In order to determine whether bioavailability limits the biodegradability of petroleum hydrocarbons in aged soils, both the biodegradation and abiotic desorption rates of PAHs and n-alkanes were measured at various time points in six different aged soils undergoing slurry bioremediation treatment. Alkane biodegradation rates were always much greater than the respective desorption rates, indicating that these saturated hydrocarbons apparently do not need to be dissolved into the aqueous phase prior to metabolism by soil microorganisms. The biodegradation of PAHs was generally not mass-transfer rate limited during the initial phase, while it often became so at the end of the treatment period when biodegradation rates equaled abiotic desorption rates. However, in all cases where PAH biodegradation was not observed or PAH removal temporarily stalled, bioavailability limitations were not deemed responsible for this recalcitrance since these PAHs desorbed rapidly from the soil into the aqueous phase. Consequently, aged PAHs that are often thought to be recalcitrant due to bioavailability limitations may not be so and therefore may pose a greater risk to environmental receptors than previously thought.

In an effort to determine whether bioavailability limitations are responsible for the slow or incomplete hydrocarbon biodegradation in aged soils, both the rate of desorption (rdes) and biodegradation (rbio) was measured for n-alkanes and polynuclear aromatic hydrocarbons (PAHs) at different times during the slurry biotreatment of six different soils. While all n-alkanes were biodegraded to various degrees depending on their respective carbon number and the soil organic matter content, none of them were desorbed to a significant extent, indicating that these saturated hydrocarbons do not need to be transferred from the soil particles into the aqueous phase in order to be metabolized by microorganisms. Most two- and three-ring PAHs biodegraded as fast as they were desorbed (rbio = rdes); that is, desorption rates controlled biodegradation rates. By contrast, the biodegradation kinetics of four-, five-, and six-ring PAHs was limited by microbial factors during the initial phase (rbio < rdes) while becoming mass-transfer rate limited during the final phase of bioremediation treatment (rbio = rdes). Whenever PAH biodegradation stalled or did not occur at all (rbio = 0), it was never due to bioavailability limitations (rdes >> 0) but was more likely caused by microbial factors. such as the absence of specific PAH degraders or cometabolic substrates. Consequently, PAHs that are found to be microbially recalcitrant in aged soils may not be so because of limited bioavailability and thus could pose a greater risk to the environment than previously thought.

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