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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 Sr87/86 ${}^{87/86}\mathrm{S}\mathrm{r}$, Os187/188 ${}^{187/188}\mathrm{O}\mathrm{s}$, 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. Plain Language Summary: Boron naturally exists in two forms—11B and 10B. Measuring the ratio of these two forms of boron within marine shells allows us to estimate how alkaline the ocean was in the past, which is related to how much carbon dioxide is in the atmosphere. Before we can do this calculation though, we need to know some other parameters, one of which is the relative abundance of the two forms of boron in the ocean at the time (which we call δ11Bsw). Preexisting studies have estimated δ11Bsw at particular times, and here we combine them to generate a full reconstruction across the last 65 million years, accounting for uncertainties. Our reconstruction is informed by limiting the rate at which δ11Bsw can change, based on model simulations. We provide a set of plausible evolutions of δ11Bsw which can be used in future work when calculating past ocean pH. Key Points: We reconstruct the temporal evolution of seawater isotope ratios of boron, strontium, lithium, and osmium over the last 65 million yearsThe evolution of seawater boron isotope ratio shows similarity to the evolution of strontium, lithium and osmium isotope ratiosRandomly drawn, smooth time series are provided for use in uncertainty propagation in calculation of palaeo pH [ABSTRACT FROM AUTHOR]

Coral reef ecosystems are delicately balanced and are thus prone to disruption by stressors such as storms, disease, climate variability and natural disasters. Most tropical coral populations worldwide are now in rapid decline owing to additional anthropogenic pressures, such as global warming, ocean acidification and a variety of local stressors. One such problem is the addition of excess sediment and nutrients flux to reefs from increased soil erosion from land use changes. Here we present century‐long Ba/Ca records from two Siderastrea siderea colonies as a proxy for local riverine discharge and sediment flux to the southern Mesoamerican Barrier Reef System (MBRS). The coral colonies have linear extension trends, which can be seen as a first‐order indicator for coral health and response. The coral colony that exhibits a decline in linear extension rate from the forereef of the MBRS, mainly receives riverine input from Honduras, whilst the coral from the backreef, which does not exhibit a decline in extension rate, primarily receives riverine input from more sparsely populated regions of Belize. Coral Ba/Ca increased (>70%) through time in the forereef colony, while the backreef colony showed little long‐term increase in Ba/Ca over the last century. Our results suggest that increasing sediment supply may have played a role in the decline of forereef skeletal extension in the southernmost MBRS region, likely stemming from increasing land‐use changes in Honduras. Key Points: Coral skeletal Ba/Ca measured by LA‐ICP‐MS is a proxy for river discharge and sediment flux to the reefs in this studySkeletal Ba/Ca has increased in forereef corals that mainly receive riverine flux from HondurasResults suggest that changing land‐use around the Mesoamerican Barrier Reef System could be influencing long‐term coral growth trends [ABSTRACT FROM AUTHOR]

Rationale: Organisms that grow a hard carbonate shell or skeleton, such as foraminifera, corals or molluscs, incorporate trace elements into their shell during growth that reflect the environmental change and biological activity they experienced during life. These geochemical signals locked within the carbonate are archives used in proxy reconstructions to study past environments and climates, to decipher taxonomy of cryptic species and to resolve evolutionary responses to climatic changes. Methods: Here, we use laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) as a time‐resolved acquisition to quantify the elemental composition of carbonate shells and skeletons. We present the LABLASTER (Laser Ablation BLASt Through Endpoint in R) package, which imports a single time‐resolved LA‐ICP‐MS analysis, then detects when the laser has ablated through the carbonate as a function of change in signal over time and outputs key summary statistics. We provide two examples within the package: a fossil planktic foraminifer and a tropical coral skeleton. Results: We present the first R package that automates the selection of desired data during data reduction workflows. This is achieved by automating the detection of when the laser has ablated through a sample using a smoothed time series, followed by removal of off‐target data points. The functions are flexible and adjust dynamically to maximise the duration of the desired geochemical target signal, making this package applicable to a wide range of heterogenous bioarchives. Visualisation tools for manual validation are also included. Conclusions: LABLASTER increases transparency and repeatability by algorithmically identifying when the laser has either ablated fully through a sample or across a mineral boundary and is thus no longer documenting a geochemical signal associated with the desired sample. LABLASTER's focus on better data targeting means more accurate extraction of biological and geochemical signals. [ABSTRACT FROM AUTHOR]

