The Role of Biogenic and Anthropogenic Hydrocarbons in Aging of Atmospheric Soot

Atmospheric soot is often found to be internally mixed with other aerosol constituents, yet the processes responsible for the soot aging are not well understood. We have conducted a systematic study on the role of several representative biogenic and anthropogenic volatile organic compounds (VOCs), including monoterpenes and aromatics, in atmospheric aging of combustion soot. Aging experiments were conducted in a fluoropolymer chamber on size-classified soot aerosols in the presence of a VOC and an oxidant, either ozone or photolytically generated hydroxyl radical (OH). The evolution in the aging state of soot was monitored from measurements of the particle mobility size and mass, which were used to derive information about particle effective density, dynamic shape factor, and coating thickness. When exposed to VOC and oxidant, soot particles promptly gain mass due to condensation of low-volatility and partitioning of semi-volatile VOC oxidation products. Depending on the VOC, the increase in the particle mass is accompanied by an increase or a decrease in the particle mobility diameter. In either case, the effective density of coated soot particles increases during aging because the condensed material fills in the voids of fractal soot aggregates, forcing their restructuring. The latter is confirmed by thermal denuding experiments, which show an increase in the effective density for soot that was first aged and then heated to remove the coating from the soot core. Hygroscopic and optical properties of soot are significantly altered by aging. Upon humidification, the coating absorbs water, increasing in volume and causing an additional restructuring of soot aggregates. Coated particles are sufficiently hygroscopic to activate to cloud droplets at atmospherically relevant water supersaturations. Aged soot shows stronger light absorption and scattering, with an enhancement magnitude depending on the coating thickness and nature of the coating precursor. The rate of aging and corresponding changes in the properties of soot are enhanced in the presence of nitrogen oxides (NOx = NO + NO2), a common combustion co-pollutant of soot. On the basis of our experimental results we conclude that biogenic and anthropogenic VOCs play a significant role in the atmospheric aging of combustion soot, shortening its atmospheric lifetime while enhancing impacts on air quality and climate.