The microbial biodegradation of xenobiotic compounds in soil and ground water is constrained by the laws of thermodynamics. Bioremediation is being investigated in a rhizosphere environment in which higher plants provide carbon and energy to sustain the microbial population. Toluene, phenol, trichloroethylene and trichloroethane have been fed in separate experiments to a pilot scale system with alfalfa growing in sandy soil containing less than 10% of silt. It is well known that microbial populations are numerous in the root zone of healthy vegetation. Root exudates can stimulate aerobic microbial biodegradation of compounds which by themselves support growth poorly or not at all. Polynuclear aromatic compounds such as phenanthrene, anthracene, and pyrene, which are not very soluble in water, and chlorinated aliphatic hydrocarbons such as trichloroethylene are examples of compounds that can be biodegraded in the rhizosphere when root exudates are present to enhance and sustain microbial activity. Solar driven transport processes such as water and solute movements due to evapotranspiration increase the likelihood that the contaminants will come into contact with the microorganisms and be degraded. The thermodynamic and bioenergetic aspects of transport and biodegradation in the rhizosphere are examined through a review of the literature and the analysis of experimental data collected in the pilot scale system.