Trace element ratios of Globigerina bulloides from the southwest Pacific Ocean

We present Mg/Ca data for Globigerina bulloides from 10 core top sites in the southwest Pacific Ocean analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Mg/Ca values in G. bulloides correlate with observed ocean temperatures (7°C-19°C), and when combined with previously published data, an integrated Mg/Ca-temperature calibration for 7°C-31°C is derived where Mg/Ca (mmol/mol) = 0.955 * e**(0.068 * T) (r**2 = 0.95). Significant variability of Mg/Ca values (20%-30%) was found for the four visible chambers of G. bulloides, with the final chamber consistently recording the lowest Mg/Ca and is interpreted, in part, to reflect changes in the depth habitat with ontogeny. Incipient and variable dissolution of the thin and fragile final chamber, and outermost layer concomitantly added to all chambers, caused by different cleaning techniques prior to solution-based ICPMS analyses, may explain the minor differences in previously published Mg/Ca-temperature calibrations for this species. If the lower Mg/Ca of the final chamber reflects changes in depth habitat, then LA-ICPMS of the penultimate (or older) chambers will most sensitively record past changes in near-surface ocean temperatures. Mean size-normalized G. bulloides test weights correlate negatively with ocean temperature (T = 31.8 * e**(-30.5*wtN); r**2 = 0.90), suggesting that in the southwest Pacific Ocean, temperature is a prominent control on shell weight in addition to carbonate ion levels.

Element ratio (Sr/Ca, Ba/Ca, B/Ca, and Mg/Ca) profiles throughout the larval life stage of Mytilus edulis, 2011

Rising anthropogenic CO2 in the surface ocean has raised serious concerns for the ability of calcifying organisms to secrete their shells and skeletons. Previous mollusc carbonate perturbation experiments report deleterious effects at lowered pH (7.8-7.4 pH units), including reduced shell length and thickness and deformed shell morphology. It is not clear whether the reduced shell growth results from a decrease in calcification rate due to lowered aragonite saturation or from an indirect effect on mollusc metabolism. We take a novel approach to discerning between these two processes by examining the impact of lowered pH on the 'vital-effect' associated with element ratios. Reported herein are the first element ratio (Sr/Ca, Ba/Ca, B/Ca, Mg/Ca and Mn/Ca) profiles throughout the larval life stage of Mytilus edulis. Element ratio data for individuals reared in ambient conditions provide new insights into biomineralization during larval development. Sr/Ca ratios are consistent with Sr incorporation in the mineral phase. Mg and Mn are likely hosted in an organic phase. The Ba partition coefficient of early larval shells is one of the highest reported in biogenic aragonite. The reason for the high Ba concentrations is unknown, but may reflect the assimilation of Ba from food and/or Ba concentration in an organic or amorphous carbonate phase. There is no observable difference in the way the studied elements are incorporated into the shells of individuals reared in ambient and lowered pH conditions. The reduced growth rate at lower pH may be a consequence of a disruption to the larval mollusc metabolism.

Elevated CO2 levels do not affect the shell structure of the bivalve Arctica islandica from the western Baltic

Shells of the bivalve Arctica islandica are used to reconstruct paleo-environmental conditions (e.g. temperature) via biogeochemical proxies, i.e. biogenic components that are related closely to environmental parameters at the time of shell formation. Several studies have shown that proxies like element and isotope-ratios can be affected by shell growth and microstructure. Thus it is essential to evaluate the impact of changing environmental parameters such as high pCO2 and consequent changes in carbonate chemistry on shell properties to validate these biogeochemical proxies for a wider range of environmental conditions. Growth experiments with Arctica islandica from the Western Baltic Sea kept under different pCO2 levels (from 380 to 1120 µatm) indicate no affect of elevated pCO2 on shell growth or crystal microstructure, indicating that A. islandica shows an adaptation to a wider range of pCO2 levels than reported for other species. Accordingly, proxy information derived from A. islandica shells of this region contains no pCO2 related bias.

Shell preservation of Limacina inflata in surface sediments of the Central and South Atlantic

Over 300 surface sediment samples from the Central and South Atlantic Ocean and the Caribbean Sea were investigated for the preservation state of the aragonitic test of Limacina inflata. Results are displayed in spatial distribution maps and are plotted against cross-sections of vertical water mass configurations, illustrating the relationship between preservation state, saturation state of the overlying waters, and overall water mass distribution. The microscopic investigation of L. inflata (adults) yielded the Limacina dissolution index (LDX), and revealed three regional dissolution patterns. In the western Atlantic Ocean, sedimentary preservation states correspond to saturation states in the overlying waters. Poor preservation is found within intermediate water masses of southern origin (i.e. Antarctic intermediate water (AAIW), upper circumpolar water (UCDW)), which are distinctly aragonite-corrosive, whereas good preservation is observed within the surface waters above and within the upper North Atlantic deep water (UNADW) beneath the AAIW. In the eastern Atlantic Ocean, in particular along the African continental margin, the LDX fails in most cases (i.e. less than 10 tests of L. inflata per sample were found). This is most probably due to extensive "metabolic" aragonite dissolution at the sediment-water interface combined with a reduced abundance of L. inflata in the surface waters. In the Caribbean Sea, a more complex preservation pattern is observed because of the interaction between different water masses, which invade the Caribbean basins through several channels, and varying input of bank-derived fine aragonite and magnesian calcite material. The solubility of aragonite increases with increasing pressure, but aragonite dissolution in the sediments does not simply increase with water depth. Worse preservation is found in intermediate water depths following an S-shaped curve. As a result, two aragonite lysoclines are observed, one above the other. In four depth transects, we show that the western Atlantic and Caribbean LDX records resemble surficial calcium carbonate data and delta13C and carbonate ion concentration profiles in the water column. Moreover, preservation of L. inflata within AAIW and UCDW improves significantly to the north, whereas carbonate corrosiveness diminishes due to increased mixing of AAIW and UNADW. The close relationship between LDX values and aragonite contents in the sediments shows much promise for the quantification of the aragonite loss under the influence of different water masses. LDX failure and uncertainties may be attributed to (1) aragonite dissolution due to bottom water corrosiveness, (2) aragonite dissolution due to additional CO2 release into the bottom water by the degradation of organic matter based on an enhanced supply of organic matter into the sediment, (3) variations in the distribution of L. inflata and hence a lack of supply into the sediment, (4) dilution of the sediments and hence a lack of tests of L. inflata, or (5) redeposition of sediment particles.