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Emiliania huxleyi cells were grown in artificial seawater of different Li and Ca concentrations and coccolith Li/Ca ratios determined. Coccolith Li/Ca ratios were positively correlated to seawater Li/Ca ratios only if the seawater Li concentration was changed, not if the seawater Ca concentration was changed. This Li partitioning pattern of E. huxleyi was previously also observed in the benthic foraminifer Amphistegina lessonii and inorganically precipitated calcite. We argue that Li partitioning in both E. huxleyi and A. lessonii is dominated by a coupled transmembrane transport of Li and Ca from seawater to the site of calcification. We present a refined version of a recently proposed transmembrane transport model for Li and Ca. The model assumes that Li and Ca enter the cell via Ca channels, the Li flux being dependent on the Ca flux. While the original model features a linear function to describe the experimental data, our refined version uses a power function, changing the stoichiometry of Li and Ca. The version presented here accurately predicts the observed dependence of DLi on seawater Li/Ca ratios. Our data demonstrate that minor element partitioning in calcifying organisms is partly mediated by biological processes even if the partitioning behavior of the calcifying organism is indistinguishable from that of inorganically precipitated calcium carbonate. Plain Language Summary: Marine shell‐forming organisms such as the minute, but abundant, coccolithophores (single‐celled phytoplankton) and foraminifera (single‐celled zooplankton) are not only ecologically important but also contribute significantly to the global carbonate sink. Minor elements (e.g., Sr and Li) trapped in biogenic carbonate sediments provide a window into past environmental conditions such as temperature, which is relevant for climate change. An understanding of elemental incorporation processes is required in order to correctly translate these minor element signatures into past environmental data. Here we conducted culture experiments with the coccolithophore Emiliania huxleyi to determine its Li incorporation behavior. We compare our results with previously published data on the foraminifer Amphistegina lessonii and data on synthetic calcite. The Li incorporation behavior of biogenic calcites is surprisingly similar to that of synthetic calcite. This is usually taken to mean that Li incorporation into shells should proceed inorganically. By contrast, we conclude that minor element incorporation processes in marine shell‐forming organisms always include biological processes. This is relevant to past climate reconstructions because it excludes any interpretation of minor element signatures in fossil shells based on inorganic processes only. Key Points: The Li partitioning pattern of E. huxleyi resembles that of A. lessonii and inorganic calciteLi partitioning in E. huxleyi is dominated by a coupled transmembrane transport of Li and CaThe vital effect is ubiquitous in calcifying organisms, even if it appears to be absent [ABSTRACT FROM AUTHOR]

Barium (Ba) incorporated in the calcite of many foraminiferal species is proportional to the concentration of Ba in seawater. Since the open ocean concentration of Ba closely follows seawater alkalinity, foraminiferal Ba/Ca can be used to reconstruct the latter. Alternatively, Ba/Ca from foraminiferal shells can also be used to reconstruct salinity in coastal settings where seawater Ba concentration corresponds to salinity as rivers contain much more Ba than seawater. Incorporation of a number of minor and trace elements is known to vary (greatly) between foraminiferal species and application of element/Ca ratios thus requires the use of species-specific calibrations. Here we show that calcite Ba/Ca correlates positively and linearly with seawater Ba/Ca in cultured specimens of two species of benthic foraminifera, Heterostegina depressa and Amphistegina lessonii. The slopes of the regression, however, vary 2-3 fold between these two species (0.33 and 0.78, respectively). This difference in Ba-partitioning resembles the difference in partitioning of other elements (Mg, Sr, B, Li and Na) in these foraminiferal taxa. A general trend across element partitioning for different species is described, which may help developing new applications of trace elements in foraminiferal calcite in reconstructing past seawater chemistry. [ABSTRACT FROM AUTHOR]

The shallow water benthic foraminifera Ammonia aomoriensis and Amphistegina lessonii were grown at different seawater Sr/Ca and the test Sr/Ca ratio was determined by Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry. A. aomoriensis test Sr/Ca is positively correlated with seawater Sr/Ca. The linear regression has a slope of 0.17, representing the overall Sr partitioning coefficient K DSr . The slope remains unchanged, if seawater Ca concentration is changed in order to change the seawater Sr/Ca. In the case of A. lessonii , the slopes of the linear regressions representing K DSr differ from one another i.e., 0.16 if the Sr concentration is changed and 0.32 if the Ca level is changed. This difference in K DSr can be explained by the, relative to A. aomoriensis , high Mg content of A. lessonii (ca. 40 mmol/mol), distorting the calcite lattice and weakening the discrimination against Sr. The Mg content of A. aomoriensis is too low (ca. 4 mmol/mol) to observe the influence on Sr partitioning. All data are compatible with a recently developed model for minor element partitioning in foraminifera (Nehrke et al., 2013; Mewes et al., 2015a). On the whole, our data confirm the model (applicability of the model to Sr and dependence of the calcite Sr/Ca on seawater Sr/Ca, as opposed to seawater Sr concentration), and improve our understanding of the model (influence of calcite Mg/Ca on Sr partitioning). [ABSTRACT FROM AUTHOR]

