Description: 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 (∆δ11B) and pH (∆pH). A number of subtly different techniques have been used to estimate ∆pH 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 estimates alongside limitations on the rate of change of δ11Bsw from modelling, and combine these into 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 87/86Sr, 187/188Os, 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.

Description: Present estimates of the biogeochemical cycles of calcium, strontium and potassium in the ocean reveal large imbalances between known input and output fluxes. Using pore fluid, incubation and solid sediment data from North Pacific multi-corer cores we show that, contrary to the common paradigm, the top centimetres of abyssal sediments can be an active site of authigenic precipitation of clay minerals. In this region, clay authigenesis is the dominant sink for potassium and strontium and consumes nearly all calcium released from benthic dissolution of calcium carbonates. These observations support the idea that clay authigenesis occurring over broad regions of the world ocean may be a major buffer for ocean chemistry on the time scale of the ocean overturning circulation, and key to the long-term stability of Earth’s climate. Key Points North Pacific red clay sediments are a sink for marine calcium, strontium and potassium Authigenic formation of clay minerals is prevalent in pelagic sediments throughout the North Pacific The main mechanism for clay formation is recrystallisation of aluminosilicates, neoformation can occur in biogenic silica rich sediments

Description: Boron isotopes in marine carbonates are increasingly used to reconstruct seawater pH and atmospheric pCO2 through Earth’s history. While isotope ratio measurements from individual laboratories are often of high quality, it is important that records generated in different laboratories can equally be compared. Within this Boron Isotope Intercomparison Project (BIIP), we characterised the boron isotopic composition (commonly expressed in δ11B) of two marine carbonates: Geological Survey of Japan carbonate reference materials JCp‐1 (coral Porites) and JCt‐1 (giant clam Tridacna gigas). Our study has three foci: (i) to assess the extent to which oxidative pre‐treatment, aimed at removing organic material from carbonate, can influence the resulting δ11B; (ii) to determine to what degree the chosen analytical approach may affect the resultant δ11B, and (iii) to provide well‐constrained consensus δ11B values for JCp‐1 and JCt‐1. The resultant robust mean and associated robust standard deviation (s*) for un‐oxidised JCp‐1 is 24.36 ± 0.45‰ (2s*), compared with 24.25 ± 0.22‰ (2s*) for the same oxidised material. For un‐oxidised JCt‐1, respective compositions are 16.39 ± 0.60‰ (2s*; un‐oxidised) and 16.24 ± 0.38‰ (2s*; oxidised). The consistency between laboratories is generally better if carbonate powders were oxidatively cleaned prior to purification and measurement.

Description: The boron isotopic ratio of 11B/10B (δ11BSRM951) and trace element composition of marine carbonates are key proxies for understanding carbon cycling (pH) and palaeoceanographic change. However, method validation and comparability of results between laboratories requires carbonate reference materials. Here, we report results of an inter‐laboratory comparison study to both assign δ11BSRM951 and trace element compositions to new synthetic marine carbonate reference materials (RMs), NIST RM 8301 (Coral) and NIST RM 8301 (Foram) and to assess the variance of data among laboratories. Non‐certified reference values and expanded 95% uncertainties for δ11BSRM951 in NIST RM 8301 (Coral) (+24.17‰ ± 0.18‰) and NIST RM 8301 (Foram) (+14.51‰ ± 0.17‰) solutions were assigned by consensus approach using inter‐laboratory data. Differences reported among laboratories were considerably smaller than some previous inter‐laboratory comparisons, yet discrepancies could still lead to large differences in calculated seawater pH. Similarly, variability in reported trace element information among laboratories (e.g., Mg/Ca ± 5% RSD) was often greater than within a single laboratory (e.g., Mg/Ca 〈 2%). Such differences potentially alter proxy‐reconstructed seawater temperature by more than 2 °C. These now well‐characterised solutions are useful reference materials to help the palaeoceanographic community build a comprehensive view of past ocean changes.

Description: Key Points: - High resolution carbonate chemistry, δ13C-DIC, and particle flux measurements in the NE Pacific sheds light on the upper oceancalcium carbonate and alkalinity cycles. - Based on this sampling campaign, there isevidence for substantial CaCO3 dissolution in the mesopelagic zone above the saturation horizon. - Dissolution experiments, observations, and modeling suggest that shallow CaCO3 dissolutionis coupled to the consumption of organic carbon, through a combination of zooplankton grazing and oxic respiration within particle microenvironments. The cycling of biologically produced calcium carbonate (CaCO3) in the ocean is a fundamental component of the global carbon cycle. Here, we present experimental determinations of in situcoccolith and foraminiferal calcite dissolution rates.We combine these rates with solid phase fluxes,dissolved tracers, and historical data to constrain the alkalinity cycle in the shallow North Pacific Ocean.The in situ dissolution rates of coccolithophores demonstrate a nonlinear dependence on saturation state. Dissolution ratesof all three major calcifying groups (coccoliths, foraminifera, and aragonitic pteropods)aretoo slow to explainthe patternsofboth CaCO3sinking fluxand alkalinity regenerationin the NorthPacific.Usinga combination of dissolved and solid-phase tracers, we document a significant dissolution signal in seawater supersaturated for calcite. Driving CaCO3dissolutionwith acombination of ambient saturation state and oxygen consumption simultaneously explainssolid-phase CaCO3flux profiles and patterns of alkalinity regeneration across the entire N. Pacific basin. Wedo not need to invokethe presence ofcarbonate phases with higher solubilities.Instead, biomineralization and metabolic processesintimately associatethe acid (CO2) and the base (CaCO3) in the same particles,driving the coupled shallow remineralization of organic carbonand CaCO3.The linkage of these processes likely occurs through a combination of dissolution due to zooplankton grazing and microbial aerobic respiration withindegrading particle aggregates.The coupling of these cyclesacts as a major filter on the export of both organic and inorganic carbon to the deep ocean.

Description: The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO 2 ) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO 2 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 CO 2 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 CO 2 thresholds in biological and cryosphere evolution. Editor’s summary The concentration of atmospheric carbon dioxide is a fundamental driver of climate, but its value is difficult to determine for times older than the roughly 800,000 years for which ice core records are available. The Cenozoic Carbon dioxide Proxy Integration Project (CenCO2PIP) Consortium assessed a comprehensive collection of proxy determinations to define the atmospheric carbon dioxide record for the past 66 million years. This synthesis provides the most complete record yet available and will help to better establish the role of carbon dioxide in climate, biological, and cryosphere evolution. — H. Jesse Smith

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.