Description: Calcium and magnesium concentrations in seawater have varied over geological time scales. On short time scales, variations in the major ion composition of seawater influences coccolithophorid physiology and the chemistry of biogenically produced coccoliths. Validation of those changes via controlled laboratory experiments is a crucial step in applying coccolithophorid based paleoproxies for the reconstruction of past environmental conditions. Therefore, we examined the response of two species of coccolithophores, Emiliania huxleyi and Coccolithus braarudii, to changes in the seawater Mg/Ca ratio (≈0.5 to 10 mol/mol) by either manipulating the magnesium or calcium concentration under controlled laboratory conditions. Concurrently, seawater Sr/Ca ratios were also modified (≈2 to 40 mmol/mol), while keeping salinity constant at 35. The physiological response was monitored by measurements of the cell growth rate as well as the production rates of particulate inorganic and organic carbon, and chlorophyll a. Additionally, coccolithophorid calcite was analyzed for its elemental composition (Sr/Ca and Mg/Ca) as well as isotope fractionation of calcium and magnesium (Δ44/40Ca and Δ26/24Mg). Our results reveal that physiological rates were substantially influenced by changes in seawater calcium rather than magnesium concentration within the range estimated to have occurred over the past 250 million years when coccolithophores appear in the fossil record. All physiological rates of E. huxleyi decreased at a calcium concentration above 25 mmol L−1, whereas C. braarudii displayed a higher tolerance to increased seawater calcium concentrations. Partition coefficient of Sr was calculated as 0.36 ± 0.04 (±2σ) independent of species. Partition coefficient of Mg2+ increased with increasing seawater Ca2+ concentrations in both coccolithophore species. Calcium isotope fractionation was constant at 1.1 ± 0.1‰ (±2σ) and not altered by changes in seawater Mg/Ca ratio. There is a well-defined inverse linear relationship between calcium isotope fractionation and partition coefficient of Sr2+ in all experiments, suggesting similar controls on both proxies in the investigated species. Magnesium isotope ratios were relatively stable for seawater Mg/Ca ratios ranging from 1 to 5, with a higher degree of fractionation in Emiliania huxleyi (by ≈0.2‰ in Δ26/24Mg). Although Mg/Ca ratios in the calcite of coccolithophores and foraminifera are similar, the former have considerably higher Δ26/24Mg (by 〉+3‰), presumably due to differences in calcification mechanisms between the two taxa. These observations suggest, a physiological control over magnesium elemental and isotopic fractionation during the process of calcification in coccolithophores.

Description: Coccolithophore calcite refers to the plates of calcium carbonate (CaCO3) produced by the calcifying phytoplankton, coccolithophores. The empirical study of the elemental composition has a great potential in the development of paleoproxies. However, the difficulties to separate coccolithophore carbonates from organic phases hamper the investigation of coccoliths magnesium to calcium ratios (Mg/Ca) in biogeochemical studies. Magnesium (Mg) is found in organic molecules in the cells at concentrations up to 400 times higher than in inorganically precipitated calcite in present-day seawater. The aim of this study was to optimize a reliable procedure for organic Mg removal from coccolithophore samples to ensure reproducibility in measurements of inorganic Mg in calcite. Two baseline methods comprising organic matter oxidations with (1) bleach and (2) hydrogen peroxide (H2O2) were tested on synthetic pellets, prepared by mixing reagent grade CaCO3 with organic matter from the non-calcifying marine algae Chlorella autotrophica and measured with an ICP-AES (inductively coupled plasma-atomic emission spectrometer). Our results show that treatments with a reductive solution [using hydroxylamine-hydrochloride (NH2OH·HCl + NH4OH)] followed by three consecutive oxidations (using H2O2) yielded the best cleaning efficiencies, removing 〉99% of organic Mg in 24 h. P/Ca and Fe/Ca were used as indicators for organic contamination in the treated material. The optimized protocol was tested in dried coccolithophore pellets from batch cultures of Emiliania huxleyi, Calcidiscus leptoporus and Gephyrocapsa oceanica. Mg/Ca of treated coccolithophores were 0.151 ± 0.018, 0.220 ± 0.040, and 0.064 ± 0.023 mmol/mol, respectively. Comparison with Mg/Ca literature coccolith values, suggests a tight dependence on modern seawater Mg/Ca, which changes as a consequence of different seawater origins (〈10%). The reliable determination of Mg/Ca and Sr/Ca, and the low levels of organic contamination (Fe/Ca and P/Ca) make this protocol applicable to field and laboratory studies of trace elemental composition in coccolithophore calcite