Can the pattern of foraminiferal intratest trace element variations be explained by Ca dilution during biomineralization?

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

Rare earth elements in Andaman Island surface water : geochemical tracers for the monsoon

The Asian summer monsoon affects the lives of billions of people. With the aim of identifying geochemical tracers for the monsoon related freshwater input from the major rivers draining into the Bay of Bengal and Andaman Sea we have taken surface seawater samples from various locations up and down the Andaman Islands during 2011. Importantly, in some locations samples have been taken in March, July and November, covering most of a seasonal cycle and different monsoon phases. Samples were collected from the side of small wooden boats or while swimming and were filtered within a few hours at 0.45 or 0.22 microns using the vacuum produced by a water jet or a hand operated peristaltic pump. Filtered and unfiltered samples were acidified to < pH 2 and analysed for Y and the REEs with an automated online preconcentration ICP-MS technique [1]. The local input of REEs from streams and sediment rich areas such as mangrove environments is clearly identified by middle REE enrichments in the shale normalised patterns of some samples. These middle REE bulges accompany large increases in dissolved REE concentrations at some locations, especially for the July samples obtained during the peak monsoon season with frequent storms. Y/Ho fractionation aslo occurs during the local input of dissolved REEs with affected samples having lower Y/Ho ratios. Conversly, some samples, in particular those taken after heavy rainfall in March, show strong REE scavenging accompanied by the prefferential removal of dissolved light REEs and higher Y/Ho ratios. The time series at a location away from local input sources shows remarkably similar REE patterns and concentraions in March and July. Then in October-November, following the peak in monsoon river discharge, the dissolved REE concentration increases by almost a factor of 2. The notable exception to this seasonal pattern is the Ce anomally which is around 0.3 in March and November but 0.6 in July, implying less oxidative removal of Ce(IV) during the peak summer monsoon rains. With the exception of elevated dissolved Ce concentrations, the North Pacific Deep Water normalised REE patterns are similar to those reported for offshore samples from the Bay of Bengal and Andaman Sea [2]. These seawater normalised patterns are distinctive having a middle REE enriched arc with similar light and heavy REE values suggesting the input from large rivers in the region is traceable using seawater REE chemistry. [1] Hathorne et al. (2012), Online preconcentration ICP-MS analysis of rare earth elements in seawater, Geochem. Geophys. Geosyst., 13, Q01020, doi:10.1029/2011GC003907. [2] Amakawa et al. (2000), Geochim. Cosmochim. Acta 64, 1715-1727

Past changes in riverine input and ocean circulation in the Gulf of Guinea

Large river systems draining the West African Monsoon area deliver sediments and dissolved trace elements into the Gulf of Guinea (GoG) in the easternmost equatorial Atlantic. The different catchment areas of these river systems are characterized by different geological ages and rock types releasing distinct radiogenic neodymium isotope compositions during weathering which are supplied to the GoG. The main rivers discharging into the GoG are the Niger, the Sanaga, the Nyong and the Ntem with present day εNd signatures of -10.5 [1], -12.3, -12.5 and -28.1 [2], respectively. These riverine inputs mix with the tropical Atlantic surface waters. At intermediate water depths Antarctic Intermediate Water (AAIW) prevails whereas the deep basin at this location is mainly filled with NADW. We focus on a marine sediment core that was recovered off the Sanaga and Ntem Rivers and we reconstruct changes in riverine inputs and in mixing of surface and deep water masses over the past 140,000 years. Changes in riverine inputs most likely reflecting latitudinal shifts of the rainfall zones across the different catchment areas were obtained from the Nd isotope signatures of the residual detrital fraction of the sediment. Sediment leachates of several GoG core top samples reflect the riverine input from nearby rivers indicating transport of particles coated in the rivers. Both the sediment leachates and the residual detrital fraction show similar patterns, with shifts towards radiogenic values during the interglacials and least radiogenic values during glacial periods. This shift in εNd values may be attributed to the migration of the rainfall zones towards the north during interglacial times and thus implies the increased influence of the northern rivers, the Sanaga and Nyong. The oxidatively-reductively cleaned planktonic foraminiferal calcite of the core top samples in the GoG reflects surface seawater signatures. Non-reductively cleaned planktonic foraminiferal tests and cleaned shallow endo-benthic and epi-benthic foraminiferal tests were used to acquire information about past bottom waters. Difficulties in cleaning down core foraminiferal samples were experienced and these samples appear to be contaminated by secondary manganese and iron bearing phases, even after cleaning. Those phases may have overprinted the original surface water Nd isotope composition in the planktonic foraminiferal tests. As the planktonic and benthic foraminiferal values are overall similar to the sediment leachates, the foraminiferal isotope signatures are most likely overprinted by isotopic signals originating from the rivers due to remobilization processes in the sediments and formation of secondary phases such as Mn-carbonates, which are attached to the foraminiferal calcites. References: [1] Goldstein et al. (1984) Earth and Planetary Science Letter 70, 221-236. [2] Weldeab et al. (2011) Geophysical Research Letter 38, pp. 5

