The formation of nitro-aromatic compounds under high NO&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt; and anthropogenic VOC conditions in urban Beijing, China
Authors: Wang Yujue , Hu Min , Wang Yuchen , Zheng Jing , Shang Dongjie , Yang Yudong , Liu Ying , Li Xiao , Tang Rongzhi , Zhu Wenfei , Du Zhuofei , Wu Yusheng , Guo Song , Wu Zhijun , Lou Shengrong , Hallquist Mattias , Yu Jian Zhen 
Published: June 2019

Abstract. Nitro-aromatic compounds (NACs), as important contributors to the light absorption by brown carbon, have been widely observed in various ambient atmospheres; however, their formation in the urban atmosphere was little studied. In this work, we report an intensive field study of NACs in summer 2016 at an urban Beijing site, characterized by both
high-NOx and anthropogenic VOC dominated conditions. We investigated the factors that influence NAC formation (e.g., NO2, VOC precursors, RH and photolysis) through quantification of eight NACs, along with major components in fine particulate matter, selected volatile organic compounds, and gases. The average total concentration of the quantified NACs was 6.63 ng m−3, higher than those reported in other summertime studies (0.14–6.44 ng m−3). 4-Nitrophenol (4NP, 32.4 %) and 4-nitrocatechol (4NC,
28.5 %) were the top two most abundant NACs, followed by
methyl-nitrocatechol (MNC), methyl-nitrophenol (MNP), and
dimethyl-nitrophenol (DMNP). The oxidation of toluene and benzene in the
presence of NOx was found to be a more dominant source of NACs than primary biomass burning emissions. The NO2 concentration level was found to be an important factor influencing the secondary formation of NACs. A transition from low- to high-NOx regimes coincided with a shift from
organic- to inorganic-dominated oxidation products. The transition
thresholds were NO2 ∼ 20 ppb for daytime and
NO2∼25 ppb for nighttime conditions. Under low-NOx conditions, NACs increased with NO2, while the NO3- concentrations and (NO3-)/NACs ratios were lower, implying organic-dominated products. Under high-NOx conditions, NAC concentrations did not further increase with NO2, while the
NO3- concentrations and (NO3-)/NACs ratios showed
increasing trends, signaling a shift from organic- to inorganic-dominated
products. Nighttime enhancements were observed for 3M4NC and 4M5NC, while
daytime enhancements were noted for 4NP, 2M4NP, and DMNP, indicating
different formation pathways for these two groups of NACs. Our analysis
suggested that the aqueous-phase oxidation was likely the major formation
pathway of 4M5NC and 3M5NC, while photo-oxidation of toluene and benzene in
the presence of NO2 could be more important for the formation of
nitrophenol and its derivatives. Using the (3M4NC+4M5NC) ∕ 4NP ratios as an indicator of the relative contribution of aqueous-phase and gas-phase
oxidation pathways to NAC formation, we observed that the relative
contribution of aqueous-phase pathways increased at elevated ambient RH and
remained constant at RH > 30 %. We also found that the
concentrations of VOC precursors (e.g., toluene and benzene) and aerosol
surface area acted as important factors in promoting NAC formation, and
photolysis as an important loss pathway for nitrophenols.