrital index and TOC/TN (total organic carbon to total nitrogen) ratio records, and covaries with a notable decreasing trend recorded in compiled pCO2 data of different basins. We propose that influx of isotopically light Zn from weathered volcanic rocks associated with submarine large igneous provinces and/or (sub)tropic Indian continental volcanics is likely responsible for the δ66Zn decrease. We infer that the recovery of δ66Zn was caused by continued high primary production and an inevitable decline in the flux of light Zn as volcanic terrains were progressively weathered. The ultimate cessation of OAE 2 may have been a consequence of the same effect, with the nutrient supply from weathering reaching a minimum threshold to maintain productivity-anoxia feedback.

Cephalopod carbonate geochemistry underpins studies ranging from Phanerozoic, global-scale change to outcrop-scale paleoecological reconstructions. Interpreting these data hinges on assumed similarity to model organisms, such as Nautilus, and generalization from other molluscan biomineralization processes. Aquarium rearing and capture of wild Nautilus suggest shell carbonate precipitates quickly (35 μm/day) in oxygen isotope equilibrium with seawater. Other components of Nautilus shell chemistry are less well-studied but have potential to serve as proxies for paleobiology and paleoceanography. To calibrate the geochemical response of cephalopod δ15Norg, δ13Corg, δ13Ccarb, δ18Ocarb, and δ44/40Cacarb to modern anthropogenic environmental change, we analyzed modern, historical, and subfossil Nautilus macromphalus from New Caledonia. Samples span initial human habitation, colonialization, and industrial pCO2 increase. This sampling strategy is advantageous because it avoids the shock response that can affect geochemical change in aquarium experiments. Given the range of living depths and more complex ecology of Nautilus, however, some anthropogenic signals, such as ocean acidification, may not have propagated to their living depths. Our data suggest some environmental changes are more easily preserved than others given variability in cephalopod average living depth. Calculation of the percent respired carbon incorporated into the shell using δ13Corg, δ13Ccarb, and Suess-effect corrected δ13CDIC suggests an increase in the last 130 years that may have been caused by increasing carbon dioxide concentration or decreasing oxygen concentration at the depths these individuals inhabited. This pattern is consistent with increasing atmospheric CO2 and/or eutrophication offshore of New Caledonia. We find that δ44/40Ca remains stable across the last 130 years. The subfossil shell from a cenote may exhibit early δ44/40Ca diagenesis. Questions remain about the proportion of dietary vs ambient seawater calcium incorporation into the Nautilus shell. Values of δ15N do not indicate trophic level change in the last 130 years, and the subfossil shell may show diagenetic alteration of δ15N toward lower values. Future work using historical collections of Sepia and Spirula may provide additional calibration of fossil cephalopod geochemistry.

The Paleocene‐Eocene Thermal Maximum is marked by a prominent negative carbon‐isotope excursion, reflecting the injection of thousands of gigatons of isotopically light carbon into the atmosphere. The sources of the isotopically light carbon remain poorly constrained. Utilizing a multiproxy geochemical analysis (osmium isotopes, mercury, sulfur, and platinum group elements) of two Paleocene‐Eocene boundary records, we present evidence that a comet impact and major volcanic activity likely contributed to the environmental perturbations during the Paleocene‐Eocene interval. Additionally, Earth system model simulations indicate that stratospheric sulfate aerosols, commensurate with the impact magnitude, were likely to have caused transient cooling and reduced precipitation. Plain Language Summary The Paleocene‐Eocene Thermal Maximum (~55.9 Ma) records a period of climate warming associated with the injection of thousands of gigatons of carbon into the atmosphere. However, the sources of the carbon are still unclear. Our study uses geochemical data (osmium isotopes, mercury, sulfur, and platinum group elements) of two North Atlantic Ocean drill cores across the Paleocene‐Eocene interval to suggest that both a comet impact and large‐scale volcanism occurred at that time. The comet is estimated to be small (~3.3 km diameter) with ~0.4 Gt carbon and thus cannot be responsible for the Paleocene‐Eocene Thermal Maximum. However, climate modeling suggests that the comet impact might have caused transient cooling and reduced precipitation.

Carbon dioxide release during Deccan Traps volcanism and the Chicxulub impact likely contributed to the Cretaceous-Paleogene (K-Pg) mass extinction; however, the intensity and duration of CO2 input differed between the two events. Large and rapid addition of CO2 to seawater causes transient decreases in pH, [CO32–], and carbonate mineral saturation states. Compensating mechanisms, such as dissolution of seafloor sediment, reduced biomineralization, and silicate weathering, mitigate these effects by increasing the same parameters. The calcium isotope ratios (δ44/40Ca) of seawater and marine carbonates are hypothesized to respond to these perturbations through weathering/carbonate deposition flux imbalances and/or changes in fractionation between carbonate minerals and seawater. We used a high-precision thermal ionization mass spectrometry method to measure δ44/40Ca values of aragonitic bivalve and gastropod mollusk shells from the K-Pg interval of the López de Bertodano Formation on Seymour Island, Antarctica. Well-preserved shells spanning the late Maastrichtian (ca. 67 Ma) to early Danian (ca. 65.5 Ma) have δ44/40Ca values ranging from −1.89‰ to −1.57‰ (seawater [sw]). Shifts in δ44/40Ca inversely correlate with sedimentological indicators of saturation state. A negative excursion begins before and continues across the K-Pg boundary. According to a simple mass-balance model, neither input/output flux imbalances nor change in the globally integrated bulk carbonate fractionation factor can produce variations in seawater δ44/40Ca sufficient to explain the measured trends. The data are consistent with a dynamic molluscan Ca isotope fractionation factor sensitive to the carbonate geochemistry of seawater. The K-Pg extinction appears to have occurred during a period of carbonate saturation state variability caused by Deccan volcanism.

