In the shallow terrestrial subsurface, bioavailability often controls biodegradation rates of various hydrophobic organic pollutants, such as hydrocarbons. Microorganism‐mediated depletion of n‐alkanes and polycyclic aromatic hydrocarbons (PAHs) in the vadose zone proceeds with distinctively different rates and kinetics. The observed disparity in biodegradation dynamics between these two classes of hydrocarbons are described here in terms of the Best equation, which allows for a complex process of hydrocarbon contaminant depletion to be explained in terms of the physically relevant processes. This equation combines terms describing contributions of two key elements of hydrocarbon biodegradation—the intrinsic catabolic activity of microorganisms and the mass transfer process delivering substrate to active microorganisms. If substrate supply is slow, biodegradation process is availability‐limited because microorganisms consume the substrate faster than it can be delivered. Conversely, when the mass transfer of substrate is faster than the microbial consumption, biodegradation rate tends to be controlled by metabolic kinetics.
The evaluation conducted in this study ascertains that the critical factor limiting the rate and extent of PAH biodegradation is the mass transfer rather than the intrinsic microbial activity that appears to govern the rate of n‐alkane biodegradation. The specifics of mass transfer are determined by the magnitude of the substrate–soil interactions. Whereas sorption of n‐alkanes is controlled by weak hydrophobic and van der Waals forces, PAHs tend to bind to the soil matrix by much stronger electron‐donor–acceptor interactions. Stronger interactions between aromatic compounds and soil components translate into the higher activation energies for desorption of PAHs and therefore a slower mass transfer process. This aspect of the substrate–soil interaction explains a more prominent effect of mass transfer limitation on biodegradation dynamics of PAHs compared to that of the corresponding n‐alkanes.