Structural and hygroscopic changes of soot during heterogeneous reaction with O3

Soot aerosols are ubiquitous in the atmosphere and play an important role in global and regional radiative balance and climate. Their environmental impact, however, greatly depends on their structure, composition, particle size, and morphology. In this study, the structural changes of a model soot (Printex U) during a heterogeneous reaction with 80 ppm O3 at 298 K were investigated using in situ Raman spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and transmission electron microscopy (TEM). Hygroscopic changes due to heterogeneous reaction with O3 were also studied by water sorption analyzer. The consumption of amorphous carbon (D3 band) and disordered graphitic lattice (D4 band) of soot by ozonization was confirmed by the decrease in the full widths at half maximum and their relative integrated intensities (percentages of integrated areas). Oxygen containing surface species including ketone, lactone, and anhydride were also observed in Raman and IR spectra of ozonized soot. The ozonized soot showed more compacted aggregates with a smaller average diameter of primary particles (29.9 ± 7.7 nm) and a larger fractal dimension (1.81 ± 0.08) when compared with fresh soot (36.9 ± 9.4 nm, and 1.61 ± 0.10). The ozonization reaction leads to an enhancement of hygroscopicity of soot due to the decrease in particle diameter and the formation of oxygen containing surface species.