Organic nitrate formation in the radical-initiated oxidation of model aerosol particles in the presence of NOx

Using a flow tube reactor coupled to a chemical ionization mass spectrometer, the Cl-initiated oxidation of solid and supercooled liquid brassidic acid (BA, trans-13-docosenoic acid) particles was investigated in the presence of NO and NO2. For the first time, organic nitrate formation from the heterogeneous oxidation of model organic aerosols in the presence of NO was observed, but none was formed by the addition of up to 600 ppb of NO2. Also, no nitrate formation was observed in liquid particles, but the nitrate yields in the solid particles were measured to be as large as 6% with a negative temperature dependence over the range 259-293 K. The corresponding effective activation energy of -7.5 (+/- 4.4) kJ mol(-1) suggests that the mechanism of particulate organic nitrate formation is analogous to the termolecular gas-phase reaction of RO2 + NO -> ROONO* ->(M) RONO2. The yields are smaller than those from analogous gas-phase reactions, but this may result from photodissociation of the nitrate by the UV (355 nm) laser for which there is indirect evidence. Additionally, enhanced rates of the RO2 + RO2 reactions in the condensed phase could lead to smaller nitrate yields. The results suggest that slower diffusion of the RO2 radicals in the solid particles compared to the liquid particles makes the RO2 + NO reaction competitive with the RO2 + RO2 reactions and results in nitrate formation near the surface of the particle. The organic nitrates formed in these experiments are observed intact after the reacted particles have been vaporized at temperatures up to 380 degrees C suggesting that they are thermally stable in the troposphere and may enable long-range transport of NOx if they photodissociate on the timescale of days. The findings from these experiments are not specific to unsaturated carboxylic acids but should apply to nearly all particulate hydrocarbons, and they indicate that the particle phase could be important in determining how organic aerosols evolve chemically through radical-initiated oxidation in polluted atmospheres.