A quantitative interpretation of recent experimental results on stable carbon isotope fractionation by aerobic CH4-oxidizing bacteria

A quantitative model of recent laboratory experiments on carbon isotope fractionation by methane-oxidizing bacteria is proposed. The simulated experimental apparatus consists of a bacterial culture with a constant liquid volume, a gas headspace and a methane bubbling mechanism. The relative effects of bacterial growth and transport phenomena that do not depend on cell density are clarified. In all calculations, gas-liquid mass transfer is defined by unconstrained model parameters. Limited mass transfer from the culture into the headspace, rather than the incomplete dissolution of substrate-rich bubbles, seems to have caused an apparent decrease in the measured carbon isotope fractionation. The experimenters attributed this fractionation shift to a growing imbalance among kinetic rates as methane consumption by bacteria increases. Model predictions support this interpretation but also show that changes in carbon isotope fractionation in the course of the experiments cannot be unambiguously correlated with bacterial cell density unless gas-liquid mass transfer parameters are calibrated. Simulations of other laboratory experiments indicate that a reported change in carbon isotope fractionation could, in part at least, be the result of experimental conditions rather than the emergence of a different methane oxidation pathway postulated by the experimenters. A careful evaluation of mass transfer from the liquid culture into the gas headspace is warranted in this type of experiments since isotope fractionation factors are likely to be used in a wide variety of environmental contexts.