Supercritical fluid extraction (SFE) conditions using pure CO2 from 40 to 150 degrees C were developed that allow sequential extraction of PCBs associated with "rapidly desorbing, moderately, slowly, and very slowly desorbing" sites on historically contaminated sediments and soil. Five samples with individual PCB concentrations ranging from a few to similar to 100 000 ng/g all showed PCBs associated with each type of site, but the fraction of PCBs associated with rapidly desorbing or slowly desorbing sites varied greatly from sample to sample. Although some small differences in the desorption behavior of individual PCBs was observed from a particular sample, the differences among samples were much greater demonstrating that the sample matrix and not the PCB identity was most important in controlling desorption behavior. When all five samples were compared, simple considerations concerning sample particle size, water content, organic content, and PCB concentration could not predict desorption behavior, demonstrating that PCB desorption processes depend on multiple sample characteristics. Comparison of the quantity vs distribution of PCBs on the fast to very slow sites indicates that association with slowly desorbing sites is not limited by the number of sites, but rather that PCBs on historically contaminated samples tend to distribute among the various sites available.