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The kinetics of the reactions of H3O+, NO+, O2+˙ and O−˙ with n-hexane, 3-methylpentane, 2,5-dimethylhexane and 2,3-dimethylheptane were studied experimentally under several selected ion flow tube (SIFT) conditions: in a Profile 3 instrument in He and N2 carrier gases at 300 K and in the Voice200 instrument in N2 carrier gas at 300 and 393 K – where the effect of the extraction lens voltage was also assessed. It was found that H3O+ ions react differently than expected, with reaction rates slower than collisional. Instead of transferring a proton, they associate and form fragment product ions [M–H]+. NO+ ions react via hydride ion transfer. O2+˙ ions react via charge transfer followed by fragmentation that is highly sensitive to the temperature and the ion extraction lens voltage. Negative ions did not react, except for the O−˙ ion, which reacted via an associative detachment process. Computational analysis using Density Functional Theory (DFT) provided insights into the exothermicities and exergodicities of these reactions. A notable result is that proton transfer from H3O+ does not take place despite its potential exothermicity; this is important for the interpretation of proton transfer reaction (PTR) and SIFT mass spectrometry data. [ABSTRACT FROM AUTHOR]

Selected Ion Flow Tube Mass Spectrometry (SIFT-MS) is a soft ionisation technique based on gas phase ion–molecule reaction kinetics for the quantification of trace amounts of volatile organic compound vapours. One of its previous limitations is difficulty in resolving isomers, although this can now be overcome using different reactivities of several available reagent cations and anions (H3O+, NO+, O2+˙, O−˙, OH−, O2−˙, NO2−, NO3−). Thus, the ion–molecule reactions of these eight ions with all isomers of the aromatic compounds cymene, cresol and ethylphenol were studied to explore the possibility of their immediate identification and quantification without chromatographic separation. Rate coefficients and product ion branching ratios determined experimentally for the 72 reactions are reported. DFT calculations of their energetics confirmed the feasibility of the suggested reaction pathways. All positive ion reactions proceeded fast but largely did not discriminate between the isomers. The reactivity of the anions was much more varied. In all cases, OH− reacts by proton transfer forming (M–H); NO2− and NO3− were unreactive. The differences observed for product ion branching ratios can be used to identify isomers approximately. [ABSTRACT FROM AUTHOR]

Isoprene and monoterpene emissions to the atmosphere are generally dominated by biogenic sources. The oxidation of these compounds can lead to the production of secondary organic aerosol; however the impact of this chemistry in polluted urban settings has been poorly studied. Isoprene and monoterpenes can form secondary organic aerosol (SOA) heterogeneously via anthropogenic–biogenic interactions, resulting in the formation of organosulfate (OS) and nitrooxy-organosulfate (NOS) species. Delhi, India, is one of the most polluted cities in the world, but little is known about the emissions of biogenic volatile organic compounds (VOCs) or the sources of SOA. As part of the DELHI-FLUX project, gas-phase mixing ratios of isoprene and speciated monoterpenes were measured during pre- and post-monsoon measurement campaigns in central Delhi. Nocturnal mixing ratios of the VOCs were substantially higher during the post-monsoon (isoprene: (0.65±0.43) ppbv; limonene: (0.59±0.11) ppbv; α -pinene: (0.13±0.12) ppbv) than the pre-monsoon (isoprene: (0.13±0.18) ppbv; limonene: 0.011±0.025 (ppbv); α -pinene: 0.033±0.009) period. At night, isoprene and monoterpene concentrations correlated strongly with CO during the post-monsoon period. Filter samples of particulate matter less than 2.5 µm in diameter (PM 2.5) were collected and the OS and NOS content analysed using ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS 2). Inorganic sulfate was shown to facilitate the formation of isoprene OS species across both campaigns. Sulfate contained within OS and NOS species was shown to contribute significantly to the sulfate signal measured via AMS. Strong nocturnal enhancements of NOS species were observed across both campaigns. The total concentration of OS and NOS species contributed an average of (2.0±0.9) % and (1.8±1.4) % to the total oxidized organic aerosol and up to a maximum of 4.2 % and 6.6 % across the pre- and post-monsoon periods, respectively. Overall, this study provides the first molecular-level measurements of SOA derived from isoprene and monoterpene in Delhi and demonstrates that both biogenic and anthropogenic sources of these compounds can be important in urban areas. [ABSTRACT FROM AUTHOR]

