Secondary aerosol formation and oxidation capacity in photooxidation in the presence of Al_2O_3 seed particles and SO_2

To investigate the sensitivity of secondary aerosol formation and oxidation capacity to NOx in homogeneous and heterogeneous reactions, a series of irradiated toluene/NOx/air and ?-pinene/NOx/air experiments were conducted in smog chambers in the absence or presence of Al2O3 seed particles. Various concentrations of NOx and volatile organic compounds(VOCs) were designed to simulate secondary aerosol formation under different scenarios for NOx. Under "VOC-limited" conditions, the increasing NOx concentration suppressed secondary aerosol formation, while the increasing toluene concentration not only contributed to the increase in secondary aerosol formation, but also led to the elevated oxidation degree for the organic aerosol. Sulfate formation was suppressed with the increasing NOx due to a decreased oxidation capacity of the photooxidation system. Secondary organic aerosol(SOA) formation also decreased with the presence of high concentration of NOx, because organo-peroxy radicals(RO2) react with NOx instead of with peroxy radicals(RO2 or HO2), resulting in the formation of volatile organic products. The increasing concentration of NOx enhanced the formation of sulfate, nitrate and SOA under "NOx-limited" conditions, in which the heterogeneous reactions played an important role. In the presence of Al2O3 seed particles, a synergetic promoting effect of mineral dust and NOx on secondary aerosol formation in heterogeneous reactions was observed in the photooxidation. This synergetic effect strengthened the positive relationship between NOx and secondary aerosol formation under "NOx-limited" conditions but weakened or even overturned the negative relationship between NOx and secondary aerosol formation under "VOC-limited" conditions. Sensitivity of secondary aerosol formation to NOx seemed different in homogeneous and heterogeneous reactions, and should be both taken into account in the sensitivity study. The sensitivity of secondary aerosol formation to NOx was further investigated under "winter-like" and NH3-rich conditions. No obvious difference for the sensitivity of secondary aerosol formation except nitrate to NOx was observed.

To investigate the sensitivity of secondary aerosol formation and oxidation capacity to NOx in homogeneous and heterogeneous reactions, a series of irradiated toluene/NOx/air and α-pinene/NOx/air experiments were conducted in smog chambers in the absence or presence of Al2O3 seed particles. Various concentrations of NOx and volatile organic compounds（VOCs） were designed to simulate secondary aerosol formation under different scenarios for NOx. Under ＂VOC-limited＂ conditions, the increasing NOx concentration suppressed secondary aerosol formation, while the increasing toluene concentration not only contributed to the increase in secondary aerosol formation, but also led to the elevated oxidation degree for the organic aerosol. Sulfate formation was suppressed with the increasing NOx due to a decreased oxidation capacity of the photooxidation system. Secondary organic aerosol（SOA） formation also decreased with the presence of high concentration of NOx, because organo-peroxy radicals（RO2） react with NOx instead of with peroxy radicals（RO2 or HO2）, resulting in the formation of volatile organic products. The increasing concentration of NOx enhanced the formation of sulfate, nitrate and SOA under ＂NOx-limited＂ conditions, in which the heterogeneous reactions played an important role. In the presence of Al2O3 seed particles, a synergetic promoting effect of mineral dust and NOx on secondary aerosol formation in heterogeneous reactions was observed in the photooxidation. This synergetic effect strengthened the positive relationship between NOx and secondary aerosol formation under ＂NOx-limited＂ conditions but weakened or even overturned the negative relationship between NOx and secondary aerosol formation under ＂VOC-limited＂ conditions. Sensitivity of secondary aerosol formation to NOx seemed different in homogeneous and heterogeneous reactions, and should be both taken into account in the sensitivity study. The sensitivity of secondary aerosol formation to NOx was further investigated under ＂winter-like＂ and NH3-rich conditions. No obvious difference for the sensitivity of secondary aerosol formation except nitrate to NOx was observed.