An urban photochemistry study in Santiago de Chile

During spring time 2002 a field experiment was carried out in the Metropolitan Area of Santiago de Chile at three monitoring sites located along a SW–NE transect that represents upwind, downtown and downwind conditions, respectively. Three consecutive days (30 October–01 November 2002) reflecting different photochemical and meteorological conditions were selected. These days included two workdays and one holiday and thus the effect of different primary emissions could be investigated. A variety of trace gas measurements (O3, NOx, CO, volatile organic compounds (VOC)) were obtained at these sites. Alkanes represent the largest VOC fraction at all sites, followed by aromatics and alkenes, the smallest fractions are represented by the alkynes or isoprene. Regarding reactivity ranking propene equivalent values show that during morning hours, alkenes are the most reactive compounds, at noon, aromatics are dominant, and in the afternoon isoprene becomes important. Alkanes do not contribute more than 20% to the total air mass reactivity despite being present at the higher concentration levels. Regarding liquefied petroleum gas (LPG) impacts, we find a threefold decrease of concentrations at the eastern side of the city—and no significant trend at Downtown Santiago—which we ascribe to a switch to natural gas in the higher income eastern side of town. The generation of ozone impacts above 50 ppbv is mainly due to anthropogenic traffic-related hydrocarbons. In addition, traffic emissions are contributing most to the formation of secondary organic aerosols (SOA). A model study was carried out, applying a Lagrange trajectory model coupled with photochemical and aerosol modules. The model results are in good agreement with the observations. Additionally, the relative contribution of the respective hydrocarbons to the ozone production in an air parcel along the trajectory was computed. The model also indicates SOA formation by means of oxidation of higher alkanes, alkenes, and aromatics, the latter being the major contributors to those secondary pollutants.