Evaluation of anthropogenic secondary organic aerosol tracers from aromatic hydrocarbons

Abstract. Products of secondary organic aerosol (SOA) from aromatic volatile organic compounds (VOCs) – 2,3-dihydroxy-4-oxopentanoic acid, dicarboxylic acids, nitromonoaromatics, and furandiones – were evaluated for their potential to serve as anthropogenic SOA tracers with respect to their (1) ambient concentrations and detectability in PM_2.5 in Iowa City, IA, USA; (2) gas–particle partitioning behaviour; and (3) source specificity by way of correlations with primary and secondary source tracers and literature review. A widely used tracer for toluene-derived SOA, 2,3-dihydroxy-4-oxopentanoic acid was only detected in the particle phase (F_p = 1) at low but consistently measurable ambient concentrations (averaging 0.3 ng m⁻³). Four aromatic dicarboxylic acids were detected at relatively higher concentrations (9.1–34.5 ng m⁻³), of which phthalic acid was the most abundant. Phthalic acid had a low particle-phase fraction (F_p =  0.26) likely due to quantitation interferences from phthalic anhydride, while 4-methylphthalic acid was predominantly in the particle phase (F_p = 0.82). Phthalic acid and 4-methylphthalic acid were both highly correlated with 2,3-dihydroxy-4-oxopentanoic acid (r_s = 0.73, p = 0.003; r_s = 0.80, p < 0.001, respectively), suggesting that they were derived from aromatic VOCs. Isophthalic and terephthalic acids, however, were detected only in the particle phase (F_p = 1), and correlations suggested association with primary emission sources. Nitromonoaromatics were dominated by particle-phase concentrations of 4-nitrocatechol (1.6 ng m⁻³) and 4-methyl-5-nitrocatechol (1.6 ng m⁻³) that were associated with biomass burning. Meanwhile, 4-hydroxy-3-nitrobenzyl alcohol was detected in a lower concentration (0.06 ng m⁻³) in the particle phase only (F_p = 1) and is known as a product of toluene photooxidation. Furandiones in the atmosphere have only been attributed to the photooxidation of aromatic hydrocarbons; however the substantial partitioning toward the gas phase (F_p  ≤  0.16) and their water sensitivity limit their application as tracers. The outcome of this study is the demonstration that 2,3-dihydroxy-4-oxopentanoic acid, phthalic acid, 4-methylphthalic acid, and 4-hydroxy-3-nitrobenzyl alcohol are good candidates for tracing SOA from aromatic VOCs.