Experimental determination of the partitioning of representative organic pollutants to the air-water interface.

Using glancing-angle laser-induced fluorescence (GALIF) spectroscopy as a probe, the partitioning of naphthalene, fluoranthene, pyrene, umbelliferone, phenol red, and bisphenol A from bulk solution to the air-water interface was examined in both pure water and aqueous solutions of 6 mM octanol. Previous studies provided similar Langmuir adsorption isotherms for anthracene and imidazole 2-carboxaldehyde. The surface partitioning behaviour of each compound in both environments was well described using a Langmuir adsorption model; partitioning coefficients were derived from the fits to such isotherms. Only the PAH molecules, naphthalene, fluoranthene and pyrene, saw an enhancement in the surface partitioning in octanol solution compared to pure water. The surface partitioning to pure water surfaces could be fairly well described using a one parameter linear free energy relationship based on either solubility or KOW.

Reactive Uptake of Gas-Phase NO2 by Urban Road Dust in the Dark.

Road dust constitutes a prominent source of anthropogenic particulate matter, making its heterogeneous interactions with common atmospheric gas-phase compounds important. Here, we show that three distinct samples of urban road dust-including dust samples collected from city streets in summer and winter, and an urban park in summer-react with NO2 in the dark, forming NO and surface nitrite. The loss of NO2 ranged from ∼2 to 13% of its gas-phase concentration and scaled with its concentration as well as with the mass of the road dust sample. The uptake of NO2 by the winter dust was ∼4 times greater than that seen from summer street dust, which was in turn greater than that by the park dust. The conversion ratio of NO2 → NO ranged from 0.06 to 0.8 NO produced per NO2 lost and was greatest for the summer park dust. Exposure of the summer road dust to NO2 roughly doubles the concentration of inorganic nitrite anion in the dust but does not produce nitrate. The formation of NO and photolabile nitrite products means that heterogeneous NO x reactions occurring on the surface of road dust in the dark could have wide implications for the oxidative potential of urban areas.