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The symbiotic planktonic foraminifera Orbulina universa inhabits open ocean oligotrophic ecosystems where dissolved nutrients are scarce and often limit biological productivity. It has previously been proposed that O. universa meets its nitrogen (N) requirements by preying on zooplankton, and that its symbiotic dinoflagellates recycle metabolic 'waste ammonium' for their N pool. However, these conclusions were derived from bulk 15N-enrichment experiments and model calculations, and our understanding of N assimilation and exchange between the foraminifer host cell and its symbiotic dinoflagellates remains poorly constrained. Here, we present data from pulse-chase experiments with 13C-enriched inorganic carbon, 15N-nitrate, and 15N-ammonium, as well as a 13C- and 15N- enriched heterotrophic food source, followed by TEM (transmission electron microscopy) coupled to NanoSIMS (nanoscale secondary ion mass spectrometry) isotopic imaging to visualize and quantify C and N assimilation and translocation in the symbiotic system. High levels of 15N-labelling were observed in the dinoflagellates and in foraminiferal organelles and cytoplasm after incubation with 15N-ammonium, indicating efficient ammonium assimilation. Only weak 15N-assimilation was observed after incubation with 15N-nitrate. Feeding foraminifers with 13C- and 15N-labelled food resulted in dinoflagellates that were labelled with 15N, thereby confirming the transfer of 15N-compounds from the digestive vacuoles of the foraminifer to the symbiotic dinoflagellates, likely through recycling of ammonium. These observations are important for N isotope-based palaeoceanographic reconstructions, as they show that δ15N values recorded in the organic matrix in symbiotic species likely reflect ammonium recycling rather than alternative N sources, such as nitrates.

The removal of exchangeable oxygen from diatom opal prior to δ18Odiatom analysis is a crucial first step before analyzing frustule oxygen isotopes for paleoceanographic applications. We present the results of experiments that quantify the temperature-dependent reactivity of biogenic silica with water under laboratory conditions. We demonstrate that controlled exchange between rinse water and diatom opal at room temperature results in predictable alteration of δ18Odiatom, after vacuum dehydroxylation. Diatom samples equilibrated with an 18O-enriched δ18Oequil. water solution of +94.4‰ at ~21 °C for 70 hr prior to dehydroxylation yield δ18Odiatom data that can be directly interpreted with existing empirical δ18Odiatom versus temperature relationships. We compare sediment trap-based δ18Odiatom temperature data with modern δ18Oforam temperatures. Finally, we present an ~220 year record of δ18Odiatom data from an eastern Pacific Guaymas Basin boxcore, analyzed using the microfluorination technique, that indicates diatom chlorophyll maximum (Chlmax) temperatures have shifted from a period during the late eighteenth and nineteenth centuries that was 8 °C cooler during the fall bloom relative to mean annual alkenone Uk′37 sea surface temperature, to the late twentieth century when we observe no difference between alkenone sea surface temperature and diatom Chlmax. These data suggest a twentieth century seasonal shift in the timing of fall upwelling and Guaymas Basin stratification breakdown that could be due to reduced upwelling efficiency and/or increased summer mixed layer thermal stratification.

Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) is an increasingly popular analytical technique, that is able to provide spatially resolved, minimally destructive analyses of heterogeneous materials. The data produced by this technique are inherently complex, and require extensive processing and subjective expert interpretation to produce useful compositional data. At present, laboratories employ diverse protocols for data processing, and the reporting of these protocols is usually insufficient to allow data processing to be independently replicated, rendering the resulting data untraceable. Importantly, different expert users can obtain significantly different results from the same raw data using nominally identical processing workflows, depending on how ‘contaminants’ are identified and excluded, and which regions of signal are selected as representative of the composition of the sample. The irreproducibility of LA-ICPMS is a significant problem for the technique, but the complexity of the raw data has been a major hindrance to developing traceable data processing workflows. Here, we present LAtools – a free, open-source Python package for LA-ICPMS data processing designed with reproducibility at its core. The software performs basic data processing with similar efficacy to existing software, and brings a number of new data selection algorithms to facilitate reproducible reduction of LA-ICPMS data. We discuss the key advances of LAtools, and compare its output to trace metal analysis of marine CaCO3 (foraminifera) processed both manually and with Iolite, and to manually processed trace element data from zircon grains.

