The fluoride (F) distribution in enamel lining the occlusal fissures of human molars and premolars is difficult to investigate by normal microsampling techniques, yet this information is of importance as fissures are particularly susceptible to caries. We have used the proton probe to map the distribution of F and Ca in sections of 17 molar teeth collected from Danish and New Zealand populations. The caries status of the sectioned fissure was determined by microradiography or visually after drying. The probe scans were graphed as density images, surface plots and topographical plots. Sound enamel bordering grooves and fissures showed a high-F surface layer, in 1 sample approximately 60 microm wide near the fissure bottom but gradually widening to double this width near the fissure opening, and up to 200 microm wide in grooves, while underlying enamel had a low and almost constant F level. In this respect fissure and groove enamel resembled smooth surface enamel. The F concentration fluctuated along the surface layer, reaching maximum values ranging from 1,800 to 4,200 ppm in 5 non-carious fissures. Incipient caries in fissure enamel usually but not always resulted in an increase in F in the outer layer, the F maximum values in 5 such samples ranging from 1,900 to 7,200 ppm. F maximum values in outer enamel were higher in 7 samples showing advanced caries, 2, 700-10,000 ppm. The lesion subsurface body usually showed normal F values, as did carious dentine in the advanced lesions. The variable characteristics of the outer layer in sound fissure enamel are likely to be the result of a developmental process rather than environmental influences. The fact that we normally failed to find increased F concentrations in subsurface carious fissure enamel or in underlying carious dentine suggests that F does not diffuse into the deep part of fissure lesions, and probably has minimal effect on slowing the progress of such lesions, a suggestion in accord with clinical findings on the F effect on fissure caries.