We report high-resolution, high-precision δ44/40Ca, δ88/86Sr, and 87Sr/86Sr records spanning the Permian-Triassic boundary (PTB) from the Meishan and Dajiang carbonate successions in south China. The goal of the study was to understand the behavior of Ca and Sr isotopes during a time period in Earth history characterized by severe biological and environmental perturbations, including a major mass extinction, flood basalt volcanism, ocean acidification, and sea level fluctuations. Dajiang displays negative δ44/40Ca and δ88/86Sr excursions and invariant 87Sr/86Sr ratios in the

Cretaceous oceanic anoxic event 2 (OAE2) is thought to have been contemporary with extensive volcanism and the release of large quantities of volcanic CO2 capable of triggering marine anoxia through a series of biogeochemical feedbacks. High-resolution reconstructions of atmospheric CO2 concentrations across the initiation of OAE2 suggest that there were also two distinct pulses of CO2 drawdown coeval with increased organic carbon burial. These fluctuations in CO2 likely led to significant climatic changes, including fluctuations in temperatures and the hydrological cycle. Paleofire proxy records suggest that wildfire was a common occurrence throughout the Cretaceous Period, likely fueled by the estimated high atmospheric O2 concentrations at this time. However, over geological time scales, the likelihood and behavior of fire are also controlled by other factors such as climate, implying that CO2-driven climate changes should also be observable in the fossil charcoal record. We tested this hypothesis and present a high-resolution study of fire history through the use of fossil charcoal abundances across the OAE2 onset, and we compared our records to the estimated CO2 fluctuations published from the same study sites. Our study illustrates that inferred wildfire activity appears to relate to changes in CO2 occurring across the onset of OAE2, where periods of CO2 drawdown may have enabled an increase in fire activity through suppression of the hydrological cycle. Our study provides further insight into the relationships between rapid changes in the carbon cycle, climate, and wildfire activity, illustrating that CO2 and climate changes related to inferred wildfire activity can be detected despite the estimated high Cretaceous atmospheric O2 concentrations.

Oceanic Anoxic Event 2 (OAE2; c. 94.5–93.9 Ma) offers insight into the mechanisms of past climate change linked to organic productivity and carbon sequestration. It has been studied extensively, but the vast majority of data come from marine records, thus providing an incomplete view of past climate dynamics. Here we integrate new high-resolution data and published records on depositional environments, the carbon-isotope composition of bulk organic carbon (δ13Corg) and plant cuticles (δ13Ccut), and stomatal-index values, a proxy for pCO2, in well-preserved terrestrial through marginal-marine archives of the initial phase of OAE2. The study area is located on the western margin of the Western Interior Seaway (southwestern Utah). Age constraints are based on a new U-Pb bentonite age and correlation to an orbitally calibrated interval of the Bridge Creek Limestone. n-Alkane abundance suggests predominance of terrestrial contributions to bulk organic carbon for most samples. Despite similarities between carbon-isotope variations and transgressive-regressive shoreline movements, it is argued that δ13Corg and δ13Ccut are not strongly affected by local variables. A series of negative, ~2‰ carbon-isotope excursions is identified and attributed to changes in the size and isotopic value of the atmospheric CO2 reservoir. The temporal spacing of these anomalies (80–120 kyr) is consistent with changes in insolation modulated by orbital eccentricity. A systematic, phase-shifted relationship between the negative carbon-isotope excursions and transgressive increments further suggests a link between carbon-cycle perturbations and meter-scale sea-level change on the 100-kyr time scale. A conceptual model involving insolation-controlled aquifer charge/discharge and biomass burial/degradation in the monsoonal belt is proposed. The framework presented here is available to facilitate further research on the interplay of terrestrial and oceanic carbon reservoirs during OAE2.