Modern observations of planktic foraminifera from sediment trap studies help to constrain the regional ecology of paleoceanographically valuable species. Results from a weekly-resolved sediment trap time series (2008–2014) in the northern Gulf of Mexico demonstrate that 92% of Globorotalia truncatulinoides flux occurs in winter (January, February, and March), and that encrusted and non-encrusted individuals represent calcification in distinct depth habitats. We use individual foraminiferal analysis (IFA) of G. truncatulinoides tests to investigate differences in the elemental (Mg/Ca) and isotopic composition (δ18O and δ13C) of the encrusted and non-encrusted ontogenetic forms of G. truncatulinoides, and to estimate their calcification depth in the northern Gulf of Mexico. We estimate that non-encrusted and encrusted G. truncatulinoides have mean calcification depths of 66 ± 9 m and 379 ± 76 m, respectively. We validate the Mg/Ca-calcification temperature relationship for G. truncatulinoides and demonstrate that the δ18O and Mg/Ca of the non-encrusted form is a suitable proxy for winter surface mixed layer conditions in the Gulf of Mexico. Care should be taken not to combine encrusted and non-encrusted individuals of G. truncatulinoides for down core paleoceanographic studies.

Some species of planktic foraminifera inhabiting oligotrophic surface water environments are in an obligate symbiotic relationship with dinoflagellate microalgae, which can assimilate carbon (C) through photosynthesis. However, the mechanism and dynamics of C photosynthate translocation to the foraminiferal host, and related benefits for the dinoflagellates in this symbiotic association, are poorly constrained. As a consequence, the role of planktic foraminifera as autotroph organisms in ocean surface ecosystems is not well understood. Here, we performed pulse-chase experiments with 13C-enriched dissolved inorganic carbon, followed by TEM and quantitative NanoSIMS isotopic imaging to visualize photosynthetic C assimilation by individual symbiotic dinoflagellates and subsequent translocation to their Orbulina universa host. Although most of the dinoflagellate population migrates out of the host endoplasm onto external spines during the day, our observations show that a small fraction remains inside the host cell during daytime. All symbionts, whether outside or inside the foraminifera cell, effectively assimilate C into starch nodules during daytime photosynthesis. At the onset of night, all dinoflagellates from the exterior spine–ectoplasm region migrate back into the foraminiferal cell. During the night, respiration by dinoflagellates and carbon translocation to the host, likely in the form of lipids, greatly reduces the abundance of starch in dinoflagellates. Dinoflagellate mitosis is only observed at night, with a substantial contribution of carbon fixed during the previous day contributing to the production of new biomass.

The oxygen isotope (δ18O) compositions of final chamber fragments of individual shells of the planktic foraminifer Orbulina universa were measured in situ via secondary ion mass spectrometry (SIMS) and by traditional gas-source mass spectrometry (GSMS) entailing acid digestion of sampled calcite. The paired SIMS-GSMS analyses were performed on final chamber fragments of fossil shells taken from the top of a sediment core (Holocene) as well as shells grown in laboratory culture. Multiple iterations of SIMS-GSMS analyses were conducted on final chamber fragments treated with a variety of cleaning protocols. The series of paired analyses yielded an average SIMS-GSMS δ18O offset (Δ18OSIMS-GSMS) of −0.9 ± 0.1‰ (±2 SE). The volume of material analyzed in 10-μm SIMS spots is ~105 times smaller than that analyzed by GSMS; hence, the extent to which these Δ18OSIMS-GSMS values represent real differences in analyte vs. instrumental factors remains unclear. Possible contributing factors to the SIMS-GSMS δ18O difference include sample-standard mismatch by SIMS, differences in standardization of SIMS and GSMS, and non-calcite contaminants in samples. Although the two datasets are consistently offset, SIMS values reproduce inter-shell δ18O variability delineated by shell fragment GSMS values. This strong positive covariance proved useful for bringing the two datasets into agreement (i.e. Δ18OSIMS-GSMS = 0), and confirms that SIMS-based foraminifer δ18O values record changes in calcification temperature and/or δ18O of seawater. Whether shells of foraminifer taxa with differing microcrystalline structures, chemical composition, and/or preservation histories register a similar Δ18OSIMS-GSMS value is a subject of ongoing testing.

