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Carbonate minerals contain stable isotopes of carbon and oxygen with different masses whose abundances and bond arrangement are governed by thermodynamics. The clumped isotopic value Δi is a measure of the temperature-dependent preference of heavy C and O isotopes to clump, or bond with or near each other, rather than with light isotopes in the carbonate phase. Carbonate clumped isotope thermometry uses Δi values measured by mass spectrometry (Δ47, Δ48) or laser spectroscopy (Δ638) to reconstruct mineral growth temperature in surface and subsurface environments independent of parent water isotopic composition. Two decades of analytical and theoretical development have produced a mature temperature proxy that can estimate carbonate formation temperatures from 0.5 to 1,100°C, with up to 1–2°C external precision (2 standard error of the mean). Alteration of primary environmental temperatures by fluid-mediated and solid-state reactions and/or Δi values that reflect nonequilibrium isotopic fractionations reveal diagenetic history and/or mineralization processes. Carbonate clumped isotope thermometry has contributed significantly to geological and biological sciences, and it is poised to advance understanding of Earth's climate system, crustal processes, and growth environments of carbonate minerals. ▪ Clumped heavy isotopes in carbonate minerals record robust temperatures and fluid compositions of ancient Earth surface and subsurface environments. ▪ Mature analytical methods enable carbonate clumped Δ47, Δ48, and Δ638 measurements to address diverse questions in geological and biological sciences. ▪ These methods are poised to advance marine and terrestrial paleoenvironment and paleoclimate, tectonics, deformation, hydrothermal, and mineralization studies.

The δ18O of carbonate minerals that formed at Earth's surface is widely used to investigate paleoclimates and paleo-elevations. However, a multitude of hydrologic processes can affect δ18O values, including mixing, evaporation, distillation of parent waters, and carbonate growth temperatures. We combined traditional carbon and oxygen isotope analyses with clumped (Δ47) and triple oxygen isotopes (Δ′17O) analyses in oyster shells (Acutostrea idriaensis) of the Goler Formation in southern California (USA) to obtain insights into surface temperatures and δ18O values of meteoric waters during the early Eocene hothouse climate. The Δ47-derived temperatures ranged from 9 °C to 20 °C. We found a correlation between the δ18O of growth water (δ18Ogw) (calculated using Δ47 temperatures and δ18O of carbonate) and the δ13C values of shells. The Δ′17O values of shell growth waters (0.006‰–0.013‰ relative to Vienna standard mean ocean water–standard light Antarctic precipitation [VSMOW-SLAP]) calculated from Δ′17O of carbonate (−0.087‰ to −0.078‰ VSMOW-SLAP) were lower than typical meteoric waters. These isotopic compositions are consistent with oyster habitation in an estuary. We present a new triple oxygen isotope mixing model to estimate the δ18O value of freshwater supplying the estuary (δ18Ofw). The reconstructed δ18Ofw of −11.3‰ to −14.7‰ (VSMOW) is significantly lower than the δ18Ogw of −4.4‰ to −9.9‰ that would have been calculated using “only” Δ47 and δ18O values of carbonate. This δ18Ofw estimate supports paleogeographic reconstructions of a Paleogene river fed by high-elevation catchments of the paleo–southern Sierra Nevada. Our study highlights the potential for paired Δ47 and Δ′17O analyses to improve reconstructions of meteoric water δ18O, with implications for understanding ancient climates and elevations.

During the Mid-Miocene Climatic Optimum (MMCO, 14.7–17.3 Ma), global temperatures were warmer than present, and similar to predicted temperatures for the coming century. Limited paleoclimate data exist from the tropics during this period, despite its potential as an analog for future climate conditions. This study presents new subannual stable isotope data (δ18O and δ13C) from a large population of Miocene Turritella gastropods from the Jimol and Castilletes Formations of the Guajira Peninsula, Colombia. Turritellids are aragonitic marine mollusks that live in shallow coastal waters, and their rapid growth rates allow for high-resolution subannual records. We compare these fossils to modern Turritella gastropods from multiple tropical localities to reconstruct subannual climate conditions. The seasonal range in δ18O in the modern shells correlates with the seasonal variance of local precipitation, once temperature seasonality is accounted for. The Miocene fossils show larger (in some cases >2‰) seasonal variation in δ18O than modern Turritella from the same location, suggesting increased seasonality of precipitation in Miocene northern Colombia relative to today. We propose that this increased seasonality of precipitation was due to a more northerly position of the Intertropical Convergence Zone during the mid-Miocene. The resulting wet Miocene paleoenvironment is in stark contrast to semiarid conditions on the Guajira Peninsula today, indicating that this area of tropical South America has undergone a drastic environmental change since the Miocene.