Astronomically-forced insolation cycles (“Milankovitch cycles”) serve as a primary control on climate, and when preserved in the stratigraphic record, they provide a high-resolution in situ chronometer. These celestial rhythms derive from the fundamental frequencies of the Solar System, and Earth's precession constant. The fundamental frequencies of Earth and Mars presently define a secular resonance of 2:1 (2.4 Myr to 1.2 Myr), and are hypothesized to have undergone a transition between 50–100 Ma, due to the chaotic behavior of the Solar System. In this study, a 15-Myr long cyclostratigraphic record from the mid-latitude Western Interior Seaway (WIS; spanning 82–97 Ma) is assembled to quantify eccentricity amplitude modulation (AM) and obliquity AM, which could reveal the 2:1 resonance when present. Ten high-precision radioisotopic dates from the study interval permit a rigorous anchoring of the floating astrochronologies for comparison with theoretical astronomical models. The analysis is complimented by the construction of an astronomically tuned δ 13 C org composite for the early Cenomanian-early Campanian, which allows a new assessment of linkages between million-year scale astronomical forcing and perturbations of the Late Cretaceous carbon cycle. Evaluation of the La2004 model reveals a switch of eccentricity modulation from 2.4-Myr cycles to a 1.2-Myr cycle from 90 to 86.5 Ma, followed by a return to a 2.4 Myr cycle in younger strata, compatible with observations from the WIS composite. These two resonance transitions are absent in the La2010d and La2011 models. Among 11 solutions calculated by Zeebe (2017) , some show resonance transitions during this period, but none of them match the geological record with respect to the observed long eccentricity modulation. The results of this study also suggest that positive carbon isotope excursions are closely related to obliquity power minima, but this interpretation will require further analysis for full confirmation.

Proximal marine strata of the North American Western Interior Basin (WIB) preserve a rich record of biotic turnover during Oceanic Anoxic Event 2 (OAE2; ca. 94 Ma), a pronounced Late Cretaceous carbon cycle perturbation interpreted to reflect global warming, widespread hypoxia, and possible ocean acidification. To develop a more robust synthesis of paleobiologic and geochemical data sets spanning this Earth-life transition, we drilled the 131 m Smoky Hollow #1 Core (SH#1), on the Kaiparowits Plateau of southern Utah, USA, recovering the Cenomanian–Turonian Boundary (CTB) interval in the Tropic Shale Formation. A 17.5 m positive excursion in high-resolution bulk carbon isotope chemostratigraphy (δ13Corg) of SH#1 characterizes the most expanded OAE2 record recovered from the mid-latitudes of the WIB.Depleted values in a paired carbonate carbon isotope (δ13Ccarb) chemostratigraphy cyclically punctuate the OAE2 excursion. These depletions correspond to intervals in the core with a higher degree of carbonate diagenesis and correlate well to an existing sequence stratigraphic framework of flooding surfaces in the shoreface facies of the Markagunt Plateau (∼100 km west). We detect statistically significant evidence for astronomical cycles in the δ13Ccarb data set, imparted by diagenesis at flooding surfaces, and develop a floating astronomical time scale (ATS) for the study interval. Stable eccentricity cycles (405 k.y.) align with stratigraphic sequences and associated trends in sedimentation rate, and short eccentricity cycles (∼100 k.y.) pace nested parasequences. These results confirm an astronomical signal and, therefore, climatic forcing of relative sea level during OAE2 in the WIB. Furthermore, cross-basin correlation of the ATS and expanded δ13C chemostratigraphy of SH#1 suggests that these transgressive-regressive parasequences modulated siliciclastic sediment delivery in the seaway and contributed to deposition of prominent rhythmically bedded CTB units across the WIB, including the Bridge Creek Limestone. The presented approach to analysis of these proximal offshore siliciclastic facies links early diagenetic influences on chemostratigraphy to astronomically modulated sequence stratigraphic horizons, and helps to resolve rates of paleobiologic and paleoenvironmental change during a significant Mesozoic carbon cycle perturbation.

Fluctuations in depositional conditions during the onset of severe climate events in Earth history predispose stratigraphic archives to hiatuses, often hindering complete reconstructions of paleoclimate events and their triggers. Several studies have proposed that a hiatus of unknown duration exists at the base of Oceanic Anoxic Event 2 (OAE2) in the North American Western Interior Basin at the base Turonian global boundary stratotype section and point (GSSP) in Pueblo, Colorado, which potentially influences integrated radioisotopic, biostratigraphic, and astrochronologic age models of the Cenomanian-Turonian boundary interval. To quantify the duration of this hiatus, refine the chronology of OAE2, and assess marine geochemical perturbations associated with the onset of the event, we present new 40Ar/39Ar dates from regional bentonites along with a new proximal-distal chemostratigraphic transect of the epeiric Western Interior Basin (WIB), including initial osmium isotope (Osi) and stable carbon isotope (δ13C) data. The new 40Ar/39Ar age determinations confirm and further constrain previous estimates of Cenomanian-Turonian boundary timing. Further, the regional chemostratigraphic synthesis demonstrates the conformity of the OAE2 successions correlated to Pueblo, shows that the duration of the lag between the onset of the Osi and δ13C excursions is ∼60 k.y., and thus constrains the magnitude of the pre-OAE2 hiatus in Pueblo to less than this value. The new astronomically tuned, conformable Osi record across the onset of OAE2 captures a geologically rapid onset of large igneous province volcanism, consistent with other records, such that the addition of CO2 to the ocean-atmosphere system may have driven changes in marine carbonate chemistry. Additionally, the refined chronostratigraphy of OAE2 and the Cenomanian-Turonian boundary in the central WIB improves correlation with other records, such as those in the Eagle Ford Group, Texas. The correlations highlight that discrepancies among OAE2 age models from globally distributed sections commonly stem from differing definitions of the event and uncertainties associated with astronomical tuning, in addition to stratigraphic preservation.

