Spatial and temporal variation of surface ozone, NO and NO2 at urban, suburban, rural and industrial sites in the southwest of the Iberian Peninsula

Surface ozone is one of the most important photochemical pollutants in the low atmosphere, causing damage to human health, vegetation, materials and climate. The weather (high temperatures and high solar radiation), orography (presence of the Guadalquivir valley) and anthropogenic (the cities of Cadiz, Cordoba, Huelva and Seville and two important industrial complexes) characteristics of the southwestern Iberian Peninsula make this region ideal for the formation and accumulation of ozone. To increase the knowledge of ozone behaviour in this area, the monthly, daily and weekly variations of ozone and its precursors, nitrogen oxides (NOx = NO + NO2), were analysed over a 4-year period (2003 to 2006). Using the k-means cluster technique, 12 representative stations of five different areas with different ozone behaviour were selected from a total of 29 monitoring sites. This is the first time that the analysis of these atmospheric pollutants has been carried out for the whole area, allowing therefore a complete understanding of the dynamics and the relationships of these compounds in this region. The results showed an opposite behaviour among ozone and NO and NO2 concentrations in urban and suburban zones, marked by maximums of ozone (minimums NOx) in spring and summer and minimums (maximums) in autumn and winter. A seasonal behaviour, with lower amplitude, was also observed in rural and industrial areas for ozone concentrations, with the NO and NO2 concentrations remaining at low and similar values during the year in rural zones due to the absence of emission sources in their surroundings. The daily cycles of ozone in urban, suburban and industrial sites registered a maximum value in the early afternoon (14:00–17:00 UTC) while for NOx two peaks were observed, at 7:00–10:00 UTC and 20:00–22:00. In the case of rural stations, no hourly peak of ozone or NOx was registered. The weekend effect was studied by using a statistical contrast tests (Student’s t). The results indicated that only areas influenced by important traffic emissions presented a weekend effect for NO and NO2, whereas an ozone weekend effect was not detected in any case.