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. The Environmental Simulation Chamber made of Quartz fromthe University “Alexandru Ioan Cuza” (ESC-Q-UAIC), at Iasi, Romania, wasused to investigate the gas-phase reaction rate coefficients for fournitrocatechols toward OH radicals under simulated atmospheric conditions.Employing relative rate techniques at a temperature of 298 ± 2 K and a total air pressure of 1 atm, the obtained rate coefficients (in 10−12 cm3 s−1) were as follows: k3NCAT = (3.41 ± 0.37) for 3-nitrocatechol and k5M3NCAT = (5.55 ± 0.45) for 5-methyl-3-nitrocatechol at 365 nm, using CH3ONO photolysis as OH radicals source and dimethyl ether and cyclohexane as reference compounds, and k4NCAT = (1.27 ± 0.19) for 4-nitrocatechol andk4M5NCAT = (0.92 ± 0.14) for 4-methyl-5-nitrocatechol at 254 nm using H2O2 as OH radicals source and dimethyl ether and methanol as reference compounds. The photolysis rates in the actinic region, scaled to atmospheric relevant conditions by NO2 photolysis, were evaluated for 3-nitrocatechol and 5-methyl-3-nitrocatechol: J3NCAT = (3.06 ± 0.16) × 10−4 s−1 and J5M3NCAT = (2.14 ± 0.18) × 10−4 s−1, respectively. The photolysis rate constants at 254 nm were measured for 4-nitrocatechol and 4-methyl-5-nitrocatechol and the obtained values are J4NCAT = (6.7 ± 0.1) × 10−5 s−1 and J4M5NCAT = (3.2 ± 0.3) × 10−5 s−1. Considering the obtainedresults, our study suggests that photolysis may be the main degradationprocess for 3-nitrocatechol and 5-methyl-3-nitrocatechol in the atmosphere,with a photolytic lifetime in the atmosphere of up to 2 h. Results arediscussed in terms of the reactivity of the four nitrocatechols under investigationtoward OH-radical-initiated oxidation and their structural features. Therate coefficient values of the nitrocatechols are also compared with thoseestimated from the structure-activity relationship for monocyclic aromatichydrocarbons and assessed in relation to their gas-phase IR spectra.Additional comparison with similar compounds is also presented, underliningthe implications toward possible degradation pathways and atmosphericbehaviour.

atmospheric chemistry and physics

Investigations into the gas-phase photolysis and OH radical kinetics of nitrocatechols: implications of intramolecular interactions on their atmospheric behaviour