Coupled modeling of biogeochemical cycles leads to improved constraints on elemental fluxes and helps to identify mechanisms that drive secular variations in isotopic records. Here, we develop a coupled strontium-sulfur isotope mass-balance model to examine the Early Cretaceous marine sulfate (δ34Ssw) and strontium (87Sr/86Sr) isotope records. We also present an expanded marine barite S isotope record and pyrite S isotope record for the Early Cretaceous with updated age models in line with the Geologic Time Scale 2012. Collectively constraining the primary input fluxes that drive both Sr and S cycles – hydrothermal and weathering – helps to identify which parameters primarily control coherent, oppositional, and divergent isotopic perturbations. With the primary input fluxes constrained in the coupled model, the importance of additional factors responsible for secular changes in δ34Ssw can be examined. Model results indicate that emplacement of the Ontong Java-Manihiki-Hikurangi Plateau, along with elevated mid-ocean ridge spreading rates, increased continental arc volcanism, and eruption of additional large igneous provinces, all contributed to the Early Cretaceous ~5‰ negative δ34Ssw shift and maintained low δ34Ssw over long time scales. The coupled strontium-sulfur modeling was able to demonstrate that a complex interplay of changes in multiple S cycle parameters – not simply total weathering and hydrothermal fluxes – was required to produce this major shift and new alternate state within the S isotope record. In addition, coupled modeling highlights the differences in chemical behavior (volatility) between S and Sr. Review of S cycle modeling and examination of a variety of initial conditions indicates a distinctly different range of δ34S values for the total weathering flux, weathered evaporite-pyrite ratios, the pyrite burial fraction, and the global integrated fractionation factor for pyrite burial compared to those used in previous S cycle models. Coupling the Sr cycle to other biogeochemical cycles that also reflect a balance between hydrothermal and riverine inputs offers a powerful tool for interpreting marine isotopic records.

Oceanic Anoxic Event 2 (OAE2; ~94.5 Ma) occurred in the latest Cenomanian and represents a perturbation to the global carbon cycle. The event is geochemically recorded in shales and limestones of the Western Interior Basin of North America and is additionally marked by foraminiferal bio-events (e.g., turnovers, extinctions). These bio-events are attributed to changing paleoceanographic conditions and circulation patterns in the Western Interior Seaway related to the onset of OAE2. Here we investigate the paleoenvironment near the southwestern edge of the seaway during OAE2 by integrating microfossil and geochemical records from the lower beds of the Tokay Tongue (Mancos Shale) at Carthage, New Mexico, USA. We demonstrate that this locality represents an expanded section of OAE2 based on temporal constraints from carbon isotope chemostratigraphy and the occurrence of regional marker ash-fall deposits (bentonites), limestones and other carbonate-rich beds. Prior to the onset of OAE2, a unique assemblage of benthic foraminiferal morphologies suggests the presence of a distinct water mass in the southwestern part of the seaway compared to coeval neritic and distal sites. Microfossil assemblages record the Benthonic Zone, a typical OAE2 bio-event, with some distinctions. The event is still identifiable and thereby useful in marking the earliest stages of OAE2. Early in OAE2, calcareous nannofossil and foraminiferal assemblages indicate intervals of high productivity. The dominance of biserial planktic foraminifera (Planoheterohelix spp.) suggests the development of photic zone euxinia with intensification of OAE2. During OAE2, epifaunal trochospiral benthic foraminifera (Gavelinella dakotaensis) suggest intervals of improved conditions related to food availability and seafloor ventilation. Later, as increased surface water productivity and subsequent food availability prevailed at the seafloor through the end of the OAE2 interval, benthic foraminifera were abundant and assemblages were dominated by infaunal, low oxygen tolerant species (Neobulimina albertensis), suggesting prevailing dysoxia. We attribute differences in the expression of bio-events and foraminiferal community composition at Carthage to the influence of freshwater runoff from the western margin that drove high-productivity conditions throughout OAE2.

Early Cretaceous (145–100 Ma) rocks record a ∼5‰ negative shift in the sulfur isotope composition of marine sulfate, the largest shift observed over the past 130 m.y. Two hypotheses have been proposed to explain this shift: (1) massive evaporite deposition associated with rifting during opening of the South Atlantic, and (2) increased inputs of volcanically derived sulfur due to eruption of large igneous provinces. Each process produces a very different impact on marine sulfate concentrations, which in turn affects several biogeochemical phenomena that regulate the global carbon cycle and climate. Here we present sulfur isotope data from Resolution Guyot, Mid-Pacific Mountains (North Pacific Ocean), that track sympathetically with strontium isotope records through the ∼5‰ negative sulfur isotope shift. We employ a linked sulfur-strontium isotope mass-balance model to identify the mechanisms driving the sulfur isotope evolution of the Cretaceous ocean. The model only reproduces the coupled negative sulfur and strontium isotope shifts when both hydrothermal and weathering fluxes increase. Our results indicate that marine sulfate concentrations increased significantly during the negative sulfur isotope shift and that enhanced hydrothermal and weathering input fluxes to the ocean played a dominant role in regulating the marine sulfur cycle and CO 2 exchange in the atmosphere-ocean system during this interval of rapid biogeochemical change.

