OBJECTIVE The research was designed to examine the growth of in vitro carious lesions in dental enamel using nanoindentation and time-of-flight secondary ion mass spectroscopy (TOF-SIMS). This was intended to give maps of mechanical properties and chemistry over the cross-section of the lesions. METHODS Incipient carious lesions were grown on the buccal faces of 20 human premolars by exposure to acid for 3, 5, 7 or 14 days. The lesions were then cut in cross-section normal to the exposed surface. The lesions' cross-sections were then examined using nanoindentation and TOF-SIMS. RESULTS The earliest lesions (3 days of acid exposure) showed little evidence of lesion growth, but the 5, 7 and 14 days of exposure all gave lesions with a weak, demineralized interior, but a stronger, less demineralized surface zone. The thickness of the surface zone was found to diminish with the length of exposure to acid, but it was still present even after 14 days of exposure. CONCLUSIONS The results indicate that carious lesions develop subsurface and that the surface zone forms by a coupled diffusion process. Mechanically the lesion has a strong surface layer, but a very weak interior which makes the lesion vulnerable to mechanical loading. However, the presence of a surface zone that retains a high mineral content and is mechanically strong suggests that lesion development can be arrested and possibly reversed even when the lesions are relatively mature.