Photolysis of 3-Nitro-1,2,4-triazol-5-one: Mechanisms and Products

Insensitive munitions formulations that include 3-nitro-1,2,4-triazol-5-one (NTO) are replacing traditional explosive compounds. While these new formulations have superior safety characteristics, the compounds have greater environmental mobility, raising concern over potential contamination and cleanup of training and manufacturing facilities. Here, we examine the mechanisms and products of NTO photolysis in simulated sunlight to further inform NTO degradation in sunlit surface waters. We demonstrate that NTO produces singlet oxygen and that dissolved oxygen increases the NTO photolysis rate in deionized water. The rate of NTO photolysis is independent of concentration and decreases slightly in the presence of Suwannee River Natural Organic Matter. The apparent quantum yield of NTO generally decreases as pH increases, ranging from 2.0 × 10^-5 at pH 12 to 1.3 × 10^-3 at pH 2. Bimolecular reaction rate constants for NTO with singlet oxygen and hydroxyl radical were measured to be (1.95 ± 0.15) × 10⁶ and (3.28 ± 0.23) × 10¹⁰ M^-1 s^-1, respectively. Major photolysis reaction products were ammonium, nitrite, and nitrate, with nitrite produced in nearly stoichiometric yield upon the reaction of NTO with singlet oxygen. Environmental half-lives are predicted to span from 1.1 to 5.7 days. Taken together, these data enhance our understanding of NTO photolysis under environmentally relevant conditions.