Paleotemperature reconstructions linked to Deccan traps volcanic greenhouse gas emissions and associated feedbacks in the lead-up to the end-Cretaceous meteorite impact and extinction document local and global climate trends during a key interval of geologic history. Here, we present a new clumped-isotope-based paleotemperature record derived from fossil bivalves from the Maastrichtian type region, in southeast Netherlands and northeast Belgium. Clumped isotope data documents a mean temperature of 19.2 ± 3.8 °C, consistent with other Maastrichtian temperature estimates, and an average seawater δ18O value of −0.3 ± 0.9 ‰ VSMOW for the region during the latest Cretaceous (67.1–66.0 Ma). A notable temperature increase at ~66.4 Ma is interpreted to be a regional manifestation of the globally-defined Late Maastrichtian Warming Event, linking Deccan Traps volcanic CO2 emissions prior to the end-Cretaceous extinction to climate change in the Maastricht region. Fluctuating seawater δ18O values coinciding with temperature changes suggest alternating influences of warm, salty southern-sourced waters and cooler, fresher northern-sourced waters from the Arctic Ocean. This new paleotemperature record contributes to the understanding of regional and global climate response to large-scale volcanism and ocean circulation changes leading up to a catastrophic mass extinction.

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.

Increased use and improved methodology of carbonate clumped isotope thermometry has greatly enhanced our ability to interrogate a suite of Earth‐system processes. However, interlaboratory discrepancies in quantifying carbonate clumped isotope (Δ47) measurements persist, and their specific sources remain unclear. To address interlaboratory differences, we first provide consensus values from the clumped isotope community for four carbonate standards relative to heated and equilibrated gases with 1,819 individual analyses from 10 laboratories. Then we analyzed the four carbonate standards along with three additional standards, spanning a broad range of δ47 and Δ47 values, for a total of 5,329 analyses on 25 individual mass spectrometers from 22 different laboratories. Treating three of the materials as known standards and the other four as unknowns, we find that the use of carbonate reference materials is a robust method for standardization that yields interlaboratory discrepancies entirely consistent with intralaboratory analytical uncertainties. Carbonate reference materials, along with measurement and data processing practices described herein, provide the carbonate clumped isotope community with a robust approach to achieve interlaboratory agreement as we continue to use and improve this powerful geochemical tool. We propose that carbonate clumped isotope data normalized to the carbonate reference materials described in this publication should be reported as Δ47 (I‐CDES) values for Intercarb‐Carbon Dioxide Equilibrium Scale., Key Points The exclusive use of carbonate reference materials is a robust method for the standardization of clumped isotope measurementsMeasurements using different acid temperatures, designs of preparation lines, and mass spectrometers are statistically indistinguishableWe propose new consensus values for a set of seven carbonate reference materials and updated guidelines to report clumped isotope measurements

The future in the past A major cause of uncertainties in climate projections is our imprecise knowledge of how much warming should occur as a result of a given increase in the amount of carbon dioxide in the atmosphere. Paleoclimate records have the potential to help us sharpen that understanding because they record such a wide variety of environmental conditions. Tierney et al. review the recent advances in data collection, statistics, and modeling that might help us better understand how rising levels of atmospheric carbon dioxide will affect future climate. Science , this issue p. eaay3701

