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.

Unreported VOC Emissions from Road Transport Including from Electric Vehicles.

There are widespread policy assumptions that the phase-out of gasoline and diesel internal combustion engines will over time lead to much reduced emissions of Volatile Organic Compounds (VOCs) from road transport and related fuels. However, the use of real-world emissions measurements from a new mobile air quality monitoring station demonstrated a large underestimation of alcohol-based species in road transport emissions inventories. Scaling of industry sales statistics enabled the discrepancy to be attributed to the use of ancillary solvent products such as screenwash and deicer which are not included in internationally applied vehicle emission methodologies. A fleet average nonfuel nonexhaust VOC emission factor of 58 ± 39 mg veh-1 km-1 was calculated for the missing source, which is greater than the total of all VOCs emitted from vehicle exhausts and their associated evaporative fuel losses. These emissions are independent of the vehicle energy/propulsion system and therefore applicable to all road vehicle types including those with battery-electric powertrains. In contrast to predictions, vehicle VOC emissions may actually increase given a predicted growth in total vehicle kilometers driven in a future electrified fleet and will undergo a complete VOC respeciation due to the source change.

The impact of plug-in fragrance diffusers on residential indoor VOC concentrations.

Plug-in fragrance diffusers are one of myriad volatile organic compound-containing consumer products that are commonly found in homes. The perturbing effects of using a commercial diffuser indoors were evaluated using a study group of 60 homes in Ashford, UK. Air samples were taken over 3 day periods with the diffuser switched on and in a parallel set of control homes where it was off. At least four measurements were taken in each home using vacuum-release into 6 L silica-coated canisters and with >40 VOCs quantified using gas chromatography with FID and MS (GC-FID-QMS). Occupants self-reported their use of other VOC-containing products. The variability between homes was very high with the 72 hour sum of all measured VOCs ranging between 30 and >5000 µg m-3, dominated by n/i-butane, propane, and ethanol. For those homes in the lowest quartile of air exchange rate (identified using CO2 and TVOC sensors as proxies) the use of a diffuser led to a statistically significant increase (p-value < 0.02) in the summed concentration of detectable fragrance VOCs and some individual species, e.g. alpha pinene rising from a median of 9 µg m-3 to 15 µg m-3 (p-value < 0.02). The observed increments were broadly in line with model-calculated estimates based on fragrance weight loss, room sizes and air exchange rates.

Evaluating major anthropogenic VOC emission sources in densely populated Vietnamese cities.

Volatile organic compounds (VOCs) play an important role in urban air pollution, both as primary pollutants and through their contribution to the formation of secondary pollutants, such as tropospheric ozone and secondary organic aerosols. In this study, more than 30 VOC species were continuously monitored in the two most populous cities in Vietnam, namely Ho Chi Minh City (HCMC, September-October 2018 and March 2019) and Hanoi (March 2019). In parallel with ambient VOC sampling, grab sampling was used to target the most prevalent regional-specific emission sources and estimate their emission factors (EFs). Emission ratios (ERs) obtained from ambient sampling were compared between Vietnamese cities and other cities across the globe. No significant differences were observed between HCMC and Hanoi, suggesting the presence of similar sources. Moreover, a good global agreement was obtained in the spatial comparison within a factor of 2, with greater ER for aromatics and pentanes obtained in the Vietnamese cities. The detailed analysis of sources included the evaluation of EF from passenger cars, buses, trucks, motorcycles, 3-wheeled motorcycles, waste burning, and coal-burning emissions. Our comparisons between ambient and near-source concentration profiles show that road transport sources are the main contributors to VOC concentrations in Vietnamese cities. VOC emissions were calculated from measured EF and consumption data available in Hanoi and compared with those estimated by a global emission inventory (EDGAR v4.3.2). The total VOC emissions from the road transport sector estimated by the inventory do not agree with those calculated from our observations which showed higher total emissions by a factor of 3. Furthermore, the inventory misrepresented the VOCs speciation, mainly for isoprene, monoterpenes, aromatics, and oxygenated compounds. Accounting for these differences in regional air quality models would lead to improved predictions of their impacts and help to prioritise pollution reduction strategies in the region.

