Modeling and interpreting bioavailability of organic contaminant mixtures in subsurface environments

Bioavailability often controls the fate of organic contaminants in surface and subsurface aquatic environments. Bioavailability can be limited by sorption, mass transfer, and intrinsic biodegradation potential and can be further altered by the presence of other compounds. This paper reviews current perspectives on the processes influencing subsurface contaminant bioavailability, how these processes are modeled, and how the relative role of the various processes can be assessed through bioavailability indices. Although these processes are increasingly well understood, the use of sophisticated models and indices often are precluded by an inability to estimate the many parameters that are associated with complex models. Nonetheless, the proper representation of sorption, mass transfer, biodegradation, and co-solute effects can be critical in predicting bio-attenuation. The influence of these processes on contaminant fate is illustrated with numerical simulations for the simultaneous degradation of toluene (growth substrate) and trichloroethylene (nongrowth cometabolite) in hypothetical, aerobic, solid-water systems. The results show how the relative impacts on contaminant fate of the model's various component processes depends upon system conditions, including co-solute concentrations. Slow biodegradation rates increase the inhibition effects of a cometabolite and suppress the rate enhancement effects of a growth substrate. Irrespective of co-solute effects, contaminant fate is less sensitive to biodegradation processes in systems with strong sorption and slow desorption rates. Bioavailability indices can be used to relate these findings and to help identify appropriate modeling simplifications. In general, however, there remains a need to redefine such indices in order that bioavailability concepts can be better incorporated into site characterization, remediation design, and regulatory oversight.