Yields and molecular composition of gas-phase and secondary organic aerosol from the photooxidation of the volatile consumer product benzyl alcohol: formation of highly oxygenated and hydroxy nitro-aromatic compounds

Abstract

Abstract. Recently, volatile chemical products (VCPs) have been increasingly recognized as important precursors for secondary organic aerosol (SOA) and ozone in urban areas. However, their atmospheric chemistry, physical transformation, and impact on climate, environment, and human health remain poorly understood. Here, the yields and chemical composition at the molecular level of gas- and particle-phase products originating from the photooxidation of one of these VCPs, benzyl alcohol (BnOH), are reported. The SOA was generated in the presence of seed aerosol from nebulized ammonium sulfate solution in a 14.5 m3 smog chamber operated in flow mode. More than 50 organic compounds containing nitrogen and/or up to seven oxygen atoms were identified by mass spectrometry. While a detailed non-targeted analysis has been made, our primary focus has been to examine highly oxygenated and nitro-aromatic compounds. The major components include ring-opening products with a high oxygen-to-carbon ratio (e.g., malic acid, tartaric acids, arabic acid, trihydroxy-oxo-pentanoic acids, and pentaric acid) and ring-retaining products (e.g., benzaldehyde, benzoic acid, catechol, 3-nitrobenzyl alcohol, 4-nitrocatechol, 2-hydroxy-5-nitrobenzyl alcohol, 2-nitrophloroglucinol, 3,4-dihydroxy-5-nitrobenzyl alcohol). The presence of some of these products in the gas and particle phases simultaneously provides evidence of their gas–particle partitioning. These oxygenated oxidation products made dominant contributions to the SOA particle composition in both low- and high-NOx systems. Yields, organic mass to organic carbon ratio, and proposed reaction schemes for selected compounds are provided. The aerosol yield was 5.2 % for BnOH/H2O2 at an SOA concentration of 52.9 µg m−3 and ranged between 1.7 % and 8.1 % for BnOH / NOx at an SOA concentration of 40.0–119.5 µg m−3.

Quantifying primary oxidation products in the OH-initiated reaction of benzyl alcohol

“…As found in other systems, epoxides can effectively lead to SOA formation (Paulot et al, 2009;Chan et al, 2010). Other fragmentation products found in Jaoui et al also suggest that fragmentation products can form with high O:C ratios and may quickly partition to SOA (Jaoui et al, 2023). Here, we detect products with masses congruent with both the hydroxy oxopentenal and epoxide products.…”

“…A previous study of the chemical composition of the SOA formed via OH oxidation of benzyl alcohol observed C6 compounds, such as nitrocatechol (Charan et al, 2020;Jaoui et al, 2023). In the present study, we observed nitrocatechol as well as other C6 compounds such as phenol and catechol.…”

“…Benzyl alcohol is used in soaps and perfumes, and is also used as a solvent in the manufacture of paints, inks, lacquers, and epoxies (Wang, 2015). In a previous study, the aerosol mass yield of benzyl alcohol was found to have a high mass yield under a variety of conditions-even approaching unity (Charan et al, 2020;Jaoui et al, 2023).…”