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Between 1992 and 2018, the breeding population of Adélie penguins around Anvers Island, Antarctica declined by 98%. In this region, natural climate variability drives five‐year cycling in marine phytoplankton productivity, leading to phase‐offset five‐year cycling in the size of the krill population. We demonstrate that the rate of change of the Adélie breeding population also shows five‐year cycling. We link this population response to cyclical krill scarcity, a phenomenon which appears to have arisen from the interaction between climate variability and climate change trends. Modeling suggests that, since at least 1980, natural climate variability has driven cycling in this marine system. However, anthropogenic climate change has shifted conditions so that fewer years in each cycle now prompt strong krill recruitment, triggering intervals of krill scarcity that result in drastic declines in Adélie penguins. Our results imply that climate change can amplify the impacts of natural climate oscillations across trophic levels, driving cycling across species and disrupting food webs. The findings indicate that climate variability plays an integral role in driving ecosystem dynamics under climate change. [ABSTRACT FROM AUTHOR]

Marine and continental records (1) show an abrupt negative shift in carbon isotope values at ~55.8 Myr ago. This carbon isotope excursion (CIE) is consistent with the release of a massive amount of isotopically light carbon into the atmosphere and was associated with a dramatic rise in global temperatures termed the Palaeocene-Eocene thermal maximum (PETM). Greenhouse gases released during the CIE, probably including methane, have often been considered the main cause of PETM warming. However, some evidence from the marine record suggests that warming directly preceded the CIE (2-4), raising the possibility that the CIE and PETM may have been linked to earlier warming with different origins. Yet pre-CIE warming is still uncertain. Disentangling the sequence of events before and during the CIE and PETM is important for understanding the causes of, and Earth system responses to, abrupt climate change. Here we show that continental warming of about 5°C preceded the CIE in the Bighorn Basin, Wyoming. Our evidence, based on oxygen isotopes in mammal teeth (which reflect temperature-sensitive fractionation processes) and other proxies, reveals a marked temperature increase directly below the CIE, and again in the CIE. Pre-CIE warming is also supported by a negative amplification of [δ.sup.13]C values in soil carbonates below the CIE. Our results suggest that at least two sources of warming--the earlier of which is unlikely to have been methane--contributed to the PETM., Abrupt warming during the PETM coincided with a profound reorganization of mammalian fauna as the first representatives of several modern groups dispersed among the northern continents (5). In North America, [...]

A high-resolution record of Eocene paleotemperature variation is preserved within the high southern latitude, marine shelf succession of the La Meseta Formation on Seymour Island, off the NE side of the Antarctic Peninsula. [sup.87] Sr[sup.86] Sr ratios of bivalve shell carbonate indicate that the La Meseta Formation spans virtually the entire Eocene, and suggest the presence of an early middle Eocene unconformity. Paleoclimatic and paleoceanographic inferences are based on the stable oxygen and carbon isotope values of two genera of bivalves collected with a high degree of stratigraphic resolution within the formation, and with multiple replicate samples from each horizon. [[delta]sup.18] O data indicate roughly 10[degrees] C of cooling from the early Eocene climatic optimum (~15[degrees] C) through the end of the Eocene (minimum ~5 [degrees] C), much of which took place in two comparatively short intervals at ca. 52 and ca. 41 Ma. Many features of the isotope curves generated from this Eocene shelf section are apparent in [[delta]sup.18] O and [[delta]sup.13] C data from the Southern and global oceans, including warm intervals that likely correspond to the early and middle Eocene climatic optima (EECO and MECO). A rapid middle Eocene shift to much more positive values is the most significant in the section and reflects a drop to universally cooler temperatures in the late middle and late Eocene that might also be associated with a short-lived glacial advance. However, even using a somewhat depleted value for [[delta]sup.18] O of seawater in the Antarctic peninsular region, average Seymour Island shelf-water paleotemperatures did not reach freezing before the end of the Eocene. [[delta]sup.13] C data similarly reflect the documented middle Eocene surface ocean enrichment followed by more negative values, but depletion is much more pronounced on Seymour Island and persists for the remainder of the Eocene, suggesting a combination of upwelling, metabolic effects, and/or atypical carbon cycling on the shelf in this region. Isotope data capture information about changes in the paleoenvironment that also had consequences for the biota, as published paleontological records document marked change in the nature of terrestrial and marine biota at this time. The fact that middle Eocene cooling and biotic turnover in the Peninsular region correspond well in time to the proposed initial opening of Drake Passage suggests that the formation of gateways, in addition to changes in [pCO.sub.2], had significant consequences for the Earth's climate system during the Paleogene. Keywords: stable isotope, Eocene, climate, bivalve, Antarctica, strontium.