We present a new method that quantifies the oxygen isotope geochemistry of Laurentide ice-sheet (LIS) meltwater across the last deglaciation, and reconstruct decadal-scale variations in the δ18O of LIS meltwater entering the Gulf of Mexico between ∼18 and 11 ka. We employ a technique that combines laser ablation ICP-MS (LA-ICP-MS) and oxygen isotope analyses on individual shells of the planktic foraminifer Orbulina universa to quantify the instantaneous δ18Owater value of Mississippi River outflow, which was dominated by meltwater from the LIS. For each individual O. universa shell, we measure Mg/Ca (a proxy for temperature) and Ba/Ca (a proxy for salinity) with LA-ICP-MS, and then analyze the same O. universa for δ18O using the remaining material from the shell. From these proxies, we obtain δ18Owater and salinity estimates for each individual foraminifer. Regressions through data obtained from discrete core intervals yield δ18Ow vs. salinity relationships with a y-intercept that corresponds to the δ18Owater composition of the freshwater end-member. Our data suggest that from 15.5 through 14.6 ka, estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from −11‰ to −21‰ VSMOW, which is consistent with δ18O values from both regional precipitation and the low-elevation, southern margin of the LIS. During the Bølling and Allerød (14.0 through 13.3 ka), estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from −22‰ to −38‰ VSMOW. These values suggest a dynamic melting history of different parts of the LIS, with potential contributions to Mississippi River outflow from both the low-elevation, southern margin of the LIS and high-elevation, high-latitude domes in the LIS interior that were transported to the ablation zone. Prior to ∼15.5 ka, the δ18Owater value of the Mississippi River was similar to that of regional precipitation or low-latitude LIS meltwater, but the Ba concentration in the Mississippi basin was affected by changes in weathering within the watershed, complicating Ba-salinity relationships in the Gulf of Mexico. After 13 ka, our data suggest Mississippi River outflow did not influence surface salinity above our Gulf of Mexico Orca Basin core site. Rather, we hypothesize that open ocean conditions prevailed as sea level rose and the paleoshoreline at the southern edge of North America retreated northward.

Mg/Ca ratio paleothermometry in foraminifera is an important tool for the reconstruction and interpretation of past environments. However, existing Mg/Ca:temperature relationships for planktic species inhabiting middle- and high-latitude environments are limited by a lack of information about the development and impact of low-Mg/Ca ratio “crusts” and the influence of the carbonate system on Mg/Ca ratios in these groups. To address this, we cultured individual specimens of Neogloboquadrina incompta and Neogloboquadrina pachyderma in seawater across a range of temperature (6°–12°C) and pH (7.4–8.2). We found by laser ablation inductively couple mass spectrometry analyses of shells that culture-grown crust calcite in N. incompta had a lower Mg/Ca ratio than ontogenetic calcite formed at the same temperature, suggesting that temperature is not responsible for the low-Mg/Ca ratio of neogloboquadrinid crusts. The Mg/Ca:temperature relationship for ontogenetic calcite in N. incompta was consistent with the previously published culture-based relationship, and no significant relationship was found between Mg/Ca ratios and pH in this species. However, the Mg/Ca ratio in laboratory-cultured N. pachyderma was much higher than that reported in previous core top and sediment trap samples, due to lack of crust formation in culture. Application of our ontogenetic calcite-specific Mg/Ca:temperature relationships to fossil N. pachyderma and N. incompta from five intervals in cores from the Santa Barbara Basin and the Bering Sea shows that excluding crust calcite in fossil specimens may improve Mg/Ca-based temperature estimates.

