Chemical kinetics were determined for the reactions of ozone and hydroxyl radicals with the three cyanotoxins microcystin-LR (MC-LR), cylindrospermopsin (CYN) and anatoxin-a (ANTX). The second-order rate constants (k(O3)) at pH 8 were 4.1 +/- 0.1 x 10(5) M-1 s(-1) for MC-LR, similar to 3.4 x 10(5) M-1 s(-1) for CYN, and similar to 6.4 x 10(4) M-1 s(-1) for ANTX. The reaction of ozone with MC-LR exhibits a k(O3) similar to that of the conjugated diene in sorbic acid (9.6 +/- 0.3 x 10(5) M-1 s(-1)) at pH 8. The pH dependence and value of k(O3) for CYN at pH > 8 (similar to 2.5 +/- 0.1 x 10(6) M-1 s(-1)) are similar to deprotonated amines of 6-methyluracil. The k(O3) of ANTX at pH > 9 (similar to 8.7 +/- 2.2 x 10(5) M-1 s(-1)) agrees with that of neutral diethylamine, and the value at pH < 8 (2.8 +/- 0.2 x 10(4) M-1 s(-1)) corresponds to an olefin. Second-order rate constants for reaction with OH radicals ((OH)-O-center dot), k(OH) for cyanotoxins were measured at pH 7 to be 1.1 +/- 0.01 x 10(10) M-1 s(-1) for MC-LR, 5.5 +/- 0.01 x 10(9) M-1 s(-1) for CYN, and 3.0 +/- 0.02 x 10(9) M-1 s(-1) for ANTX. Natural waters from Switzerland and Finland were examined for the influence of variations of dissolved organic matter, SUVA254, and alkalinity on cyanotoxin oxidation. For a Swiss water (1.6 mg/L DOC), 0.2, 0.4, and 0.8 mg/L ozone doses were required for 95% oxidation of MC-LR, CYN, and ANTX, respectively. For the Finnish water (13.1 mg/L DOC), > 2 mg/L ozone dose was required for each toxin. The contribution of hydroxyl radicals to toxin oxidation during ozonation of natural water was greatest for ANTX > CYN > MC-LR. Overall, the order of reactivity of cyanotoxins during ozonation of natural waters corresponds to the relative magnitudes of the second-order rate constants for their reaction with ozone and (OH)-O-center dot. Ozone primarily attacks the structural moieties responsible for the toxic effects of MC-LR, CYN, and ANTX, suggesting that ozone selectively detoxifies these cyanotoxins.