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RATIONALE: Embedding resins are widely used to fix carbonates for high-precision sample preparation and high-resolution sampling. However, these embedding materials are difficult to remove after sample preparation and are known to affect the accuracy of carbonate stable isotope analyses. Nevertheless, their impact on clumped isotope analysis, which is particularly sensitive to contamination artifacts, has so far not been tested. The observation that running resin-containing samples decreased the reproducibility of clumped isotope values for internal laboratory carbonate standards and increased the external standard deviation (SD 0.061-0.088) compared to the long-term observations (0.034), prompted us to set up an experiment to test the influence of resin addition on instrument performance. METHODS: Here we analyzed the stable and clumped isotope composition of a pure calcium carbonate standard (ETH-4) mixed with three types of embedding resins in 2:1 and 1:1 proportions. Our aim was to assess how resin addition affects isotope analyses. RESULTS: We found that none of the stable isotopic values were significantly different. The δ13 C values were -10.22 ± 0.07 (mean ± SD) for pure ETH-4, while the δ13 C values of ETH-4 mixed with embedding resins in 2:1 and 1:1 proportions were -10.21 ± 0.06 and -10.18 ± 0.06, respectively (p > 0.05). The δ18 O values were -18.82 ± 0.11 for pure ETH-4 versus -18.81 ± 0.09 and -18.82 ± 0.08 for 2:1 and 1:1 ETH-4:resin mixtures, respectively (p > 0.05). Given the large uncertainty in our results, we did not find significant differences between different mixtures in the carbonate clumped isotope values (Δ47 ), with 0.458 ± 0.107, 0.464 ± 0.086, and 0.417 ± 0.089 in pure ETH-4 and ETH-4 with 2:1 and 1:1 resin mixtures, respectively (p > 0.05). However, a resin-related bias in the results might be masked by the large uncertainty. The measured ETH-4 values in our study are similar to the InterCarb values (δ13 C = -10.20, δ18 O = -18.81, Δ47 = 0.450, InterCarb-Carbon Dioxide Equilibrium Scale). However, the external SD of Δ47 in sessions measuring ETH-4 with resins is higher than in sessions without deliberate resin addition for the same measuring period. CONCLUSIONS: We find that the potential contamination from the resin addition leads to a larger variability for Δ47 values in sessions measuring ETH-4 including resins. We therefore recommend purification of embedded samples using a contamination trap with Porapak prior to analysis, if possible, or avoiding resins during sample preparation and workup, as well as monitoring the measurement quality during and after sessions with samples containing embedding resins.
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Clumped isotope thermometry can independently constrain the formation temperatures of carbonates, but a lack of precisely temperature-controlled calibration samples limits its application on aragonites. To address this issue, we present clumped isotope compositions of aragonitic bivalve shells grown under highly controlled temperatures (1-18°C), which we combine with clumped isotope data from natural and synthetic aragonites from a wide range of temperatures (1-850°C). We observe no discernible offset in clumped isotope values between aragonitic foraminifera, mollusks, and abiogenic aragonites or between aragonites and calcites, eliminating the need for a mineral-specific calibration or acid fractionation factor. However, due to non-linear behavior of the clumped isotope thermometer, including high-temperature (>100°C) datapoints in linear clumped isotope calibrations causes them to underestimate temperatures of cold (1-18°C) carbonates by 2.7 ± 2.0°C (95% confidence level). Therefore, clumped isotope-based paleoclimate reconstructions should be calibrated using samples with well constrained formation temperatures close to those of the samples.
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Documenting the seasonal temperature cycle constitutes an essential step toward mitigating risks associated with extreme weather events in a future warmer world. The mid-Piacenzian Warm Period (mPWP), 3.3 to 3.0 million years ago, featured global temperatures approximately 3°C above preindustrial levels. It represents an ideal period for directed paleoclimate reconstructions equivalent to model projections for 2100 under moderate Shared Socioeconomic Pathway SSP2-4.5. Here, seasonal clumped isotope analyses of fossil mollusk shells from the North Sea are presented to test Pliocene Model Intercomparison Project 2 outcomes. Joint data and model evidence reveals enhanced summer warming (+4.3° ± 1.0°C) compared to winter (+2.5° ± 1.5°C) during the mPWP, equivalent to SSP2-4.5 outcomes for future climate. We show that Arctic amplification of global warming weakens mid-latitude summer circulation while intensifying seasonal contrast in temperature and precipitation, leading to an increased risk of summer heat waves and other extreme weather events in Europe's future.
