The chemical interactions of hydrophobic organic contaminants with soils and sediments may result in strong binding and slow subsequent release rates that significantly affect remediation rates and endpoints. In order to illustrate the recalcitrance of chemical to degradation on sites, a sorption mechanism of intraparticle sequestration was postulated to operate on chemical remediation sites. Pseudo-first order sequestration kinetics is used in the study with the hypothesis that sequestration is an irreversibly surface-mediated process. A mathematical model based on mass balance equations was developed to describe the fate of chemical degradation in soil/water microcosm systems. In the model, diffusion was represented by Fick's second law, local sorption-desorption by a linear isotherm, irreversible sequestration by a pseudo-first order kinetics and biodegradation by Monod kinetics. Solutions were obtained to provide estimates of chemical concentrations. The mathematical model was applied to a benzene biodegradation batch test and simulated model responses correlated well compared to measurements of biodegradation of benzene in the batch soil/water microcosm system. A sensitivity analysis was performed to assess the effects of several parameters on model behavior. Overall chemical removal rate decreased and sequestration increased quickly with an increase in the sorption partition coefficient. When soil particle radius, a, was greater than 1 mm, an increase in radius produced a significant decrease in overall chemical removal rate as well as an increase in sequestration. However, when soil particle radius was less than 0.1 mm, an increase in radius resulted in small changes in the removal rate and sequestration. As pseudo-first order sequestration rate increased, both chemical removal rate and sequestration increased slightly. Model simulation results showed that desorption resistance played an important role in the bioavailability of organic chemicals in porous media. Complete biostabilization of chemicals on remediation sites can be achieved when the concentration of the reversibly sorbed chemical reduces to zero (i.e., undetectable), with a certain amount of irreversibly sequestrated chemical left inside the soil particle solid phase. ?? 2006 Springer Science + Business Media B.V.