Chemical Synthesis of Multifunctional Air Pollutants: Terpene-Derived Nitrooxy Organosulfates

Nitrooxy organosulfates derived from terpenes (NOS_TP) represent an important class of products formed between anthropogenic pollution (e.g., SO₂ and NO) and natural emissions. NOS_TP compounds have been consistently detected in atmospheric environments under varying urban influences. Their chemical linkages to both anthroposphere and biosphere make them valuable markers for tracking anthroposphere-biosphere interactions. However, their quantification, formation, and transformation kinetics in atmospheric aerosols are hindered due to the lack of NOS_TP standards. In this work, we developed two routes for the first concise chemical synthesis of eight NOS_TP from terpenes including α-pinene, β-pinene, limonene, limonaketone, and β-caryophyllene. Subsequently, six of the synthesized NOS_TP were for the first time positively identified in ambient aerosol samples, clarifying certain misidentifications in previous studies. More significantly, the availability of authentic standards allows irrefutable observation of three carbon skeleton-rearranged NOS_TP, two derived from α-pinene, and one derived from β-caryophyllene, revealing the occurrence of previously unrecognized transformation pathways in the formation of NOS_TP. Two synthesized NOS_TP from β-pinene and limonene could not be detected, likely due to rapid hydrolysis of their immediate hydroxynitrate precursors outcompeting sulfation. Such mechanistic evidence is valuable in understanding the atmospheric chemistry of NOS_TP and related compounds. This work demonstrates the usefulness of authentic standards in probing the NOS_TP formation mechanisms in the atmosphere. Comparison of NOS_TP ambient samples collected from four Chinese cities in two winter months indicates that anthropogenic chemical factors could outcompete terpene emissions in the formation of NOS_TP.