Photolysis frequency of nitrophenols derived from ambient measurements

Nitrophenols, a class of important intermediate products from the oxidation of aromatics, can participate in photochemistry and influence the atmospheric oxidative capacity. However, the reported photolysis frequencies of nitrophenols show considerable discrepancies. Here, measurements of nitrophenol, and methyl nitrophenol using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) at both urban and regional sites in southern China are used to constrain photolysis frequencies of nitrophenols. Considerable concentrations with a campaign average of 58 ± 32 ppt for nitrophenol and 97 ± 59 ppt for methyl nitrophenol were observed at the regional site. Based on the in-situ measurement dataset, a steady-state calculation was performed along with a zero-dimensional box model to analyze the budgets of nitrophenols. The result indicates that both primary emission and photolysis have significant impacts on nitrophenols. Primary emission contributes up to 88 % of the total nitrophenols production while photolysis accounts for up to 98 % of the total removal rate. The dominant sink of nitrophenols is photolysis with a rate of about 3.5 % ± 1.3 % of j_NO for nitrophenol and 2.4 % ± 1.0 % of j_NO for methyl nitrophenol. The results of this study suggest that using advanced mass spectrometry to accurately measure ambient nitrophenols, supplemented by an observation-based box model for budget analysis, provides an important indication for determining photolysis rate constants of nitrophenols.