Low stable carbon isotope fractionation by coccolithophore RubisCO

The 13C/12C ratio of carbon compounds is used to identify sources and sinks in the global carbon cycle. However, the relatively enriched 13C content observed for marine organic carbon remains enigmatic. The majority of oceanic carbon is fixed by algae and cyanobacteria via the Calvin–Benson–Bassham cycle, yet isotopic discrimination by the CO2 fixation enzyme, RubisCO (ribulose 1,5-bisphosphate carboxylase/oxygenase), has only been measured for a single marine cyanobacterium. Different forms of RubisCO occur in different phytoplankton species (overall amino acid identity varying by as much as ∼75%) and thus may vary in the degree to which they fractionate carbon. Here we measured isotope discrimination by RubisCO from the coccolithophore Emiliania huxleyi, a cosmopolitan species used as a marine algal model.E. huxleyi RubisCO discriminated substantially less (ε = 11.1‰) against 13CO2 than other RubisCO enzymes (18–29‰), despite having Michaelis–Menten kinetic parameters (KCO2KCO2 = 72 μM; Vmax = 0.66 μmol min−1 mg−1 protein) similar to those measured for RubisCO enzymes from different organisms. If widespread, decreased isotope discrimination of 13C by phytoplankton RubisCO may be a major factor influencing the enriched 13C content of marine organic carbon. This finding emphasizes the necessity of (a) determining ε values for RubisCOs of other marine phytoplankton and (b) re-evaluation of δ13C values from physiological, environmental, and geological studies.