Stable isotope ratios and trace elements in modern mammal tooth enamel

Bioapatite from mammal tooth enamel is a popular biomineral used in the reconstruction of palaeoenvironment and palaeodiet. It records information about the animal’s environment and diet on a sub-annual scale and is proven to be highly resistant to diagenesis, allowing the preservation of its original chemical composition through archaeological and geological timescales. In this study, stable carbon and oxygen isotope analysis are used as a stepping stone to investigate the use of other chemical proxies for the reconstruction of environment and diet from mammal teeth. Concentration profiles of trace element distributions (measured with μXRF and cross-validated with Laser Ablation ICP-MS) and stable isotope ratios (13Cap, 18Oc & 18Op) are combined to test the reliability of trace element profiles from mammal teeth in recording seasonal changes in environment and diet of the animal. A method is presented that links the various geochemical records within a tooth sequence using mineralization sequences and oxygen isotope seasonality. This way, a 3 year trace element and stable isotope record from horse tooth enamel is created showing seasonal variation in trace elements and isotope ratios linked to changes in climatic conditions and diet through the animal’s lifetime. This study shows how an entire new set of trace element proxies, that can be measured quickly and non-destructively, may yield information on palaeoenvironment and palaeodiet. These trace element measurements yield information from precious archaeological samples that could otherwise be obtained solely through destructive sampling. The versatility of the μXRF and LA- ICP-MS methods opens up a wide range of applications for trace element analysis in archaeology

Reconstructing seasonality through stable-isotope and trace-element analyses of the Proserpine stalagmite, Han-sur-Lesse cave, Belgium : indications for climate-driven changes during the last 400 years

Fast-growing speleothems allow for the reconstruction of palaeoclimate down to a seasonal scale. Additionally, annual lamination in some of these speleothems yields highly accurate age models for these palaeoclimate records, making these speleothems valuable archives for terrestrial climate. In this study, an annually laminated stalagmite from the Han-sur-Lesse cave (Belgium) is used to study the expression of the seasonal cycle in northwestern Europe during the Little Ice Age. More specifically, two historical 12-year-long growth periods (ca. 1593-1605 CE and 1635-1646 CE) and one modern growth period (1960-2010 CE) are analysed on a sub-annual scale for their stable-isotope ratios (delta C-13 and delta O-18) and trace-element (Mg, Sr, Ba, Zn, Y, Pb, U) contents. Seasonal variability in these proxies is confirmed with frequency analysis. Zn, Y and Pb show distinct annual peaks in all three investigated periods related to annual flushing of the soil during winter. A strong seasonal in-phase relationship between Mg, Sr and Ba in the modern growth period reflects a substantial influence of enhanced prior calcite precipitation (PCP). In particular, PCP occurs during summers when recharge of the epikarst is low. This is also evidenced by earlier observations of increased delta C-13 values during summer. In the 17th century intervals, there is a distinct antiphase relationship between Mg, Sr and Ba, suggesting that processes other than PCP, i.e. varying degrees of incongruent dissolution of dolomite, eventually related to changes in soil activity and/or land-use change are more dominant. The processes controlling seasonal variations in Mg, Sr and Ba in the speleothem appear to change between the 17th century and 1960-2010 CE. The Zn, Y, Pb, and U concentration profiles; stable-isotope ratios; and morphology of the speleothem laminae all point towards increased seasonal amplitude in cave hydrology. Higher seasonal peaks in soil-derived elements (e.g. Zn and Y) and lower concentrations of host-rock-derived elements (e.g. Mg, Sr, Ba) point towards lower residence times in the epikarst and higher flushing rates during the 17th century. These observations reflect an increase in water excess above the cave and recharge of the epikarst, due to a combination of lower summer temperatures and increased winter precipitation during the 17th century. This study indicates that the transfer function controlling Mg, Sr and Ba seasonal variability varies over time. Which process is dominant - either PCP, soil activity or dolomite dissolution - is clearly climate driven and can itself be used as a palaeoenvironment proxy

Radiolitid rudists: An underestimated archive for cretaceous climate reconstruction?