Two negative carbon isotope excursions (3.5–6.5‰) across the Wuchiapingian-Changhsingian boundary (WCB) are observed globally (sections in China, Canada, and Iran); however, the causative mechanism of these excursions is debated. Here, high-resolution osmium isotope (187Os/188Os or Osi) chemostratigraphy of four globally correlated WCB sections (3 in China - Meishan, Shangsi and Lianyuan and 1 in Canada - Buchanan Lake) show two separate Osi excursions to less radiogenic compositions that are coincident with the carbon isotope shifts for two of the South China sections (Lianyuan, Meishan). In contrast, only a single Osi excursion to less radiogenic compositions, coinciding with the earliest Changhsingian carbon isotope shift, is observed for the Shangsi and Buchanan Lake sections. The Osi shift is interpreted to reflect increased unradiogenic Os input from basaltic magmatism in South China, possibly related to the Emeishan large igneous province (LIP). However, 187Os/188Os data suggest that only the earliest Changhsingian volcanism had global impact on both the ocean and atmosphere. The lack of any evidence for a biotic event associated with the WCB therefore may have been due to the more regional rather than global impact of volcanism during the latest Wuchiapingian. In contrast, during the earliest Changhsingian, volcanism was sufficient to cause a more global signal in the ocean osmium record, but was inadequate, or too prolonged, to drive any significant environmental change. Volcanism, however, may have provided the isotopically light carbon that drove the negative carbon isotope excursions across the WCB.

The Coniacian-Santonian interval has been proposed as the youngest of the Cretaceous ocean anoxic events (OAE3), but this designation has long been debated. OAE3 is associated with a long-lasting (∼3 myr) succession of black shales from the central and South Atlantic, Caribbean region, and the North American Western Interior; in the Western Interior it is characterized by an abrupt increase in total organic carbon (TOC) and corresponding trace metal indicators for anoxia. However, the modern concept of OAEs is predicated on detection of global carbon cycle perturbations as recorded by substantial carbon isotope excursions (CIE), and the protracted Coniacian-Santonian black shale interval does not have a large CIE. A more conservative definition of OAE3 might limit the event to the modest positive carbon isotope excursion restricted to the upper Coniacian Scaphites depressus Ammonite Zone. Trace metal proxies suggest that oxygen levels abruptly declined prior to the onset of this CIE in the Western Interior Sea (WIS), but it is unknown whether regional anoxic conditions were confined to sediments/pore waters, or how anoxia may have affected the biota. In an effort to characterize the oxygenation history of the WIS and to better understand the nature of the hypothesized OAE3, we present micropaleontological evidence of declining oxygen in bottom waters prior to the event using benthic foraminifera, which are sensitive to dissolved oxygen. Changes in benthic foraminiferal abundances suggest a decline in oxygen at least 1-myr prior to the CIE (including a nadir immediately below the start of the excursion), improving bottom water oxygen during the CIE, and re-establishment of persistent anoxia following the isotope excursion. Anoxia endured for nearly 3 myr in the central seaway, showing some signs of recovery toward the top of the Niobrara Formation. Our findings suggest that declining oxygen concentrations in the seaway eventually reached a tipping point, after which dissolved oxygen quickly dropped to zero. The late Coniacian CIE is an exception to the trend of declining oxygen in the WIS, and part of a larger pattern in the oxygenation history of the Niobrara Formation which suggests that it does not adhere to standard black shale models. Transgressive periods, including the Fort Hays Limestone and the lower limestone unit of the Smoky Hill Shale (which corresponds to the CIE) are relatively oxic, while periods of highstand (i.e., most of the Smoky Hill) correspond to deteriorating oxygen conditions. This contrasts with the standard black shale model for sea level and oxygen, where transgressions typically correlate with maximum TOC enrichment, interpreted to result from both sediment condensation and oxygen deficiency. The association of global carbon burial/anoxia (as indicated by carbon isotopes) with a regional increase in oxygen and decrease in organic matter preservation is reminiscent of the Cenomanian-Turonian Greenhorn Limestone, which contains OAE2. In both cases, the facies are not typical black shales, but instead have appreciable carbonate content. Western Interior redox trends support the rejection of the original concept of a protracted Coniacian-Santonian OAE3 because it is not a distinct “event.” Increasing local oxygen during the late Coniacian CIE also argues against a narrower OAE designation for this event, because the excursion can't be tied to anoxia here or anywhere else it has been described. Nevertheless, the Late Coniacian Event (as we prefer to call this CIE) still represents an important perturbation of the global carbon cycle. This is emblematic of the shift away from widespread, discrete anoxic events during the ongoing paleoceanographic reorganization of the Late Cretaceous, even as large carbon cycle perturbations continued.

