Solid-phase supported profluorescent nitroxide probe for the determination of aerosol-borne reactive oxygen species

Reactive oxygen species (ROS) and free radicals play important roles in the chemical transformation and adverse health effects of environmental aerosols. This work presents a simple and sensitive method for sampling and analysis of ROS using a packed column coated with a profluorescent nitroxide scavenger, proxyl fluorescamine (PF). Quantification was performed by extraction and analysis using HPLC with fluorescence detection. For comparison, the conventional method of collecting aerosols into dichlorofluorescin (DCFH) aqueous solution was used as a reference.

The method was successfully applied to the determination of ROS in a model secondary organic aerosol (SOA) system generated by ozonolysis of nicotine, as well as in secondhand tobacco smoke (SHS). ROS concentrations between 50–565 nmol m⁻³ were detected in fresh SOA and SHS samples. After SHS aging for 22 h, 13–18% of the initial ROS mass remained, suggesting the presence of persistent ROS. The new method offers better stability and reproducibility along with sensitivity comparable to that of DCFH (method detection limit of 3.2 and 1.4 nmol m⁻³ of equivalent H₂O₂ for PF and DCFH respectively). The PF probe was stable during storage at room temperature and not reactive with ozone or NO_x, whereas DCFH in the particle-collecting liquid system was strongly influenced by ozone and NO_x interferences. This case study provides a good basis for employing solid-phase supported PF for field measurement of specific ROS in other combustion systems (i.e. biomass burning, candles, and diesel exhaust) and environmental aerosols.