Understanding the response of temperature to elevated atmospheric CO2 during past greenhouse intervals such as the Late Cretaceous can constrain hypotheses of expected future warming tied to the rise of modern atmospheric CO2 levels. Here we present new reconstructions of Gulf and Atlantic Coast coastal marine temperatures through the late Campanian (∼76–72 Ma) and Maastrichtian (72 Ma–66 Ma), as determined by carbonate clumped isotope analysis of marine bivalves and gastropods. We find temperatures in the range of ∼7–25 °C across multiple sites located between 31°N and 36°N paleolatitude, and cooler temperatures of ∼3–14 °C at sites around 39°N paleolatitude. Temperatures agree across a variety of taxa, indicating no appreciable organism-specific vital effects. The calculated paleotemperatures are very similar to modern marine temperatures at the same locations, despite the Late Cretaceous generally being considered a warmer interval. Clumped isotope temperatures are cooler than published temperatures from a nearby site measured using the TEX86 paleotemperature proxy, revealing a potential warm bias in TEX86 temperature estimates. The best agreement between clumped isotope and TEX86 temperatures is achieved when using the TEX 86 L calibration over TEX 86 H or BAYSPAR calibrations.

In order to assess the potential of the honeycomb oyster Pycnodonte vesicularis for the reconstruction of palaeoseasonality, several specimens recovered from late Maastrichtian strata in the Neuquén Basin (Argentina) were subject to a multi-proxy investigation, involving scanning techniques and trace element and isotopic analysis. Combined CT scanning and light microscopy reveals two calcite microstructures in P. vesicularis shells (vesicular and foliated calcite). Micro-XRF analysis and cathodoluminescence microscopy show that reducing pore fluids were able to migrate through the vesicular portions of the shells (aided by bore holes) and cause recrystallization of the vesicular calcite. This renders the vesicular portions not suitable for palaeoenvironmental reconstruction. In contrast, stable isotope and trace element compositions show that the original chemical composition of the foliated calcite is well-preserved and can be used for the reconstruction of palaeoenvironmental conditions. Stable oxygen and clumped isotope thermometry on carbonate from the dense hinge of the shell yield sea water temperatures of 11°C, while previous TEX86H palaeothermometry yielded much higher temperatures. The difference is ascribed to seasonal bias in the growth of P. vesicularis, causing warm seasons to be underrepresented from the record, while TEX86H palaeothermometry seems to be biased towards warmer surface water temperatures. The multi-proxy approach employed here enables us to differentiate between well-preserved and diagenetically altered portions of the shells and provides an improved methodology for reconstructing palaeoenvironmental conditions in deep time. While establishing a chronology for these shells was complicated by growth cessations and diagenesis, cyclicity in trace elements and stable isotopes allowed for a tentative interpretation of the seasonal cycle in late Maastrichtian palaeoenvironment of the Neuquén Basin. Attempts to independently verify the seasonality in sea water temperature by Mg ∕ Ca ratios of shell calcite are hampered by significant uncertainty due to the lack of proper transfer functions for pycnodontein oysters. Future studies of fossil ostreid bivalves should target dense, foliated calcite rather than sampling bulk or vesicular calcite. Successful application of clumped isotope thermometry on fossil bivalve calcite in this study indicates that temperature seasonality in fossil ostreid bivalves may be constrained by the sequential analysis of well-preserved foliated calcite samples using this method.

The Midcontinent Rift System (MRS) is a Late Mesoproterozoic (∼1.1 Ga) sequence of volcanic and sedimentary rocks exposed in the Lake Superior Region of North America. The MRS continues to be the focus of much research due to its economic mineral deposits as well as its archive of Precambrian life and tectonic processes. In order to constrain the post-depositional thermal history of the MRS, samples were analyzed for carbonate clumped isotope composition and organic thermal maturity. Clumped isotope values from sedimentary/early-diagenetic samples were partially reset during burial to temperatures between 68 and 75 °C. Solid-state reordering models indicate that maximum burial temperatures of 125–155 °C would reset the clumped isotope values to the observed temperature range prior to the onset of regional cooling and uplift. Clumped isotope results from late-stage veins in the White Pine Mine encompass a greater temperature range (49–116 °C), indicative of spatially variable hydrothermal activity and vein emplacement after burial temperatures fell below 100 °C during regional cooling and uplift. Clumped isotope and organic thermal maturity data do not indicate significant spatial differences in thermal history along the MRS. Observed variability in bulk organic matter composition and biomarker indices are therefore more likely a result of shifts in primary productivity or early-degradation processes. These results demonstrate that the MRS experienced a spatially consistent, relatively mild thermal history (125–155 °C) and is therefore a valuable archive for understanding the Late Mesoproterozoic environment.