The base of the Campanian Stage does not have a ratified Global Stratotype Section and Point (GSSP); however, several potential boundary markers have been proposed including the base of the Scaphites leei III ammonite Zone and the base of the paleomagnetic Chron C33r. Calcareous nannofossil assemblages from the Smoky Hill Member of the Niobrara Formation in the central Western Interior Seaway, USA were analyzed from two localities to determine relevant biohorizons and their relationships to these potential boundary markers. In a previous study, the Aristocrat Angus 12-8 core (Colorado) was astrochronologically dated and constrained using macrofossil zonations and radiometric ages. The Smoky Hill Member type area (Kansas) provides an expanded interval with good to excellent nannofossil preservation. Five biohorizons are useful for recognition of the Santonian/Campanian transition within the Smoky Hill Member type area, and three are useful in the Aristocrat Angus 12-8 core. The first occurrences (FOs) of Aspidolithus parcus parcus and Aspidolithus parcus constrictus , as well as the last occurrences (LOs) of Zeugrhabdotus moulladei , Helicolithus trabeculatus specimens larger than 7 μm, and Zeugrhabdotus biperforatus are in close stratigraphic proximity to the base of the Scaphites leei III Zone and the base of Chron C33r.

Chromium offers a redox sensitive isotopic proxy with potential for tracing past oxygen levels in the oceans. We explore this potential in a pelagic succession of marine carbonate sediment deposited during Cretaceous Ocean Anoxic Event 2 (OAE 2) in the Western Interior Seaway, Colorado (WIS), using the USGS Portland #1 Core. Reduction of Cr(VI) causes light isotopes of Cr to preferentially partition into Cr(III). Because Cr(VI) is the thermodynamically favoured species in oxygenated seawater, and Cr(III) is relatively insoluble under the same conditions, increased removal of Cr(III) into anoxic marine sediment during ocean anoxic events should cause positive shifts in seawater δ53Cr values. This assumes that isotopic fractionation associated with all Cr removal fluxes from the oceans was constant during OAE 2 and that there was no change in Cr input fluxes to the oceans. Here, we report findings that counter this prediction, namely evidence for a negative shift in seawater δ53Cr during OAE 2 of ∼1.1‰ in the WIS. The magnitude of the excursion depends on the speciation of Cr removed in this setting over the duration of OAE 2, as well as the fractionation factor accompanying the removal flux of chromate into carbonate sediment, both of which are uncertain. The δ53Cr excursion reaches values as low −0.09‰ during OAE 2, which is indistinguishable from the high-temperature igneous rock baseline value of −0.124 ± 0.101‰ (2σ). Moreover, the minima in the δ53Cr profile coincides with a peak in Cr concentrations in the study core, as well as anomalous enrichments of other trace metals of basaltic affinity. Building on previous studies linking OAE 2 to a massive episode of submarine volcanic activity, we attribute the decrease in carbonate δ53Cr values during OAE 2 to the expansion of a hydrothermal superplume created during eruptions of the Caribbean Large Igneous Province (LIP). This metal laden plume, enriched in Cr(III) and probably anoxic, moved from deep waters of the eruption site in the eastern Pacific into deep waters of the proto-North Atlantic through an oceanic gateway in the Central Americas. Once inside, anoxic metal-rich waters upwelled against the surrounding continental margins, where isotopically unfractionated Cr(III), whose solubility was improved by organic complexation and/or oxidation to Cr(VI), mixed with the isotopically heavy pool of oceanic chromate in surface waters above the redoxcline. Application of a simple mixing equation shows that hydrothermal Cr contributed >90% of the authigenic Cr in the trace metal enriched interval of the study core. The increased flux of hydrothermal Cr was large enough to mask the expected isotopic response of the ocean Cr cycle to increasing anoxia. We consider this interpretation to be robust, in that it is not substantially affected by uncertainty in the speciation of hydrothermal Cr, nor uncertainty in the fractionation factor ( Δ sw CaCO 3 ) associated with chromate removal into marine carbonate sediment, which we measured in the modern Caribbean Sea to be −0.46 ± 0.14‰ (2σ).

Variations in the Earth's orbit and spin vector are a primary control on insolation and climate; their recognition in the geological record has revolutionized our understanding of palaeoclimate dynamics, and has catalysed improvements in the accuracy and precision of the geological timescale. Yet the secular evolution of the planetary orbits beyond 50 million years ago remains highly uncertain, and the chaotic dynamical nature of the Solar System predicted by theoretical models has yet to be rigorously confirmed by well constrained (radioisotopically calibrated and anchored) geological data. Here we present geological evidence for a chaotic resonance transition associated with interactions between the orbits of Mars and the Earth, using an integrated radioisotopic and astronomical timescale from the Cretaceous Western Interior Basin of what is now North America. This analysis confirms the predicted chaotic dynamical behaviour of the Solar System, and provides a constraint for refining numerical solutions for insolation, which will enable a more precise and accurate geological timescale to be produced.

