Heterogeneous ozonation of suspended malathion and chlorpyrifos particles

The heterogeneous ozonation of suspended malathion and chlorpyrifos particles are studied in real-time with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The pesticide particles with the diameter of hundreds of nanometers are generated by the homogeneous nucleation method using azelaic acid as nucleus. The reactions are carried out in an aerosol reaction chamber under ambient pressure (1 atm) and room temperature (298 K), respectively. The time-of-flight mass spectra of the solid-state ozonation products of malathion and chlorpyrifos are obtained. The assignments of the mass spectra reveal that the major ozonation products of malathion particles are s-(1,2-diethoxycarbonyl)ethyl-O,O-dimethylphosphorothioate (malaoxon), 2-mercapto-succinic acid diethylester, 1,2-dicarbethoxyethyl-dimethoxyphosphinyldisulfide and bis(1,2-bis-ethoxycarbonyl-ethyl)disulfide. The experimental results reveal that water vapor can enhance the formation of malaoxon, 2-mercapto-succinic acid diethylester and bis(1,2-bis-ethoxycarbonyl-ethyl)disulfide. In the case of chlorpyrifos, the sole ozonation product observed is 3,5,6-trichloro-2-pyridyl-diethylphosphate (chlorpyrifos oxon). The pathways of heterogeneous ozonation of malathion and chlorpyrifos particles are proposed. The atmospheric lifetimes of malathion and chlorpyrifos particles towards ozone reaction are estimated based on the time-dependent mass spectrometric signals obtained.