Photochemically processed urban emissions were characterized at a mountain top location, free from local sources, within the Mexico City Metropolitan Area. Analysis of the Mexico City emission plume demonstrates a strong correlation between secondary organic aerosol and odd oxygen (O3 + NO2). The measured oxygenated‐organic aerosol correlates with odd oxygen measurements with an apparent slope of (104–180) μg m−3 ppmv−1 (STP) and r2 > 0.9. The dependence of the observed proportionality on the gas‐phase hydrocarbon profile is discussed. The observationally‐based correlation between oxygenated organic aerosol mass and odd oxygen may provide insight into poorly understood secondary organic aerosol production mechanisms by leveraging knowledge of gas‐phase ozone production chemistry. These results suggest that global and regional models may be able to use the observed proportionality to estimate SOA as a co‐product of modeled O3 production until more complete models of SOA formation become available.

Many recent models underpredict secondary organic aerosol (SOA) particulate matter (PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much better understood, we investigate the correlation of odd-oxygen ([O_x]≡[O₃]+[NO₂]) and the oxygenated component of organic aerosol (OOA), which is interpreted as a surrogate for SOA. OOA and O_x measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h) and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 μg m⁻³/ppm (STP) in Houston during time periods affected by large petrochemical plant emissions to as high as 160 μg m⁻³/ppm in Mexico City, where typical values were near 120 μg m⁻³/ppm. On several days in Mexico City, the [OOA]/[O_x] ratio decreased by a factor of ~2 between 08:00 and 13:00 local time. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the O_x production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[O_x] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed ratio. Although not succesful in reproducing the atmospheric observations presented, modeling <i>P</i>(SOA)/<i>P</i>(O_x) can serve as a useful test of photochemical models using improved formulation mechanisms for SOA

A growing number of epidemiological studies conducted worldwide suggest an increase in the occurrence of adverse health effects in populations living, working, or going to school near major roadways. A study was designed to assess traffic emissions impacts on air quality and particle toxicity near a heavily traveled highway. In an attempt to describe the complex mixture of pollutants and atmospheric transport mechanisms affecting pollutant dispersion in this near-highway environment, several real-time and time-integrated sampling devices measured air quality concentrations at multiple distances and heights from the road. Pollutants analyzed included U.S. Environmental Protection Agency (EPA)-regulated gases, particulate matter (coarse, fine, and ultrafine), and air toxics. Pollutant measurements were synchronized with real-time traffic and meteorological monitoring devices to provide continuous and integrated assessments of the variation of near-road air pollutant concentrations and particle toxicity with changing traffic and environmental conditions, as well as distance from the road. Measurement results demonstrated the temporal and spatial impact of traffic emissions on near-road air quality. The distribution of mobile source emitted gas and particulate pollutants under all wind and traffic conditions indicated a higher proportion of elevated concentrations near the road, suggesting elevated exposures for populations spending significant amounts of time in this microenvironment. Diurnal variations in pollutant concentrations also demonstrated the impact of traffic activity and meteorology on near-road air quality. Time-resolved measurements of multiple pollutants demonstrated that traffic emissions produced a complex mixture of criteria and air toxic pollutants in this microenvironment. These results provide a foundation for future assessments of these data to identify the relationship of traffic activity and meteorology on air quality concentrations and population exposures.