The climate and environmental significance of the Deccan Traps large igneous province of west-central India has been the subject of debate in paleontological communities. Nearly one million years of semi-continuous Deccan eruptive activity spanned the Cretaceous-Paleogene boundary, which is renowned for the extinction of most dinosaur groups. Whereas the Chicxulub impactor is acknowledged as the principal cause of these extinctions, the Deccan Traps eruptions are believed to have contributed to extinction patterns and/or enhanced ecological pressures on biota during this interval of geologic time. We present the first coupled records of biogenic carbonate clumped isotope paleothermometry and mercury concentrations as measured from a broad geographic distribution of marine mollusk fossils. These fossils preserve evidence of simultaneous increases in coastal marine temperatures and mercury concentrations at a global scale, which appear attributable to volcanic CO2 and mercury emissions. These early findings warrant further investigation with additional records of combined Late Cretaceous temperatures and mercury concentrations of biogenic carbonate., The relative role of the Deccan Traps volcanic activity versus the role of the Chicxulub impact event in terms of potential contributions to the Cretaceous-Paleogene (K-Pg) mass extinction has been subject to longstanding debate. Here, the authors observe a global signal of abruptly increased ocean temperatures and elevated [Hg] in the same biogenic carbonate specimens, prior to the impact event but aligning with the onset of Deccan volcanism.

The Western Interior Seaway (WIS) was a shallow and expansive body of water that covered the central United States during the Late Cretaceous. Attempts to reconstruct temperatures in the seaway using the oxygen isotopic composition of biogenic carbonates have suffered from uncertainty in the oxygen isotopic composition of seawater (δ 18 O w ) in the semi-restricted basin. We present new reconstructed temperature and δ 18 O w data from marine and estuarine environments in the WIS and freshwater environments in WIS source rivers, derived from clumped isotope analyses of bivalve and gastropod shells. We find temperatures of 5–21 °C, δ 18 O w values below contemporaneous Gulf of Mexico marine sites, and a strong correlation between δ 18 O w and environmental setting. We propose that decreasing δ 18 O w values reflect decreasing salinity driven by an increasing contribution of continental runoff. Using a two-end-member salinity-δ 18 O w mixing model, we estimate salinities of 29–35 psu (practical salinity units) for the deep marine, 20–32 psu for the shallow marine, and 11–26 psu for the estuarine environments of the WIS. New climate model simulations agree with reconstructed temperatures and salinities and suggest the presence of salinity driven stratification within the seaway.

Soil carbonates are important paleoclimate archives, but interpretations of their isotopic compositions (δ18O, δ13C, and Δ47) are hampered by uncertainty in the annual timing of their accumulation. Several previous studies have inferred the annual timing of soil carbonate formation by comparing modern air/soil temperatures with temperatures estimated from the clumped isotopic composition (TΔ47) of Holocene soil carbonates. Here, we compile the existing Δ47 data to first consider if recent changes in Δ47 standardization methods alters the apparent seasonal biases. Then we explore the importance of various environmental parameters on soil carbonate TΔ47 and discuss implications for associated paleoclimate reconstructions. Most soil carbonates record TΔ47 values higher than mean annual air temperature, but the residual varies from −4 to +24 °C. Δ47 values for most observed soil profiles do not vary with depth. We find that the grain size of the soil matrix, timing of precipitation, and presence of vegetation each explain a portion of the observed variance in seasonal bias and can be used to aid in interpretations of TΔ47 values from paleosols. In some soil carbonates, a warm-season bias in TΔ47 is accompanied with calculated δ18O values of soil water that appear to be biased toward the δ18O of summer rainfall. Most estimated values of δ18O of soil water are within 2‰ of the δ18O values of mean annual rainfall. Where possible, paleoclimate reconstructions should consider precipitation timing, soil texture, and vegetation cover to aid in identifying the seasonal bias of soil carbonate stable isotopic compositions.

