Chlorophyll a (chl a) fluorescence was used to determine tire effects of treatments with gaseous HF ol aqueous solutions of NaF on the photosynthetic apparatus of spinach prior to the appearance of visible injury. Placing the petioles in 2 mM NaF for 3 h? resulted in the accumulation of 240 ppm F in leaf blades. The second oldest leaves of spinach plants accumulated similar concentrations (270 ppm Fl when the plants were exposed to gaseous HF at 5 mu g F m(-3) for 6 days. These NaF and HF treatments did not result in visible injury nor did they affect F-o, F-m or F-v/F-m. However, during the slow (>2 s) induction kinetics, fluorescence quenching in fluoride-treated leaves increased during the P to S phase and the M peak was no longer resolved. This was due, in part, to increased photochemical quenching. The results are consistent with a reduced ability to develop or maintain a trans-thylakoid proton gradient in chloroplasts containing elevated concentrations off.