Carbonyls in the metropolitan area of Mexico City: calculation of the total photolytic rate constants Kp(s(-1)) and photolytic lifetime (tau) of ambient formaldehyde and acetaldehyde

A great number of studies on the ambient levels of formaldehyde and other carbonyls in the urban rural and maritime atmospheres have been published because of their chemical and toxicological characteristics, and adverse health effects. Due to their toxicological effects, it was considered necessary to measure these compounds at different sites in the metropolitan area of Mexico City, and to calculate the total rate of photolytic constants and the photolytic lifetime of formaldehyde and acetaldehyde. Four sites were chosen. Sampling was carried out at different seasons and atmospheric conditions. The results indicated that formaldehyde was the most abundant carbonyl, followed by acetone and acetaldehyde. Data sets obtained from the 4 sites were chosen to calculate the total rate of photolysis and the photolytic lifetime for formaldehyde and acetaldehyde. Maximum photolytic rate values were obtained at the maximum actinic fluxes, as was to be expected.     

Evaluation of the community multiscale air quality (CMAQ) model version 4.5: Sensitivities impacting model performance; Part II—particulate matter

This paper is Part II in a pair of papers that examines the results of the Community Multiscale Air Quality (CMAQ) model version 4.5 (v4.5) and discusses the potential explanations for the model performance characteristics seen. The focus of this paper is on fine particulate matter (PM_2.5) and its chemical composition. Improvements made to the dry deposition velocity and cloud treatment in CMAQ v4.5 addressing compensating errors in 36-km simulations improved particulate sulfate (SO₄²⁻) predictions. Large overpredictions of particulate nitrate (NO₃⁻) and ammonium (NH₄⁺) in the fall are likely due to a gross overestimation of seasonal ammonia (NH₃) emissions. Carbonaceous aerosol concentrations are substantially underpredicted during the late spring and summer months, most likely due, in part, to a lack of some secondary organic aerosol (SOA) formation pathways in the model. Comparisons of CMAQ PM_2.5 predictions with observed PM_2.5 mass show mixed seasonal performance. Spring and summer show the best overall performance, while performance in the winter and fall is relatively poor, with significant overpredictions of total PM_2.5 mass in those seasons. The model biases in PM_2.5 mass cannot be explained by summing the model biases for the major inorganic ions plus carbon. Errors in the prediction of other unspeciated PM_2.5 (PM_Other) are largely to blame for the errors in total PM_2.5 mass predictions, and efforts are underway to identify the cause of these errors.