We investigated the effect of CO 2 and primary production on the carbon isotopic fractionation of alkenones and particulate organic matter (POC) during a natural phytoplankton bloom dominated by the coccolithophore Emiliania huxleyi. In nine semi-closed mesocosms ($11 m 3 each), three different CO 2 partial pressures (pCO 2 ) in triplicate represented glacial ($180 ppmv CO 2 ), present ($380 ppmv CO 2 ), and year 2100 ($710 ppmv CO 2 ) CO 2 conditions. The largest shift in alkenone isotopic composition (4-5&) occurred during the exponential growth phase, regardless of the CO 2 concentration in the respective treatment. Despite the difference of $500 ppmv, the influence of pCO 2 on isotopic fractionation was marginal (1-2&). During the stationary phase, E. huxleyi continued to produce alkenones, accumulating cellular concentrations almost four times higher than those of exponentially dividing cells. Our isotope data indicate that, while alkenone production was maintained, the interaction of carbon source and cellular uptake dynamics by E. huxleyi reached a steady state. During stationary phase, we further observed a remarkable increase in the difference between d 13 C of bulk organic matter and of alkenones spanning 7-12&. We suggest that this phenomenon is caused mainly by a combination of extracellular release of 13 C-enriched polysaccharides and subsequent particle aggregation induced by the production of transparent exopolymer particles (TEP).