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Atmospheric peroxides, especially hydrogen peroxide (H2O2), are essential oxidants. The peroxide concentration is closely related to the extent of OH radicals and the O3 cycle in the tropospheric atmospheric chemistry. However, only a few studies have investigated their atmospheric concentrations in China because of inadequacies in the measurement techniques or higher costs of analytical instruments. Therefore, it is essential to design a suitable analysis method of peroxides with higher sensitivity, lower detection limit, and low cost. In view of that, this study investigated the optimum analysis conditions of two H2O2 analytical techniques: the high-performance liquid chromatography (HPLC) with fluorescence detection using two-enzyme catalysis of horseradishperoxidase (HRP method) and Hemin (Hemin method). Furthermore, these two analysis methods were systematically compared in terms of detection limit, calibration curve, precision, accuracy, and applicability for the first time. The findings showed that the HRP method had a lower detection limit, higher sensitivity, and better applicability for detecting H2O2 and methyl hydroperoxide (MHP) than the Hemin method. Moreover, the HRP method is better suitable for H2O2 and MHP detection, which requires low detection limits and high sensitivity. Besides this, the Hemin method is inexpensive and is more suitable for detecting hydroxyl alkyl peroxides (C ≥ 3). The atmospheric concentrations (average) of H2O2 and MHP were 0.60 ± 0.37 ppb and 0.081 ± 0.039 ppb, respectively, as determined by the HRP method. Importantly, atmospheric peroxide concentrations were higher on sunny days than on cloudy days in Beijing in September 2016. H2O2 concentrations showed a diurnal variation with the lowest value in the morning and two peaks at 13:00–17:00. In contrast, MHP concentrations were lowest in the morning and highest after 17:00. Photochemical reactions were responsible for the production of H2O2 and MHP. The reactions of O3 and olefins emitted by motor vehicles also caused H2O2 concentration to increase during the evening rush hour.

Comparison of Fluorescent Techniques Using Two Enzymes Catalysed for Measurement of Atmospheric Peroxides