Atmospheric Chemistry Special Feature: Effect of intrinsic organic carbon on the optical properties of fresh diesel soot

摘要

This study focuses on the retrieval of the normalized mass absorption cross section (MAC) of soot using theoretical calculations that incorporate new measurements of the optical properties of organic carbon (OC) intrinsic to fresh diesel soot. Intrinsic OC was extracted by water and an organic solvent, and the complex refractive index of the extracted OC was derived at 532 and 355-nm wavelengths using cavity ring-down aerosol spectrometry. The extracted OC was found to absorb weakly in the visible wavelengths and moderately at blue wavelengths. The mass ratio of OC and elemental carbon (EC) in the collected particles was evaluated using a thermo-optical method. The measured EC/OC ratio in the soot exhibited substantial variability from measurement to measurement, ranging between 2 and 5. To test the sensitivity of the MAC to this variability, three different EC/OC ratios (2∶1, 1∶1, and 1∶2) were chosen as representative. Particle size and spherule morphology were estimated using scanning electron microscopy, and the soot was found to be primarily in the form of aggregates with a dominant aggregate diameter mode in the range 200–250 nm. The measured refractive index of the extracted OC was used with a variety of theoretical models to calculate the MAC of internally mixed diesel soot at 532 and 355 nm. We conclude that Rayleigh–Debye–Gans theory on clusters of coated spherules and T-matrix of a solid EC spheroid coated by intrinsic OC are both consistent with previous measurements; however, Rayleigh–Debye–Gans theory provides a more realistic physical model for the calculation