Neha Sareen

Glyoxal-methylglyoxal cross-reactions in secondary organic aerosol formation.

Glyoxal (G) and methylglyoxal (MG) are potentially important secondary organic aerosol (SOA) precursors. Previous studies of SOA formation by G and MG have focused on either species separately; however, G and MG typically coexist in the atmosphere. We studied the formation of secondary organic material in aqueous aerosol mimic mixtures containing G and MG with ammonium sulfate. We characterized the formation of light-absorbing products using UV-vis spectrophotometry. We found that absorption at 280 nm can be described well using models for the formation of light-absorbing products by G and MG in parallel. Pendant drop tensiometry measurements showed that surface tension depression by G and MG in these solutions can be modeled as a linear combination of the effects of G and MG alone. Product species were identified using chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol CIMS). Peaks consistent with G-MG cross-reaction products were observed, accounting for a significant fraction of detected product mass, but most peaks could be attributed to self-reaction. We conclude that cross-reactions contribute to SOA mass from uptake of G and MG, but they are not required to accurately model the effects of this process on aerosol surface tension or light absorption.

Surfactants from the gas phase may promote cloud droplet formation

Clouds, a key component of the climate system, form when water vapor condenses upon atmospheric particulates termed cloud condensation nuclei (CCN). Variations in CCN concentrations can profoundly impact cloud properties, with important effects on local and global climate. Organic matter constitutes a significant fraction of tropospheric aerosol mass, and can influence CCN activity by depressing surface tension, contributing solute, and influencing droplet activation kinetics by forming a barrier to water uptake. We present direct evidence that two ubiquitous atmospheric trace gases, methylglyoxal (MG) and acetaldehyde, known to be surface-active, can enhance aerosol CCN activity upon uptake. This effect is demonstrated by exposing acidified ammonium sulfate particles to 250 parts per billion (ppb) or 8 ppb gas-phase MG and/or acetaldehyde in an aerosol reaction chamber for up to 5 h. For the more atmospherically relevant experiments, i.e., the 8-ppb organic precursor concentrations, significant enhancements in CCN activity, up to 7.5% reduction in critical dry diameter for activation, are observed over a timescale of hours, without any detectable limitation in activation kinetics. This reduction in critical diameter enhances the apparent particle hygroscopicity up to 26%, which for ambient aerosol would lead to cloud droplet number concentration increases of 8–10% on average. The observed enhancements exceed what would be expected based on Köhler theory and bulk properties. Therefore, the effect may be attributed to the adsorption of MG and acetaldehyde to the gas–aerosol interface, leading to surface tension depression of the aerosol. We conclude that gas-phase surfactants may enhance CCN activity in the atmosphere.

Photochemical Aging of Light-Absorbing Secondary Organic Aerosol Material

Dark reactions of methylglyoxal with NH4(+) in aqueous aerosols yield light-absorbing and surface-active products that can influence the physical properties of the particles. Little is known about how the product mixture and its optical properties will change due to photolysis as well as oxidative aging by O3 and OH in the atmosphere. Here, we report the results of kinetics and product studies of the photochemical aging of aerosols formed by atomizing aqueous solutions of methylglyoxal and ammonium sulfate. Experiments were performed using aerosol flow tube reactors coupled with an aerosol chemical ionization mass spectrometer (Aerosol-CIMS) for monitoring gas- and particle-phase compositions. Particles were also impacted onto quartz windows in order to assess changes in their UV-visible absorption upon oxidation. Photooxidation of the aerosols leads to the formation of small, volatile organic acids including formic acid, acetic acid, and glyoxylic acid. The atmospheric lifetime of these species during the daytime is predicted to be on the order of minutes, with photolysis being an important mechanism of degradation. The lifetime with respect to O3 oxidation was observed to be on the order of hours. O3 oxidation also leads to a net increase in light absorption by the particles due to the formation of additional carbonyl compounds. Our results are consistent with field observations of high brown carbon absorption in the early morning.

Surface-Active Organics in Atmospheric Aerosols

Surface-active organic material is a key component of atmospheric aerosols. The presence of surfactants can influence aerosol heterogeneous chemistry, cloud formation, and ice nucleation. We review the current state of the science on the sources, properties, and impacts of surfactants in atmospheric aerosols.