Chemical Analysis of Exhaled Vape Emissions: Unraveling the Complexities of Humectant Fragmentation in a Human Trial Study.

Electronic cigarette smoking (or vaping) is on the rise, presenting questions about the effects of secondhand exposure. The chemical composition of vape emissions was examined in the exhaled breath of eight human volunteers with the high chemical specificity of complementary online and offline techniques. Our study is the first to take multiple exhaled puff measurements from human participants and compare volatile organic compound (VOC) concentrations between two commonly used methods, proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and gas chromatography (GC). Five flavor profile groups were selected for this study, but flavor compounds were not observed as the main contributors to the PTR-ToF-MS signal. Instead, the PTR-ToF-MS mass spectra were overwhelmed by e-liquid thermal decomposition and fragmentation products, which masked other observations regarding flavorings and other potentially toxic species associated with secondhand vape exposure. Compared to the PTR-ToF-MS, GC measurements reported significantly different VOC concentrations, usually below those from PTR-ToF-MS. Consequently, PTR-ToF-MS mass spectra should be interpreted with caution when reporting quantitative results in vaping studies, such as doses of inhaled VOCs. Nevertheless, the online PTR-ToF-MS analysis can provide valuable qualitative information by comparing relative VOCs in back-to-back trials. For example, by comparing the mass spectra of exhaled air with those of direct puffs, we can conclude that harmful VOCs present in the vape emissions are largely absorbed by the participants, including large fractions of nicotine.

Ultrafast Excited-State Proton Transfer in 4-Nitrocatechol: Implications for the Photochemistry of Nitrophenols.

Nitrophenols are a class of environmental contaminants that exhibit strong absorption at atmospherically relevant wavelengths, prompting many studies of their photochemical degradation rates and mechanisms. Despite the importance of photochemical reactions of nitrophenols in the environment, the ultrafast processes in electronically excited nitrophenols are not well understood. Here, we present an experimental study of ultrafast electron dynamics in 4-nitrocatechol (4NC), a common product of biomass burning and fossil fuel combustion. The experiments are accompanied by time-dependent quantum mechanical calculations to help assign the observed transitions in static and transient absorption spectra and to estimate the rates of singlet-to-triplet intersystem crossing. Our results suggest that electronic triplet states are not efficiently populated upon 340 nm excitation, as efficient proton transfer occurs in the excited state on a time scale of a few picoseconds in water and tens of picoseconds in 2-propanol. This suggests that triplet states do not play a significant role in the photochemical reactions of 4NC in the environment and, by extension, in nitrophenols in general. Instead, consideration should be given to the idea that this class of molecules may serve as strong photoacids.

Photochemical Degradation of 4-Nitrocatechol and 2,4-Dinitrophenol in a Sugar-Glass Secondary Organic Aerosol Surrogate.

The roles that chemical environment and viscosity play in the photochemical fate of molecules trapped in atmospheric particles are poorly understood. The goal of this work was to characterize the photolysis of 4-nitrocatechol (4NC) and 2,4-dinitrophenol (24DNP) in semisolid isomalt as a new type of surrogate for glassy organic aerosols and compare it to photolysis in liquid water, isopropanol, and octanol. UV/vis spectroscopy was used to monitor the absorbance decay to determine the rates of photochemical loss of 4NC and 24DNP. The quantum yield of 4NC photolysis was found to be smaller in an isomalt glass (2.6 × 10-6) than in liquid isopropanol (1.1 × 10-5). Both 4NC and 24NDP had much lower photolysis rates in water than in organic matrices, suggesting that they would photolyze more efficiently in organic aerosol particles than in cloud or fog droplets. Liquid chromatography in tandem with mass spectrometry was used to examine the photolysis products of 4NC. In isopropanol solution, most products appeared to result from the oxidation of 4NC, in stark contrast to photoreduction and dimerization products that were observed in solid isomalt. Therefore, the photochemical fate of 4NC, and presumably of other nitrophenols, should depend on whether they undergo photodegradation in a liquid or semisolid organic particle.

Isomeric Identification of the Nitroindole Chromophore in Indole + NO3 Organic Aerosol.

Oxidation of indole by nitrate radical (NO3) was previously proposed to form nitroindole, largely responsible for the brown color of indole secondary organic aerosol (SOA). As there are seven known nitroindole isomers, we used chromatographic separation to show that a single nitroindole isomer is produced in the indole + NO3 reaction and definitively assigned it to 3-nitroindole by comparison with chromatograms of nitroindole standards. Mass spectra of aerosolized 3-nitroindole particles were recorded with an aerosol mass spectrometer and directly compared to mass spectra of SOA from smog chamber oxidation of indole by NO3 in order to help identify peaks unique to nitroindole (m/z 162, 132, and 116). Quantum chemical calculations were done to determine the energetics of hypothesized indole + NO3 intermediates and products. The combination of these data suggests a mechanism, wherein a hydrogen atom is first abstracted from the N-H bond in indole, followed by isomerization to a carbon-centered radical in the 3-position and followed by addition of NO2. Alternative mechanisms involving a direct abstraction of a H atom from a C-H bond or a NO3 addition to the ring are predicted to be energetically unfavorable from large barriers for the initial reaction steps.