Unprecedented Ambient Sulfur Trioxide (SO₃) Detection: Possible Formation Mechanism and Atmospheric Implications

Sulfur trioxide (SO₃) is a crucial compound for atmospheric sulfuric acid (H₂SO₄) formation, acid rain formation, and other atmospheric physicochemical processes. During the daytime, SO₃ is mainly produced from the photo-oxidation of SO₂ by OH radicals. However, the sources of SO₃ during the early morning and night, when OH radicals are scarce, are not fully understood. We report results from two field measurements in urban Beijing during winter and summer 2019, using a nitrate-CI-APi-LTOF (chemical ionization-atmospheric pressure interface-long-time-of-flight) mass spectrometer to detect atmospheric SO₃ and H₂SO₄. Our results show the level of SO₃ was higher during the winter than during the summer, with high SO₃ levels observed especially during the early morning (∼05:00 to ∼08:30) and night (∼18:00 to ∼05:00 the next day). On the basis of analysis of SO₂, NO_x, black carbon, traffic flow, and atmospheric ions, we suggest SO₃ could be formed from the catalytic oxidation of SO₂ on the surface of traffic-related black carbon. This previously unidentified SO₃ source results in significant H₂SO₄ formation in the early morning and thus promotes sub-2.5 nm particle formation. These findings will help in understanding urban SO₃ and formulating policies to mitigate secondary particle formation in Chinese megacities.