Global ice volume (sea level) and deep‐sea temperature are key measures of Earth's climatic state. We synthesize evidence for multi‐centennial to millennial ice‐volume and deep‐sea temperature variations over the past 40 million years, which encompass the early glaciation of Antarctica at ∼34 million years ago (Ma), the end of the Middle Miocene Climate Optimum, and the descent into bipolar glaciation from ∼3.4 Ma. We compare different sea‐level and deep‐water temperature reconstructions to build a resource for validating long‐term numerical model‐based approaches. We present: (a) a new template synthesis of ice‐volume and deep‐sea temperature variations for the past 5.3 million years; (b) an extended template for the interval between 5.3 and 40 Ma; and (c) a discussion of uncertainties and limitations. We highlight key issues associated with glacial state changes in the geological record from 40 Ma to present that require attention in further research. These include offsets between calibration‐sensitive versus thermodynamically guided deep‐sea paleothermometry proxy measurements; a conundrum related to the magnitudes of sea‐level and deep‐sea temperature change at the Eocene‐Oligocene transition at 34 Ma; a discrepancy in deep‐sea temperature levels during the Middle Miocene; and a hitherto unquantified non‐linear reduction of glacial deep‐sea temperatures through the past 3.4 million years toward a near‐freezing deep‐sea temperature asymptote, while sea level stepped down in a more uniform manner. Uncertainties in proxy‐based reconstructions hinder further distinction of "reality" among reconstructions. It seems more promising to further narrow this using three‐dimensional ice‐sheet models with realistic ice‐climate‐ocean‐topography‐lithosphere coupling, as computational capacities improve. Plain Language Summary: Global ice volume (hence, sea level) and deep‐sea temperature are important measures of Earth's climatic state. To better understand Earth's climate cycles in response to its orbitally driven insolation cycles, we evaluate and synthesize evidence for ice‐volume (sea‐level) and deep‐sea temperature variations at multi‐centennial to millennial resolution throughout the last 40 million years. These last 40 million years encompass the major build‐up of Antarctic glaciation from about 34 million years ago, and development of extensive Northern Hemisphere ice sheets from about 3.4 million years ago. We present a new template synthesis of ice‐volume (sea‐level) and deep‐sea temperature for the past 5.3 million years, with extension through the interval between 5.3 and 40 Ma with wider uncertainties. We also highlight a number of remaining questions about major climate transitions, including the early glaciation history of Antarctica, the end of the so‐called Middle Miocene Climate Optimum from about ∼14.5 Ma, and the descent over the past several million years into conditions with extensive ice‐age maxima in both hemispheres. Key Points: New synthesis of sea level and deep‐sea temperature over 40 million years, at millennial resolution, across seven different methodsDiscrepancies between Eocene‐Oligocene and Middle Miocene sea‐level reconstructions are highlighted for focussed future researchPlio‐Pleistocene glacial deep‐sea temperature asymptoted to a freezing limit by ∼1.25–0.9 Ma; glacial sea‐level minima decreased ∼linearly [ABSTRACT FROM AUTHOR]

A new matrix‐matched reference material has been developed – NFHS‐2‐NP (NIOZ Foraminifera House Standard‐2‐Nano‐Pellet) – with element mass fractions, and isotope ratios resembling that of natural foraminiferal calcium carbonate. A 180–355 µm size fraction of planktic foraminifera was milled to nano‐particles and pressed to pellets. We report reference and information values for mass fractions of forty‐six elements measured by six laboratories as well as for 87Sr/86Sr (three laboratories), δ13C, δ18O (five laboratories) and 206,207,208Pb/204Pb isotope ratios (one laboratory) determined by ICP‐MS, ICP‐OES, MC‐ICP‐MS, isotope ratio mass spectrometry, WD‐XRF and TIMS. Inter‐ and intra‐pellet elemental homogeneity was tested using multiple LA‐ICP‐MS analyses in two laboratories applying spot sizes of 60 and 70 µm. The LA‐ICP‐MS results for most of the elements relevant as proxies for palaeoclimate research show RSD values < 3%, demonstrating a satisfactory homogeneous composition. Homogeneity of 87Sr/86Sr ratios of the pellet was verified by repeated LA‐MC‐ICP‐MS by two laboratories. Information values are reported for Pb isotope ratios and δ13C, δ18O values. The homogeneity for these isotope systems remains to be tested by LA‐MC‐ICP‐MS and secondary‐ion mass spectrometry. Overall, our results confirm the suitability of NFHS‐2‐NP for calibration or monitoring the quality of in situ geochemical techniques. [ABSTRACT FROM AUTHOR]

