Vapor Condensation and Coating Evaporation Are Both Responsible for Soot Aggregate Restructuring.

Fresh soot is made of fractal aggregates, which often appear collapsed in atmospheric samples. A body of work has concluded that the collapse is caused by liquid shells when they form by vapor condensation around soot aggregates. However, some recent studies argue that soot remains fractal even when engulfed by the shells, collapsing only when the shells evaporate. To reconcile this disagreement, we investigated soot restructuring under conditions ranging from capillary condensation to full encapsulation, also including condensate evaporation. In these experiments, airborne fractal aggregates were exposed to vapors of wetting liquids, and particle size was measured before and after coating loss, allowing us to isolate the contribution from condensation toward restructuring. We show the existence of three distinct regions along the path connecting the initial fractal and final collapsed aggregates, where minor restructuring occurs already at zero vapor supersaturation due to capillary condensation. Increasing supersaturation increases the amount of condensate, producing a more notable aggregate shrinkage. At even higher supersaturations, the aggregates become encapsulated, and subsequent condensate evaporation leaves behind fully compacted aggregates. Hence, for wetting liquids, minor restructuring begins already during capillary condensation and significant restructuring occurs as the coating volume increases. However, at this time, we cannot precisely quantify the contribution of condensate evaporation to the full aggregate compaction.

Single Parameter for Predicting the Morphology of Atmospheric Black Carbon.

Black carbon (BC) from fuel combustion is an effective light absorber that contributes significantly to direct climate forcing. The forcing is altered when BC combines with other substances, which modify its mixing state and morphology, making the evaluation of its atmospheric lifetime and climate impact a challenge. To elucidate the associated mechanisms, we exposed BC aerosol to supersaturated vapors of different chemicals to form thin coatings and measured the coating mass required to induce the restructuring of BC aggregates. We found that studied chemicals fall into two distinct groups based on a single dimensionless parameter, χ, which depends on the diameter of BC monomer spheres and the coating material properties, including vapor supersaturation, molar volume, and surface tension. We show that when χ is small (low-volatility chemicals), the highly supersaturated vapor condenses uniformly over aggregates, including convex monomers and concave junctions in between monomers, but when χ is large (intermediate-volatility chemicals), junctions become preferred. The aggregates undergo prompt restructuring when condensation in the junctions dominates over condensation on monomer spheres. For a given monomer diameter, the coating distribution is mostly controlled by vapor supersaturation. The χ factor can be incorporated straightforwardly into atmospheric models to improve simulations of BC aging.