Effect of Relative Humidity on Secondary Brown Carbon Formation in Aqueous Droplets. 2020

Nethmi Y Kasthuriarachchi, and Laura-Hélèna Rivellini, and Xi Chen, and Yong Jie Li, and Alex K Y Lee
Department of Civil and Environmental Engineering, National University of Singapore, Singapore 117576, Singapore.

Atmospheric brown carbon (BrC) is a significant contributor to particulate light absorption. Reactions between small aldehydes and reduced nitrogen species have been shown to produce secondary BrC in atmospheric droplets. These reactions can be substantially accelerated upon droplet evaporation. Despite aqueous droplets undergoing continuous water evaporation and uptake in response to the surrounding relative humidity (RH), secondary BrC formation in these droplets under various RH conditions remains poorly understood. In this work, we investigate BrC formation from reactions of two aqueous-phase precursors, glyoxal and methylglyoxal, with ammonium sulfate or glycine in aqueous droplets after drying at a range of RH (30-90%). Our results illustrate, for the first time, that BrC production varies as a function of RH. For all four chemical reaction systems being investigated, mass absorption efficiencies (MAE, m2/g C) of aqueous aerosol products (from 270 to 512 nm wavelength range) generally increase with reducing RH to reach a maximum at ∼55-65% RH and subsequently decrease, caused by further drying. Chemical characterization using high-resolution aerosol mass spectrometry shows that the formation of nitrogen-containing organic species also follows a similar variation with RH. Our observations reveal that the acceleration of BrC production from evaporation of water may be diminished by other factors, such as limited particle-phase water content, phase transition, and volatility of reactants and products. Overall, our results highlight that intermediate RH conditions in the atmosphere may be more efficient in secondary BrC formation, indicating that the effect of RH needs to be included in atmospheric models for a more accurate representation of light-absorbing aerosol formation in aqueous droplets.

UI MeSH Term Description Entries
D002244 Carbon A nonmetallic element with atomic symbol C, atomic number 6, and atomic weight [12.0096; 12.0116]. It may occur as several different allotropes including DIAMOND; CHARCOAL; and GRAPHITE; and as SOOT from incompletely burned fuel. Carbon-12,Vitreous Carbon,Carbon 12,Carbon, Vitreous
D006037 Glyoxal A 2-carbon aldehyde with carbonyl groups on both carbons. Ethanedial,Ethanedione
D006813 Humidity A measure of the amount of WATER VAPOR in the air. Humidities
D000336 Aerosols Colloids with a gaseous dispersing phase and either liquid (fog) or solid (smoke) dispersed phase; used in fumigation or in inhalation therapy; may contain propellant agents. Aerosol
D000645 Ammonium Sulfate Sulfuric acid diammonium salt. It is used in CHEMICAL FRACTIONATION of proteins. Sulfate, Ammonium
D014867 Water A clear, odorless, tasteless liquid that is essential for most animal and plant life and is an excellent solvent for many substances. The chemical formula is hydrogen oxide (H2O). (McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) Hydrogen Oxide

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