Using a Flow Through device to reconstruct the thermal gradient in the water column based on G. inflata Mg/Ca

We present Mg/Ca analyses performed via a Flow Through sequential dissolution device connected to an ICP-OES on the planktonic foraminifer Globorotalia inflata. The aim of the study is to explore the possibility to reconstruct the thermal gradient in the water column by separating non-crusted and crusted calcite phases in the tests of G. inflata using the difference between their Mg/Ca ratios as a measure of the thermal gradient. An important assumption is that the non-crusted part of the tests is calcified in shallow, warmer water than the crusted part. For analyses a range of different preparation steps were used to determine the ideal way of separating the phases. Foraminifer tests were (not) cleaned, (not) crushed, and (not) pulverized before online analysis with the FT device. To analyze samples with a FT device the foraminifer tests are placed on a filter with a mesh of 0.45 μm preventing clay minerals to wash through. A sequential dissolution protocol first rinses the samples with buffered Seralpur water before QD HNO3 is added in small steps to create a ramp of increasing acid strength. As acid is kept constant at each concentration for several minutes, dissolution of a specific calcite phase can take place. Initial results show that it is most effective to slightly crush the tests without applying standard cleaning procedures, but rather analyze them without cleaning. Samples were selected from the South Atlantic (core tops and specific downcore samples) and the Mediteterranean (plankton tows). All samples were chosen based on previous work on them to provide comparison with routinely analysed Mg/Ca ratios. The South Atlantic samples have been analyzed extensively as bulk samples separated in difference size fractions and crusted vs. non-crusted (Groeneveld and Chiessi). The Mediterranean samples were not only analyzed as bulk samples but also by Laser Ablation ICP-MS (von Raden et al.). Results show that bulk analyses are reliably reproduced by the FT method, especially for samples which are dominated by crusted calcite. Samples which were uncrusted often gave much higher Mg/Ca ratios than the bulk analyses. These higher Mg/Ca ratios mainly occur in the plankton tow samples and were also identified with Laser Ablation ICP-MS. A possible reason for this could be the presence of a high Mg amorphous calcite layer on the outside of foraminifer tests which have not completed their calcification yet as was recently also pointed out in several other studies. Identification of the crusted and uncrusted phases, and therewith a thermal gradient, seems to give the expected differences but a more rigorous statistical treatment is needed to pinpoint singular dissolution phases

Minimal influence of recrystallization on middle Miocene benthic foraminiferal stable isotope stratigraphy in the eastern equatorial Pacific

Stable carbon and oxygen isotopes (δ13C and δ18O) of foraminiferal tests are amongst the most important tools in paleoceanography, but the extent to which recrystallization can alter the isotopic composition of the tests is not well known. Here we compare three middle Miocene (16–13 Ma) benthic foraminiferal stable isotope records from eastern equatorial Pacific sites with different diagenetic histories to investigate the effect of recrystallization. To test an extreme case, we analyzed stable isotope compositions of benthic foraminifera from Integrated Ocean Drilling Program Site U1336, for which the geochemistry of bulk carbonates and associated pore waters indicates continued diagenetic alteration in sediments > 14.7 Ma. Despite this diagenetic overprinting, the amplitudes and absolute values of the analyzed U1336 stable isotopes agree well with high-resolution records from better preserved Sites U1337 and U1338 nearby. Our results suggest that although benthic foraminiferal tests of all three sites show some degree of textural changes due to recrystallization, they have retained their original stable isotope signatures. The good agreement of the benthic foraminiferal stable isotope records demonstrates that recrystallization occurred extremely rapidly (< 100 kyr) after deposition. This is confirmed by the preservation of orbital cyclicities in U1336 stable isotope data and δ18O values being different to inorganic calcite that would precipitate from U1336 pore waters during late recrystallization. The close similarity of the benthic foraminiferal stable isotope records between the sites allows the well-resolved paleomagnetic results of Site U1336 to be transferred to Sites U1337 and U1338 improving the global geological timescale

Controls on calcium isotope fractionation in cultured planktic foraminifera, Globigerinoides ruber and Globigerinella siphonifera

