Isotope fractionation during Ca exchange on clay minerals in a marine environment

In order to interpret marine porewater profiles it is mandatory to understand the behavior of calcium (Ca) and its isotopes during cation exchange in marine sediments. It has been proposed that the exchange of adsorbed Ca2+ for ammonium, which is a product of organic matter decomposition, results in the releases of light Ca from clay minerals into the porewater (Teichert et al., 2009). In order to investigate the effect of ammonium on Ca isotope fractionation, experiments with clay mineral separates (illites, montmorillonite, kaolinite) and natural marine sediments from the North Atlantic (Integrated Ocean Drilling Project Site U1306A) in artificial seawater were carried out at different temperatures (4, 14, 21 °C) and ammonium concentrations (100, 140, 180 mM).The results of the adsorption experiments, carried out in artificial seawater, show that during adsorption of Ca2+ the light Ca isotopes are favored over the heavier Ca isotopes. This effect is most prominent for the illite samples (1000lnα = −0.82 to −1.15) and kaolinite sample (1000lnα = −1.23 to −2.76), whereas montmorillonite and the natural marine sediments show smaller degrees of fractionation from the fluid in the range of −0.46 to +0.06‰. Determination of the desorbed Ca2+ is based on the adsorbed Ca2+ left on the exchanger and reveals that the desorbed Ca2+ has a significantly different isotopic signature from the surrounding fluid. In general, the degree of Ca isotope fractionation is dependent on the ammonium concentration, and does not show significant influence of temperature. Modeling the Ca2+ desorption induced by ammonium adsorption demonstrates, that according to the prevailing mineralogy and porewater:sediment ratio, desorbed Ca2+ has the potential to shift the porewater isotopy by up to −2.5‰ and needs to be considered when interpreting Ca isotope porewater profiles.