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  • 1
    Publication Date: 2008-01-01
    Electronic ISSN: 1541-5856
    Topics: Biology , Geosciences
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  • 2
    Publication Date: 2023-02-08
    Description: The Middle Eocene Climatic Optimum (MECO) was a gradual warming event and carbon cycle perturbation that occurred between 40.5 and 40.1 Ma. A number of characteristics, including greater-than-expected deep-sea carbonate dissolution, a lack of globally-coherent negative δ 13 40 C excursion in marine carbonates, a duration longer than the characteristic timescale of carbon-cycle recovery, and the absence of a clear trigger mechanism, challenge our current understanding of the Earth system and its regulatory feedbacks. This makes the MECO one of the most enigmatic events in the Cenozoic, dubbed a middle Eocene ‘carbon cycle conundrum’. Here we use boron isotopes in planktic foraminifera to better constrain pCO2 changes over the event. Over the MECO itself, we find that pCO2 rose by only 0.55-0.75 doublings, thus requiring a much more modest carbon injection than previously indicated by the alkenone δ 13 C-pCO2 proxy. In addition, this rise in pCO2 was focused around the peak of the 400 kyr warming trend. Before this, considerable global carbonate δ 18 O change was asynchronous with any coherent ocean pH (and hence pCO2) excursion. This finding suggests that middle Eocene climate (and perhaps a nascent cryosphere) was highly sensitive to small changes in radiative forcing.
    Type: Article , PeerReviewed
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  • 3
    Publication Date: 2023-02-08
    Description: Rationale To detect the small changes in past pH, the boron isotope ratio of coral carbonates, expressed as the δ11B value, needs to be both precise and accurate (2sd〈〈1‰). Boron measurements by Multi‐collector Inductively Coupled Plasma Mass Spectrometry (MC‐ICPMS) requires the boron to be carefully purified before analysis, which is time consuming, and requires specialist training. Here, we use the prepFAST‐MC that enables the automatic extraction of B (up to 25 ng load) from a CaCO3 matrix. Methods Samples were purified using the prepFAST‐MC automated system with a ~25‐μL column of Amberlite IRA743 resin. Boron isotope measurements were performed byMC‐ICPMS. The effect of matrix load, speed of sample load onto the column, and blank contamination were tested to evaluate the effect on the purification process. The optimised protocol was tested on various standards and samples of aragonite corals. Results The blank contribution for the approach is ~60 pg and is negligible given our sample size (〈0.2% sample size). Efficiency of matrix removal is demonstrated with the addition of up to 1.6 mg of dissolved low‐B calcium carbonate to NIST SRM 951 with no impact on the accuracy of δ11B values. The Japanese Geological Survey Porites reference material JCp‐1, boric acid standard NIST SRM 951, and seawater, all processed on the prepFAST‐MC, give δ11B values within error of literature values (δ11BJCp‐1 = 24.31 ±0.20‰ (2sd, n=20); δ11BNIST 951 = ‐0.02 ±0.15‰ (2sd, n=13) and δ11BSeawater = 39.50 ±0.06 ‰ (2sd, n=2)). Results obtained from the coral Siderastrea siderea purified with the prepFAST‐MC show an average offset from the manual ion exchange protocols of Δδ11B=0.01 ±0.28‰ (2sd, n=12). Conclusions Our study demonstrates the capacity of the prepFAST‐MC to generate accurate and reproducible δ11B values for a range of material, without fractionation, with efficient matrix removal and with negligible blank contribution.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2024-02-07
    Description: Laser ablation multi-collector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) has become a valuable tool for the in situ measurement of the boron isotope composition of geological samples at high (tens to hundreds of μm) spatial resolution. That said, this application suffers from significant analytical challenges. We focus in this study on the underlying processes of two of the main causes for inaccuracies using this technique. We provide empirical evidence that not only Ca ions (Sadekov et al. 2019, Standish et al. 2019, Evans et al. 2019) but also Ar ions, that are reflected within the flight tube of the mass spectrometer, are the source for previously reported issues with spectral baselines. We also address the impact of plasma conditions on the instrumental mass fractionation as a source for matrix- and mass-load-related analytical biases. Comparing experimental data with the results of a dedicated release and diffusion model (RDM) we estimate that a close to complete (~ 97%) release of boron from the sample aerosol is needed to allow for consistently accurate LA boron isotope measurement results without the need for corrections.
    Type: Article , PeerReviewed
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  • 5
    Publication Date: 2024-06-17
    Description: Key Points: - We reconstruct the temporal evolution of seawater isotope ratios of boron, strontium, lithium, and osmium over the last 65 million years - The evolution of seawater boron isotope ratio shows similarity to the evolution of strontium, lithium and osmium isotope ratios - Randomly drawn, smooth time series are provided for use in uncertainty propagation in calculation of palaeo pH The boron isotope ratio of seawater (δ11Bsw) is a parameter which must be known to reconstruct palaeo pH and CO2 from boron isotope measurements of marine carbonates. Beyond a few million years ago, δ11Bsw is likely to have been different to modern. Palaeo δ11Bsw can be estimated by simultaneously constraining the vertical gradients in foraminiferal δ11B (Δδ11B) and pH (ΔpH). A number of subtly different techniques have been used to estimate ΔpH in the past, all broadly based on assumptions about vertical gradients in oxygen, and/or carbon, or other carbonate system constraints. In this work we pull together existing data from previous studies, alongside a constraint on the rate of change of δ11Bsw from modeling. We combine this information in an overarching statistical framework called a Gaussian Process. The Gaussian Process technique allows us to bring together data and constraints on the rate of change in δ11Bsw to generate random plausible evolutions of δ11Bsw. We reconstruct δ11Bsw, and by extension palaeo pH, across the last 65Myr using this novel methodology. Reconstructed δ11Bsw is compared to other seawater isotope ratios, namely ,87/86 Sr, 187/188 Os , and δ7Li, which we also reconstruct with Gaussian Processes. Our method provides a template for incorporation of future δ11Bsw constraints, and a mechanism for propagation of uncertainty in δ11Bsw into future studies.
    Type: Article , PeerReviewed
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