Rudist shells are important archives for palaeoenvironmental reconstructions in the greenhouse world of the Cretaceous. Radiolitids, a family of rudists became very abundant dwellers of the shallow marine carbonate platforms during the Cretaceous. Still, due to the complex structure of their low-Mg calcite outer shell layer, radiolitids are often deemed unsuitable for palaeoenvironmental reconstructions. The aim of this study is to present a combination of petrographic (transmitted light microscopy and cathodoluminescence microscopy) and elemental analyses (high-resolution μXRF and stable isotope) to investigate radiolitid shells for diagenetic alteration and to make them accessible as an archive for environmental conditions during the mid-Cretaceous. Four Eoradiolitites shells were analysed in detail: two right valves (RV), a left valve (LV) with an articulated RV and an isolated LV. Three shell structure types have been identified, including a non-compact, compact and celluloprismatic types. The compact structure type was identified in the LVs while the other two types were observed exclusively in the RVs. Radiolitid shell material composed of the non-compact and the compact structure types can be used as palaeoenvironmental archives as it preserved seasonal signals in both, shell growth structure and isotopic records, while celluloprismatic shell structures are less suitable for reconstructions due to diagenetic alteration. The alternation of dark and light lamellae in both valves, RV and LV, provide information on the intertidal living habitat of the shell-producing organism and its life span. Cretaceous; radiolitid rudists; petrographic and rlemental analyses; right and left valves; palaeoenvironmental reconstructio

Absolute seasonal temperature estimates from clumped isotopes in bivalve shells suggest warm and variable greenhouse climate

Seasonal variability in sea surface temperatures plays a fundamental role in climate dynamics and species distribution. Seasonal bias can also severely compromise the accuracy of mean annual temperature reconstructions. It is therefore essential to better understand seasonal variability in climates of the past. Many reconstructions of climate in deep time neglect this issue and rely on controversial assumptions, such as estimates of sea water oxygen isotope composition. Here we present absolute seasonal temperature reconstructions based on clumped isotope measurements in bivalve shells which, critically, do not rely on these assumptions. We reconstruct highly precise monthly sea surface temperatures at around 50 °N latitude from individual oyster and rudist shells of the Campanian greenhouse period about 78 million years ago, when the seasonal range at 50 °N comprised 15 to 27 °C. In agreement with fully coupled climate model simulations, we find that greenhouse climates outside the tropics were warmer and more seasonal than previously thought. We conclude that seasonal bias and assumptions about seawater composition can distort temperature reconstructions and our understanding of past greenhouse climates

Assessing the effects of embedding resins on carbonate stable and clumped isotope analyses

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 δ13C values were −10.22 ± 0.07‰ (mean ± SD) for pure ETH-4, while the δ13C 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 δ18O 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 (δ13C = −10.20‰, δ18O = −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

Temperature Dependence of Clumped Isotopes (∆47) in Aragonite

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

Characterization of quantitative flow ratio and fractional flow reserve discordance using doppler flow and clinical follow-up

The physiological mechanisms of quantitative flow ratio and fractional flow reserve disagreement are not fully understood. We aimed to characterize the coronary flow and resistance profile of intermediate stenosed epicardial coronary arteries with concordant and discordant FFR and QFR. Post-hoc analysis of the DEFINE-FLOW study. Anatomical and Doppler-derived physiological parameters were compared for lesions with FFR+QFR− (n = 18) vs. FFR+QFR+ (n = 43) and for FFR−QFR+ (n = 34) vs. FFR−QFR− (n = 139). The association of QFR results with the two-year rate of target vessel failure was assessed in the proportion of vessels (n = 195) that did not undergo revascularization. Coronary flow reserve was higher [2.3 (IQR: 2.1–2.7) vs. 1.9 (IQR: 1.5–2.4)], hyperemic microvascular resistance lower [1.72 (IQR: 1.48–2.31) vs. 2.26 (IQR: 1.79–2.87)] and anatomical lesion severity less severe [% diameter stenosis 45.5 (IQR: 41.5–52.5) vs. 58.5 (IQR: 53.1–64.0)] for FFR+QFR− lesions compared with FFR+QFR+ lesions. In comparison of FFR−QFR+ vs. FFR-QFR- lesions, lesion severity was more severe [% diameter stenosis 55.2 (IQR: 51.7–61.3) vs. 43.4 (IQR: 35.0–50.6)] while coronary flow reserve [2.2 (IQR: 1.9–2.9) vs. 2.2 (IQR: 1.9–2.6)] and hyperemic microvascular resistance [2.34 (IQR: 1.85–2.81) vs. 2.57 (IQR: 2.01–3.22)] did not differ. The agreement and diagnostic performance of FFR using hyperemic stenosis resistance (> 0.80) as reference standard was higher compared with QFR and coronary flow reserve. Disagreement between FFR and QFR is partly explained by physiological and anatomical factors. Clinical Trials Registration https://www.clinicaltrials.gov; Unique identifier: NCT01813435. Graphical abstract: Changes in central physiological and anatomical parameters according to FFR and QFR match/mismatch quadrants

