Automation of boron chromatographic purification for δ11 B analysis of coral aragonite.

RATIONALE: To detect the small changes in past pH, the boron isotope ratio of coral carbonates, expressed as the δ11 B value, needs to be both precise and accurate (2sd <<1‰). Boron measurements by Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) require the boron to be carefully purified before analysis, which is time consuming, and requires specialist training. Here, we use the prepFAST-MC method 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 by MC-ICPMS. The effects of matrix load, speed of sample loading onto the column, and blank contamination were tested to evaluate the effects 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 δ11 B values. The Japanese Geological Survey Porites reference material JCp-1, boric acid standard NIST SRM 951, and seawater, all processed on the prepFAST-MC system, give δ11 B values within error of literature values (δ11 BJCp-1 = 24.31 ± 0.20‰ (2sd, n = 20); δ11 BNIST 951 = -0.02 ± 0.15‰ (2sd, n = 13) and δ11 BSeawater = 39.50 ± 0.06‰ (2sd, n = 2)). Results obtained from the coral Siderastrea siderea purified with the prepFAST-MC system show an average offset from the manual ion-exchange protocols of Δδ11 B = 0.01 ± 0.28‰ (2sd, n = 12). CONCLUSIONS: Our study demonstrates the capacity of the prepFAST-MC method to generate accurate and reproducible δ11 B values for a range of materials, without fractionation, with efficient matrix removal and with negligible blank contribution.

Toward a Cenozoic history of atmospheric CO2.

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO2) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO2 beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO2 record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO2 thresholds in biological and cryosphere evolution.

Atmospheric CO2 during the Mid-Piacenzian Warm Period and the M2 glaciation.

The Piacenzian stage of the Pliocene (2.6 to 3.6 Ma) is the most recent past interval of sustained global warmth with mean global temperatures markedly higher (by ~2-3 °C) than today. Quantifying CO2 levels during the mid-Piacenzian Warm Period (mPWP) provides a means, therefore, to deepen our understanding of Earth System behaviour in a warm climate state. Here we present a new high-resolution record of atmospheric CO2 using the δ11B-pH proxy from 3.35 to 3.15 million years ago (Ma) at a temporal resolution of 1 sample per 3-6 thousand years (kyrs). Our study interval covers both the coolest marine isotope stage of the mPWP, M2 (~3.3 Ma) and the transition into its warmest phase including interglacial KM5c (centered on ~3.205 Ma) which has a similar orbital configuration to present. We find that CO2 ranged from [Formula: see text]ppm to [Formula: see text]ppm, with CO2 during the KM5c interglacial being [Formula: see text]ppm (at 95% confidence). Our findings corroborate the idea that changes in atmospheric CO2 levels played a distinct role in climate variability during the mPWP. They also facilitate ongoing data-model comparisons and suggest that, at present rates of human emissions, there will be more CO2 in Earth's atmosphere by 2025 than at any time in at least the last 3.3 million years.