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Aquecimento Global , Estações do Ano , Europa (Continente) , Temperatura , Animais , Mudança Climática , Fósseis , Modelos ClimáticosRESUMO
Bivalve shells are increasingly used as archives for high-resolution paleoclimate analyses. However, there is still an urgent need for quantitative temperature proxies that work without knowledge of the water chemistry-as is required for δ18O-based paleothermometry-and can better withstand diagenetic overprint. Recently, microstructural properties have been identified as a potential candidate fulfilling these requirements. So far, only few different microstructure categories (nacreous, prismatic and crossed-lamellar) of some short-lived species have been studied in detail, and in all such studies, the size and/or shape of individual biomineral units was found to increase with water temperature. Here, we explore whether the same applies to properties of the crossed-acicular microstructure in the hinge plate of Arctica islandica, the microstructurally most uniform shell portion in this species. In order to focus solely on the effect of temperature on microstructural properties, this study uses bivalves that grew their shells under controlled temperature conditions (1, 3, 6, 9, 12 and 15°C) in the laboratory. With increasing temperature, the size of the largest individual biomineral units and the relative proportion of shell occupied by the crystalline phase increased. The size of the largest pores, a specific microstructural feature of A. islandica, whose potential role in biomineralization is discussed here, increased exponentially with culturing temperature. This study employs scanning electron microscopy in combination with automated image processing software, including an innovative machine learning-based image segmentation method. The new method greatly facilitates the recognition of microstructural entities and enables a faster and more reliable microstructural analysis than previously used techniques. Results of this study establish the new microstructural temperature proxy in the crossed-acicular microstructures of A. islandica and point to an overarching control mechanism of temperature on the micrometer-scale architecture of bivalve shells across species boundaries.
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Adaptação Fisiológica/fisiologia , Exoesqueleto/química , Exoesqueleto/crescimento & desenvolvimento , Bivalves/crescimento & desenvolvimento , Laboratórios , Temperatura , Animais , Processamento de Imagem Assistida por Computador/métodos , Aprendizado de Máquina , Microscopia Eletrônica de Varredura/métodos , Paleontologia/métodos , Porosidade , Software , Água/químicaRESUMO
The Cretaceous-Paleogene (K-Pg) mass extinction is marked globally by elevated concentrations of iridium, emplaced by a hypervelocity impact event 66 million years ago. Here, we report new data from four independent laboratories that reveal a positive iridium anomaly within the peak-ring sequence of the Chicxulub impact structure, in drill core recovered by IODP-ICDP Expedition 364. The highest concentration of ultrafine meteoritic matter occurs in the post-impact sediments that cover the crater peak ring, just below the lowermost Danian pelagic limestone. Within years to decades after the impact event, this part of the Chicxulub impact basin returned to a relatively low-energy depositional environment, recording in unprecedented detail the recovery of life during the succeeding millennia. The iridium layer provides a key temporal horizon precisely linking Chicxulub to K-Pg boundary sections worldwide.
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The Devonian Frasnian-Famennian (F-F) boundary marks one of the five main extinction intervals of the Phanerozoic Aeon. This time was characterized by two pulses of oceanic anoxia, named the Lower and Upper Kellwasser events, during which massive marine biodiversity losses occurred. This paper presents high-resolution magnetic susceptibility, X-ray fluorescence elemental geochemistry and carbon isotope datasets obtained from the Steinbruch Schmidt F-F boundary section (Germany). These records lead to an astronomical time calibration of the environmental changes associated with the two ocean anoxia pulses. Cyclostratigraphic interpretation indicates deposition of the black argillaceous Lower and Upper Kellwasser horizons over ~ 90 and ~ 110 kyr, respectively; approximately equivalent to the duration of one short eccentricity cycle. This study confirms that the succession of events within the Upper Kellwasser event is paced by obliquity, under a low-eccentricity orbit. Hence, astronomical insolation forcing likely contributed to the expansion of ocean anoxia and other environmental perturbations associated with these two crises. The new floating chronology established for the Steinbruch Schmidt section is anchored in numerical time by means of a radio-isotopic date, obtained from a bentonite layer interbedded between the two Kellwasser horizons. After anchoring, this time scale gives a high-precision age of 371.870 ± 0.108 Ma for the F-F boundary.
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The study of stable isotopes in fossil bioapatite has yielded useful results and has shown that bioapatites are able to faithfully record paleo-environmental and paleo-climatic parameters from archeological to geological timescales. In an effort to establish new proxies for the study of bioapatites, intra-tooth records of enamel carbonate stable isotope ratios from a modern horse are compared with trace element profiles measured using laboratory micro X-Ray Fluorescence scanning. Using known patterns of tooth eruption and the relationship between stable oxygen isotopes and local temperature seasonality, an age model is constructed that links records from six cheek upper right teeth from the second premolar to the third molar. When plotted on this age model, the trace element ratios from horse tooth enamel show a seasonal pattern with a small shift in phase compared to stable oxygen isotope ratios. While stable oxygen and carbon isotopes in tooth enamel are forced respectively by the state of the hydrological cycle and the animal's diet, we argue that the seasonal signal in trace elements reflects seasonal changes in dust intake and diet of the animal. The latter explanation is in agreement with seasonal changes observed in carbon isotopes of the same teeth. This external forcing of trace element composition in mammal tooth enamel implies that trace element ratios may be used as proxies for seasonal changes in paleo-environment and paleo-diet.