Tracing timing of growth in cultured molluscs using strontium spiking

Introduction: Growth experiments present a powerful tool for determining the effect of environmental parameters on growth and carbonate composition in biogenic calcifiers. For successful proxy calibration and biomineralization studies, it is vital to identify volumes of carbonate precipitated by these organisms at precise intervals during the experiment. Here, we investigate the use of strontium labelling in mollusc growth experiments. Methods: Three bivalve species (Cerastoderma edule, Mytilus edulis and Ostrea edulis) were grown under monitored field conditions. The bivalves were regularly exposed to seawater with elevated concentrations of dissolved strontium chloride (SrCl2). In addition, the size of their shells was determined at various stages during the experiment using calliper measurements and digital photography. Trace element profiles were measured in cross sections through the shells of these molluscs using laser ablation ICPMS and XRF techniques. Results: Our results show that doses of dissolved strontium equivalent to 7-8 times the background marine value (~0.6 mmol/L) are sufficient to cause reproducible peaks in shell-incorporated strontium in C. edule and M. edulis shells. No negative effects were observed on shell calcification rates. Lower doses (3-5 times background values) resulted in less clearly identifiable peaks, especially in M. edulis. Strontium spiking labels in shells of O. edulis are more difficult to detect, likely due to their irregular growth. Discussion: Strontium spiking is a useful technique for creating time marks in cultured shells and a reproducible way to monitor shell size during the growing season while limiting physical disturbance of the animals. However, accurate reconstructions of growth rates at high temporal resolution require frequent spiking with high doses of strontium

The fossil bivalve Angulus benedeni benedeni: A potential seasonally resolved stable-isotope-based climate archive to investigate Pliocene temperatures in the southern North Sea basin

Bivalves record seasonal environmental changes in their shells, making them excellent climate archives. However, not every bivalve can be used for this end. The shells have to grow fast enough so that micrometre- to millimetre-sampling can resolve sub-annual changes. Here, we investigate whether the bivalve Angulus benedeni benedeni is suitable as a climate archive. For this, we use ca. 3-million-year-old specimens from the Piacenzian collected from a temporary outcrop in the Port of Antwerp area (Belgium). The subspecies is common in Pliocene North Sea basin deposits, but its lineage dates back to the late Oligocene and has therefore great potential as a high-resolution archive. A detailed assessment of the preservation of the shell material by micro-X-ray fluorescence, X-ray diffraction, and electron backscatter diffraction reveals that it is pristine and not affected by diagenetic processes. Oxygen isotope analysis and microscopy indicate that the species had a longevity of up to a decade or more and, importantly, that it grew fast and large enough so that seasonally resolved records across multiple years were obtainable from it. Clumped isotope analysis revealed a mean annual temperature of 13.5±3.8°C. The subspecies likely experienced slower growth during winter and thus may not have recorded temperatures year-round. This reconstructed mean annual temperature is 3.5°C warmer than the pre-industrial North Sea and in line with proxy and modelling data for this stratigraphic interval, further solidifying A. benedeni benedeni's use as a climate recorder. Our exploratory study thus reveals that Angulus benedeni benedeni fossils are indeed excellent climate archives, holding the potential to provide insight into the seasonality of several major climate events of the past ∼25 million years in northwestern Europe