Excessive accumulation of reactive oxygen species (ROS) in the body can lead to a redox imbalance and result in cellular and tissue damage. Since ROS are highly reactive, traditional offline methods may underestimate their true concentration. In this study, we developed an online monitoring system for particle-bound ROS based on the fluorescent probe 2′,7′-dichlorofluorescin (DCFH), which consists of an Aerosol Collector and a Fluorescence Detector. The performance of the system was evaluated in terms of collection efficiency, instrument calibration, and comparison with offline methods. The results demonstrate that the collection efficiency of the system is over 93%, the calibration correlation coefficient (R²) is 99.75%, and the online system reduces ROS loss due to offline methods by more than 60%. The system has a temporal resolution of 20 min and the limit of detection of the system was 1.9 nmol H₂O₂/m³. Field observations revealed that particle-bound ROS exhibited similar diurnal variations to O₃, and photochemical reactions were the main factors affecting its diurnal variation.

In this study, the chemical compositions of PM_2.5 (particulate matter < 2.5 μm) and the molecular compositions of methanol-soluble organic carbon (MSOC) in suburban Shanghai during summer were measured to investigate the molecular characteristics of organic aerosol (OA) under high humidity. Diurnal variation analysis reveals the influence of relative humidity (RH) on secondary organic aerosol (SOA) components. Organosulfates (OSs), particularly nitrooxy-OSs, exhibit a positive correlation with increasing humidity rather than atmospheric oxidants in this high-humidity site. This suggests that high RH can promote the formation of OSs, possibly through enhancing particle surface area and volume, and creating a favorable environment for aqueous-phase or heterogeneous reactions in the particle phase. A considerable proportion of CHOS compounds may be derived from anthropogenic aliphatic hydrocarbon derivatives. These compounds exhibit slightly elevated daytime concentrations due to increased emissions of long-chain aliphatics from sources such as diesel combustion, as well as photochemically enhanced oxidation to OSs. In contrast, CHONS compounds increased at night, driven by high-humidity liquid-phase oxidation. Terpenoid derivatives accounted for 13.4% of MSOC and contributed over 40% to nighttime CHONS. These findings highlight humidity’s important role in driving daytime and nighttime processing of anthropogenic and biogenic precursors to form SOA, even under low SO₂ and NO_x conditions.