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.

Avoiding high ozone pollution in Delhi, India.

Surface ozone is a major pollutant threatening public health, agricultural production and natural ecosystems. While measures to improve air quality in megacities such as Delhi are typically aimed at reducing levels of particulate matter (PM), ozone could become a greater threat if these measures focus on PM alone, as some air pollution mitigation steps can actually lead to an increase in surface ozone. A better understanding of the factors controlling ozone production in Delhi and the impact that PM mitigation measures have on ozone is therefore critical for improving air quality. Here, we combine in situ observations and model analysis to investigate the impact of PM reduction on the non-linear relationship between volatile organic compounds (VOC), nitrogen oxides (NOx) and ozone. In situ measurements of NOx, VOC, and ozone were conducted in Delhi during the APHH-India programme in summer (June) and winter (November) 2018. We observed hourly averaged ozone concentrations in the city of up to 100 ppbv in both seasons. We performed sensitivity simulations with a chemical box model to explore the impacts of PM on the non-linear VOC-NOx-ozone relationship in each season through its effect on aerosol optical depth (AOD). We find that ozone production is limited by VOC in both seasons, and is particularly sensitive to solar radiation in winter. Reducing NOx alone increases ozone, such that a 50% reduction in NOx emissions leads to 10-50% increase in surface ozone. In contrast, reducing VOC emissions can reduce ozone efficiently, such that a 50% reduction in VOC emissions leads to ∼60% reduction in ozone. Reducing PM alone also increases ozone, especially in winter, by reducing its dimming effects on photolysis, such that a 50% reduction in AOD can increase ozone by 25% and it also enhances VOC-limitation. Our results highlight the importance of reducing VOC emissions alongside PM to limit ozone pollution, as well as benefitting control of PM pollution through reducing secondary organic aerosol. This will greatly benefit the health of citizens and the local ecosystem in Delhi, and could have broader application for other megacities characterized by severe PM pollution and VOC-limited ozone production.