Description: Recently Hathorne et al. (2009) documented large intratest trace element (TE) variations in planktonic foraminifera from a single sediment trap sample that could not be explained by variations in water column properties. The laser ablation ICP-MS depth profiles of trace elements through the test walls revealed strong positive correlations between Li, Mg, Mn and Ba resulting from the mixing of a lower TE outer calcite with a higher TE inner calcite. In contrast Sr/Ca ratios remained relatively constant throughout the test wall. These intratest TE variations likely result from biomineralization processes and therefore should be explained by any valid biomineralization model. However, changes in calcite precipitation rate, crystal structure, or the chemical composition of the internal calcification reservoir could not, by themselves, fully account for the pattern of cation intratest variability. Here I expand on this work and investigate if a model of coral biomineralization by Sinclair and Risk (2006) can be adapted to explain the pattern of intratest TE variability in foraminifera. It is clear that the low Mg calcite secreting foraminifera must reduce the Mg/Ca ratio of the calcifying solution by at least a factor of 10 (e.g. Hathorne et al., 2009) and it has been suggested this is achieved by active removal of Mg from the calcification reservoir, although the actual mechanisms remain debatable (e.g. Bentov and Erez, 2006). However, a recent study of the calcification of a low Mg calcite species in the laboratory found a large shortcoming in the amount of Ca potentially provided by seawater transported to the site of calcification in vacuoles compared to a conservative estimate of the amount required to form the new calcite wall (de Nooijer et al., 2009a). This suggests active Ca transport to the site of calcification is required to provide sufficient Ca. If Ca specific, this Ca addition would effectively dilute the TE content (including Mg) of the calcification reservoir to varying degrees and potentially cause the positive TE correlations seen across the test wall. Sinclair and Risk (2006) used this dilution model to successfully explain some TE correlations in coral skeletons. This model can be effectively adapted to foraminifera as it accounts for recent observations of foraminiferal calcification including the transport of seawater by liquid endocytosis to the calcification site and an elevated pH at the site of calcification (Bentov et al., 2009; de Nooijer et al., 2009a, 2009b). This model therefore provides a powerful tool with which to integrate constraints from experimental observation with those from micro-analytical measurements to improve the accuracy, precision and scale of the palaepalaeoceanographic application of foraminiferal geochemistry. Bentov and Erez (2006) Geochem. Geophys. Gepsyst. 7, Q01P08. Bentov et al. (2009) PNAS 106, 21500. de Nooijer et al. (2009a) Biogeosciences 6, 2669. de Nooijer et al. (2009b) PNAS 106, 15374. Hathorne et al. (2009) Paleoceanography 24, PA4204. Sinclair and Risk (2006) Geochim. Cosmochim. Acta 70, 3855.

Description: Quantifying the spatial and temporal sea surface temperature (SST) and salinity changes of the Indo-Pacific Warm Pool is essential to understand the role of this region in connection with abrupt climate changes particularly during the last deglaciation. In this study we reconstruct SST and seawater δ18O of the tropical eastern Indian Ocean for the past 40,000 years from two sediment cores (GeoB 10029-4, 1°30′S, 100°08′E, and GeoB 10038-4, 5°56′S, 103°15′E) retrieved offshore Sumatra. Our results show that annual mean SSTs increased about 2–3 °C at 19,000 years ago and exhibited southern hemisphere-like timing and pattern during the last deglaciation. Our SST records together with other Mg/Ca-based SST reconstructions around Indonesia do not track the monsoon variation since the last glacial period, as recorded by terrestrial monsoon archives. However, the spatial SST heterogeneity might be a result of changing monsoon intensity that shifts either the annual mean SSTs or the seasonality of G. ruber towards the warmer or the cooler season at different locations. Seawater δ18O reconstructions north of the equator suggest fresher surface conditions during the last glacial and track the northern high-latitude climate change during the last deglaciation. In contrast, seawater δ18O records south of the equator do not show a significant difference between the last glacial period and the Holocene, and lack Bølling Allerød and Younger Dryas periods suggestive of additional controls on annual mean surface hydrology in this part of the Indo-Pacific Warm Pool.

Description: Incorporation of boron into foraminiferal shells is thought to be primarily governed by the carbonate chemistry of the ambient seawater, suggesting that it can be reconstructed from B/Ca ratios. To this end, B/Ca ratios of the benthic foraminifer Planulina wuellerstorfi from South Atlantic core top samples have been analyzed using laser ablation−inductively coupled plasma−mass spectroscopy (LA-ICP-MS) to provide additional information on intratest trace element heterogeneity. Results show that boron is heterogeneously distributed within and between shells, with content variations of approximately ±43% displayed within a single shell. B/Ca is higher in the youngest chambers, opposite to the observed between-chamber variability of Mg/Ca. This may be explained by ontogenetic changes of physiological processes that increase the pH of the calcifying fluid and thus the borate concentration while decreasing Mg/Ca to promote calcification. Despite this heterogeneity, mean B/Ca ratios are positively correlated with the deepwater calcite saturation state (Δ[CO32–]), in line with previous studies. We apply this empirical relationship to reconstruct Δ[CO32–] for the late Pleistocene to Holocene using samples from a depth transect in the equatorial Atlantic. Reconstructed Δ[CO32–] values confirm previous studies suggesting that CaCO3-oversaturated North Atlantic Deep Water was reduced during glacial periods, whereas CaCO3-undersaturated Antarctic Bottom Water expanded vertically and propagated northwards. In summary, our data demonstrate that bulk B/Ca in P. wuellerstorfi reliably reflects variations in Δ[CO32–], despite the strong physiological control of boron incorporation.

Description: The rare earth elements (REEs) with their systematically varying properties are powerful tracers of continental inputs, particle scavenging intensity and the oxidation state of seawater. However, their generally low (∼pmol/kg) concentrations in seawater and fractionation potential during chemical treatment makes them difficult to measure. Here we report a technique using an automated preconcentration system, which efficiently separates seawater matrix elements and elutes the preconcentrated sample directly into the spray chamber of an ICP-MS instrument. The commercially available “seaFAST” system (Elemental Scientific Inc.) makes use of a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate REEs and other metals while anions and alkali and alkaline earth cations are washed out. Repeated measurements of seawater from 2000 m water depth in the Southern Ocean allows the external precision (2σ) of the technique to be estimated at 〈23% for all REEs and 〈15% for most. Comparison of Nd concentrations with isotope dilution measurements for 69 samples demonstrates that the two techniques generally agree within 15%. Accuracy was found to be good for all REEs by using a five point standard addition analysis of one sample and comparing measurements of mine water reference materials diluted with a NaCl matrix with recommended values in the literature. This makes the online preconcentration ICP-MS technique advantageous for the minimal sample preparation required and the relatively small sample volume consumed (7 mL) thus enabling large data sets for the REEs in seawater to be rapidly acquired.