Description: The Early Eocene Climate Optimum (EECO, which occurred about 51 to 53 million years ago)1, was the warmest interval of the past 65 million years, with mean annual surface air temperature over ten degrees Celsius warmer than during the pre-industrial period2,3,4. Subsequent global cooling in the middle and late Eocene epoch, especially at high latitudes, eventually led to continental ice sheet development in Antarctica in the early Oligocene epoch (about 33.6 million years ago). However, existing estimates place atmospheric carbon dioxide (CO2) levels during the Eocene at 500–3,000 parts per million5,6,7, and in the absence of tighter constraints carbon–climate interactions over this interval remain uncertain. Here we use recent analytical and methodological developments8,9,10,11 to generate a new high-fidelity record of CO2 concentrations using the boron isotope (δ11B) composition of well preserved planktonic foraminifera from the Tanzania Drilling Project, revising previous estimates6. Although species-level uncertainties make absolute values difficult to constrain, CO2 concentrations during the EECO were around 1,400 parts per million. The relative decline in CO2 concentration through the Eocene is more robustly constrained at about fifty per cent, with a further decline into the Oligocene12. Provided the latitudinal dependency of sea surface temperature change for a given climate forcing in the Eocene was similar to that of the late Quaternary period13, this CO2 decline was sufficient to drive the well documented high- and low-latitude cooling that occurred through the Eocene14. Once the change in global temperature between the pre-industrial period and the Eocene caused by the action of all known slow feedbacks (apart from those associated with the carbon cycle) is removed2,3,4, both the EECO and the late Eocene exhibit an equilibrium climate sensitivity relative to the pre-industrial period of 2.1 to 4.6 degrees Celsius per CO2 doubling (66 per cent confidence), which is similar to the canonical range (1.5 to 4.5 degrees Celsius15), indicating that a large fraction of the warmth of the early Eocene greenhouse was driven by increased CO2 concentrations, and that climate sensitivity was relatively constant throughout this period.

Description: The geochemical composition of foraminiferal tests is a valuable archive for the reconstruction of paleo-climatic, -oceanographic and -ecological changes. However, dissolution of biogenic calcite and precipitation of inorganic calcite (overgrowth and recrystallization) at the seafloor and in the sediment column can potentially alter the original geochemical composition of the foraminiferal test, biasing any resulting paleoenvironmental reconstruction. The δ11B of planktic foraminiferal calcite is a promising ocean pH-proxy but the effect of diagenesis is still poorly known. Here we present new δ11B, δ13C, δ18O, Sr/Ca and B/Ca data from multiple species of planktic foraminifera from time-equivalent samples for two low latitude sites: clay-rich Tanzanian Drilling Project (TDP) Site 18 from the Indian Ocean containing well-preserved (‘glassy’) foraminifera and carbonate-rich Ocean Drilling Program (ODP) Site 865 from the central Pacific Ocean hosting recrystallized (‘frosty’) foraminifera. Our approach makes the assumption that environmental conditions were initially similar at both sites so most chemical differences are attributable to diagenesis. Planktic foraminiferal δ18O and δ13C records show offsets in both relative and absolute values between the two sites consistent with earlier findings that these isotopic ratios are strongly influenced by diagenetic alteration. Sr/Ca and B/Ca ratios in planktic foraminiferal calcite are also offset between the two sites but there is little change in the relative difference between surface and deep dwelling taxa. In contrast, δ11B values indicate no large differences between well-preserved and recrystallized foraminifera suggesting that despite extensive diagenetic alteration the δ11B of biogenic calcite appears robust, potentially indicative of a lack of free exchange of boron between pore fluids and the recrystallizing CaCO3. Our finding may remove one potential source of uncertainty in δ11B based pH reconstructions and provide us with greater confidence in our ability to reconstruct pH in the ancient oceans from at least some recrystallized foraminiferal calcite. However, further investigations should extend this approach to test the robustness of our findings across a range of taphonomies, ages and burial settings.

