CH3Cl emissions by freshly harvested tubers of 61 potato cultivars ranged from less than 4 to 650 ng g−1 f. wt d−1. In experiments with Anna, the cultivar displaying the highest release rate, maximum emission of CH3Cl occurred at 20°C but the rate diminished after 48 h, a decrease due in part to inhibition of CH3Cl release by the accumulation of CH3Cl in the headspace. In 1995 and 1996, CH3Cl emission by tubers was first detectable 6 wk before the normal harvest date. If tubers were stored at 20°C immediately following harvest, release attained a maximum of 350 ng g−1 f. wt d−1 about 4 d after harvest, falling to less than 4 ng g−1 f. wt d−1 within 3 wk of harvest. On storage at 6°C post-harvest, maximum release of CH3Cl (c. 600 ng g−1) was delayed until 5 wk after harvest and release fell below 4 ng g−1 f. wt d−1 after 200 d. Release of CH3Cl was not significantly affected by cutting or bruising tuber tissue, and CH3Cl biosynthesis occurred in both core and superficial tissues of the tuber. The S-methyl group of either L- or D-methionine acted as a precursor of CH3Cl in sliced tubers, but the methylating system was specific for Cl−. An isotope dilution technique using C2H3Cl demonstrated that the amount of CH3Cl metabolized by the intact tuber was approximately 36% of the net release. However, investigations with 14CH3Cl showed that only a small proportion (7%) of the CH3Cl metabolized was fixed in involatile form in the tuber. In both skin and core tissues, fixed 14C was located primarily (80%) in the fraction soluble in phosphate buffer, but the specific activity of skin tissue was about twice that of core tissue. Autoradiography demonstrated that 14C fixation in the tuber was greatest within the lenticels, possibly indicating a microflora adapted to use the locally high concentrations of CH3Cl. Significant 14C fixation was also associated with the periderm but was not attributable to labelling of the O-methyl groups of the phenolic components of suberin. Within the core of the tuber, 14C fixation was located primarily in the phloem, pith and medullary rays.