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This paper analyses surface ozone measurements at five stations in an urban area (Valladolid) in the upper Spanish plateau over the period 2002–2020. Temporal evolutions, the relationship between ozone and other pollutants such as nitrogen oxides, and the assessment of the ozone concentration trend during the study period were analysed. Daily evolution of ozone at all the stations showed mean maximum concentrations in the afternoon, 15:00 GMT, with values ranging between 73.8 and 80.9 µg m−3, evidencing the influence of photochemical processes favoured by solar radiation in ozone formation. The lowest levels were recorded at night and in the early morning, 7:00 GMT, and were between 23.4 and 32.3 µg m−3, related with the reduction by NO reactions and deposition processes. A broad spring–summer peak between May and July was seen, with the highest values in the latter, with a mean value of up to 73.8 µg m−3. The variation in the monthly mean ozone concentrations of the different percentiles was analysed using a harmonic model. The empirical equation described the experimental values satisfactorily, with a confidence level of 95% and coefficients of determination above 80%, confirming the major decreasing trend in the ozone peak values over the study period.

Analysis of Ozone Concentrations between 2002–2020 in Urban Air in Northern Spain