Description: The response of the marine carbon cycle to changes in atmospheric CO2 concentrations will be determined, in part, by the relative response of calcifying and non-calcifying organisms to global change. Planktonic foraminifera are responsible for a quarter or more of global carbonate production, therefore understanding the sensitivity of calcification in these organisms to environmental change is critical. Despite this, there remains little consensus as to whether, or to what extent, chemical and physical factors affect foraminiferal calcification. To address this, we directly test the effect of multiple controls on calcification in culture experiments and core-top measurements of Globigerinoides ruber. We find that two factors, body size and the carbonate system, strongly influence calcification intensity in life, but that exposure to corrosive bottom waters can overprint this signal post mortem. Using a simple model for the addition of calcite through ontogeny, we show that variable body size between and within datasets could complicate studies that examine environmental controls on foraminiferal shell weight. In addition, we suggest that size could ultimately play a role in determining whether calcification will increase or decrease with acidification. Our models highlight that knowledge of the specific morphological and physiological mechanisms driving ontogenetic change in calcification in different species will be critical in predicting the response of foraminiferal calcification to future change in atmospheric pCO2.

Description: The isotopic composition of boron (δ11B) in marine carbonates is well established as a proxy for past ocean pH, however, its robust application to palaeo-environments relies on the generation of species-specific calibrations. Existing calibrations utilising the deep-sea coral (DSC) Desmophyllum dianthus highlight the potential application of this pervasive species to pH reconstructions of intermediate depth waters. Nevertheless, considerable uncertainty remains regarding the estimation of seawater pH from these bulk skeletal δ11B measurements, likely resulting from microstructural heterogeneities in δ11B of D. dianthus. To circumvent this problem, thus improving the reliability of the D. dianthus δ11B-pH calibration, we present a new δ11B calibration of micro-sampled fibrous aragonite from this species. Modern coral specimens recovered from the Atlantic, Pacific, and Southern Oceans, micro-sampled using microdrilling, micromilling, and laser cutting extraction, were analysed for trace element (B/Ca, Mg/Ca, Sr/Ca, and U/Ca) and boron isotopic composition. We find the best calibration against the δ11B of borate in local ambient seawater (a function of pH and taken from hydrographic data sets; pH range 7.57 to 8.05) utilises δ11B measurements of fibres with likely slow growth rates and minimal contamination from adjacent microstructures (identified by low Mg/Ca) for each coral specimen. This new calibration exhibits a stronger, and better-defined dependence on ambient seawater pH compared to bulk coral δ11B; δ11Bfibre = (0.93 ± 0.17) × δ11Bborate + (12.02 ± 2.63). We suggest that the majority of the variability in measured δ11B between replicate bands of fibrous aragonite from a D. dianthus specimen can be explained by small incorporation of non-fibrous aragonite and surface impurities during microsampling and growth rate effects. This study confirms the utility of D. dianthus as an archive of precise palaeo-pH (± 0.07 pH units), provided that suitable sampling strategies are applied.

Description: Structure-based inhibitor design has led to the discovery of a number of potent inhibitors of glycogen phosphorylase b (GPb), N-acyl derivatives of β-d-glucopyranosylamine, that bind at the catalytic site of the enzyme. The first good inhibitor in this class of compounds, N-acetyl-β-d-glucopyranosylamine (NAG) (Ki = 32 μM), has been previously characterized by biochemical, biological and crystallographic experiments at 2.3 Å resolution. Bioisosteric replacement of the acetyl group by trifluoroacetyl group resulted in an inhibitor, N-trifluoroacetyl-β-d-glucopyranosylamine (NFAG), with a Ki = 75 μM. To elucidate the structural basis of its reduced potency, we determined the ligand structure in complex with GPb at 1.8 Å resolution. To compare the binding mode of N-trifluoroacetyl derivative with that of the lead molecule, we also determined the structure of GPb–NAG complex at a higher resolution (1.9 Å). NFAG can be accommodated in the catalytic site of T-state GPb at approximately the same position as that of NAG and stabilize the T-state conformation of the 280s loop by making several favourable contacts to Asn284 of this loop. The difference observed in the Ki values of the two analogues can be interpreted in terms of subtle conformational changes of protein residues and shifts of water molecules in the vicinity of the catalytic site, variations in van der Waals interaction, and desolvation effects.