Coral resilience to ocean acidification is largely determined by the degree of physiological control corals can exert on their calcifying fluid carbonate chemistry. In this study, the boron isotopic composition (δ11B) of a Porites colony growing on a reef flat on Kiritimati Island in the equatorial central Pacific is examined to quantify the sensitivity of calcifying fluid pH (pHcf) to ambient environmental conditions. Skeletal δ11B along the growth axis of one annual growth band was determined with bulk analysis and by laser ablation (LA) MC‐ICP‐MS. Furthermore, the oxygen and carbon isotopic composition, trace element ratios, and skeletal density were quantified. Sclerochronological data were interpreted in the context of simultaneous recordings of reef flat seawater pH (pHsw), temperature, salinity, and water depth, and by measurements of these parameters on the fore‐reef. A recent model of pHcf upregulation, after optimization with seasonally resolved data, was used to simulate pHcf variability on a diurnal scale. Results showed that on a seasonal scale, Porites pHcf is upregulated compared to ambient seawater: both bulk and LA‐MC‐ICP‐MS derived δ11B resulted in a mean pHcf of 8.35 pH units. Calcifying fluid pH upregulation primarily followed variations in seawater temperatures, that is likely related to the control of temperature on calcification rate. On the reef flat, the diurnal range in pHsw was substantially higher (0.29 pH units) than on the fore‐reef (0.07 pH units). However, model results suggest that the high diurnal variability in reef flat pHsw resulted only in a limited variability in Porites pHcf. Plain Language Summary: Ocean acidification and the associated decline in seawater pH has impacted the ability of many marine organisms to calcify. However, tropical corals do not precipitate their aragonite skeletons from seawater, but instead from a calcifying fluid located between skeleton and living tissue. The chemistry of this calcifying fluid is modified by physiological processes. This study examines the sensitivity of the calcifying fluid pH to variations in environmental conditions. Seawater pH, temperature, salinity, and water depth on a reef flat at Kiritimati Island in the central Pacific were monitored for 1 year. The calcifying fluid pH of a synchronously precipitated annual growth band of a Porites colony was determined using boron isotope analysis with dissolution of samples and novel laser ablation at enhanced resolution. Furthermore, a numerical model predicted calcifying fluid pH variability at a diurnal scale based on the environmental and geochemical data collected. Results indicate that on a seasonal scale, seawater temperatures rather than seawater pH primarily control the calcifying fluid pH. Further geochemical analysis suggests that this is related to the temperature dependency of the calcification rate. On a diurnal scale, model results suggest no elevated variability in calcifying fluid pH despite highly variable reef flat seawater conditions. Key Points: Porites calcifying fluid pH was investigated using conventional and laser ablation boron isotope analysis, and a calcification modelOn a seasonal scale, Porites calcifying fluid pH followed mainly seawater temperatures that control calcification ratesOn a diurnal scale, model estimates suggest limited calcifying fluid pH variability despite highly variable reef flat seawater conditions [ABSTRACT FROM AUTHOR]

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: (a) to assess the extent to which oxidative pre‐treatment, aimed at removing organic material from carbonate, can influence the resulting δ11B; (b) to determine to what degree the chosen analytical approach may affect the resultant δ11B; and (c) 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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) 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 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 system, 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 system 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 method to generate accurate and reproducible δ11B values for a range of materials, without fractionation, with efficient matrix removal and with negligible blank contribution. [ABSTRACT FROM AUTHOR]

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 δ13C 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 δ13C‐pCO2 proxy. In addition, this rise in pCO2 was focused around the peak of the 400 kyr warming trend. Before this, considerable global carbonate δ18O 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. Plain Language Summary: Geoscientists often look to periods of global warming in the geological past to understand how the Earth responds to input of atmospheric CO2. However, during the Middle Eocene Climatic Optimum (or MECO) 40 million years ago, the Earth did not respond in the way one would expect, given what we know from these earlier warming events. The MECO poses a number of puzzles for geoscientists relating to what caused it and why the Earth system responded in the way it did. Before we can hope to answer these questions, however, we need to know what atmospheric CO2 levels were in the middle Eocene and how much they changed over the MECO event. Here we use boron isotope ratios in fossil plankton shells to tell us how ocean pH (which predominantly reflects CO2 levels) changed over the MECO. We show that relatively little change in CO2 at this time were associated with large‐scale changes in climate. This suggests that during the Eocene, when CO2 levels were similar to those likely to be reached by the end of this century, the Earth's climate (and possibly ice sheets) was very sensitive to minor disturbances. Key Points: We present a new record of pCO2 across the MECO, from boron isotopes in foraminifera from multiple ocean drilling sitesIncorporating carbon cycle modeling, our data indicate pCO2 rise of about two thirds of a doubling across the eventpCO2 change during the MECO onset warming was limited, indicating heightened climate sensitivity or a nonthermal component to δ18O change [ABSTRACT FROM AUTHOR]