Rationale The clumped isotope paleothermometer, a new proxy widely applicable in studies of paleoclimate, tectonics, and paleontology, relates the abundance of doubly substituted isotopologues of carbonate-derived CO2 to the temperature of formation of the carbonate phase. As this technique becomes more widely used, more is discovered about the effects of everyday laboratory procedures on the clumped isotopic composition of CO2 gas. Methods Preparation of CO2 for clumped isotope analysis requires the removal of isobaric contaminants prior to measurement, achieved dynamically by passing the CO2 through a gas chromatography column using a helium carrier gas or cryogenically pumping CO2 through a static trap filled with Porapak™ Q (PPQ) material. The stable and clumped isotopic compositions of carbonate standards prepared at PPQ trap temperatures between −40°C and −10°C were measured by isotope ratio mass spectrometry to evaluate potential artifacts introduced by the static PPQ trap method. Results The stable isotopic composition of carbonates run at temperatures below −20°C was fractionated, despite achieving >99% retrieval of gas at temperatures as cold as −30°C. The δ13C and δ18O values decreased by ~0.01 and ~0.03 ‰/(°C below −20°C). The raw Δ47 values decreased by 0.003–0.005 ‰/(°C below −20°C), but the final reference-frame-corrected values (Δ47-RFAC) were unaffected as long as the carbonate samples and standard gases were prepared identically. Conclusions Preparing carbonate samples for clumped isotope analysis using a PPQ trap that is too cold can result in erroneous stable isotopic compositions. New and existing labs using the static PPQ trap cleaning procedure should determine the ideal PPQ trap temperature for their particular system through monitoring not only yield through the PPQ trap, but also stable isotopic composition at various PPQ trap temperatures. Copyright © 2015 John Wiley & Sons, Ltd.

Across the Eocene-Oligocene transition, the oxygen isotopic composition (δ18O) of benthic and planktonic foraminifera increased by over 1‰. This shift is thought to represent a combination of global cooling and the growth of a large ice sheet on the Antarctic continent. To determine the contribution of each of these factors to the total change in δ18O, we measured the clumped isotopic composition of planktonic foraminifera tests from Ocean Drilling Program Site 689 in the Southern Ocean. Near-surface temperatures were ~12°C in the intervals 0–1.5 Myr before and 1–2 Myr after the major (Oi-1) transition, in agreement with estimates made using other proxies at nearby sites. Temperatures cooled by 0.4 ± 1.1°C between these intervals, indicating that the long-term change in δ18O seen in planktonic foraminifera at this site is predominantly due to changes in ice volume. A larger instantaneous cooling may have occurred during Oi-1 but is not captured in this study due to sampling resolution. The corresponding change in the isotopic composition of seawater (δ18Osw) is 0.75 ± 0.23‰, which is within the range of previous estimates, and represents global ice growth equivalent to roughly ~110–120% of the volume of the modern Antarctic ice sheet or ~80–90 m of eustatic sea level change.

