Variation of Radiative Properties During Black Carbon Aging: Theoretical and Experimental Intercomparison

A theoretical black carbon (BC) aging model is developed to account for three typical evolution stages, namely, freshly emitted aggregates, coated BC by soluble material, and BC particles undergoing further hygroscopic growth. The geometric-optics surface-wave (GOS) approach is employed to compute the BC single-scattering properties at each aging stage, which are subsequently compared with laboratory measurements. Theoretical calculations are consistent with measurements in extinction and absorption cross sections for fresh BC aggregates, but overestimate the scattering cross sections for BC mobility diameters of 155, 245, and 320 nm, because of uncertainties associated with theoretical calculations for small particles as well as laboratory scattering measurements. The measured optical cross sections for coated BC by sulfuric acid and for those undergoing further hygroscopic growth are captured by theoretical calculations using a concentric core-shell structure, with differences of less than 20%. This suggests that the core-shell shape represents the realistic BC coating morphology reasonably well in this case, which is consistent with the observed strong structure compaction during aging. We find that the absorption and scattering properties of fresh BC aggregates vary by up to 60% due to uncertainty in the BC refractive index, which, however, is a factor of two smaller in the case of coated BC particles. Sensitivity analyses on the BC morphology show that the optical properties of fresh BC aggregates are more sensitive to fractal dimension than primary spherule size. The absorption and scattering cross sections of coated BC particles vary by more than a factor of two due to different coating structures. We find an increase of 20-250% in absorption and a factor of 3-15 in scattering during aging, significantly depending on coating morphology and aging stages. Applying the aging model to CalNex 2010 field measurements, we show that the resulting BC direct radiative forcing (DRF) first increases from 1.5 to 1.7 W m-2 and subsequently decreases to 1.0 W m-2 during the transport from the Los Angeles Basin to downwind regions, as a result of the competition between absorption enhancement due to coating and dilution of BC concentration. The BC DRF can vary by up to a factor of two due to differences in BC coating morphology. Thus, an accurate estimate of BC DRF requires the incorporation of a dynamic BC aging process that accounts for realistic morphology in climate models, particularly for the regional analysis with high atmospheric heterogeneity.