Rationale: Boron isotope analysis of marine carbonates by laser ablation multi‐collector inductively coupled plasma mass spectrometry (LA‐MC‐ICP‐MS) offers the potential for rapid sample throughput, and the means to examine micron‐scale variations in the δ11B signatures of fossil skeletons and shells/tests of marine organisms. Existing studies demonstrate an acceptable level of reproducibility is achievable, but also typically show a level of accuracy outside the limits required by most applications. Here we investigate matrix interference effects as a cause of inaccuracy and imprecision. Methods: Analyses were performed on a standard format Thermo Scientific Neptune Plus MC‐ICP mass spectrometer coupled to a New Wave Research 193 nm ArF laser ablation system. The effects of matrix interference on δ11B analysis were investigated through analyses of a set of reference materials with differing B/Ca ratios. Three approaches to correct for matrix‐induced effects were trialled: (1) use of matrix‐matched standards, (2) utilisation of the relationship between δ11B inaccuracy and11B/43Ca, 11B/40ArCa4+ or 11B/Cainterference from three reference materials with known δ11B values and varying B/Ca ratios, and (3) direct characterisation of the (sloping) interference itself. Results: Matrix interference from scattered Ca ions on 10B can impede both the accuracy and the reproducibility of δ11B analysis by LA‐MC‐ICP‐MS. Based on analyses of two in‐house reference materials, deep sea coral PS69/3181 and inorganic calcite UWC‐1, we find approach 2, following the 11B/Cainterference relationship, gives the best mean accuracies (within 0.4‰ of solution values) and external reproducibilities (± 0.5‰ 2 SD for PS69/3181). This approach has been applied to analyses of an annual growth cycle of a Siderastrea siderea coral and eight Cibicidoides wuellerstorfi benthic foraminifera. Both coral and foraminifera data match solution MC‐ICP‐MS analyses within reported uncertainties. Conclusions: LA‐MC‐ICP‐MS can produce accurate and precise δ11B data to a 0.5‰ (2σ) level on <0.3 ng B after correction for Ca interference effects. [ABSTRACT FROM AUTHOR]

Paleoclimate records suggest that a rapid major transient Antarctic glaciation occurred across the Oligocene‐Miocene transition (OMT; ca. 23 Ma; ~50‐m sea level equivalent in 200–300 kyr). Orbital forcing has long been cited as an important factor determining the timing of the OMT glacial event. A similar orbital configuration occurred 1.2 Myr prior to the OMT, however, and was not associated with a major climate event, suggesting that additional mechanisms play an important role in ice sheet growth and decay. To improve our understanding of the OMT, we present a boron isotope‐based CO2 record between 22 and 24 Ma. This new record shows that δ11B/CO2 was comparatively stable in the million years prior to the OMT glaciation and decreased by 0.7‰ (equivalent to a CO2 increase of ~65 ppm) over ~300 kyr during the subsequent deglaciation. More data are needed, but we propose that the OMT glaciation was triggered by the same forces that initiated sustained Antarctic glaciation at the Eocene‐Oligocene transition: long‐term decline in CO2 to a critical threshold and a superimposed orbital configuration favorable to glaciation (an eccentricity minimum and low‐amplitude obliquity change). When comparing the reconstructed CO2 increase with estimates of δ18Osw during the deglaciation phase of the OMT, we find that the sensitivity of the cryosphere to CO2 forcing is consistent with recent ice sheet modeling studies that incorporate retreat into subglacial basins via ice cliff collapse with modest CO2 increase, with clear implications for future sea level rise. Key Points: CO2 levels were relatively low (~265 ppm; 2σ−111+166 ppm) and comparatively stable in the 500 kyr prior to and during the glaciationCO2 increased by ~65 ppm during the OMT deglaciation consistent with the latest generation of ice sheet modelsThe timing of the OMT glaciation is most likely controlled by both changes in CO2 and favorable orbital forcing [ABSTRACT FROM AUTHOR]