Description: A freshwater magnesium hydroxide coprecipitation method (MAGIC) has been developed to accurately and reproducibly determine low (nanomolar to subnanomolar) soluble reactive phosphorus (SRP) concentrations in freshwater. The method allows investigation of phosphorus distributions and cycling for systems in which SRP is below the detection limits of conventional methods. In natural waters, both inorganic and organic forms of P are coprecipitated; hence the method is essentially a preconcentration rather than a separation technique. Quantification of SRP on dissolved MAGIC precipitates follows a modified version of the standard molybdenum blue colorimetric method, using a spectrophotometer with ~0.1 milliabsorbance (mAbs) noise. Detection limit is 0.15 nM, improving on typical conventional colorimetric methods by a factor of ~50, with precision (RSD of triplicates) of ~10% at the 1 nM SRP level, 10% at ≤0.5 nM, and 4% to 7% at 〉1 nM. Considerable method development was necessary to eliminate or correct for multiple interferences, including a novel finding of potential interference by colored dissolved organic matter, and to optimize recovery, precision, and detection limit. The method was applied to filtered, frozen samples from western Lake Superior, showing that SRP concentrations are characterized by limited seasonal variability, largely uniform vertical distribution, and near-bottom enrichment. Concentrations ranged from 0.4 to 10.9 nM SRP, representing ~10% of the total dissolved phosphorus pool. MAGIC is an easily employed analytical method appropriate for measurement of very low SRP in lakes and rivers.

Description: The Palaeocene-Eocene Thermal Maximum(1,2) (PETM) was a global warming event that occurred about 56 million years ago, and is commonly thought to have been driven primarily by the destabilization of carbon from surface sedimentary reservoirs such as methane hydrates(3). However, it remains controversial whether such reservoirs were indeed the source of the carbon that drove the warming(1,3-5). Resolving this issue is key to understanding the proximal cause of the warming, and to quantifying the roles of triggers versus feedbacks. Here we present boron isotope data-a proxy for seawater pH-that show that the ocean surface pH was persistently low during the PETM. We combine our pH data with a paired carbon isotope record in an Earth system model in order to reconstruct the unfolding carbon-cycle dynamics during the event(6,7). We find strong evidence for a much larger (more than 10,000 petagrams)-and, on average, isotopically heavier-carbon source than considered previously(8,9). This leads us to identify volcanism associated with the North Atlantic Igneous Province(10,11), rather than carbon from a surface reservoir, as the main driver of the PETM. This finding implies that climate-driven amplification of organic carbon feedbacks probably played only a minor part in driving the event. However, we find that enhanced burial of organic matter seems to have been important in eventually sequestering the released carbon and accelerating the recovery of the Earth system(12).

Description: The supply of limiting nutrients to the low latitude ocean is controlled by physical processes linked to climate variations, but methods for reconstructing past nutrient concentrations in the surface ocean are few and indirect. Here, we present laser ablation mass spectrometry results that reveal annual cycles of P/Ca in a 4-year record from the scleractinian coral Pavona gigantea (mean P/Ca = 118 μmol mol−1). The P/Ca cycles track variations in past seawater phosphate concentration synchronously with skeletal Sr/Ca-derived temperature variations associated with seasonal upwelling in the Gulf of Panamá. Skeletal P/Ca varies seasonally by 2–3 fold, reflecting the timing and magnitude of dissolved phosphate variations. Solution cleaning experiments on drilled coral powders show that over 60% of skeletal P occurs in intracrystalline organic phases. Coral skeleton P/Ca holds promise as a proxy record of nutrient availability on time scales of decades to millennia.

Description: Past warm periods provide an opportunity to evaluate climate models under extreme forcing scenarios, in particular high ( 〉  800 ppmv) atmospheric CO2 concentrations. Although a post hoc intercomparison of Eocene ( ∼  50  Ma) climate model simulations and geological data has been carried out previously, models of past high-CO2 periods have never been evaluated in a consistent framework. Here, we present an experimental design for climate model simulations of three warm periods within the early Eocene and the latest Paleocene (the EECO, PETM, and pre-PETM). Together with the CMIP6 pre-industrial control and abrupt 4 ×  CO2 simulations, and additional sensitivity studies, these form the first phase of DeepMIP – the Deep-time Model Intercomparison Project, itself a group within the wider Paleoclimate Modelling Intercomparison Project (PMIP). The experimental design specifies and provides guidance on boundary conditions associated with palaeogeography, greenhouse gases, astronomical configuration, solar constant, land surface processes, and aerosols. Initial conditions, simulation length, and output variables are also specified. Finally, we explain how the geological data sets, which will be used to evaluate the simulations, will be developed.