Gas-Phase Oxidation of Guaiacol by NO3 Radicals: Kinetic Measurements and Implications

Abstract

Methoxyphenols, critical tracers of biomass burning emissions, are emitted in large quantities during lignin pyrolysis. Gas-phase reaction of methoxyphenols with nitrate radicals (NO₃) yields to important secondary products like nitrophenols, yet their atmospheric kinetics are far from adequate and consistent. This study investigates the gas-phase reaction kinetics of guaiacol, a key representative methoxyphenol, with NO₃ by using a controlled 30 m³ indoor chamber. Both relative rate and absolute rate methods were employed, yielding rate constants of (3.1 ± 0.2) × 10^–11 and (2.43 ± 0.19) × 10^–11 cm³ molecule^–1 s^–1, respectively, at 298 ± 2 K under dry conditions. The rate constant decreased with an increase in humidity, highlighting the inhibitory effect of water vapor on NO₃-initiated reactions. The calculated nocturnal atmospheric lifetime of guaiacol due to NO₃ reactions is less than 2 min at typical nocturnal NO₃ levels, underscoring the significance of this pathway in the budget of methoxyphenols during nighttime or within a 24 h cycle. To the best of our knowledge, this study represents the first determination of the NO₃-guaiacol rate constant using the absolute rate method and provides insights into the role of relative humidity in methoxyphenol oxidation. These findings offer critical data for understanding the atmospheric fate of biomass burning emissions and their contributions to nighttime chemistry and air quality.