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  • 1
    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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  • 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: 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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