The carbon isotope composition (δ13C) of seawater provides valuable insight on ocean circulation, air-sea exchange, the biological pump, and the global carbon cycle and is reflected by the δ13C of foraminifera tests. Here more than 1700 δ13C observations of the benthic foraminifera genus Cibicides from late Holocene sediments (δ13CCibnat) are compiled and compared with newly updated estimates of the natural (preindustrial) water column δ13C of dissolved inorganic carbon (δ13CDICnat) as part of the international Ocean Circulation and Carbon Cycling (OC3) project. Using selection criteria based on the spatial distance between samples, we find high correlation between δ13CCibnat and δ13CDICnat, confirming earlier work. Regression analyses indicate significant carbonate ion (−2.6 ± 0.4) × 10−3‰/(μmol kg−1) [CO32−] and pressure (−4.9 ± 1.7) × 10−5‰ m−1 (depth) effects, which we use to propose a new global calibration for predicting δ13CDICnat from δ13CCibnat. This calibration is shown to remove some systematic regional biases and decrease errors compared with the one-to-one relationship (δ13CDICnat = δ13CCibnat). However, these effects and the error reductions are relatively small, which suggests that most conclusions from previous studies using a one-to-one relationship remain robust. The remaining standard error of the regression is generally σ ≅ 0.25‰, with larger values found in the southeast Atlantic and Antarctic (σ ≅ 0.4‰) and for species other than Cibicides wuellerstorfi. Discussion of species effects and possible sources of the remaining errors may aid future attempts to improve the use of the benthic δ13C record.

The relationship between seawater temperature and the average Mg/Ca ratios in planktic foraminifera is well established, providing an essential tool for reconstructing past ocean temperatures. However, many species display alternating high and low Mg-bands within their shell walls that cannot be explained by temperature alone. Recent experiments demonstrate that intrashell Mg variability in Orbulina universa, which forms a spherical terminal shell, is paced by the diurnal light/dark cycle. Whether Mg-heterogeneity is also diurnally paced in species with more complex shell morphologies is unknown. Here we show that high Mg/Ca-calcite forms at night in cultured specimens of the multi-chambered species Neogloboquadrina dutertrei. Our results demonstrate that N. dutertrei adds a significant amount of calcite, and nearly all Mg-bands, after the final chamber forms. These results have implications for interpreting patterns of calcification in N. dutertrei and suggest that diurnal Mg-banding is an intrinsic component of biomineralization in planktic foraminifera.

Plankton, corals, and other organisms produce calcium carbonate skeletons that are integral to their survival, form a key component of the global carbon cycle, and record an archive of past oceanographic conditions in their geochemistry. A key aspect of the formation of these biominerals is the interaction between organic templating structures and mineral precipitation processes. Laboratory-based studies have shown that these atomic-scale processes can profoundly influence the architecture and composition of minerals, but their importance in calcifying organisms is poorly understood because it is difficult to measure the chemistry of in vivo biomineral interfaces at spatially relevant scales. Understanding the role of templates in biomineral nucleation, and their importance in skeletal geochemistry requires an integrated, multiscale approach, which can place atom-scale observations of organic-mineral interfaces within a broader structural and geochemical context. Here we map the chemistry of an embedded organic template structure within a carbonate skeleton of the foraminifera Orbulina universa using both atom probe tomography (APT), a 3D chemical imaging technique with Ångström-level spatial resolution, and time-of-flight secondary ionization mass spectrometry (ToF-SIMS), a 2D chemical imaging technique with submicron resolution. We quantitatively link these observations, revealing that the organic template in O. universa is uniquely enriched in both Na and Mg, and contributes to intraskeletal chemical heterogeneity. Our APT analyses reveal the cation composition of the organic surface, offering evidence to suggest that cations other than Ca2+, previously considered passive spectator ions in biomineral templating, may be important in defining the energetics of carbonate nucleation on organic templates.

Shells are a visible component of archaeological middens in Central California. While coastal and bay shore sites are often dominated by shells, these food items were sometimes hauled many kilometers from their collection points and are found in appreciable numbers in inland sites as well. Using oxygen and carbon stable isotope data from 44 Mytilus sp. (mussel) shells, we reconstruct shellfish seasonality harvesting at one inland site dating to the Middle Period (ca. 2500-1000 cal yrs BP), CA-SOL-364. Data show that shells were collected from nearby Suisun Marsh and were harvested almost exclusively during winter, a pattern that contrasts with coastal and bay shore sites. Such a harvesting signature is unlike that expected for a food staple or a feasting resource. We suggest mussels were harvested as a fallback food, as a source of protein or micronutrient to complement carbohydrate-rich foods that were stored and consumed during winter, or perhaps were only exploited as opportunity costs relaxed during winter, making sessile mussels an attractive subsistence pursuit.