In order to assess the potential of the honeycomb oyster Pycnodonte vesicularis for the reconstruction of palaeoseasonality, several specimens recovered from the late Maastrichtian Neuquén Basin (Argentina) were subject to a multi-proxy investigation, involving scanning techniques, trace element and isotopic analysis. Combined CT scanning and light microscopy reveals two major calcite micromorphologies in P. vesicularis shells (vesicular and foliated calcite). Micro-XRF analysis and cathodoluminescence microscopy show that reducing pore fluids were able to migrate through the vesicular portions of the shells (aided by bore holes) and cause recrystallization and precipitation of secondary carbonate in the porous micromorphology, thus rendering the vesicular portions not suitable for palaeoenvironmental reconstruction. In contrast, stable isotope and trace element compositions show that the original chemical composition of the shell is well-preserved in the denser, foliated portions, which can therefore be reliably used for the reconstruction of palaeoenvironmental conditions. Stable oxygen and clumped isotope thermometry on carbonate from the dense hinge region yield sea water temperatures of 11 °C, while previous TEX86H palaeothermometry yielded much higher temperatures. The difference is ascribed to seasonal bias in the growth of P. vesicularis, causing warm seasons to be underrepresented from the record, and TEX86H palaeothermometry being potentially biased towards warmer surface water temperatures. Superimposed on this annual mean is a seasonality in δ18O of about 1 ‰, which is ascribed to a combination of varying salinity due to fresh water input in the winter and spring season and a moderate temperature seasonality. Attempts to independently verify the seasonality in sea water temperature by Mg / Ca ratios of shell calcite are hampered by significant uncertainty due to the lack of proper transfer functions for pycnodontein oysters. The multi-proxy approach employed here enables us to differentiate between well-preserved and diagenetically altered portions of the shells and provides an improved methodology for reconstructing palaeoenvironmental conditions in deep time. While establishing a chronology for these shells was severely complicated by growth cessations and diagenesis, cyclicity in trace elements and stable isotopes allowed a tentative interpretation of the potential annual seasonal cycle in the late Maastrichtian palaeoenvironment of the Neuquén basin. Future studies of fossil ostreid bivalves should target dense foliated calcite rather than sampling bulk or vesicular calcite. Successful application of clumped isotope thermometry on fossil bivalve calcite in this study indicates that temperature seasonality in fossil ostreid bivalves may be constrained by the sequential analysis of well-preserved foliated calcite samples using this method.

RATIONALE The measurement of multiply substituted isotopologues of CO2 derived from carbonate has allowed the reconstruction of paleotemperatures from a single phase (CaCO3), circumventing uncertainty inherent in other isotopic paleothermometers. Traditional analytical techniques require relatively large amounts of carbonate (3–8 mg per replicate), which limits the applicability of the clumped isotope proxy to certain geological materials such as marine microfossils, commonly used for paleoclimate reconstructions. METHODS Clumped isotope ratio measurements of small samples were made on a new, high-efficiency, dual-reservoir sample-preparation inlet system attached to a Thermo-Finnigan MAT 253 mass spectrometer. Sample gas produced on the inlet is introduced from a 10 mL reservoir directly into the source via a capillary. Reference gas fills an identical 10 mL reservoir installed between the reference bellows and the capillary. The gas pressures in the two reservoirs are initially balanced, and are allowed to decrease together over the run. RESULTS Carbonate samples from 1 mg to 2.6 mg produced Δ47 values equivalent to those from the traditional two-bellows method with identical single-sample precision (1 SE = 0.005–0.015‰) and external standard error (SE = 0.006–0.015‰, n = 4–6). The size of sample needed to achieve good precision is controlled by the sensitivity of the mass spectrometer and the size of the fixed reservoirs and adjacent U-trap installed on our inlet. CONCLUSIONS The high-precision clumped isotope measurements of small aliquots of carbonate obtained in this method allows for the application of this proxy to a wider range of geological sample materials, such as marine microfossils, that until now have been nearly impossible to analyze given sample size limitation. Copyright © 2014 John Wiley & Sons, Ltd.

[1] We present a new hypothesis to explain the millennial-scale temperature variability recorded in ice cores known as Dansgaard-Oeschger (DO) cycles. We propose that an ice shelf acted in concert with sea ice to set the slow and fast timescales of the DO cycle, respectively. The abrupt warming at the onset of a cycle is caused by the rapid retreat of sea ice after the collapse of an ice shelf. The gradual cooling during the subsequent interstadial phase is determined by the timescale of ice-shelf regrowth. Once the ice shelf reaches a critical size, sea ice expands, driving the climate rapidly back into stadial conditions. The stadial phase ends when warm subsurface waters penetrate beneath the ice shelf and cause it to collapse. This hypothesis explains the full shape of the DO cycle, the duration of the different phases, and the transitions between them and is supported by proxy records in the North Atlantic and Nordic Seas.

