Inferring Changes in Summertime Surface Ozone-NO_x-VOC Chemistry over U.S. Urban Areas from Two Decades of Satellite...

Urban ozone (O₃) formation can be limited by NO_x, VOCs, or both, complicating the design of effective O₃ abatement plans. A satellite-retrieved ratio of formaldehyde to NO₂ (HCHO/NO₂), developed from theory and modeling, has previously been used to indicate O₃ formation chemistry. Here, we connect this space-based indicator to spatiotemporal variations in O₃ recorded by on-the-ground monitors over major U.S. cities. High-O₃ events vary nonlinearly with OMI HCHO and NO₂, and the transition from VOC-limited to NO_x-limited O₃ formation regimes occurs at higher HCHO/NO₂ value (3 to 4) than previously determined from models, with slight intercity variations. To extend satellite records back to 1996, we develop an approach to harmonize observations from GOME and SCIAMACHY that accounts for differences in spatial resolution and overpass time. Two-decade (1996-2016) multisatellite HCHO/NO₂ captures the timing and location of the transition from VOC-limited to NO_x-limited O₃ production regimes in major U.S. cities, which aligns with the observed long-term changes in urban-rural gradient of O₃ and the reversal of O₃ weekend effect. Our findings suggest promise for applying space-based HCHO/NO₂ to interpret local O₃ chemistry, particularly with the new-generation satellite instruments that offer finer spatial and temporal resolution.