Magnesium, incorporated in foraminiferal calcite (Mg/Ca CC ), is used intensively to reconstruct past seawater temperatures but, in addition to temperature, the Mg/Ca CC of foraminiferal tests also depends on the ratio of Mg and Ca in seawater (Mg/Ca SW ). The physiological mechanisms responsible for these proxy relationships are still unknown. This culture study investigates the impact of different seawater [Mg 2 + ] on calcification in two benthic foraminiferal species precipitating contrasting Mg/Ca CC : Ammonia aomoriensis , producing low-Mg calcite and Amphistegina lessonii , producing intermediate-Mg calcite. Foraminiferal growth and test thickness were determined and, Mg/Ca was analyzed using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). Results show that at present-day seawater Mg/Ca SW of ~ 5, both species have highest growth rates, reflecting their adaptation to modern seawater element concentrations. Test thickness is not significantly affected by different Mg/Ca SW . The relationship between Mg/Ca SW and Mg/Ca CC shows a distinct positive y-axis intercept, possibly reflecting at least two processes involved in foraminiferal biomineralization. The associated Mg partition (D Mg ) changes non-linearly with increasing Mg/Ca SW , hence suggesting that the D Mg is best described by an exponential function approaching an asymptote. [ABSTRACT FROM AUTHOR]

Abstract: Calcareous foraminifera are well known for their CaCO3 shells. Yet, CaCO3 precipitation acidifies the calcifying fluid. Calcification without pH regulation would therefore rapidly create a negative feedback for CaCO3 precipitation. In unicellular organisms, like foraminifera, an effective mechanism to counteract this acidification could be the externalization of H+ from the site of calcification. In this study we show that a benthic symbiont-free foraminifer Ammonia sp. actively decreases pH within its extracellular microenvironment only while precipitating calcite. During chamber formation events the strongest pH decreases occurred in the vicinity of a newly forming chamber (range of gradient ~100μm) with a recorded minimum of 6.31 (<10μm from the shell) and a maximum duration of 7h. The acidification was actively regulated by the foraminifera and correlated with shell diameters, indicating that the amount of protons removed during calcification is directly related to the volume of calcite precipitated. The here presented findings imply that H+ expulsion as a result of calcification may be a wider strategy for maintaining pH homeostasis in unicellular calcifying organisms. [Copyright &y& Elsevier]

Here we present the first multi-species comparison of modern and fossil coccolith trace metal data obtained from single liths. We present both trace metal analyses (Sr, Ca, Mg and Al) and distribution maps of individual Paleogene fossil coccoliths obtained by Secondary Ion Mass Spectrometry (SIMS). We use this data to determine the effects of variable coccolith preservation and diagenetic calcite overgrowths on the recorded concentrations of strontium and magnesium in coccolith calcite. The analysis of coccoliths from deep-ocean sediments spanning the Eocene/Oligocene transition demonstrates that primary coccolith calcite is resistant to the neomorphism that is common in planktonic foraminifera from similar depositional environments. Instead, where present, diagenetic calcite forms distinct overgrowths over primary coccolith calcite rather than replacing this calcite. Diagenetic overgrowths on coccoliths are easily distinguished in SIMS analyses on the basis of relatively higher Mg and lower Sr concentrations than co-occurring primary coccolith calcite. This interpretation is confirmed by the comparable SIMS analyses of modern cultured coccoliths of Coccolithus braarudii . Further, with diagenetic calcite overgrowth being the principle source of bias in coccolith-based geochemical records, we infer that lithologies with lower carbonate content, deposited below the palaeo-lysocline, are more likely to produce geochemical records dominated by primary coccolith calcite than carbonate-rich sediments where overgrowth is ubiquitous. The preservation of primary coccolith carbonate in low-carbonate lithologies thus provides a reliable geochemical archive where planktonic foraminifera are absent or have undergone neomorphism. [ABSTRACT FROM AUTHOR]

Abstract: The Mg/Ca ratio of foraminiferal calcite is a widely accepted and applied empirical proxy for ocean temperature. The analysis of foraminifera preserved in ocean sediments has been instrumental in developing our understanding of global climate, but the mechanisms behind the proxy are largely unknown. Analogies have been drawn to the inorganic precipitation of calcite, where the endothermic substitution of Mg for Ca is favoured at higher temperatures. However, evidence suggests that foraminiferal Mg incorporation may be more complex: foraminiferal magnesium is highly heterogeneous at the sub-micron scale, and high Mg areas coincide with elevated concentrations of organic molecules, Na, S and other trace elements. Fundamentally, the incorporation mode of Mg in foraminifera is unknown. Here we show that Mg is uniformly substituted for Ca within the calcite mineral lattice. The consistency of Mg-specific X-ray spectra gathered from nano-scale regions across the shell (‘test’) reveals that the coordination of Mg is uniform. The similarity of these spectra to that produced by dolomite shows that Mg is present in an octahedral coordination, ideally substituted for Ca in a calcite crystal structure. This demonstrates that Mg is heterogeneous in concentration, but not in structure. The degree of this uniformity implies the action of a continuous Mg incorporation mechanism, and therefore calcification mechanism, across these compositional bands in foraminifera. This constitutes a fundamental step towards a mechanistic understanding of foraminiferal calcification processes and the incorporation of calcite-bound palaeoenvironment proxies, such as Mg. [Copyright &y& Elsevier]