The air quality impacts of pre-operational hydraulic fracturing activities.

Hydraulic fracturing (fracking) is a short phase in unconventional oil and natural gas (O&G) development. Before fracking there is a lengthy period of preparation, which can represent a significant proportion of the well lifecycle. Extensive infrastructure is delivered onto site, leading to increased volumes of heavy traffic, energy generation and construction work on site. Termed the "pre-operational" period, this is rarely investigated as air quality evaluations typically focus on the extraction phase. In this work we quantify the change in air pollution during pre-operational activities at a shale gas exploration site near Kirby Misperton, North Yorkshire, England. Baseline air quality measurements were made two years prior to any shale gas activity and were used as a training dataset for random forest (RF) machine learning models. The models allowed for a comparison between observed air quality during the pre-operational phase and a counterfactual business as usual (BAU) prediction. During the pre-operational phase a significant deviation from the BAU scenario was observed. This was characterised by significant enhancements in NOx and a concurrent reduction in O3, caused by extensive additional vehicle movements and the presence of combustion sources such as generators on the well pad. During the pre-operational period NOx increased by 274 % and O3 decreased by 29 % when compared to BAU model values. There was also an increase in primary emissions of NO2 during the pre-operational phase which may have implications for the attainment of ambient air quality standards in the local surroundings. Unconventional O&G development remains under discussion as a potential option for improving the security of supply of domestic energy, tensioned however against significant environmental impacts. Here we demonstrate that the preparative work needed to begin fracking elevates air pollution in its own right, a further potential disbenefit that should be considered.

Impacts of biogenic emissions from urban landscapes on summer ozone and secondary organic aerosol formation in megacities.

The impact of biogenic emissions on ozone and secondary organic aerosol (SOA) has been widely acknowledged; nevertheless, biogenic emissions emitted from urban landscapes have been largely ignored. We find that including urban isoprene in megacities like Beijing improves not only the modeled isoprene concentrations but also its diurnal cycle. Specifically, the mean bias of the simulated isoprene concentrations is reduced from 87% to 39% by adding urban isoprene emissions while keeping the diurnal cycle the same as that in non-urban or rural areas. Further adjusting the diurnal cycle of isoprene emissions to the urban profile steers the original early morning peak of the isoprene concentration to a double quasi-peak, i.e., bell shape, consistent with observations. The efficiency of ozone generation caused by isoprene emissions in urban Beijing is found to be twice as large as those in rural areas, indicative of vital roles of urban BVOC emissions in modulating the ozone formation. Our study also shows that in the future along with NOx emission reduction, isoprene emissions from urban landscapes will become more important for the formation of ozone in urban area, and their contributions may exceed that of isoprene caused by transport from rural areas. Finally, the impact of biogenic emissions on SOA is examined, revealing that biogenic induced SOA accounts for 16% of the total SOA in urban Beijing. The effect of isoprene on SOA (iSOA) is modulated through two pathways associated with the abundance of NOx emissions, and the effect can be amplified in future when NOx emissions are reduced. The findings of our study are not limited to Beijing but also apply to other megacities or densely populated regions, suggesting an urgent need to construct an accurate emission inventory for urban landscapes and evaluate their impact on ozone and SOA in air quality planning and management.

Key Role of NO3 Radicals in the Production of Isoprene Nitrates and Nitrooxyorganosulfates in Beijing.

The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

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.

Effects of 'pre-fracking' operations on ambient air quality at a shale gas exploration site in rural North Yorkshire, England.

