One of the main hypotheses for the species causing the observed health effects of ambient particulate matter is peroxides and other reactive oxygen species (ROS). However, there is currently very little data available on the concentrations of particle-bound ROS or their behavior in different physical locations and seasons. The concentrations of particle-bound ROS were determined for various size fractions of the aerosol, ranging from 10 nm to 18 m, in Flushing, New York during the period of January and early February 2004. Sampling was carried out at 3-hour intervals using a MOUDI™ cascade impactor. The collected particles were treated with the non-fluorescent probe dichlorofluorescin (DCFH) that fluoresces when oxidized by the presence of ROS. The measured fluorescent intensities were converted into equivalent hydrogen peroxide concentrations, which were used as indicators of ROS reactivity, by calibrations using H2O2 standards. Diurnal profiles of the ROS concentrations were obtained. Correlations of the particulate ROS concentrations with the intensity of photochemical reaction, estimated secondary organic carbon (SOC) and gas phase OH and HO2 radical concentrations were explored. The intensity of photochemical reactions and gas phase radical concentrations were found to be moderate factors affecting particulate ROS concentrations. The concentrations of ROS were found to be higher in the submicron size particles of the ambient aerosol.