To explore relationships between water column hydrography and foraminiferal geochemistry in the Eastern Tropical North Pacific, we present δO18 and Mg/Ca records from three species of planktonic foraminifera, Globigerinoides ruber, Globigerina bulloides, and Globorotalia menardii, collected from a sediment trap mooring maintained in the Gulf of Tehuantepec from 2006–2012. Differences in δO18 between mixed-layer species G. ruber and G. bulloides and thermocline-dweller G. menardii track seasonal changes in upwelling. The records suggest an increase in upwelling during the peak positive phase of El Niño, and an overall reduction in stratification over the six-year period. For all three species, Mg/Ca ratios are higher than what has been reported in previous studies, and show poor correlations to calcification temperature. We suggest that low pH (7.6–8.0) and [CO32−] values (∼70–120 μmol/kg) in the mixed layer contribute to an overall trend of higher Mg/Ca ratios in this region. Laser Ablation Inductively Coupled Mass Spectrometry analyses of G. bulloides with high Mg/Ca ratios (>9 mmol/mol) reveal the presence of a secondary coating of inorganic calcite that has Mg/Ca and Mn/Ca ratios up to an order of magnitude higher than these elemental ratios in the primary calcite, along with elevated Sr/Ca and Ba/Ca ratios. Some of the samples with abnormally high Mg/Ca are found during periods of high primary productivity, suggesting the alteration may be related to changes in carbonate saturation resulting from remineralization of organic matter in oxygen-poor waters in the water column. Although similar shell layering has been observed on fossil foraminifera, this is the first time such alteration has been studied in shells collected from the water column. Our results suggest a role for seawater carbonate chemistry in influencing foraminiferal calcite trace element:calcium ratios prior to deposition on the seafloor, particularly in high-productivity, low-oxygen environments.

Scattered data interpolation and approximation techniques allow for the reconstruction of a scalar field based upon a finite number of scattered samples of the field. In general, the fidelity of the reconstruction with respect to the original scalar field tends to deteriorate as the number of samples decreases. For the situation of very sparse sampling, the results may not be acceptable at all. However, if it is known that the scalar field of interest is correlated with a known flow field - as is the case when the scalar field represents the value of an oceanographic tracer that propagates under the influence of the ocean's flow - then this knowledge can be exploited to enhance the scattered data reconstruction method. One way to exploit flow field information is to use it to construct a modified notion of distance between points. Replacing the standard Euclidean distance metric with a flow-field-aware notion of distance provides a method for extending standard scattered data interpolation methods into flow-based methods that produce superior results for very sparse data. The resulting reconstructions typically have lower root-mean-square errors than reconstructions that do not use the flow information, and qualitatively they often appear physically more realistic.

Compilations of paleoceanographic observations for the deep sea now contain a few hundred points along the oceanic margins, mid-ocean ridges, and bathymetric highs, where seawater conditions are indirectly recorded in the chemistry of buried benthic foraminiferal shells. Here we design an idealized experiment to test our predictive ability to reconstruct modern-day seawater properties by considering paleoceanographic-like data. We attempt to reconstruct the known, modern-day global distributions by using a state estimation method that combines a kinematic tracer transport model with observations that have paleoceanographic characteristics. When a modern-like suite of observations (Θ, practical salinity, seawater δ18O, δ13CDIC, PO4, NO3, and O2) is used from the sparse paleolocations, the state estimate is consistent with the withheld data at all depths below 1500 m, suggesting that the observational sparsity can be overcome. Physical features, such as the interbasin gradients in deep δ13CDIC and the vertical structure of Atlantic δ13CDIC, are accurately reconstructed. The state estimation method extracts useful information from the pointwise observations to infer distributions at the largest oceanic scales (at least 10,000 km horizontally and 1500 m vertically) and outperforms a standard optimal interpolation technique even though neither dynamical constraints nor constraints from surface boundary fluxes are used. When the sparse observations are more realistically restricted to the paleoceanographic proxy observations of δ13C, δ18O, and Cd/Ca, however, the large-scale property distributions are no longer recovered coherently. At least three more water mass tracers are likely needed at the core sites in order to accurately reconstruct the large-scale property distributions of the Last Glacial Maximum.

