Data obtained in a previous study suggested that brushite is the solubility-determining phase when enamel is first exposed to acid solution in a series of repeated equilibrations.Fluoride in solution might be expected to inhibit brushite formation, and experimental studies at low solid/solution ratio support this. We have now re-examined the effect at a very high ratio, in an attempt to mimic what happens in an enamel caries lesion. Powdered enamel was repeatedly exposed to HCl solution, 10-70 mmol/l, containing 2 ppm F, for 24 h, initially in a ratio of 1 g/3 ml. Ion activities were determined after 20 min and 24 h and potential plot diagrams constructed. In early repetitions the -log (Ca2+) (OH-)2 vs. -log (H+)3(PO43- ) points tended to follow the brushite line, rather than the hydroxyapatite (HAp) line which one would expect if enamel behaved as pure HAp. Solution F was below measurable limits after 20 min and F then had little influence on the brushite equilibrating phase. In later ( > 13) repetitions, points fell closer to the HAp line, with or without F added to the acid solution. However, added F, which was not then completely removed from solution, caused the slope of the regression line through the points to approach the Ca/P ratio of HAp, and therefore may have had a small effect in reducing the brushite phase. It is concluded that high solid/solution ratio, a previously neglected factor in enamel dissolution studies, has a profound effect in increasing the manifestation of a brushite surface phase and reducing the inhibitory effect of F on this phase.