Author(s): Linda C. Ivany (corresponding author) [1, 2]; William P. Patterson [2, 3]; Kyger C. Lohmann [1] The Eocene/Oligocene boundary, at about 33.7 Myr ago, marks one of the largest [...]

Faunal analog reconstructions suggest that Last Interglacial (MIS 5e) sea surface temperatures were cooler around Bermuda and in the Caribbean than modern climate. Here we describe new and revised clumped isotope measurements of Cittarium pica fossil shells supporting previous findings of cooler than modern temperatures in Bermuda during the Last Interglacial. We resolve temperature and δ18Ow differences between two closely located and apparently coeval sites described in Winkelstern et al. (2017), https://doi.org/10.1002/2016pa003014 through reprocessing raw isotopic data with the updated Brand/IUPAC parameters. New subannual‐resolution clumped isotope data reveal large variations in δ18Ow out of phase with seasonal temperature changes (i.e., lower δ18Ow values in winter). Supported by modern δ18Ow measurements identifying similar processes occurring today, we suggest past variations in coastal δ18Ow were driven by seasonally variable freshwater discharge from a subterranean aquifer beneath the island. Taken together, our results emphasize the importance of δ18Ow in controlling carbonate δ18O, and suggest that typical assumptions of constant δ18Ow should be made cautiously in nearshore settings and can contribute to less accurate reconstructions of paleotemperature. Key Points: Bermudan climate during the Last Interglacial period (MIS 5e) was colder than todaySubannual clumped isotope analyses capture seasonal‐scale changes in temperature and water compositionVariable discharge from an underground aquifer affects oxygen isotopic composition of coastal water during MIS 5e and today [ABSTRACT FROM AUTHOR]

Carbonate clumped isotope paleothermometry is a promising method for paleoclimate reconstructions and understanding diagenetic processes, although clumped isotope compositions (measured as Δ47 values) can be altered by recrystallization and thermal resetting. Several studies have investigated the effects of deep burial and exhumation on Δ47 values; we present Δ47 values of samples from an ~4500-m-long drill core from Andros Island, Bahamas, which represent the spectrum from shallow to deep burial conditions. These limestones and dolomites originally formed under near-surface temperature conditions, which are reflected by ~27 °C Δ47 temperatures in samples buried to <~1.3 km depth. Below this depth, calculated Δ47 temperatures increase by ~10 °C, indicating a shift from preserved near-surface temperatures to diagenetically modified values. Importantly, this shift is not accompanied by a change in δ18O and δ13C values or cathodoluminescence, and non-uniform micrometer-scale crystallization is observed in both Δ47-altered and unaltered rocks. Similar Δ47 temperatures recorded by each carbonate phase suggest that mineral-specific differences are minor. Finegrained dolomites and calcites are viable materials for recording surface temperature conditions, and both are susceptible to alteration of their primary clumped isotope abundances during burial diagenesis. Our results demonstrate that original Δ47 values of fine-grained carbonates can be altered under mild diagenetic conditions. [ABSTRACT FROM AUTHOR]

