AbstractNitrate radicals are being recognized as key intermediates in a growing list of important chemical processes in the atmosphere. Here, the role of nitrate radicals (NO3) in tropospheric chemistry is discussed, with special emphasis on results from field measurements, most of which have been made by differential optical absorption spectroscopy (DOAS), with matrix‐isolation electron spin resonance being an alternative technique. Nitrate radicals were observed in the atmosphere at peak mixing ratios of 350 ppt. Long‐term observation of NO3 shows that 24‐h averages in rural air masses are closer to a few ppt. Nevertheless, the NO3 radical plays an important role in the non‐photochemical conversion of NOx to HNO3. Also, NO3 is a strong oxidizing agent and initiates the night‐time removal of atmospheric trace species such as olefins, aromatic hydrocarbons, and organic sulfur compounds. Finally, night‐time peroxy radical production and release of reactive halogen species from sea salt aerosol might be initiated by NO3 reactions.
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