Assessment of risk and remediation strategies at contaminated sites requires that both the amounts of contaminants present and their potential for release from materials and soils be evaluated. The release, or dissolution, of polycyclic aromatic hydrocarbons (PAHs) from contaminated materials to water was therefore investigated. To facilitate investigations of PAH dissolution from physically disparate materials such as solid coal tars, creosote, oil, and spent oxide, an experimental method for measuring dissolved PAHs was developed employing dialysis tubing in a batch-type system. This was validated and compared to aqueous-phase PAH concentrations measured using more traditional techniques and also predicted using Raoult's law. The experimental procedure was successfully used to determine ‘near equilibrium' aqueous concentrations of PAHs, but it could only be used to determine relative rates of approach to equilibrium as the dialysis tubing effected the rate constants. It was found that the contaminant materials influenced dissolution, in particular the close to equilibrium concentrations. For materials chemically similar to PAHs, such as nonaqueous-phase liquids (NAPLs), the concentrations could be predicted using Raoult's law. For materials that were chemically dissimilar to PAHs, such as spent oxide, release was more thermodynamically favorable than for NAPLs.