The warm climate of Bermuda today is modulated by the nearby presence of the Gulf Stream current. However, iceberg scours in the Florida Strait and the presence of ice-rafted debris in Bermuda Rise sediments indicate that, during the last deglaciation, icebergs discharged from the Laurentide Ice Sheet traveled as far south as subtropical latitudes. We present evidence that an event of similar magnitude affected the subtropics during the Last Interglacial, potentially due to melting of the Greenland Ice Sheet. Using the clumped isotope paleothermometer, we found temperatures similar to 10 degrees C colder and seawater delta O-18 values similar to 2% lower than modern in Last Interglacial Cittarium pica shells from Grape Bay, Bermuda. In contrast, Last Interglacial shells from Rocky Bay, Bermuda, record temperatures only slightly colder and seawater delta O-18 values similar to modern, likely representing more typical Last Interglacial conditions in Bermuda outside of a meltwater event. The significantly colder ocean temperatures observed in Grape Bay samples illustrate the extreme sensitivity of Bermudian climate to broad-scale ocean circulation changes. They indicate routine meltwater transport in the North Atlantic to near-equatorial latitudes, which would likely have resulted in disruption of the Atlantic Meridional Overturning Circulation. These data demonstrate that future melting of the Greenland Ice Sheet, a potential source of the Last Interglacial meltwater event, could have dramatic climate effects outside of the high latitudes.

The cause of the end-Cretaceous (KPg) mass extinction is still debated due to difficulty separating the influences of two closely timed potential causal events: eruption of the Deccan Traps volcanic province and impact of the Chicxulub meteorite. Here we combine published extinction patterns with a new clumped isotope temperature record from a hiatus-free, expanded KPg boundary section from Seymour Island, Antarctica. We document a 7.8±3.3 °C warming synchronous with the onset of Deccan Traps volcanism and a second, smaller warming at the time of meteorite impact. Local warming may have been amplified due to simultaneous disappearance of continental or sea ice. Intra-shell variability indicates a possible reduction in seasonality after Deccan eruptions began, continuing through the meteorite event. Species extinction at Seymour Island occurred in two pulses that coincide with the two observed warming events, directly linking the end-Cretaceous extinction at this site to both volcanic and meteorite events via climate change., The cause of the end-Cretaceous mass extinction is still debated due to difficulties separating the influences of two closely-timed potential causal events (massive volcanism and meteorite impact). Here, the authors link the extinction to both kill mechanisms through a new paleotemperature record.

During the last glacial period, the Laurentide Ice Sheet sporadically discharged huge numbers of icebergs through the Hudson Strait into the North Atlantic Ocean, leaving behind distinct layers of ice-rafted debris in the ocean sediments. Perplexingly, these massive discharge events-Heinrich events-occurred during the cold portion of millennial-scale climate oscillations called Dansgaard-Oeschger cycles. This is in contrast to the expectation that ice sheets expand in colder climates and shrink in warmer climates. Here we use an ice sheet model to show that the magnitude and timing of Heinrich events can be explained by the same processes that drive the retreat of modern marine-terminating glaciers. In our model, subsurface ocean warming associated with variations in the overturning circulation increases underwater melt along the calving face, triggering rapid margin retreat and increased iceberg discharge. On millennial timescales, isostatic adjustment causes the bed to uplift, isolating the terminus from subsurface warming and allowing the ice sheet to advance again until, at its most advanced position, it is poised for another Heinrich event. This mechanism not only explains the timing and magnitude of observed Heinrich events, but also suggests that ice sheets in contact with warming oceans may be vulnerable to catastrophic collapse even with little atmospheric warming.