The middle Cretaceous was a period characterized by elevated sea-floor spreading rates, enhanced volcanism, high atmospheric CO2 levels, warming temperatures, and the peak eustatic highstand of the Mesozoic. Two well-known perturbations in the global carbon cycle mark this interval – the Cenomanian-Turonian Oceanic Anoxic Event 2 (OAE2) and the Mid-Cenomanian Event (MCE). Although studies during the past two decades have arrived at a consensus that the Caribbean Large Igneous Province (LIP) likely played a key role in triggering OAE2, arguably the most significant perturbation of the Late Cretaceous, the detailed environmental developments during the Mid-Late Cenomanian leading up to it have only recently been the focus of investigations. This study, based on previous studies of the Middle Cenomanian – Early Turonian climate, tectonics, sea level, and carbon isotope chemostratigraphy, tests plausible environmental scenarios to explain the behavior of the Middle Cenomanian to Early Turonian carbon cycle, via isotope-mass balance calculation in a simple carbon cycle box model. The model experiments successfully reproduce two distinctive features observed in the Mid-Late Cenomanian δ13C curves - 1) decoupling of δ13Ccarb and δ13Corg reflecting increasing isotope fractionation in response to steadily rising pCO2, driven by enhanced volcanic degassing of mantle-derived CO2, which likely preceded the presumed peak volcanism of the Caribbean LIP; and 2) a long-lived, secondary positive excursion that documents enhanced organic carbon burial in shallow shelf seas that expanded during global sea-level rise and highstand. We demonstrate a plausible combination of environmental forcings that pre-conditioned the mid-Cretaceous ocean-atmosphere system for a massive perturbation, OAE2.

Expansive Late Cretaceous lacustrine deposits of East Asia offer unique stratigraphic records to better understand regional responses to global climate events, such as oceanic anoxic events (OAEs), and terrestrial organic carbon burial dynamics. This study presents bulk organic carbon isotopes ( δ 13 C org ), elemental concentrations (XRF), and initial osmium ratios ( 187 Os/ 188 Os, Os i ) from the Turonian–Coniacian Qingshankou Formation, a ∼5 Ma lacustrine mudstone succession in the Songliao Basin of northeast China. A notable δ 13 C org excursion ( ∼ + 2.5 ‰ ) in organic carbon-lean Qingshankou Members 2–3 correlates to OAE3 in the Western Interior Basin (WIB) of North America within temporal uncertainty of high-precision age models. Decreases in carbon isotopic fractionation ( Δ 13 C) through OAE3 in the WIB and Songliao Basin, suggest that significantly elevated global rates of organic carbon burial drew down pCO 2 , likely cooling climate. Despite this, Os i chemostratigraphy demonstrates no major changes in global volcanism or weathering trends through OAE3. Identification of OAE3 in a lake system is consistent with lacustrine records of other OAEs (e.g., Toarcian OAE), and underscores that terrestrial environments were sensitive to climate perturbations associated with OAEs. Additionally, the relatively radiogenic Os i chemostratigraphy and XRF data confirm that the Qingshankou Formation was deposited in a non-marine setting. Organic carbon-rich intervals preserve no compelling Os i evidence for marine incursions, an existing hypothesis for generating Member 1's prolific petroleum source rocks. Based on our results, we present a model for water column stratification and source rock deposition independent of marine incursions, detailing dominant biogeochemical cycles and lacustrine organic carbon burial mechanisms.

During the Cretaceous, widespread black shale deposition occurred during a series of Oceanic Anoxic Events (OAEs). Multiple processes are known to control the deposition of marine black shales, including changes in primary productivity, organic matter preservation, and dilution. OAEs offer an opportunity to evaluate the relative roles of these forcing factors. The youngest of these events—the Coniacian to Santonian OAE 3—resulted in a prolonged organic carbon burial event in shallow and restricted marine environments including the Western Interior Seaway. New high-resolution isotope, organic, and trace metal records from the latest Turonian to early Santonian Niobrara Formation are used to characterize the amount and composition of organic matter preserved, as well as the geochemical conditions under which it accumulated. Redox sensitive metals (Mo, Mn, and Re) indicate a gradual drawdown of oxygen leading into the abrupt onset of organic carbon-rich (up to 8%) deposition. High Hydrogen Indices (HI) and organic carbon to total nitrogen ratios (C:N) demonstrate that the elemental composition of preserved marine organic matter is distinct under different redox conditions. Local changes in δ13C indicate that redox-controlled early diagenesis can also significantly alter δ13Corg records. These results demonstrate that the development of anoxia is of primary importance in triggering the prolonged carbon burial in the Niobrara Formation. Sea level reconstructions, δ18O results, and Mo/total organic carbon ratios suggest that stratification and enhanced bottom water restriction caused the drawdown of bottom water oxygen. Increased nutrients from benthic regeneration and/or continental runoff may have sustained primary productivity.

