The work supported Environmental Monitoring Systems Laboratory, U.S. Environmental Protection Agency in its effort to monitor the hazardous composition, if any, of fly ash from various types of incinerators using different types of combustible materials. The analytical determination of dioxins in environmental samples in the parts per billion, trillion, and quadrillion levels requires meticulous, time-consuming, and very complex sample preparation and analysis procedures. A major part of the task was devoted to the evaluation of various extraction techniques of fly ash and cleanup of sample extracts by column chromatography. Several chromatographic media and eluting solvents were investigated. Each step in the sample preparation was evaluated by using 14C-radiolabeled 2,3,7,8-tetrachlorodibenzo-p-dioxin and octochlorodibenzo-p-dioxin as a tracer. Radiolabeled dioxin allows the analyst to stop and evaluate each step of the procedure, each extract, and each column eluate fraction by liquid scintillation computing. To validate the radiometric assay, dioxin was confirmed by gas chromatography/mass spectrometry. The report contains recovery data of spiked 2,3,7,8-tetrachlorodibenzo-p-dioxin and octochlorodibenzo-p-dioxin in carbon-free fly ash and fly ash containing from 0.1% to 10% carbon.