Specimens of two species of planktic foraminifera, Globigerinoides ruber and Globigerinella siphonifera, were grown under controlled laboratory conditions at a range of temperatures (18–31 °C), salinities (32–44 psu) and pH levels (7.9–8.4). The shells were examined for their calcium isotope compositions (δ44/40Ca) and strontium to calcium ratios (Sr/Ca) using Thermal Ionization Mass Spectrometry and Inductively Coupled Plasma Mass Spectrometry. Although the total variation in δ44/40Ca (∼0.3‰) in the studied species is on the same order as the external reproducibility, the data set reveals some apparent trends that are controlled by more than one environmental parameter. There is a well-defined inverse linear relationship between δ44/40Ca and Sr/Ca in all experiments, suggesting similar controls on these proxies in foraminiferal calcite independent of species. Analogous to recent results from inorganically precipitated calcite, we suggest that Ca isotope fractionation and Sr partitioning in planktic foraminifera are mainly controlled by precipitation kinetics. This postulation provides us with a unique tool to calculate precipitation rates and draws support from the observation that Sr/Ca ratios are positively correlated with average growth rates. At 25 °C water temperature, precipitation rates in G. siphonifera and G. ruber are calculated to be on the order of 2000 and 3000 μmol/m2/h, respectively. The lower δ44/40Ca observed at ⩾29 °C in both species is consistent with increased precipitation rates at high water temperatures. Salinity response of δ44/40Ca (and Sr/Ca) in G. siphonifera implies that this species has the highest precipitation rates at the salinity of its natural habitat, whereas increasing salinities appear to trigger higher precipitation rates in G. ruber. Isotope effects that cannot be explained by precipitation rate in planktic foraminifera can be explained by a biological control, related to a vacuolar pathway for supply of ions during biomineralization and a pH regulation mechanism in these vacuoles. In case of an additional pathway via cross-membrane transport, supplying light Ca for calcification, the δ44/40Ca of the reservoir is constrained as −0.2‰ relative to seawater. Using a Rayleigh distillation model, we calculate that calcification occurs in a semi-open system, where less than half of the Ca supplied by vacuolization is utilized for calcite precipitation. Our findings are relevant for interpreting paleo-proxy data on δ44/40Ca and Sr/Ca in foraminifera as well as understanding their biomineralization processe

Constraining the oceanic barium cycle with stable barium isotopes

Highlights • We present a Ba isotope data set of seawater, river waters and biogenic particles. • Ba isotope signatures of upper ocean waters are heavier than river and deep waters. • Adsorption of lighter Ba isotopes on biogenic particles induces the fractionation. • Ba isotopes trace land–sea interactions and ocean mixing processes. • Decoupling of Ba from major nutrients confirms Ba to be a biointermediate element. Abstract The distribution of barium (Ba) concentrations in seawater resembles that of nutrients and Ba has been widely used as a proxy of paleoproductivity. However, the exact mechanisms controlling the nutrient-like behavior, and thus the fundamentals of Ba chemistry in the ocean, have not been fully resolved. Here we present a set of full water column dissolved Ba (DBa) isotope (δ137BaDBa) profiles from the South China Sea and the East China Sea that receives large freshwater inputs from the Changjiang (Yangtze River). We find pronounced and systematic horizontal and depth dependent δ137BaDBa gradients. Beyond the river influence characterized by generally light signatures (0.0 to +0.3‰+0.3‰), the δ137BaDBa values in the upper water column are significantly higher (+0.9‰+0.9‰) than those in the deep waters (+0.5‰+0.5‰). Moreover, δ137BaDBa signatures are essentially constant in the entire upper 100 m, in which dissolved silicon isotopes are fractionated during diatom growth resulting in the heaviest isotopic compositions in the very surface waters. Combined with the decoupling of DBa concentrations and δ137BaDBa from the concentrations of nitrate and phosphate this implies that the apparent nutrient-like fractionation of Ba isotopes in seawater is primarily induced by preferential adsorption of the lighter isotopes onto biogenic particles rather than by biological utilization. The subsurface δ137BaDBa distribution is dominated by water mass mixing. The application of stable Ba isotopes as a proxy for nutrient cycling should therefore be considered with caution and both biological and physical processes need to be considered. Clearly, however, Ba isotopes show great potential as a new tracer for land–sea interactions and ocean mixing processes

South Asian monsoon history over the past 60 kyr recorded by radiogenic isotopes and clay mineral assemblages in the Andaman Sea

The Late Quaternary variability of the South Asian (or Indian) monsoon has been linked with glacial‐interglacial and millennial scale climatic changes but past rainfall intensity in the river catchments draining into the Andaman Sea remains poorly constrained. Here we use radiogenic Sr, Nd, and Pb isotope compositions of the detrital clay‐size fraction and clay mineral assemblages obtained from sediment core NGHP Site 17 in the Andaman Sea to reconstruct the variability of the South Asian monsoon during the past 60 kyr. Over this time interval εNd values changed little, generally oscillating between −7.3 and −5.3 and the Pb isotope signatures are essentially invariable, which is in contrast to a record located further northeast in the Andaman Sea. This indicates that the source of the detrital clays did not change significantly during the last glacial and deglaciation suggesting the monsoon was spatially stable. The most likely source region is the Irrawaddy river catchment including the Indo‐Burman Ranges with a possible minor contribution from the Andaman Islands. High smectite/(illite + chlorite) ratios (up to 14), as well as low 87Sr/86Sr ratios (0.711) for the Holocene period indicate enhanced chemical weathering and a stronger South Asian monsoon compared to marine oxygen isotope stages 2 and 3. Short, smectite‐poor intervals exhibit markedly radiogenic Sr isotope compositions and document weakening of the South Asian monsoon, which may have been linked to short‐term northern Atlantic climate variability on millennial time scales