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Photooxidation products resulting from volatile organic compounds (VOCs) reacting with sunlight are important contributors to gas-phase air pollution. We characterized the product-weighted mutagenic potencies (rev m 3 mgC -1 h -1 ) in Salmonella TA100 of atmospheres resulting from the hydroxyl radical (OH)-initiated photochemical oxidation of 11 C 4 or C 5 alkenes or dienes in the presence of nitric oxide (NO) and from the ozonolysis of four VOCs without NO (isoprene; 1,3-pentadiene; 1,4-pentadiene; and 1,3-butadiene). Irradiated atmospheres from precursors with a single C═C bond (3-methyl-1-butene, 2-methyl-1-butene, cis/trans -2-pentene, 2-methyl-2-butene, 1-butene, and 1-pentene) had low potencies (<5), whereas linear dienes with terminal C═C bonds had high potencies (50-65). Dienes with a branched structure (isoprene) or internal C═C bonds (1,3-pentadiene) had intermediate potencies (15-20). No VOCs were mutagenic without photochemical oxidation. VOCs+O 3 in the dark produced less mutagenic atmospheres than photochemistry in the presence of NO. Atmospheres induced primarily C to T and C to A mutations, the main base substitutions in nonsmoker lung cancer. Atmospheres from the photooxidation of isoprene and 1,3-pentadiene also induced GG to TT, the signature mutation of peroxyacetyl nitrate. Five molecular compositions identified by Chemical Ionization Mass Spectrometry (CIMS), most containing nitrogen, correlated ( r = 0.76-0.85) with the mutagenic potencies of irradiated atmospheres; most had a likely nitrate functional group. Assessment of the mutagenicity of emitted VOCs should consider VOC photooxidation products, especially dienes with terminal C═C bonds, as these products likely contribute to overall health effects from ambient air pollution.

The interaction of sunlight with volatile organic compounds (VOCs) emitted from various sources results in mutagenic photooxidation products that contribute substantially to air pollution. Evaporation of gasoline is one such source of VOCs; however, no studies have evaluated the mutagenicity of the photooxidation products of gasoline vapors or of many of the non-aromatic constituent VOCs of gasoline. Here we determined the mutagenicity in Salmonella TA100 of atmospheres generated in a steady-state atmospheric simulation chamber by irradiating gasoline and individual non-aromatic VOCs in the presence of nitrogen oxides (NO X ) in air. In addition to gasoline, we evaluated α-pinene; 2-pentene; ethanol; isobutanol; isoprene; and 2,2,4-trimethylpentane (isooctane). Cells were exposed at the air-agar interface to the atmospheres for 1, 2, 4, 8, or 16 h. Atmospheres generated in the dark were not mutagenic. However, under irradiation all atmospheres other than that of 2,2,4-trimethylpentane were mutagenic, with mutagenic potencies spanning 8.6-fold. The mutagenicity was due exclusively to direct-acting, late-generation photooxidation products. The non-aromatic VOCs studied here contributed little to the mutagenic potency of the photooxidation products of gasoline. However, the sum of the mutagenic potencies of these atmospheres plus those from the photooxidation of some aromatic VOCs in gasoline measured here and elsewhere (Riedel et al., Atmos Environ, 178:164, 2018) accounted for 71% of the mutagenic potency of the photooxidation products of gasoline vapor. In photochemical mixtures with strong biogenic contributions, isoprene products may also contribute significantly to mutagenic potency. Strategies to reduce the emissions of gasoline and those VOCs whose photooxidation products are most mutagenic would reduce VOC-associated air pollution and improve public health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Aqueous film-forming foams (AFFFs) are used in firefighting applications and often contain per- and polyfluoroalkyl substances (PFAS), which can detrimentally impact environmental and biological health. Incineration is a potential disposal method for AFFFs, which may produce secondary PFAS and other air pollutants. We used online chemical ionization mass spectrometry (CIMS) to measure volatile PFAS emissions from incinerating AFFF concentrate solutions. We quantified perfluorinated carboxylic acids (PFCAs) during the incineration of legacy and contemporary AFFFs. These included trifluoroacetic acid, which reached mg m -3 quantities in the incinerator exhaust. These PFCAs likely arose as products of incomplete combustion of AFFF fluorosurfactants with lower peak furnace temperatures yielding higher PFCA concentrations. We also detected other short-chain PFAS, and other novel chemical products in AFFF combustion emissions. The volatile headspace above AFFF solutions contained larger ( C ≥ 8), less oxidized PFAS detected by CIMS. We identified neutral PFAS resembling fluorotelomer surfactants (e.g., fluorotelomer sulfonamide alkylbetaines and fluorotelomer thioether amido sulfonates) and fluorotelomer alcohols in contemporary AFFF headspaces. Directly comparing the distinct chemical spaces of AFFF volatile headspace and combustion byproducts as measured by CIMS provides insight toward the chemistry of PFAS during thermal treatment of AFFFs.