Particle-Phase Photoreactions of HULIS and TMIs Establish a Strong Source of H₂O₂ and Particulate Sulfate in the Winter North China Plain

During haze periods in the North China Plain, extremely high NO concentrations have been observed, commonly exceeding 1 ppbv, preventing the classical gas-phase H₂O₂ formation through HO₂ recombination. Surprisingly, H₂O₂ mixing ratios of about 1 ppbv were observed repeatedly in winter 2017. Combined field observations and chamber experiments reveal a photochemical in-particle formation of H₂O₂, driven by transition metal ions (TMIs) and humic-like substances (HULIS). In chamber experiments, steady-state H₂O₂ mixing ratios of 116 ± 83 pptv were observed upon the irradiation of TMI- and HULIS-containing particles. Correspondingly, H₂O₂ formation rates of about 0.2 ppbv h^–1 during the initial irradiation periods are consistent with the H₂O₂ rates observed in the field. A novel chemical mechanism was developed explaining the in-particle H₂O₂ formation through a sequence of elementary photochemical reactions involving HULIS and TMIs. Dedicated box model studies of measurement periods with relative humidity >50% and PM_2.5 ≥ 75 μg m^–3 agree with the observed H₂O₂ concentrations and time courses. The modeling results suggest about 90% of the particulate sulfate to be produced from the SO₂ reaction with OH and HSO₃^– oxidation by H₂O₂. Overall, under high pollution, the H₂O₂-caused sulfate formation rate is above 250 ng m^–3 h^–1, contributing to the sulfate formation by more than 70%.