Description: Highlights • Calcification fluid pH and [precipitating DIC] are positively correlated in all corals. • [Precipitating DIC] and coral calcification rate are positively correlated in all but one outlier coral. • Corals cultured at high seawater pCO2 usually have low fluid pH and [precipitating DIC]. • Maintaining high [precipitating DIC] at high seawater pCO2 is at the expense of other calcification processes. Abstract Ocean acidification typically reduces calcification in tropical marine corals but the mechanism for this process is not understood. We use skeletal boron geochemistry (B/Ca and δ11B) to reconstruct the calcification fluid DIC of corals cultured over both high and low seawater pCO2 (180, 400 and 750 μatm). We observe strong positive correlations between calcification fluid pH and concentrations of the DIC species potentially implicated in aragonite precipitation (be they CO32−, HCO3− or HCO3− + CO32−). Similarly, with the exception of one outlier, the fluid concentrations of precipitating DIC species are strongly positively correlated with coral calcification rate. Corals cultured at high seawater pCO2 usually have low calcification fluid pH and low concentrations of precipitating DIC, suggesting that a reduction in DIC substrate at the calcification site is responsible for decreased calcification. The outlier coral maintained high pHCF and DICCF at high seawater pCO2 but exhibited a reduced calcification rate indicating that the coral has a limited energy budget to support proton extrusion from the calcification fluid and meet other calcification demands. We find no evidence that increasing seawater pCO2 enhances diffusion of CO2 into the calcification site. Instead the overlying [CO2] available to diffuse into the calcification site appears broadly comparable between seawater pCO2 treatments, implying that metabolic activity (respiration and photosynthesis) generates a similar [CO2] in the vicinity of the calcification site regardless of seawater pCO2.

Description: Radiocarbon and uranium-thorium dating results are presented from a genus of calcitic Antarctic cold-water octocorals (family Coralliidae), which were collected from the Marie Byrd Seamounts in the Amundsen Sea (Pacific sector of the Southern Ocean) andwhich to date have not been investigated geochemically. The geochronological results are set in contextwith solution and laser ablation-basedelement/Ca ratios (Li, B,Mg,Mn, Sr,Ba, U,Th). Octocoral radiocarbon ages on living corals are in excellent agreement with modern ambient deep-water Δ14C, while multiple samples of individual fossil coral specimens yielded reproducible radiocarbon ages. Provided that local radiocarbon reservoir ages can be derived for a given time, fossil Amundsen Sea octocorals should be reliably dateable by means of radiocarbon. In contrast to the encouraging radiocarbon findings, the uranium-series data are more difficult to interpret. The uranium concentration of these calcitic octocorals is an order of magnitude lower than in the aragonitic hexacorals that are conventionally used for geochronological investigations. While modern and Late Holocene octocorals yield initial δ234U in good agreement with modern seawater, our results reveal preferential inward diffusion of dissolved alpha-recoiled 234U and its impact on fossil coral δ234U. Besides alpha-recoil related 234U diffusion, high-resolution sampling of two fossil octocorals further demonstrates that diagenetic uraniummobility has offset apparent coral U-series ages. Combined with the preferential alpha-recoil 234U diffusion, this process has prevented fossil octocorals from preserving a closed system U-series calendar age for longer than a few thousand years. Moreover, several corals investigated contain significant initial thorium, which cannot be adequately corrected for because of an apparently variable initial 232Th/230Th. Our results demonstrate that calcitic cold-water corals are unsuitable for reliable U-series dating. Mg/Ca ratios within single octocoral specimens are internally strikingly homogeneous, and appear promising in terms of their response to ambient temperature. Magnesium/lithium ratios are significantly higher than usually observed in other deep marine calcifiers and for many of our studied corals are remarkably close to seawater compositions. Although this family of octocorals is unsuitable for glacial deep-water Δ14C reconstructions, our findings highlight some important differences between hexacoral (aragonitic) and octocoral (calcitic) biomineralisation. Calcitic octocorals could still be useful for trace element and some isotopic studies, such as reconstruction of ambient deep water neodymium isotope composition or pH, via boron isotopic measurements.

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