The Critical Role of Synthetic Chemistry in Elucidating Mechanisms, Product Identification, and Quantitation in Atmospheric Gas-Phase and Multiphase Chemistry of Volatile Organic Emissions

Dear Colleagues,

Considerable progress has been made towards elucidating the mechanisms of secondary organic aerosol (SOA) formation from the photochemical oxidation of volatile organic compounds (VOCs), both biological and anthropogenic in origin, and in identifying individual SOA components. A key factor in understanding SOA formation, composition, and behavior has been the availability of authentic standards serving as intermediates for verification of putative SOA formation pathways, structural verification of products, quantitation of SOA components, and assessment of both the analytical methodology and physicochemical properties of SOAs. Several examples taken from the investigation of the atmospheric chemistry of isoprene—an area of some familiarity to the editor—can exemplify the importance of synthetic chemistry. Synthesis of isoprene epoxydiols (IEPOX) established the putative IEPOX pathway as the major contributor to isoprene-derived SOA under low-NOx conditions and enabled structural confirmation of isoprene-SOA marker compounds. Availability of authentic isomeric isoprene hydroxyhydroperoxides (ISOPOOH) led to the revelation that field monitoring by gas chromatography and proton transfer reaction mass spectrometry degraded the first-generation ISOPOOH isomers, yielding methylvinylketone and acrolein, products associated with high-NOx chemistry, confounding the interpretation of isoprene oxidation pathways.

To date, the picture regarding all aspects of SOA research is far from complete, and continued advances in multiple areas will require the availability of authentic standards. The following, but by no means comprehensive list of topics includes reconciling low-volatility isoprene SOA with high concentrations of semi-volatile marker compounds as determined by widely applied analytical procedures; the extent of oligomeric species in terms of aerosol composition; the importance of hydroperoxides in initial accretion reactions and subsequent generation of ROS and other radical species in particles; the dependence of the quantitation of potentially labile aerosol components on analytical methodology; changes in aerosol composition and properties during aging; the interdependence of physicochemical properties of SOA on composition and environmental factors; identification of the nitrate ester contribution to SOA; mechanisms of formation and the identification and quantitation of organosulfates and implications for the atmospheric sulfur budget; the impact of climate change on the evolution of SOA properties; the composition of fine particulate matter and its impact on human health.

We invite contributions on synthetic efforts and the application of newly synthesized compounds to advancing our understanding of atmospheric processes affecting SOA.

Prof. Avram Gold
Prof. Jason Surratt
Guest Editors

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