This paper presents the results of laboratory studies on the condensational uptake of gaseous organic compounds in the exhaust of a light-duty gasoline engine onto preexisting sulfate and nitrate seed particles. Significant condensation of the gaseous organic compounds in the exhaust occurs onto these inorganic particles on a time scale of 25 min. The amount of condensed organic mass (COM) is proportional to the seed particle mass, suggesting that the uptake is due to dissolution determined by the equilibrium partitioning between gas phase and particles, not adsorption. The amount of dissolution in unit seed mass, S, decreases as a power function with increased dilution of the exhaust, ranging from 0.23 g g(-1) at a dilution ratio of 81, to 0.025 g g(-1) at a dilution ratio of 2230. It increases nonlinearly with increasing concentration of the total hydrocarbons in the gas phase (THC), rising from 0.12 g g(-1) to 0.26 g g(-1) for a CTHC increase of 1 to 18 mu g m(-3), suggesting that more organics are partitioned into the particles at higher gas phase concentrations. In terms of gas-particle partitioning, the condensational uptake of THC gases in gasoline engine exhaust can account for up to 30% of the total gas + particle THC. The organic mass spectrum of COM has the largest fragment at m/z 44, with mass ratios of mass fragments 43/44 and 57/44 at 0.59 and 2.91, much lower than those reported for gasoline engine primary organic aerosols. The mass fragment 44/total organic mass ratio of 0.097 indicates that COM contains large oxygenated components. By incorporating the present findings, regional air quality modelling results suggest that the condensational uptake of THC onto sulfate particles alone can be comparable to the primary particle mass under moderately polluted ambient conditions. These findings are important for modelling and regulating the air quality impacts of gasoline vehicular emissions.
We report the observation of a series of perylene bisimide derivatives containing two or three perylene moieties. Dramatically different assembling behavior can be observed under ambient conditions on highly oriented pyrolitic graphite (HOPG) surface with scanning tunneling microscopy (STM). The dihedral angles between the perylene moieties are suggested to be sensitively dependent on the linker units. The linear linker units could make the perylene moieties with spatial configuration be observed on the surface. The length of linear connecting parts would also influence the dihedral angles. The fundamental processes occurring at solid-liquid interfaces have been found, because of the extended observation time or elevated temperatures. All these results would help to comprehend the conformational polymorphism of carrier transport in the organic thin films.
The neutralization of acidic aerosols by ammonia has been studied through experiments which combine ambient air with laboratory generated sulfuric acid aerosol. Results indicated that acidic aerosol mixed with organic free air and ammonia was neutralized on a time scale < 1 min, consistent with expectations. However, in the presence of ambient organic gases and ammonia, the rate of aerosol neutralization is significantly reduced. This reduction in ammonia uptake was concurrent with an increase in the amount of particle phase organics. A steady state in the NH4+/SO42- in the presence of organic gases was established on time scales of 10 min to several hours, corresponding to NH3 uptake coefficients in the range of 4 x 10(-3)-2 x 10(-4). The degree to which neutralization was slowed was dependent upon the initial ammonia concentration and the organic mass added to the aerosols. These results suggest that inorganic equilibrium thermodynamic models may overestimate the rate of ammonia uptake and that ambient particles may remain acidic for longer than previously expected.