Competition of Partitioning and Reaction Controls Brown Carbon Formation from Butenedial in Particles

Organic reactions in atmospheric particles impact human health and climate, such as by the production of brown carbon. Previous work suggests that reactions are faster in particles than in bulk solutions because of higher reactant concentrations and pronounced surface-mediated processes. Additionally, dialdehydes may have accelerated reactions in particles, as has been shown for the glyoxal reaction with ammonium sulfate (AS). Here, we examine the competition between evaporation and reaction of butenedial, a semivolatile dialdehyde, and reduced nitrogen (NH_X) in bulk solutions and levitated particles with mass spectrometry (MS). Pyrrolinone is the major product of butenedial/AS bulk solutions, indicating brown carbon formation via accretion reactions. By contrast, pyrrolinone is completely absent in all MS measurements of comparable levitated particles suspended in a pure N₂ stream. Pyrrolinone is only produced in levitated butenedial particles exposed to gas-phase ammonia, without enhanced reaction kinetics previously observed for glyoxal and other systems. Despite butenedial's large Henry's law constant and fast reaction with NH_X compared to glyoxal, the brown carbon pathway competes with evaporation only in polluted regions with extreme NH_X. Therefore, accurate knowledge of effective volatilities or Henry's law constants for complex aerosol matrices is required when chemistry studied in bulk solutions is extrapolated to atmospheric particles.