Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

Abstract

Abstract. Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols) leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH•) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92–179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS), indicative of alcohols, carbonyl compounds, and/or epoxides. Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS/MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (e.g., as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOAAQ.