Box model investigation of the effect of soot particles on ozone downwind from an urban area through heterogeneous reactions.

Soot can provide additional surface area where heterogeneous reactions can take place in the atmosphere. These reactions are dependent on the number of reactive sites on the soot surface rather than the soot surface area per se. A box model, MOCCA, is used to investigate the effects of introducing heterogeneous reactions on soot into air parcel passing over an urban area and traveling downwind. The model was run at two soot mass concentrations of 2 microg/m3 and 20 microg/m3 with a surface density of n-hexane and decane. Signifcant change in gasphase concentration was only observed for the higher soot concentration. Due to the noncatalytic nature of the heterogeneous reactions, soot sites are rapidly consumed, and soot site concentrations are greatly reduced shortly after emissions are turned off. Notable changes in gaseous concentrations due to the introduction of heterogeneous reactions are not observed in the urban setting. The impact of heterogeneous reactions is more evident after emissions are turned off (i.e. downwind from the urban center). These changes are minimal for the condition that used n-hexane surface density. For conditions that used decane soot, NOx concentrations showed a slight increase, with NO being higher in the daytime and NO2 at night. The maximum O3 reduction observed when using the higher soot concentration is 7 ppb, downwind of the urban center. Change in O3 concentration was less than 1 ppb when using the lower soot loading. The observed effects of heterogeneous reactions on soot decrease with time.

Simulating organic aerosol formation during the photooxidation of toluene/NOx mixtures: comparing the equilibrium and kinetic assumption.

Organic compounds contribute an appreciable mass to particulate matter and thus impact the hygroscopic and radiative properties of an aerosol distribution. Being able to predict the chemical and physical properties of aerosols based on their size and composition is critical to assessing their impact on air quality, visibility, and climate change. In this study, a comparison was performed between an equilibrium and a kinetic model for simulating organic aerosol formation during the photooxidation of toluene/NO/isopropyl nitrite mixtures. Both models used an explicit gas-phase toluene scheme (University of Leeds Master Chemical Mechanism version 3.0) and provided a prediction of individual products partitioned to the aerosol phase. After incorporating a heterogeneous wall reaction scheme regenerating NOx from HNO3 and HNO2, the gas-phase scheme was able to simulate the observed toluene decay within 5% and NO decay within 30% for all of the chamber experiments. The models reproduced the general magnitude of the aerosol yields but suggest a weaker trend dependence on aerosol mass loading. A few nonvolatile compounds were predicted to compose the majority of the aerosol-phase mass with multifunctional organic nitrates being the dominant organic aerosol functional group. The hygroscopic diameter growth factor for the organic phase was predicted to be 1.1 at a relative humidity of 79%. We conclude with a list of recommended laboratory experiments to help constrain and validate aerosol process models.

Evaluating a Canadian regional air quality model using ground-based observations in north-eastern Canada and United States.

The simulated concentrations from a numerical 3-dimensional regional air quality model (MC2AQ) are compared to those of ground-based observations in north-eastern Canada and the United States. The model has oxidant chemistry for both inorganic and organic species and deposition routines driven online by a mesoscale compressible community meteorological model (MC2). A standard emission inventory of anthropogenic, natural and biogenic sources for the year 1990 for 21 atmospheric trace species was used in the simulation. The model was run for July 1999, because of the occurrence of a high ozone episode and the availability of the monitoring data for surface O3, SO2, NO, NO2 and NOx. The comparisons during the episode show that the model performs quite well for predicting concentrations and diurnal variations of the surface ozone. The predictions for other gaseous species show some discrepancies with observations, but they are consistent with the results from other models evaluated in the literature. The uncertainties in the emission inventory for these species might be the main causes of the discrepancies. Further studies are needed to improve the predictability of SO and NOx, especially as the model is developed to include particulate matter formation as a result of these gaseous precursors.