Biometric characteristics of Orbulina universa (d'Orbigny) were used to differentiate two morphotypes present in sediment trap samples collected from the Cariaco Basin, Venezuela. Specifically, wall thickness and weight-area relationships were used to separate shells into thin (Mthin) and thick (Mthick) morphotypes. Mthick (mean thickness=19-41μm) comprises 75% of the total O. universa in these samples and has morphometric characteristics similar to that of the previously described Type I Caribbean genotype, whereas Mthin (mean thickness=6-22μm) is comparable to the Type III Mediterranean genotype. The flux of Mthick increases during periods of upwelling, whereas Mthin flux shows no systematic relationship with changing hydrographic regimes in the basin. The δ18O and δ13C of Mthick are on average 0.34% higher and 0.38% lower, respectively, than those of Mthin, suggesting that they calcify their final spherical chamber at different depths in the water column and/or differ in their vital effects on shell geochemistry. Additionally, the absolute offset in the stable isotopic compositions of the two morphotypes varies as a function of surface ocean stratification. During periods of upwelling, the δ18O and δ13C absolute offsets between Mthin and Mthick are on average -0.15 and 0.25%, whereas average δ18O and δ13C absolute offsets between these two morphotypes increase to -0.54 and 0.41% during non-upwelling periods. We attribute the higher δ18O and δ13C offsets during non-upwelling periods to a difference in final chamber calcification depth and the combined effects of temperature (δ18O), δ13CDIC (δ13C), irradiance (δ13C) and [CO32-] (δ18O and δ13C). These data provide field evidence that thin and thick morphotypes of O. universa likely experience different environmental conditions during the formation of their final chamber and, therefore, should not be combined in geochemical analyses for reconstructing past surface ocean conditions. Finally, we introduce a new proxy for reconstructing past surface ocean stratification changes via the use of Mthin and Mthick δ18O and δ13C offsets.

A paleo-data compilation with 492 δ13C and δ18O observations provides the opportunity to better sample the Last Glacial Maximum (LGM) and infer its global properties, such as the mean δ13C of dissolved inorganic carbon. Here, the paleo-compilation is used to reconstruct a steady-state water-mass distribution for the LGM, that in turn is used to map the data onto a 3D global grid. A global-mean marine δ13C value and a self-consistent uncertainty estimate are derived using the framework of state estimation (i.e., combining a numerical model and observations). The LGM global-mean δ13C is estimated to be 0.14‰ ± 0.20‰ at the two standard error level, giving a glacial-to-modern change of 0.32‰ ± 0.20‰. The magnitude of the error bar is attributed to the uncertain glacial ocean circulation and the lack of observational constraints in the Pacific, Indian, and Southern Oceans. To halve the error bar, roughly four times more observations are needed, although strategic sampling may reduce this number. If dynamical constraints can be used to better characterize the LGM circulation, the error bar can also be reduced to 0.05 to 0.1‰, emphasizing that knowledge of the circulation is vital to accurately map δ13C in three dimensions.

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is becoming a widespread technique for analyzing elemental ratios in foraminiferal calcite. Here we focus on optimizing LA-ICP-MS for high-resolution depth profiling of elemental ratios through shell walls. This application reveals intrashell variability and provides a unique opportunity to quantify trace element incorporation over short time scales of calcification by an individual foraminifer. High-resolution depth profiling requires careful consideration of both ablation and analytical conditions required to resolve differences in shell chemistry across sub-micron shell thickness. We present laser ablation profiles of NIST SRM 610 standard glass data (in cps) and elemental/Ca ratios (in mmol/mol) from foraminiferal calcite obtained over a range of operating conditions using a Photon Machines 193nm UV excimer laser-ablation system, equipped with a dual-volume ANU HelEx chamber, coupled to an Agilent 7700x quadrupole ICP-MS. Different combinations of energy density, repetition rate, and mass spectrometer cycle time can yield varying elemental profiles. This variability can mimic and/or mask real intrashell trace element heterogeneity in foraminifer shells. At low (

Geochemical observations indicate that planktic foraminifer test Mg/Ca is heterogeneous in many species, thereby challenging its use as a paleotemperature proxy for paleoceanographic reconstructions. We present Mg/Ca and Ba/Ca data collected by laser ablation ICP-MS from the shells of Orbulina universa cultured in controlled laboratory experiments. Test calcite was labeled with Ba-spiked seawater for 12 h day or night calcification periods to quantify the timing of intratest Mg-banding across multiple diurnal cycles. Results demonstrate that high Mg bands are precipitated during the night whereas low Mg bands are precipitated during the day. Data obtained from specimens growing at 20 °C and 25 °C show that Mg/Ca ratios in both high and low Mg bands increase with temperature, and average test Mg/Ca ratios are in excellent agreement with previously published empirical calibrations based on bulk solution ICP-MS analyses. In general, Mg band concentrations decrease with increasing pH and/or [CO2-3] but this effect decreases as experimental temperatures increase from 20 °C to 25 °C. We suggest that mitochondrial uptake of Mg2+ from the thin calcifying fluid beneath streaming rhizopodial filaments may provide the primary locus for Mg2+ removal during test calcification, and that diurnal variations in either mitochondrial density or activity produce Mg banding. These results demonstrate that Mg banding is an inherent component of test biomineralization in O. universa and show that the Mg/Ca paleothermometer remains a fundamental tool for reconstructing past ocean temperatures from fossil foraminifers.

In this study, we present experimental results from the planktic foraminifer Orbulina universa, cultured in the laboratory. We demonstrate that the δ13C of shell calcite precipitated in 13C-labeled seawater for 24h can be resolved and accurately measured using Secondary Ion Mass Spectrometry (SIMS). Specimens maintained at 20°C were transferred from ambient seawater (δ13CDIC=+1.3‰) into seawater with δ13CDIC=+51.5‰ and enriched [Ba2+] for 24h. Specimens were then transferred into ambient seawater with elevated [87Sr] for 6-9h of calcification, followed by a transfer back into unlabeled ambient seawater until gametogenesis. This technique produced O. universa shells with calcite layers of distinct geochemical signatures. We quantify the spatial positions of trace element labels in the shells using laser ablation ICP-MS depth profiling. Using fragments from the same shells, we quantify intrashell δ13Ccalcite using SIMS with a 6 or 8μm spot (2 SD range ±0.5‰ to 1.7‰). Measured δ13Ccalcite values in O. universa shell layers precipitated in ambient seawater are within 2‰ of predicted δ13Ccalcite values. In 13C-labeled bands of calcite, 6μm SIMS spot measurements are within 2‰ of predicted δ13Ccalcite values, whereas 8μm SIMS spots yield intermediate, mixed values. The spatial agreement between trace element and carbon isotope data suggests that 13C and cation tracers are synchronously incorporated into shell calcite. These results demonstrate the ability of SIMS δ13C measurements to resolve ~10μm features in foraminifer shell calcite using a 6μm spot, and highlight the potential of this technique for addressing questions about ecology, biomineralization, and paleoceanography. © 2014 .

Understanding the coupling of oxygen, carbon, and sulfur cycles in the past is critical for reconstructing the history of biogeochemical cycles, paleoclimatic variations, and oceanic chemistry. The abundance of sulfur isotopes (δ34S) in sulfate from ancient marine carbonates, or carbonate-associated sulfate (CAS), is commonly used, along with other archives (mainly evaporites and barite), to estimate the δ34S of seawater throughout Earth history. Analyses of CAS from hand-picked foraminifera are potentially valuable because this group of organisms is used in numerous paleoceanographic studies. They could provide coupled, high-resolution records of δ13C, δ18O, and δ34S isotopic changes directly linked to orbitally tuned records of climate change through the Cenozoic. Such measurements have not previously been possible due to limitations of sensitivity in conventional IRMS-based techniques. However, the recent development of CAS analysis by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) now allows us to work on samples containing just a few nmol of sulfur with accuracy for δ34S values approaching 0.1‰ and, consequently, to analyze hand-picked samples of foraminifera shells. Here we report the results of culture experiments with the planktonic species Orbulina universa, that establish a shell:seawater δ34S calibration for future applications to the fossil record. Our new method uses