Global warming lowers the solubility of gases in the ocean and drives an enhanced hydrological cycle with increased nutrient loads delivered to the oceans, leading to increases in organic production, the degradation of which causes a further decrease in dissolved oxygen. In extreme cases in the geological past, this trajectory has led to catastrophic marine oxygen depletion during the so-called oceanic anoxic events (OAEs). How the water column oscillated between generally oxic conditions and local/global anoxia remains a challenging question, exacerbated by a lack of sensitive redox proxies, especially for the suboxic window. To address this problem, we use bulk carbonate I/Ca to reconstruct subtle redox changes in the upper ocean water column at seven sites recording the Cretaceous OAE 2. In general, I/Ca ratios were relatively low preceding and during the OAE interval, indicating deep suboxic or anoxic waters exchanging directly with near-surface waters. However, individual sites display a wide range of initial values and excursions in I/Ca through the OAE interval, reflecting the importance of local controls and suggesting a high spatial variability in redox state. Both I/Ca and an Earth System Model suggest that the northeast proto-Atlantic had notably higher oxygen levels in the upper water column than the rest of the North Atlantic, indicating that anoxia was not global during OAE 2 and that important regional differences in redox conditions existed. A lack of correlation with calcium, lithium, and carbon isotope records suggests that neither enhanced global weathering nor carbon burial was a dominant control on the I/Ca proxy during OAE 2.

Carbon sources and sinks are key components of the climate feedback system, yet their response to external forcing remains poorly constrained, particularly for past greenhouse climates. Carbon-isotope data indicate systematic, million-year-scale transfers of carbon between surface reservoirs during and immediately after the Late Cretaceous thermal maximum (peaking in the Cenomanian-Turonian, circa 97–91 million years, Myr, ago). Here we calibrate Albian to Campanian (108–72 Myr ago) high-resolution carbon isotope records with a refined chronology and demonstrate how net transfers between reservoirs are plausibly controlled by ~1 Myr changes in the amplitude of axial obliquity. The amplitude-modulating terms are absent from the frequency domain representation of insolation series and require a nonlinear, cumulative mechanism to become expressed in power spectra of isotope time series. Mass balance modeling suggests that the residence time of carbon in the ocean-atmosphere system is—by itself—insufficient to explain the Myr-scale variability. It is proposed that the astronomical control was imparted by a transient storage of organic matter or methane in quasi-stable reservoirs (wetlands, soils, marginal zones of marine euxinic strata, and potentially permafrost) that responded nonlinearly to obliquity-driven changes in high-latitude insolation and/or meridional insolation gradients. While these reservoirs are probably underrepresented in the geological record due to their quasi-stable character, they might have provided an important control on the dynamics and stability of the greenhouse climate.

Late Cretaceous carbon isotope curves generated for localities in Europe, Asia, and the deep-sea records have provided the foundation for development of a contiguous, intercontinental chemostratigraphic framework. Despite the development of carbon isotope records from selected stratigraphic intervals in the Western Interior Basin, however, a comprehensive δ13C record comparable to those developed in Europe and Asia, and from ODP sites, had not yet been completed. This study reports a new, high-resolution Cenomanian to Campanian carbon isotope record for the central Western Interior Basin of North America that makes a key contribution to the intercontinental correlation. The curve is correlated to the well-developed molluscan biostratigraphic framework for the Western Interior Basin, as well as a revised geochronology based on integration of new radioisotopic dating and astrochronology developed in the same core records from where the δ13C data were derived. The new δ13C record reflects not only major perturbations in the global carbon cycle, such as the mid-Cenomanian Event and the Cenomanian–Turonian Ocean Anoxic Event 2, but also smaller excursions that have been recognized in records from Europe and Asia. This shows that the Western Interior shallow epeiric sea was not isolated for any appreciable part of Cenomanian to early Campanian time—it consistently recorded changes in the global marine carbon cycle observed elsewhere. A critical attribute of the chemostratigraphic dataset produced in this study is its linkage with a revised Late Cretaceous time scale. Assignment of revised ages to Western Interior carbon isotope events that are globally expressed will allow export of the improved time scale to localities within and outside the Western Interior where similar carbon isotope records have been generated. This chronostratigraphic tool will allow a number of stratigraphic and geochemical hypotheses to be more rigorously tested.

Capturing the nature of students' mental representations and how they change with learning is a primary goal in science education research. This can be challenging in spatially intense domains, such as geoscience, architecture, and engineering. In this research, we test whether sketching can be used to gauge level of expertise in geoscience, using new technology designed to facilitate this process. We asked participants with differing levels of geoscience experience to copy two kinds of geoscience images—photographs of rock formations and causal diagrams. To permit studying the process of sketching as well as the structure and content of the sketches, we used the CogSketch system (Forbus et al. 2011, Topics in Cognitive Science 3:648-666) to record the time course of sketching and analyze the sketches themselves. Relative to novices, geoscience students included more geological structures and relational symbols in their sketches of geoscience materials and were more likely to construct their sketches in a sequence consistent with the order of causal events. These differences appear to stem from differences in domain knowledge, because they did not show up in participants'sketches of materials from other fields. The findings and methods of this research