C-13 discrimination patterns in oceanic phytoplankton: likely influence of CO2 concentrating mechanisms, and implications for palaeoreconstructions

The isotopic composition of organic carbon buried in marine sediments is an appealing proxy for palaeo CO2 concentrations due to the well-documented effect of CO2 concentrations on carbon fractionation by phytoplankton. However, a number of factors, in addition to CO2 concentrations, influence this fractionation. Included among these factors are cell geometry, in particular surface/volume ratios, growth rate, and the presence of CO2 concentrating mechanisms. Other potentially confounding factors are calcification, diagenesis, and the nature of the growth-rate-limiting factor, e.g. light vs nutrients. Because of these confounding factors, palaeoreconstructions based on the isotopic composition of organic carbon (delta(13)C) will almost certainly have to be based on the isotopic signatures of organic compounds that can be associated with a single species, or group of physiologically similar species. Long-chain alkenones produced by certain species of coccolithophores may provide a suitable diagnostic marker. By combining the delta(13)C of the alkenone carbon with the delta(13)C of coccolith carbon and the Sr/Ca ratio of the coccoliths, it is possible to calculate the extent of carbon fractionation (epsilon(p)) and estimate growth rates. However, active transport of inorganic carbon tends to make epsilon(p) insensitive to CO2 concentrations when the ratio of growth rate to CO2 concentration exceeds similar to 0.285/r kg mol(-1) d(-1), where r is the effective spherical radius of the cell in microns. Palaeo CO2 concentrations calculated from alkenone and coccolith delta(13)C data capture the gross features of CO2 concentrations in the Vostok ice core, but explain only 30-35% of the variance in the latter. The absence of a higher correlation may in part reflect the impact of active transport, particularly during glacial times. The impact of active transport may have been less severe prior to the Pleistocene, since CO2 concentrations are believed to have been higher than present-day values during most of Phanerozoic time.