Evidence for a kinetically controlled burying mechanism for growth of high viscosity secondary organic aerosol

• Published in: Environmental science--processes & impacts 2020-01, Vol.22 (1), p.66-83
• Main Authors: Vander Wall, Allison C, Perraud, Véronique, Wingen, Lisa M, Finlayson-Pitts, Barbara J
• Format: Article
• Language: English
• Subjects: Aerosols; Aerosols - chemistry; Air Pollutants - chemistry; Climate; Climate effects; Equilibrium; Ethyl hexyl nitrate; Monoterpenes; Nitrates; Organic nitrates; Ozone; Semisolids; Vapor phases; Viscosity; Visibility; α-Pinene
• ISSN: 2050-7887; 2050-7895
• DOI: 10.1039/c9em00379g

Secondary organic aerosol (SOA) particles are ubiquitous in air and understanding the mechanism by which they grow is critical for predicting their effects on visibility and climate. The uptake of three organic nitrates into semi-solid SOA particles formed by α-pinene ozonolysis either with or without an OH scavenger was investigated. Four types of experiments are presented here. In Series A, uptake of the selected organic nitrates (2-ethylhexyl nitrate (2EHN); β-hydroxypropyl nitrate (HPN); β-hydroxyhexyl nitrate (HHN)) into impacted SOA particles was interrogated by attenuated total reflectance (ATR)-FTIR. In this case, equilibrium was reached and partition coefficients ( K SOA = [-ONO 2 ] SOA /[-ONO 2 ] air ) were measured to be K 2EHN = (3.2-11) × 10 4 , K HPN = (4.4-5.4) × 10 5 , and K HHN = (4.9-9.0) × 10 6 . In Series B, SOA particles were exposed on-the-fly to gas phase organic nitrates for comparison to Series A, and uptake of organic nitrates was quantified by HR-ToF-AMS analysis, which yielded similar results. In Series C (AMS) and D (ATR-FTIR), each organic nitrate was incorporated into the SOA as the particles formed and grew. The incorporation of the RONO 2 was much larger in Series C and D ( during growth ), exceeding equilibrium values determined in Series A and B ( after growth ). This suggests that enhanced uptake of organic nitrates during SOA formation and growth is due to a kinetically controlled "burying" mechanism, rather than equilibrium partitioning. This has important implications for understanding SOA formation and growth under conditions where the particles are semi-solid, which is central to accurately predicting properties for such SOA. The incorporation of organic nitrates into viscous secondary organic aerosol during particle formation is enhanced relative to expected equilibrium partitioning, and is best described by a kinetically controlled "burying" mechanism.