Air quality indicators, i.e., PM10, NO2, O3, benzo[a]pyrene, and several organic tracer compounds were evaluated in an urban traffic station, a sub-urban background station, and a rural background station of the air quality network in Catalonia (Spain) from summer to winter 2019. The main sources that contribute to the organic aerosol and PM toxicity were determined. Traffic-related air pollution dominated the air quality in the urban traffic station, while biomass burning in winter and secondary organic aerosol (SOA) in summer impact the air quality in the sub-urban and rural background stations. Health risk assessment for chronic exposure over the past decade, using WHO air quality standards, showed that NO2, PM10 and benzo[a]pyrene from traffic emissions pose an unacceptable risk to the human population in the urban traffic station. PM10 and benzo[a]pyrene from biomass burning were unacceptably high in the sub-urban and rural background stations. Toxicity tests of the PM extracts with epithelial lung cells showed higher toxicity in wintertime samples in the sub-urban and rural stations, compared to the urban traffic station. These results require different mitigation strategies for urban and rural sites in order to improve the air quality. In urban areas, traffic emissions are still dominating the air quality, despite improvements in the last years, and may directly be responsible for part of the SOA and O3 levels in sub-urban and rural areas. In these later areas, air pollution from local biomass burning emissions are dominating the air quality, essentially in the colder period of the year.