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Big datasets of air-quality pollutants and weather data allow us to review trends of NO2, NO, O3, and global radiation (GR), for Lisbon, Porto and Coimbra, with regard to the historical period of 2010–2018. GR is expected to have a considerable impact on photochemical reactions of the O3 formation mechanism. We aim to characterize daily, monthly, and yearly trends. We explore Weekday (WD) versus weekend (WE), and seasonality of O3 and NO2. We are interested to know these pollutant peak concentration variations over the years and investigate if parallels can be drawn between urban mobility indicators and these pollutants. For this purpose, economic data, European emission standards, and car stock data (fuel, age, and number of vehicles) are cross-analyzed. How are they correlated? Has it impacted NO2 and O3 variations? How do different air-quality monitoring stations (AQMS), traffic and non-traffic, compare? How is Lisbon NOx-O3 correlated? What are its implications for future scenarios? Results show that urban mobility trends and economic events are correlated with NO2 and O3 variability. Weekend effect has a partial relationship with urban mobility trends and economy as it is relatively well correlated for Lisbon but not for Porto and Coimbra. Nonetheless, weekend effect for the period of 2010–2018 is overall trending upwards for all cities. In Lisbon and Coimbra, O3 concentrations also trend upwards during the same 2010–2018 period but for Porto they do not. Regardless, for the period of 2015–2018, after the economic recession, the upwards trends of both weekend effect and overall O3 concentrations are clear for all AQMS. For AQMS peak values comparison, Lisbon traffic AQMS registered an annual averaged 8-hour daily max O3 concentration of 34.4 ppb while Lisbon non-traffic AQMS presented 39.1 ppb. Altogether, annual 8-hour daily maximum values for 2010–2018 traffic AQMS in Lisbon show an inverse relationship with fuel sales, and have concentrations fluctuating between 28–35 ppb, which is slightly higher than the 2001–2010 historical European range of 27–31 ppb. Lastly, for the 8 years data in Lisbon, it has been shown that a negative NOx-O3 correlation exists, and the study location might be VOC–sensitive. This means that as NOx concentrations decrease, O3 concentrations become exponentially higher. Further research into VOCs with better data availability is required to make more concise claims. Regardless, it can be inferred that in a future scenario where mitigation continues to escalate, through O3 emission standards and an aggressive shift of car stock to electric vehicles, achieving unprecedented rises in O3 concentrations could be observed.

Urban Ground-Level O3 Trends: Lessons from Portuguese Cities, 2010–2018