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: Highlights • Records of seawater εNdεNd are highly unradiogenic across the OMT at Ceara Rise. • Strong influence of Amazon particulate Nd on seawater εNdεNd at Ceara Rise. • Point-sourced riverine Nd influences seawater far from continental shelf. • Regional sedimentary Nd flux can be confused with water mass mixing signals. Abstract Dissolved and particulate neodymium (Nd) are mainly supplied to the oceans via rivers, dust, and release from marine sediments along continental margins. This process, together with the short oceanic residence time of Nd, gives rise to pronounced spatial gradients in oceanic 143Nd/144Nd ratios (εNdεNd). However, we do not yet have a good understanding of the extent to which the influence of riverine point-source Nd supply can be distinguished from changes in mixing between different water masses in the marine geological record. This gap in knowledge is important to fill because there is growing awareness that major global climate transitions may be associated not only with changes in large-scale ocean water mass mixing, but also with important changes in continental hydroclimate and weathering. Here we present εNdεNd data for fossilised fish teeth, planktonic foraminifera, and the Fe–Mn oxyhydroxide and detrital fractions of sediments recovered from Ocean Drilling Project (ODP) Site 926 on Ceara Rise, situated approximately 800 km from the mouth of the River Amazon. Our records span the Mi-1 glaciation event during the Oligocene–Miocene transition (OMT; ∼23 Ma). We compare our εNdεNd records with data for ambient deep Atlantic northern and southern component waters to assess the influence of particulate input from the Amazon River on Nd in ancient deep waters at this site. εNdεNd values for all of our fish teeth, foraminifera, and Fe–Mn oxyhydroxide samples are extremely unradiogenic (εNd≈−15εNd≈−15); much lower than the εNdεNd for deep waters of modern or Oligocene–Miocene age from the North Atlantic (εNd≈−10εNd≈−10) and South Atlantic (εNd≈−8εNd≈−8). This finding suggests that partial dissolution of detrital particulate material from the Amazon (εNd≈−18εNd≈−18) strongly influences the εNdεNd values of deep waters at Ceara Rise across the OMT. We conclude that terrestrially derived inputs of Nd can affect εNdεNd values of deep water many hundreds of kilometres from source. Our results both underscore the need for care in reconstructing changes in large-scale oceanic water-mass mixing using sites proximal to major rivers, and highlight the potential of these marine archives for tracing changes in continental hydroclimate and weathering.

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.