The environmental impact of many postulated CANDU (Canada Deuterium Uranium) reactor accidents depends on the behaviour of iodine isotopes. In recent years a substantial portion of Canadian iodine research has focused on experiments conducted in the intermediatescale Radioiodine Test Facility (RFT) at Whiteshell Laboratories. Because of the very low concentrations relevant to reactor accidents, much of the analysis of iodine behaviour has required the high sensitivity of a radiochemical methodology. Very low gas-phase iodine concentrations (<10–10 mol/dm3) are routinely determined, up to several times an hour, using an automated airborne iodine sampler whereas various chemical forms are distinguished using selective adsorbents. Useful information regarding the chemical speciation of iodine in the aqueous phase is obtained using solvent extraction. This paper describes the radiochemical techniques used in RTF experiments, with examples of the results thereby obtained.