Isotopes diffusion-induced fractionation

Some aspects of this phenomenon are still controversial, because diffusion-induced isotopic fractionation effects may be erroneously ascribed to differential reaction kinetics (see section 11.6.2), and vice versa. 

Basically, whenever isotopic exchanges occur between different phases (i.e., heterogeneous equilibria), isotopic fractionations are more appropriately described in terms of differential reaction rates. Simple diffusion laws are nevertheless appropriate in discussions of compositional gradients within a single phase— induced, for instance, by vacancy migration mechanisms, such as those treated in section 4.10—or whenever the isotopic exchange process does not affect the extrinsic stability of the phase. 

The same physical principles are utilized to develop isotopic models which better account for the transport of air masses at a regional scale, such as done by Fisher (1992) using a regional stable isotope model coupled to a zonally averaged global model. Other authors such as Eriksson (1965) and more recently Hendricks et al. (2000) considered the transport of water both by advective and eddy diffusive processes, the latter inducing less fractionation. 

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