3He and 4He concentrations in excess of those in water in solubility equilibrium with the atmosphere by up to two and three orders of magnitude are observed in the shallow Glacial Drift and Saginaw aquifers in the Michigan Basin. A simplified He transport model shows that in situ production is negligible and that most He excesses have a source external to the aquifer. Simulated results show that 3He and 4He fluxes entering the bottom of the Saginaw aquifer are 7.5 × 10−14 and 6.1 × 10−7 cm3 STPcm−2 yr−1, both of which are lower than fluxes entering the underlying Marshall aquifer, 1.0 × 10−13 and 1.6 × 10−6 cm3 STPcm−2 yr−1 for 3He and 4He, respectively. In contrast, He fluxes entering the Saginaw aquifer are higher than fluxes entering the overlying Glacial Drift aquifer of 5.2 × 10−14 and 1.5 × 10−7 cm3 STPcm−2 yr−1 for 3He and 4He, respectively. The unusually high He fluxes and their decreasing values from the lower Marshall to the upper Glacial Drift aquifer strongly suggest the presence of an upward cross-formational flow, with increasing He dilution toward the surface by recharge water. These fluxes are either comparable to or far greater than He fluxes in deeper aquifers around the world. Model simulations also suggest an exponential decrease in the horizontal groundwater velocity with recharge distance. Horizontal velocities vary from 13 to 2 myr−1 for the Saginaw aquifer and from 18 to 6 myr−1 for the Marshall aquifer. The highly permeable Glacial Drift aquifer displays a greater velocity range, from 250 to 5 myr−1. While Saginaw 4He ages estimated based on the simulated velocity field display an overall agreement with 14C ages, 14C and 4He ages in the Glacial Drift and Marshall aquifers deviate significantly, possibly due to simplifications introduced in the He transport model leading to calculation of first-order approximation He ages and high uncertainties in Glacial Drift 14C ages. [ABSTRACT FROM AUTHOR]

Abstract: Aragonite is easily altered during diagenesis, therefore presumed pristine when present. In effect, beyond polymorphic transformation to calcite, alteration paths of aragonite remain poorly understood despite heavy reliance on such material to produce palaeoenvironmental and chronostratigraphic interpretations. Previous work on core material from Southern McMurdo Sound, Antarctica, showed that unlike their calcitic counterparts, seemingly unaltered aragonite shell fragments invariably produced older than expected 87Sr/86Sr ages. In this study, we pursued additional analyses of these aragonite shells and of the porewater of the core to understand this discrepancy. Aragonite mineralogy was reconfirmed and elemental mapping of shell fragments revealed growth lines within the middle layer suggestive of good preservation. The outer layer, however, showed anomalously high Sr concentrations (average 4·5 ± 0·6 mole% SrCO3; ca 25 mmol mol−1 Sr/Ca) and was depleted in 18O and 13C compared to the middle layer, both features inconsistent with pristine material. The δ18O values and Sr concentrations of the porewater were used to model outer layer compositions reasonably well. Coincidentally, porewater Sr isotope composition was in general agreement with the age model of the core only at the aragonite‐bearing interval suggesting that Sr‐isotopic disequilibrium between porewater and the carbonates was the rule rather than the exception in the core. The Sr isotope compositions of the aragonite shells are most likely the result of early diagenesis as suggested by the inconsistent O and C isotope compositions between shell layers and the anomalously high Sr concentrations. We conclude that knowledge of Sr concentration and distribution in shells is critical to determine the viability of Sr stratigraphy and the scale at which it may be applied. Reliance on traditional indicators of lack of alteration, such as cathodoluminescence, Mn‐Fe concentration, and the presence of labile mineralogies to assert chronostratigraphic and palaeoenvironmental questions may produce erroneous conclusions due to obscurely altered material. [ABSTRACT FROM AUTHOR]

RATIONALE: Mass-47 CO2 clumped isotope thermometry requires relatively large (∼20 mg) samples of carbonate minerals due to detection limits and shot noise in gas source isotope ratio mass spectrometry (IRMS). However, it is unreasonable to assume that natural geologic materials are homogenous on the scale required for sampling. We show that sample heterogeneities can cause offsets from equilibrium Δ47 values that are controlled solely by end member mixing and are independent of equilibrium temperatures. METHODS: A numerical model was built to simulate and quantify the effects of end member mixing on Δ47. The model was run in multiple possible configurations to produce a dataset of mixing effects. We verified that the model accurately simulated real phenomena by comparing two artificial laboratory mixtures measured using IRMS to model output. RESULTS: Mixing effects were found to be dependent on end member isotopic composition in δ13C and δ18O values, and independent of end member Δ47 values. Both positive and negative offsets from equilibrium Δ47 can occur, and the sign is dependent on the interaction between end member isotopic compositions. The overall magnitude of mixing offsets is controlled by the amount of variability within a sample; the larger the disparity between end member compositions, the larger the mixing offset. CONCLUSIONS: Samples varying by less than 2 ‰ in both δ13C and δ18O values have mixing offsets below current IRMS detection limits. We recommend the use of isotopic subsampling for δ13C and δ18O values to determine sample heterogeneity, and to evaluate any potential mixing effects in samples suspected of being heterogonous. [ABSTRACT FROM AUTHOR]

