Optical Properties of Secondary Organic Aerosol Produced by Nitrate Radical Oxidation of Biogenic Volatile Organic Compounds

Abstract

Nighttime oxidation of biogenic volatile organic compounds (BVOCs) by nitrate radicals (NO ₃·) represents one of the most important interactions between anthropogenic and natural emissions, leading to substantial secondary organic aerosol (SOA) formation. The direct climatic effect of such SOA cannot be quantified because its optical properties and atmospheric fate are poorly understood. In this study, we generated SOA from the NO ₃· oxidation of a series BVOCs including isoprene, monoterpenes, and sesquiterpenes. The SOA were subjected to comprehensive online and offline chemical composition analysis using high-resolution mass spectrometry and optical properties measurements using a novel broadband (315–650 nm) cavity-enhanced spectrometer, which covers the wavelength range needed to understand the potential contribution of the SOA to direct radiative forcing. The SOA contained a significant fraction of oxygenated organic nitrates (ONs), consisting of monomers and oligomers that are responsible for the detected light absorption in the 315–400 nm range. The SOA created from β-pinene and α-humulene was further photochemically aged in an oxidation flow reactor. The SOA has an atmospheric photochemical bleaching lifetime of >6.2 h, indicating that some of the ONs in the SOA may serve as atmosphere-stable nitrogen oxide sinks or reservoirs and will absorb and scatter incoming solar radiation during the daytime.