The role of O2 and photoionization as well as the involvement of polycyclic aromatic hydrocarbon (PAH) cation radicals (P+) in the photodegradation of nine PAHs was examined. Photodegradation quantum yields for all PAHs increased with increasing O2 concentration, illustrating the key role of O2 in the photodegradation mechanism. In the presence of a series of electron donors (to P+), the photodegradation rate constants of most PAHs were largely unaffected at low O2 concentrations (< or = 250 microM), indicating that P+ is not extensively produced. However, at higher O2 concentrations (up to 1.2 mM), the presence of the donors substantially lowered photodegradation rates for most PAHs, indicating that P+ is produced and is arising from O2 reaction with the excited singlet state. Because little P+ was detected at low O2 concentrations and, further, because degradation rates were not enhanced in the presence of N2O, we conclude that photoionization is unimportant. With some exceptions, photodegradation can proceed through reaction of O2 with both excited singlet and triplet states of the PAHs. Our results indicate that photodegradation via the excited singlet state occurs primarily through electron transfer to O2, whereas degradation via the triplet occurs predominately through a direct reaction of O2 with the PAH within the collision complex.