Avena sativa (oats) and Lycopersicon esculentum (tomatoes) were grown in dilute nutrient solutions supplemented with Al only, F only or a combination of both. In solutions containing Al and F, shoot growth was limited when predicted Al-r (Al3+, AlOH2+ and Al(OH)(2)(+)) activities were < 0.1 mu M, activities three orders of magnitude lower than the critical value determined with Al only. The data suggest that at the activities used in these experiments, Al-r is most toxic, AlF2+ and AlF2+ are toxic to a lesser extent, and AlF3, AlF4- and F- are least toxic. Fluoride concentrations in shoots grown in solutions correlated best with positively charged AlFx3-x species (i.e. AlF2+ AlF2+) and the molar ratio of F:AI in most plants shoots was about 3:2. However, when activities of positively charged AIF(x)(3-x) species were low (< 50 mu M) and the activity of AlF3 species high (500 mu M the molar ratio of F:Al in plant shoots suggested AlF3 was taken up. These findings are discussed in relation to plant uptake and toxicity. Measured concentrations of Al-r and F- in solutions containing Al and F were compared with concentrations predicted by a computer model (GEOCHEM-PC). The method for measuring F- concentrations, using a noncomplexing buffer and F ion-selective electrode, gave good agreement with predicted F-concentrations. The 8-hydroxyquinoline method for measuring Al-r concentrations did not agree with predicted concentrations, highlighting the limitations of this method when measuring Al-r in the presence of F in a multi-ligand system with high concentrations of F and Al.