Radiocarbon in the atmosphere is regulated largely by ocean circulation, which controls the sequestration of carbon dioxide (CO(2)) in the deep sea through atmosphere-ocean carbon exchange. During the last glaciation, lower atmospheric CO(2) levels were accompanied by increased atmospheric radiocarbon concentrations that have been attributed to greater storage of CO(2) in a poorly ventilated abyssal ocean. The end of the ice age was marked by a rapid increase in atmospheric CO(2) concentrations that coincided with reduced (14)C/(12)C ratios (Delta(14)C) in the atmosphere, suggesting the release of very 'old' ((14)C-depleted) CO(2) from the deep ocean to the atmosphere. Here we present radiocarbon records of surface and intermediate-depth waters from two sediment cores in the southwest Pacific and Southern oceans. We find a steady 170 per mil decrease in Delta(14)C that precedes and roughly equals in magnitude the decrease in the atmospheric radiocarbon signal during the early stages of the glacial-interglacial climatic transition. The atmospheric decrease in the radiocarbon signal coincides with regionally intensified upwelling and marine biological productivity, suggesting that CO(2) released by means of deep water upwelling in the Southern Ocean lost most of its original depleted-(14)C imprint as a result of exchange and isotopic equilibration with the atmosphere. Our data imply that the deglacial (14)C depletion previously identified in the eastern tropical North Pacific must have involved contributions from sources other than the previously suggested carbon release by way of a deep Southern Ocean pathway, and may reflect the expanded influence of the (14)C-depleted North Pacific carbon reservoir across this interval. Accordingly, shallow water masses advecting north across the South Pacific in the early deglaciation had little or no residual (14)C-depleted signals owing to degassing of CO(2) and biological uptake in the Southern Ocean.

Rationale: The use of secondary ion mass spectrometry (SIMS) to perform micrometer‐scale in situ carbon isotope (δ13C) analyses of shells of marine microfossils called planktic foraminifers holds promise to explore calcification and ecological processes. The potential of this technique, however, cannot be realized without comparison to traditional whole‐shell δ13C values measured by gas source mass spectrometry (GSMS). Methods: Paired SIMS and GSMS δ13C values measured from final chamber fragments of the same shell of the planktic foraminifer Orbulina universa are compared. The SIMS–GSMS δ13C differences (Δ13CSIMS‐GSMS) were determined via paired analysis of hydrogen peroxide‐cleaned fragments of modern cultured specimens and of fossil specimens from deep‐sea sediments that were either untreated, sonicated, and cleaned with hydrogen peroxide or vacuum roasted. After treatment, fragments were analyzed by a CAMECA IMS 1280 SIMS instrument and either a ThermoScientific MAT‐253 or a Fisons Optima isotope ratio mass spectrometer (GSMS). Results: Paired analyses of cleaned fragments of cultured specimens (n = 7) yield no SIMS–GSMS δ13C difference. However, paired analyses of untreated (n = 18) and cleaned (n = 12) fragments of fossil shells yield average Δ13CSIMS‐GSMS values of 0.8‰ and 0.6‰ (±0.2‰, 2 SE), respectively, while vacuum roasting of fossil shell fragments (n = 11) removes the SIMS–GSMS δ13C difference. Conclusions: The noted Δ13CSIMS‐GSMS values are most likely due to matrix effects causing sample–standard mismatch for SIMS analyses but may also be a combination of other factors such as SIMS measurement of chemically bound water. The volume of material analyzed via SIMS is ~105 times smaller than that analyzed by GSMS; hence, the extent to which these Δ13CSIMS‐GSMS values represent differences in analyte or instrument factors remains unclear. [ABSTRACT FROM AUTHOR]