Molecular characterization of oxidized organic nitrogen in the polluted urban atmosphere of Beijing

Oxidized organic nitrogen (OON) serves as a crucial link between volatile organic compounds (VOCs), nitrogen oxides, ozone, and secondary organic aerosol (SOA). However, the comprehension of the molecular composition, formation mechanism, and implications of OON remains limited, particularly in urban environments influenced heavily by anthropogenic emissions. This study presents the field measurements of OON conducted at an urban site in Beijing using chemical ionization mass spectrometry with nitrate as the reagent ion. The molecular characteristics, dominant species, and oxidation states of OON were investigated. Positive matrix factorization analysis disentangled the diverse OON into factors characterized by unique fingerprint features and formation pathways. A modified workflow was used to classify the majority of OON as terpene (3.0 %), isoprene (15.2 %), aliphatic (38.1 %, containing dinitrate), and aromatic (36.0 %, containing aromatic ring retaining) OON. This highlights the significant impact of anthropogenic sources and underscores the need for stringent controls on anthropogenic VOC emissions to mitigate OON formation. Volatility estimates further indicate that aromatic and aliphatic OON, with relatively low volatility, are expected to be the primary contributors to SOA formation by condensation or gas-particle partitioning in urban Beijing. In addition, hazy weather conditions may facilitate multi-generation reactions, leading to the production of large amounts of semi-volatile dinitrate OON and promoting its conversion to SOA.