Comparison of secondary organic aerosol formation from toluene on initially wet and dry ammonium sulfate particles at moderate relative humidity

摘要

The formation of secondary organic aerosol (SOA) has been widely studied in the presence of dry seed particles at low relative humidity (RH). At higher RH, initially dry seed particles can exist as wet particles due to water uptake by the seeds as well as the SOA. Here, we investigated the formation of SOA from the photooxidation of toluene using an oxidation flow reactor in the absence of NOx under a range of OH exposures on initially wet or dry ammonium sulfate (AS) seed particles at an RH of 68 %. The ratio of the SOA yield on wet AS seeds to that on dry AS seeds, the relative SOA yield, decreased from 1.31 +/- 0.02 at an OH exposure of 4.66 +/- 10(10) molecules cm(-3) s to 1.01 +/- 0.01 at an OH exposure of 5.28 +/- 10(11) molecules cm(-3) s. This decrease may be due to the early deliquescence of initially dry AS seeds after being coated by highly oxidized toluene-derived SOA. SOA formation lowered the deliquescence RH of AS and resulted in the uptake of water by both AS and SOA. Hence the initially dry AS seeds contained aerosol liquid water (ALW) soon after SOA formed, and the SOA yield and ALW approached those of the initially wet AS seeds as OH exposure and ALW increased, especially at high OH exposure. However, a higher oxidation state of the SOA on initially wet AS seeds than that on dry AS seeds was observed at all levels of OH exposure. The difference in mass fractions of m/z 29, 43 and 44 of SOA mass spectra, obtained using an aerosol mass spectrometer (AMS), indicated that SOA formed on initially wet seeds may be enriched in earlier-generation products containing carbonyl functional groups at low OH exposures and later-generation products containing acidic functional groups at high exposures. Our results suggest that inorganic dry seeds become at least partially deliquesced particles during SOA formation and hence that ALW is inevitably involved in the SOA formation at moderate RH. More laboratory experiments conducted with a wide variety of SOA precursors and inorganic seeds under different NOx and RH conditions are warranted.