Extreme Concentrations of Nitric Oxide Control Daytime Oxidation and Quench Nocturnal Oxidation Chemistry in Delhi during Highly Polluted Episodes.

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 NOx (NO and NO2) and volatile organic compounds (VOCs) were observed, with median NOx mixing ratios of ∼200 ppbV (maximum of ∼700 ppbV). A detailed chemical box model constrained to a comprehensive suite of speciated VOC and NOx measurements revealed very low nighttime concentrations of oxidants, NO3, O3, and OH, driven by high nighttime NO concentrations. This results in an atypical NO3 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 O3 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.

Sources of non-methane hydrocarbons in surface air in Delhi, India.

Rapid economic growth and development have exacerbated air quality problems across India, driven by many poorly understood pollution sources and understanding their relative importance remains critical to characterising the key drivers of air pollution. A comprehensive suite of measurements of 90 non-methane hydrocarbons (NMHCs) (C2-C14), including 12 speciated monoterpenes and higher molecular weight monoaromatics, were made at an urban site in Old Delhi during the pre-monsoon (28-May to 05-Jun 2018) and post-monsoon (11 to 27-Oct 2018) seasons using dual-channel gas chromatography (DC-GC-FID) and two-dimensional gas chromatography (GC×GC-FID). Significantly higher mixing ratios of NMHCs were measured during the post-monsoon campaign, with a mean night-time enhancement of around 6. Like with NOx and CO, strong diurnal profiles were observed for all NMHCs, except isoprene, with very high NMHC mixing ratios between 35-1485 ppbv. The sum of mixing ratios of benzene, toluene, ethylbenzene and xylenes (BTEX) routinely exceeded 100 ppbv at night during the post-monsoon period, with a maximum measured mixing ratio of monoaromatic species of 370 ppbv. The mixing ratio of highly reactive monoterpenes peaked at around 6 ppbv in the post-monsoon campaign and correlated strongly with anthropogenic NMHCs, suggesting a strong non-biogenic source in Delhi. A detailed source apportionment study was conducted which included regression analysis to CO, acetylene and other NMHCs, hierarchical cluster analysis, EPA UNMIX 6.0, principal component analysis/absolute principal component scores (PCA/APCS) and comparison with NMHC ratios (benzene/toluene and i-/n-pentane) in ambient samples to liquid and solid fuels. These analyses suggested the primary source of anthropogenic NMHCs in Delhi was from traffic emissions (petrol and diesel), with average mixing ratio contributions from Unmix and PCA/APCS models of 38% from petrol, 14% from diesel and 32% from liquified petroleum gas (LPG) with a smaller contribution (16%) from solid fuel combustion. Detailed consideration of the underlying meteorology during the campaigns showed that the extreme night-time mixing ratios of NMHCs during the post-monsoon campaign were the result of emissions into a very shallow and stagnant boundary layer. The results of this study suggest that despite widespread open burning in India, traffic-related petrol and diesel emissions remain the key drivers of gas-phase urban air pollution in Delhi.

An increasing role for solvent emissions and implications for future measurements of volatile organic compounds.

Volatile organic compounds (VOCs) are a broad class of air pollutants which act as precursors to tropospheric ozone and secondary organic aerosols. Total UK emissions of anthropogenic VOCs peaked in 1990 at 2,840 kt yr-1 and then declined to approximately 810 kt yr-1 in 2017 with large reductions in road transport and fugitive fuel emissions. The atmospheric concentrations of many non-methane hydrocarbons (NMHC) in the UK have been observed to fall over this period in broadly similar proportions. The relative contribution to emissions from solvents and industrial processes is estimated to have increased from approximately 35% in 1990 to approximately 63% in 2017. In 1992, UK national monitoring quantified 19 of the 20 most abundant individual anthropogenic VOCs emitted (all were NMHCs), but by 2017 monitoring captured only 13 of the top 20 emitted VOCs. Ethanol is now estimated to be the most important VOC emitted by mass (in 2017 approx. 136 kt yr-1 and approx. 16.8% of total emissions) followed by n-butane (52.4 kt yr-1) and methanol (33.2 kt yr-1). Alcohols have grown in significance representing approximately 10% of emissions in 1990 rising to approximately 30% in 2017. The increased role of solvent emissions should now be reflected in European monitoring strategies to verify total VOC emission reduction obligations in the National Emissions Ceiling Directive. Adding ethanol, methanol, formaldehyde, acetone, 2-butanone and 2-propanol to the existing NMHC measurements would provide full coverage of the 20 most significant VOCs emitted on an annual mass basis. This article is part of a discussion meeting issue 'Air quality, past present and future'.

Trends in stabilisation of Criegee intermediates from alkene ozonolysis.

Criegee Intermediates (CI), formed in the ozonolysis of alkenes, play a central role in tropospheric chemistry as an important source of radicals, with stabilised CI (SCI) able to participate in bimolecular reactions, affecting climate through the formation of inorganic and organic aerosol. However, total SCI yields have only been determined for a few alkene systems, while speciated SCI yields from asymmetrical alkenes are almost entirely unknown. Here we report for the first time a systematic experimental exploration of the stabilisation of CH2OO and (CH3)2COO CI, formed from ten alkene-ozone systems with a range of different sizes and structures, under atmospherically relevant conditions in the EUPHORE chamber. Experiments in the presence of excess SO2 (an SCI scavenger) determined total SCI yields from each alkene-ozone system. Comparison of primary carbonyl yields in the presence/absence of SO2 determined the stabilisation fraction of a given CI. The results show that the stabilisation of a given CI increases as the size of the carbonyl co-product increases. This is interpreted in terms of the nascent population of CI formed following decomposition of the primary ozonide (POZ) having a lower mean energy distribution when formed with a larger carbonyl co-product, as more of the energy from the POZ is taken by the carbonyl. These findings have significant implications for atmospheric modelling of alkene ozonolysis. Higher stabilisation of small CI formed from large alkenes is expected to lead to lower radical yields from CI decomposition, and higher SCI concentrations, increasing the importance of SCI bimolecular reactions.