The formation of anthracene ion radicals in the H+-, Na+-, Fe2+-, and Fe3+-Naflon membrane was established by laser kinetic spectroscopy. The formation of ion radicals was observed to be due to (1) the two photon ionization of the anthracene molecule with the formation of the radical cation An(+.) radical and a fast electron scavenging by H+, Na+, Fe2+ and Fe3+ acting as efficient electron traps in solution and (2) the quenching of the excited anthracene by Fe3+ that leads by a redox process to the formation of An(+.) and Fe2+. It is shown that the ensuing kinetics of the ion-radical decay depends on the chemical nature of the traps. The lifetime of (T)An becomes shorter after Fe2+ or Fe3+ is introduced in the Nafion. The steady-state anthracene fluorescence is quenched by Fe3+ or Fe2+ and followed the logarithmic decay law ln(l(0)/I) where the decay in solution was seen to be proportional to the [Fe3+] or [Fe2+]. The counterions of SO3--water clusters as well as of oxygen in the reaction media strongly affect the kinetics of ion-radical reactions occurring in the Nafion membrane. The counterions and oxygen are suggested to be the traps for the generated electrons in solution. The excited state of An was shown to react with Fe3+ through electron transfer. Triplet excited anthracene molecules are quenched by Fe3+ and Fe2+ with rate constants k(q)(Fe3+) = ( 1.9+/-0.19) x 10(8) M(-1)s(-1) and k(q)(Fe2+) (1.4+/-0.11) x 10(9) M(-1)s(-1). Anthracene ion radicals are formed in the reaction with Fe3+ but not with Fe2+ on thermodynamic grounds. Fe2+ or Fe3+ being different chemical species quench with similar rates the An probe inside the Nafion membrane. Treatment of Fe3+ -Nafion with NaOH leads to precipitation of iron particles in the membrane having as consequences (1) the decrease of the observed rate for the triplet excited anthracene quenching with a concomitant decrease in the observed An(+.) yields and (2) a significant decrease of the An(+.) decay time because of the lowering of the mobility of the iron ions in solution.