Rural observations of air quality and meteorological parameters (NOx, O3, NMHCs, SO2, PM) were made over a 2.5-year period (2016-2018) before, during and after preparations for hydraulic fracturing (fracking) at a shale gas exploration site near Kirby Misperton, North Yorkshire, England. As one of the first sites to apply for permits to carry out hydraulic fracturing, it has been subject to extensive regulatory and public scrutiny, as well as the focus for a major programme of long-term environmental monitoring. A baseline period of air quality monitoring (starting 2016) established the annual climatology of atmospheric composition against which a 20-week period of intensive activity on the site in preparation for hydraulic fracturing could be compared. During this 'pre-operational phase' of work in late 2017, the most significant effect was an increase in ambient NO (3-fold) and NOx (2-fold), arising from a combination of increased vehicle activity and operation of equipment on site. Although ambient NOx increased, air quality limit values for NO2 were not exceeded, even close to the well-site. Local ozone concentrations during the pre-operational period were slightly lower than the baseline phase due to titration with primary emitted NO. The activity on site did not lead to significant changes in airborne particulate matter or non-methane hydrocarbons. Hydraulic fracturing of the well did not subsequently take place and the on-site equipment was decommissioned and removed. Air quality parameters then returned to the original (baseline) climatological conditions. This work highlights the need to characterise the full annual climatology of air quality parameters against which short-term local activity changes can be compared. Based on this study, changes to ambient NOx appear to be the most significant air quality ahead of hydraulic fracturing. However, in rural locations, concentrations at individual sites are expected to be below ambient air quality limit thresholds.

Atmospheric ethanol in London and the potential impacts of future fuel formulations.

There is growing global consumption of non-fossil fuels such as ethanol made from renewable biomass. Previous studies have shown that one of the main air quality disadvantages of using ethanol blended fuels is a significant increase in the production of acetaldehyde, an unregulated and toxic pollutant. Most studies on the impacts of ethanol blended gasoline have been carried out in the US and Brazil, with much less focus on the UK and Europe. We report time resolved measurements of ethanol in London during the winter and summer of 2012. In both seasons the mean mixing ratio of ethanol was around 5 ppb, with maximum values over 30 ppb, making ethanol currently the most abundant VOC in London air. We identify a road transport related source, with 'rush-hour' peaks observed. Ethanol is strongly correlated with other road transport-related emissions, such as small aromatics and light alkanes, and has no relationship to summer biogenic emissions. To determine the impact of road transport-related ethanol emission on secondary species (i.e. acetaldehyde and ozone), we use both a chemically detailed box model (incorporating the Master Chemical Mechanism, MCM) and a global and nested regional scale chemical transport model (GEOS-Chem), on various processing time scales. Using the MCM model, only 16% of the modelled acetaldehyde was formed from ethanol oxidation. However, the model significantly underpredicts the total levels of acetaldehyde, indicating a missing primary emission source, that appears to be traffic-related. Further support for a primary emission source comes from the regional scale model simulations, where the observed concentrations of ethanol and acetaldehyde can only be reconciled with the inclusion of large primary emissions. Although only constrained by one set of observations, the regional modelling suggests a European ethanol source similar in magnitude to that of ethane (∼60 Gg per year) and greater than that of acetaldehyde (∼10 Gg per year). The increased concentrations of ethanol and acetaldehyde from primary emissions impacts both radical and NOx cycling over Europe, resulting in significant regional impacts on NOy speciation and O3 concentrations, with potential changes to human exposure to air pollutants.

A dual channel gas chromatograph for atmospheric analysis of volatile organic compounds including oxygenated and monoterpene compounds.

A dual channel gas chromatograph with flame ionisation detectors has been used extensively for analysis of volatile organic compounds in the atmosphere and forms the basis of two monitoring instruments contributing VOC data to the World Meteorological Organisation - Global Atmosphere Watch network. Recent modifications to the methodology have broadened the scope of the instrument; to incorporate measurements of selected monoterpenes, and achieve improved accuracy in the measurement of oxygenated volatile organic compounds. Analysis of selected monoterpenes has been achieved without any significant loss of resolution of the non-methane hydrocarbons or oxygenated compounds. Quantification of 64 different VOCs of varying functionalities are reported with detection limits in the range 1-5 parts per trillion. Here we present a summary of the instrumental and calibration details for the methodology, which continues to be used on many field projects, along with a discussion of the associated measurement uncertainties.

Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean.

Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is approximately 50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.

Abiotic source of reactive organic halogens in the sub-arctic atmosphere?

Recent theoretical studies indicate that reactive organic iodocarbons such as CH2I2 would be extremely effective agents for tropospheric Arctic ozone depletion and that iodine compounds added to a Br2/BrCl mixture have a significantly greater ozone (and mercury) depletion effect than additional Br2 and BrCl molecules. Here we report the first observations of CH2I2, CH2IBr, and CH2ICl in Arctic air, as well as other reactive halocarbons including CHBr3, during spring at Kuujjuarapik, Hudson Bay. The organoiodine compounds were present atthe highest levels yet reported in air. The occurrence of the halocarbons was associated with northwesterly winds from the frozen bay, and, in the case of CHBr3, was anticorrelated with ozone and total gaseous mercury (TGM), suggesting a link between inorganic and organic halogens. The absence of local leads coupled with the extremely short atmospheric lifetime of CH2I2 indicates that production occurred in the surface of the sea-ice/overlying snowpack over the bay. We propose an abiotic mechanism for the production of polyhalogenated iodo- and bromocarbons, via reaction of HOI and/or HOBr with organic material on the quasi-liquid layer above sea-ice/snowpack, and report laboratory data to support this mechanism. CH2I2, CH2IBr, and other organic iodine compounds may therefore be a ubiquitous component of air above sea ice where they will increase the efficiency of bromine-initiated ozone and mercury depletion.

Modelling the ambient distribution of organic compounds during the august 2003 ozone episode in the southern UK.

A photochemical trajectory model containing speciated emissions of 124 non-methane volatile organic compounds (VOC), and a comprehensive description of the chemistry of VOC degradation, has been used to simulate the chemical evolution of boundary layer air masses arriving at a field campaign site in the southern UK during a widespread and prolonged photochemical pollution event in August 2003. The simulated concentrations and distributions of organic compounds at the arrival location are compared with observations of a series of hydrocarbons and carbonyl compounds, which were measured using GC-FID and multidimensional GC methods. The comparison of the simulated and observed distributions of 34 emitted hydrocarbons provides some support for the magnitude and applied emissions speciation of anthropogenic hydrocarbons, but is indicative of an under representation of the input of biogenic hydrocarbons, particularly at elevated temperatures. Simulations of the detailed distribution of ca. 1250 carbonyl compounds, formed primarily from the degradation of the 124 emitted VOC, focus on 61 aldehydes, ketones, dicarbonyls, hydroxycarbonyls and aromatic aldehydes which collectively account for ca. 90% of the simulated total molar concentration of carbonyls. The simulated distributions indicate that the photolysis of formaldehyde and alpha-dicarbonyls make major contributions to free radical production for the arrival conditions of five case study trajectories. The simulated concentrations of hydroxycarbonyls demonstrate preferential formation of the 1,4-substituted isomers (compared with 1,2- and 1,3-isomers of the same carbon number), which are formed during the initial oxidation sequence of longer chain alkanes.

A two-column method for long-term monitoring of non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (o-VOCs).

A method has been developed for concurrent analysis of C2-C7 hydrocarbons and C2-C5 oxygenated volatile organic compounds (o-VOCs) including alcohols, aldehydes, ketones and ethers. A multi-bed, Peltier-cooled adsorbent trap, consisting of Carboxen 1000 and Carbopack B, was used to acquire one sample per hour. Upon injection the sample was split in an approximately 50:50 ratio between a 50 m aluminium oxide (Al2O3) porous layer open tubular (PLOT) column and a 10 m LOWOX column. Eluents from each column were then analysed using flame ionisation detection (FID). Regular calibration of the system was performed using a standard cylinder mixture at the parts per billion by volume (ppbV) level for non-methane hydrocarbons (NMHCs) and a permeation tube method for the oxygenated species. The system is fully automated with NMHC detection limits between 1 and 10 parts per trillion by volume (pptV) and o-VOC detection limits between 10 and 40 pptV.