Suppression of new particle formation from monoterpene oxidation by NO_x

Abstract. The impact of nitrogen oxides (NO_x = NO + NO₂) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory setup. At high NO_x conditions ([BVOC] / [NO_x] < 7, [NO_x] > 23 ppb) new particle formation was suppressed. Instead, photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. When [NO] was reduced back to levels below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NO_x caused NPF to be slowed by orders of magnitude compared to analogous experiments at low NO_x conditions ([NO_x] ~300 ppt), although OH concentrations were higher. Varying NO₂ photolysis enabled showing that NO was responsible for suppression of NPF. This suggests that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent approaching −2. This exponent indicated that the overall peroxy radical concentration must have been similar when NPF occurred. Thus, permutation reactions of first-generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy-radical-like intermediates limit the rate of new particle formation.
In contrast to the strong effects on the particle numbers, the formation of particle mass was substantially less sensitive to NO_x concentrations. If at all, yields were reduced by about an order of magnitude only at very high NO_x concentrations.