The adsorption isotherms for naphthalene, phenanthrene, hexachlorobenzene, and pentachlorophenol on soil were determined in the presence of liquid and supercritical carbon dioxide. The adsorption isotherms for naphthalene, phenanthrene, and hexachlorobenzene are linear, whereas for pentachlorophenol, a slight deviation from linearity was observed. The heats of adsorption of naphthalene, phenanthrene, hexachlorobenzene, and pentachlorophenol on soil at 308 K were found to be in the range of 1–5 kcal/mol, indicating physical adsorption. The desorptive behavior of these organics from soil using supercritical carbon dioxide was also investigated, and local equilibrium theory was found to predict the desorption profiles fairly accurately. © 1993, American Chemical Society. All rights reserved.