We report the results of a yearlong noble gas study conducted in 2008-2009 together with continuous physical and chemical measurements collected in a monitoring well in an aquifer in southern Michigan. Conditions near the water table are correlated with noble gas concentrations, corresponding noble gas temperatures (NGTs), and precipitation events. This yearlong study is the first noble gas field test that has employed natural recharge and in situ monitored conditions, with minimal disturbance of the unsaturated zone. This detailed study demonstrates that significant changes in conditions near the water table can occur over a year that can greatly affect NGTs. Results show that precipitation events are detected within hours at the water table, but a lag in pressure response argues for a long time constant for gas transport within the unsaturated zone. There is strong evidence for the depletion of oxygen near the water table, which affects the noble gas air-saturated water component. During reducing conditions there is evidence for significant noble gas degassing. Rain from the passage of Hurricane Ike caused a significant shift in stable isotope ratios and injection of a large quantity of excess air and likely led to a much more oxygen-rich environment in the soil gas. Although individual models can account for NGTs over portions of the record, no single NGT model can account for all features observed over the entire study. It is likely that the NGT temperature proxy must be viewed as an average of recharge conditions over several years. [ABSTRACT FROM AUTHOR]

A sectioned and polished specimen of the coral Archohelia vicksburgensis from the early Oligocene Byram Formation (∼30 Ma) near Vicksburg, Mississippi, reveals 12 prominent annual growth bands. Stable oxygen isotopic compositions of 77 growth-band-parallel microsamples of original aragonite exhibit well-constrained fluctuations that range between −2.0 and −4.8. Variation in δ18O of coral carbonate reflects seasonal variation in temperature ranging from 12 to 24 °C about a mean of 18 °C. These values are consistent with those derived from a bivalve and a fish otolith from the same unit, each using independently derived palaeotemperature equations. Mg/Ca and Sr/Ca ratios were determined for 40 additional samples spanning five of the 12 annual bands. Palaeotemperatures calculated using elemental-ratio thermometers calibrated on modern corals are consistently lower; mean temperature from Mg/Ca ratios are 12.5 ± 1 °C while those from Sr/Ca are 5.8 ± 2.2 °C. Assuming that δ18O-derived temperatures are correct, relationships between temperature and elemental ratio for corals growing in today's ocean can be used to estimate Oligocene palaeoseawater Mg/Ca and Sr/Ca ratios. Calculations indicate that early Oligocene seawater Mg/Ca was ∼81% (4.2 mol mol−1) and Sr/Ca ∼109% (9.9 mmol mol−1) of modern values. Oligocene seawater with this degree of Mg depletion and Sr enrichment is in good agreement with that expected during the Palaeogene transition from ‘calcite’ to ‘aragonite’ seas. Lower Oligocene Mg/Ca probably reflects a decrease toward the present day in sea-floor hydrothermal activity and concomitant decrease in scavenging of magnesium from seawater. Elevated Sr/Ca ratio may record lesser amounts of Oligocene aragonite precipitation and a correspondingly lower flux of strontium into the sedimentary carbonate reservoir than today. [ABSTRACT FROM AUTHOR]

Discusses the calculation of the sigma18O values of river waters in Late Cretaceous and Paleogene basins of Alberta, Montana, Wyoming and Colorado from the isotropic composition of unaltered aragonite mollusk fossils. Water sources indicated by the close stratigraphic association of river deposits with different isotropic values.