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.

Using highly time-resolved online mass spectrometry to examine biogenic and anthropogenic contributions to organic aerosol in Beijing.

Organic aerosols, a major constituent of fine particulate mass in megacities, can be directly emitted or formed from secondary processing of biogenic and anthropogenic volatile organic compound emissions. The complexity of volatile organic compound emission sources, speciation and oxidation pathways leads to uncertainties in the key sources and chemistry leading to formation of organic aerosol in urban areas. Historically, online measurements of organic aerosol composition have been unable to resolve specific markers of volatile organic compound oxidation, while offline analysis of markers focus on a small proportion of organic aerosol and lack the time resolution to carry out detailed statistical analysis required to study the dynamic changes in aerosol sources and chemistry. Here we use data collected as part of the joint UK-China Air Pollution and Human Health (APHH-Beijing) collaboration during a field campaign in urban Beijing in the summer of 2017 alongside laboratory measurements of secondary organic aerosol from oxidation of key aromatic precursors (1,3,5-trimethyl benzene, 1,2,4-trimethyl benzene, propyl benzene, isopropyl benzene and 1-methyl naphthalene) to study the anthropogenic and biogenic contributions to organic aerosol. For the first time in Beijing, this study applies positive matrix factorisation to online measurements of organic aerosol composition from a time-of-flight iodide chemical ionisation mass spectrometer fitted with a filter inlet for gases and aerosols (FIGAERO-ToF-I-CIMS). This approach identifies the real-time variations in sources and oxidation processes influencing aerosol composition at a near-molecular level. We identify eight factors with distinct temporal variability, highlighting episodic differences in OA composition attributed to regional influences and in situ formation. These have average carbon numbers ranging from C5-C9 and can be associated with oxidation of anthropogenic aromatic hydrocarbons alongside biogenic emissions of isoprene, α-pinene and sesquiterpenes.

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.

Vertical profiles of biogenic volatile organic compounds as observed online at a tower in Beijing.

Vertical profiles of isoprene and monoterpenes were measured by a proton transfer reaction-time of flight-mass spectrometry (PTR-ToF-MS) at heights of 3, 15, 32, 64, and 102 m above the ground on the Institute of Atmospheric Physics (IAP) tower in central Beijing during the winter of 2016 and the summer of 2017. Isoprene mixing ratios were larger in summer due to much stronger local emissions whereas monoterpenes were lower in summer due largely to their consumption by much higher levels of ozone. Isoprene mixing ratios were the highest at the 32 m in summer (1.64 ± 0.66 ppbV) and at 15 m in winter (1.41 ± 0.64 ppbV) with decreasing concentrations to the ground and to the 102 m, indicating emission from the tree canopy of the surrounding parks. Monoterpene mixing ratios were the highest at the 3 m height in both the winter (0.71 ± 0.42 ppbV) and summer (0.16 ± 0.10 ppbV) with a gradual decreasing trend to 102 m, indicting an emission from near the ground level. The lowest isoprene and monoterpene mixing ratios all occurred at 102 m, which were 0.71 ± 0.42 ppbV (winter) and 1.35 ± 0.51 ppbV (summer) for isoprene, and 0.42 ± 0.22 ppbV (winter) and 0.07 ± 0.06 ppbV (summer) for monoterpenes. Isoprene in the summer and monoterpenes in the winter, as observed at the five heights, showed significant mutual correlations. In the winter monoterpenes were positively correlated with combustion tracers CO and acetonitrile at 3 m, suggesting possible anthropogenic sources.

Selective reagent ionisation-time of flight-mass spectrometry: a rapid technology for the novel analysis of blends of new psychoactive substances.

In this study we demonstrate the potential of selective reagent ionisation-time of flight-mass spectrometry for the rapid and selective identification of a popular new psychoactive substance blend called 'synthacaine', a mixture that is supposed to imitate the sensory and intoxicating effects of cocaine. Reactions with H3O(+) result in protonated parent molecules which can be tentatively assigned to benzocaine and methiopropamine. However, by comparing the product ion branching ratios obtained at two reduced electric field values (90 and 170 Td) for two reagent ions (H3O(+) and NO(+)) to those of the pure chemicals, we show that identification is possible with a much higher level of confidence then when relying solely on the m/z of protonated parent molecules. A rapid and highly selective analytical identification of the constituents of a recreational drug is particularly crucial to medical personnel for the prompt medical treatment of overdoses, toxic effects or allergic reactions.

Headspace analysis of new psychoactive substances using a Selective Reagent Ionisation-Time of Flight-Mass Spectrometer.

The rapid expansion in the number and use of new psychoactive substances presents a significant analytical challenge because highly sensitive instrumentation capable of detecting a broad range of chemical compounds in real-time with a low rate of false positives is required. A Selective Reagent Ionisation-Time of Flight-Mass Spectrometry (SRI-ToF-MS) instrument is capable of meeting all of these requirements. With its high mass resolution (up to m/Δm of 8000), the application of variations in reduced electric field strength (E/N) and use of different reagent ions, the ambiguity of a nominal (monoisotopic) m/z is reduced and hence the identification of chemicals in a complex chemical environment with a high level of confidence is enabled. In this study we report the use of a SRI-ToF-MS instrument to investigate the reactions of H3O+, O2+, NO+ and Kr+ with 10 readily available (at the time of purchase) new psychoactive substances, namely 4-fluoroamphetamine, methiopropamine, ethcathinone, 4-methylethcathinone, N-ethylbuphedrone, ethylphenidate, 5-MeO-DALT, dimethocaine, 5-(2-aminopropyl)benzofuran and nitracaine. In particular, the dependence of product ion branching ratios on the reduced electric field strength for all reagent ions was investigated and is reported here. The results reported represent a significant amount of new data which will be of use for the development of drug detection techniques suitable for real world scenarios.

Distinguishing two isomeric mephedrone substitutes with selective reagent ionisation mass spectrometry (SRI-MS).

The isomers 4-methylethcathinone and N-ethylbuphedrone are substitutes for the recently banned drug mephedrone. We find that with conventional proton transfer reaction mass spectrometry (PTR-MS), it is not possible to distinguish between these two isomers, because essentially for both substances, only the protonated molecules are observed at a mass-to-charge ratio of 192 (C12 H18NO(+)). However, when utilising an advanced PTR-MS instrument that allows us to switch the reagent ions (selective reagent ionisation) from H3O(+) (which is commonly used in PTR-MS) to NO(+), O2(+) and Kr(+), characteristic product (fragment) ions are detected: C4H10N(+) (72 Da) for 4-methylethcathinone and C5 H12N(+) (86 Da) for N-ethylbuphedrone; thus, selective reagent ionisation MS proves to be a powerful tool for fast detection and identification of these compounds.