The city of Ostrava, NE Czech Republic, is known for its industrial pollution. It has well-characterized emission sources and stable air movement patterns. These features are conveniently used to generalize on atmospheric NOx and SO2 oxidation processes. In 2021, we conducted a series of sampling campaigns to assess the isotopic fractionation conducive to NO3− and SO42− aerosols in PM10. These sampling campaigns were timed to capture varying atmospheric conditions, including climatic inversion periods, providing also insights into urban emission dynamics over the course of the year. Gaseous NOx and SO2 were collected on passive filters, while their oxidized forms, NO3− and SO42, were captured on PM10 particle filters, enabling us to analyze the transformation dynamics of these pollutants. Isotopic analyses distinguished the sources of NOx emissions—coal combustion (δ15N = −3‰) and vehicular emissions (δ15N = −7 ‰)—and allowed quantifying isotope fractionation during their conversion to NO3− (εNOx-NO3- = 11.5 ± 1.15 ‰). This fractionation, however, was influenced by seasonal variations, and appears to be notably affected by NH4NO3 decomposition during warmer months. The correlation of the NO3− to NOx ratio with PM10 and atmospheric moisture highlighted the interplay between particulate matter and humidity in relevant atmospheric transformations. Similarly, for SO2, primarily emitted from coal combustion (δ34S = −2‰), we identified distinct fractionation patterns during oxidation to SO42− encompassing both kinetic (εSO2-H2O = −1.3 ± 0.5‰) and equilibrium (εSO2- SO42- = 2.24 ± 0.67‰) effects. The SO42−/SO2 ratio was correlated with PM10 but showed no dependence on humidity. Significantly, atmospheric inversion conditions accelerated oxidation, modifying the fractionation patterns for both NOx (εNOx-NO3- = 7‰) and SO2 (εSO2- SO42-= −0.9 ± 0.3‰). Our methodology elucidates pivotal mechanisms in atmospheric pollution transformation, underlined by the tracing of NOx and SO2 to aerosol conversions via δ15N and δ34S isotopic analyses. The isotope fractionation underscores equilibrium processes in oxidation reactions, while the effect of PM10 and humidity reveals the complexity of these atmospheric oxidative transformations. The role of wet deposition in removing SO2 highlights an essential pathway in the atmospheric sulfur cycle.
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