Biomass burning emits significant quantities of intermediate-volatility and semi-volatile volatile organic compounds (I/SVOCs) in a complex mixture, probably containing many thousands of chemical species. These components are significantly more toxic and have poorly understood chemistry compared to volatile organic compounds routinely analysed in ambient air, however quantification of I/SVOCs presents a difficult analytical challenge. The gases and particles emitted during the test combustion of a range of domestic solid fuels collected from across New Delhi were sampled and analysed. Organic aerosol was collected onto Teflon (PTFE) filters and residual low-volatility gases were adsorbed to the surface of solid-phase extraction (SPE) disks. A new method relying on accelerated solvent extraction ASE) coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-ToF-MS) was developed. This highly sensitive and powerful analytical technique enabled over 3000 peaks from I/SVOC species with unique mass spectra to be detected. 15-100% of gas-phase emissions and 7-100% of particle-phase emissions were characterised. The method was analysed for suitability to make quantitative measurements of I/SVOCs using SPE disks. Analysis of SPE disks indicated phenolic and furanic compounds were important to gas-phase I/SVOC emissions and levoglucosan to the aerosol phase. Gasand particle-phase emission factors for 21 polycyclic aromatic hydrocarbons (PAHs) were derived, including 16 compounds listed by the US EPA as priority pollutants. Gas-phase emissions were dominated by smaller PAHs. New emission factors were measured (mg kg-1) for PAHs from combustion of cow dung cake (615), municipal solid waste (1022), crop residue 747), sawdust (1236), fuel wood (247), charcoal (151) and liquified petroleum gas (56). The results of this study indicate that cow dung cake and municipal solid waste burning are likely to be significant PAH sources and further study is required to quantify their impact, alongside emissions from fuel wood burning. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in air, soil and water and known to have harmful effects on human health and the environment. The diurnal and nocturnal variation of 17-PAHs in ambient particle-bound PAHs were measured in urban Beijing (China) and Delhi (India) during the summer season using GC-Q-TOF-MS. The mean concentration of particles less than 2.5 microns (PM2.5) observed in Delhi was 3.6 times higher than in Beijing during the measurement period in both the day-time and night-time. In Beijing, the mean concentration of the sum of the 17 PAHs (Σ17-PAHs) was 8.2 ± 5.1 ng m-3 in daytime, with the highest contribution from Indeno[1,2,3-cd]pyrene (12 %), while at night-time the total PAHs was 7.2 ± 2.0 ng m-3, with the largest contribution from Benzo[b]fluoranthene (14 %). In Delhi, the mean Σ17-PAHs was 13.6 ± 5.9 ng m-3 in daytime, and 22.7 ± 9.4 ng m-3 at night-time, with the largest contribution from Indeno[1,2,3-cd]pyrene in both the day (17 %) and night (20 %). Elevated mean concentrations of total PAHs in Delhi observed at night were attributed to emissions from vehicles and biomass burning and to meteorological conditions leading to their accumulation from a stable and low atmospheric boundary layer. Local emission sources were typically identified as the major contributors to total measured PAHs, however, in Delhi 25 % of the emissions were attributed to long-range atmospheric transport. Major emission sources were characterized based on the contribution from each class of PAHs, with the 4, 5, and 6 ring PAHs accounting ~ 95 % of the total PM2.5-bound PAHs mass in both locations. The high contribution of 5 ring PAHs to total PAH concentration in summer Beijing and Delhi suggests a high contribution from petroleum combustion. In Delhi, a high contribution from 6 ring PAHs was observed at night, suggesting a potential emission source from the combustion of fuel and oil in power generators, widely used in Delhi. The lifetime excess lung cancer risk (LECR) was calculated for Beijing and Delhi, with the highest estimated risk attributed to Delhi (LECR = 155 per million people), 2.2 times higher than Beijing risk assessment value (LECR = 70 per million people). Finally, we have assessed the emission control policies in each city and identified those major sectors that could be subject to mitigation measures. [ABSTRACT FROM AUTHOR]

The kinetics of the reactions of H 3 O + , NO + , O 2 + ˙ and O - ˙ with n -hexane, 3-methylpentane, 2,5-dimethylhexane and 2,3-dimethylheptane were studied experimentally under several selected ion flow tube (SIFT) conditions: in a Profile 3 instrument in He and N 2 carrier gases at 300 K and in the Voice200 instrument in N 2 carrier gas at 300 and 393 K - where the effect of the extraction lens voltage was also assessed. It was found that H 3 O + ions react differently than expected, with reaction rates slower than collisional. Instead of transferring a proton, they associate and form fragment product ions [M-H] + . NO + ions react via hydride ion transfer. O 2 + ˙ ions react via charge transfer followed by fragmentation that is highly sensitive to the temperature and the ion extraction lens voltage. Negative ions did not react, except for the O - ˙ ion, which reacted via an associative detachment process. Computational analysis using Density Functional Theory (DFT) provided insights into the exothermicities and exergodicities of these reactions. A notable result is that proton transfer from H 3 O + does not take place despite its potential exothermicity; this is important for the interpretation of proton transfer reaction (PTR) and SIFT mass spectrometry data.

Delhi, India, suffers from periods of very poor air quality, but little is known about the chemical production of secondary pollutants in this highly polluted environment. During the postmonsoon period in 2018, extremely high nighttime concentrations of NO x (NO and NO 2 ) and volatile organic compounds (VOCs) were observed, with median NO x mixing ratios of ∼200 ppbV (maximum of ∼700 ppbV). A detailed chemical box model constrained to a comprehensive suite of speciated VOC and NO x measurements revealed very low nighttime concentrations of oxidants, NO 3 , O 3 , and OH, driven by high nighttime NO concentrations. This results in an atypical NO 3 diel profile, not previously reported in other highly polluted urban environments, significantly perturbing nighttime radical oxidation chemistry. Low concentrations of oxidants and high nocturnal primary emissions coupled with a shallow boundary layer led to enhanced early morning photo-oxidation chemistry. This results in a temporal shift in peak O 3 concentrations when compared to the premonsoon period (12:00 and 15:00 local time, respectively). This shift will likely have important implications on local air quality, and effective urban air quality management should consider the impacts of nighttime emission sources during the postmonsoon period., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)