Quantum Chemical Calculations Resolved Identification of Methylnitrocatechols in Atmospheric Aerosols

摘要

Methylnitrocatechols (MNCs) are secondary organic aerosol (SOA) tracers and major contributors to atmospheric brown carbon; however, their formation and aging processes in atmospheric waters are unknown. To investigate the importance of aqueous-phase electrophilic substitution of 3-methylcatechol with nitronium ion (NO_2~+), we performed quantum calculations of their favorable pathways. The calculations predicted the formation of 3- methyl-5-nitrocatechol (3MSNC), 3-methyl-4-nitrocatechol (3M4NC), and a negligible amount of 3-methyl-6-nitro- catechol (3M6NC). MNCs in atmospheric PM_2 samples were further inspected by LC/(-)ESI-MS/MS using commercial as well as de novo synthesized authentic standards. We detected 3MSNC and, for the first time, 3M4NC. In contrast to previous reports, 3M6NC was not observed. Agreement between calculated and observed 3MSNC/3M4NC ratios cannot unambiguously confirm the electrophilic mechanism as the exclusive formation pathway of MNCs in aerosol water. However, the examined nitration by NO_2~+ is supported by (1) the absence of 3M6NC in the ambient aerosols analyzed and (2) the constant 3MSNC/3M4NC ratio in field aerosol samples, which indicates their common formation pathway. The magnitude of error one could make by incorrectly identifying 3M4NC as 3M6NC in ambient aerosols was also assessed, suggesting the importance of evaluating the literature regarding MNCs with special care.