The San Emigdio and related Pelona, Orocopia, Rand and Sierra de Salinas schists of southern California were underplated beneath the southern Sierra Nevada batholith and adjacent southern California batholith along a shallow segment of the subducting Farallon plate in Late Cretaceous to early Tertiary time. These subduction accretion assemblages represent a regional, deeply exhumed, shallowly dipping domain from an ancient slab segmentation system and record the complete life cycle of the segmentation process from initial flattening and compression to final extensional collapse. An important unresolved question regarding shallow subduction zones concerns how the thermal structure evolves during the slab flattening process. New field relationships, thermobarometry, thermodynamic modelling and garnet diffusion modelling are presented that speak to this issue and elucidate the tectonics of underplating and exhumation of the San Emigdio Schist. We document an upsection increase in peak temperature (i.e. inverted metamorphism), from 590 to 700 °C, peak pressures ranging from 8.5 to 11.1 kbar, limited partial melting, microstructural evidence for large seismic events, rapid cooling (825–380 °C Myr^−1) from peak conditions and an ‘out and back’P–T path. While inverted metamorphism is a characteristic feature of southern California schists, the presence of partial melt and high temperatures (>650 °C) are restricted to exposures with maximum depositional ages between 80 and 90 Ma. Progressive cooling and tectonic underplating beneath an initially hot upper plate following the onset of shallow subduction provide a working hypothesis explaining high temperatures and partial melting in San Emigdio and Sierra de Salinas schists, inverted metamorphism in the schist as a whole, and the observed P–T trajectory calculated from the San Emigdio body. Lower temperatures in Pelona, Orocopia and Rand schists are likewise explained in the context of this overarching model. These results are consistent with an inferred tectonic evolution from shallow subduction beneath the then recently active Late Cretaceous arc to exhumation by rapid trench-directed channelized extrusion in the subducted schist.

The clumped isotope paleothermometer, a new proxy widely applicable in studies of paleoclimate, tectonics, and paleontology, relates the abundance of doubly substituted isotopologues of carbonate-derived CO2 to the temperature of formation of the carbonate phase. As this technique becomes more widely used, more is discovered about the effects of everyday laboratory procedures on the clumped isotopic composition of CO2 gas.Preparation of CO2 for clumped isotope analysis requires the removal of isobaric contaminants prior to measurement, achieved dynamically by passing the CO2 through a gas chromatography column using a helium carrier gas or cryogenically pumping CO2 through a static trap filled with Porapak™ Q (PPQ) material. The stable and clumped isotopic compositions of carbonate standards prepared at PPQ trap temperatures between -40°C and -10°C were measured by isotope ratio mass spectrometry to evaluate potential artifacts introduced by the static PPQ trap method.The stable isotopic composition of carbonates run at temperatures below -20°C was fractionated, despite achieving99% retrieval of gas at temperatures as cold as -30°C. The δ(13)C and δ(18)O values decreased by ~0.01 and ~0.03 ‰/(°C below -20°C). The raw Δ47 values decreased by 0.003-0.005 ‰/(°C below -20°C), but the final reference-frame-corrected values (Δ47-RFAC ) were unaffected as long as the carbonate samples and standard gases were prepared identically.Preparing carbonate samples for clumped isotope analysis using a PPQ trap that is too cold can result in erroneous stable isotopic compositions. New and existing labs using the static PPQ trap cleaning procedure should determine the ideal PPQ trap temperature for their particular system through monitoring not only yield through the PPQ trap, but also stable isotopic composition at various PPQ trap temperatures.

The measurement of multiply substituted isotopologues of CO2 derived from carbonate has allowed the reconstruction of paleotemperatures from a single phase (CaCO3 ), circumventing uncertainty inherent in other isotopic paleothermometers. Traditional analytical techniques require relatively large amounts of carbonate (3-8 mg per replicate), which limits the applicability of the clumped isotope proxy to certain geological materials such as marine microfossils, commonly used for paleoclimate reconstructions.Clumped isotope ratio measurements of small samples were made on a new, high-efficiency, dual-reservoir sample-preparation inlet system attached to a Thermo-Finnigan MAT 253 mass spectrometer. Sample gas produced on the inlet is introduced from a 10 mL reservoir directly into the source via a capillary. Reference gas fills an identical 10 mL reservoir installed between the reference bellows and the capillary. The gas pressures in the two reservoirs are initially balanced, and are allowed to decrease together over the run.Carbonate samples from 1 mg to 2.6 mg produced Δ47 values equivalent to those from the traditional two-bellows method with identical single-sample precision (1 SE = 0.005-0.015‰) and external standard error (SE = 0.006-0.015‰, n = 4-6). The size of sample needed to achieve good precision is controlled by the sensitivity of the mass spectrometer and the size of the fixed reservoirs and adjacent U-trap installed on our inlet.The high-precision clumped isotope measurements of small aliquots of carbonate obtained in this method allows for the application of this proxy to a wider range of geological sample materials, such as marine microfossils, that until now have been nearly impossible to analyze given sample size limitation.