Air pollution scenario analyses of fleet replacement strategies to accomplish reductions in criteria air pollutants and 74 VOCs over India

Traffic emissions are a major source of air pollution and associated damage to human health in India. Many of the Indian metro cities urgently require cleaner transportation technologies to ensure cleaner air. Here, using newly compiled spatially disaggregated, gridded, high-resolution (0.1° × 0.1°) road transport emission inventory for India for 2030 (RTEII) of 74 speciated VOCs, CO, SO2, NOx, NH3, CH4, CO2, BC, OC and PM2.5 from varied fuels and vehicle technologies that are currently in use in India, we investigated changes in emission in response to substitution of the existing vehicular fleet by cleaner alternatives. Three “what-if” intervention scenarios were considered to assess the extent in improvement of air quality due to the reduction in the primary emission of air pollutants. The results show that significant reductions in direct emission of pollutants (Non-Methane VOCs, −91%; CO, −80%; PM2.5, 44%) including toxic VOCs (e.g., isocyanic acid, −76%; BTEX, −93%; as well as individual VOC classes (e.g., sum of OVOCs, −61% and sum of alkenes, −80%) can likely be achieved in 2030 by shifting from highly polluting Internal Combustion Engine (ICE) based 2 and 3-wheeled vehicles to Electric Vehicles (EVs) under scenario 1. The amount of secondary pollutants such as SOA and O3 that can potentially be formed from traffic also showed significant reduction of 94% and 84%, respectively, under scenario 1. Conversion of diesel fuelled vehicles to CNG under scenario 2 can lead to a larger reduction in black carbon emissions (−50%). Scenario 3, in which the benefits of scenarios 1 and 2 are combined, represents the best long-term strategy moving forward, which can result in massive emission reductions of pollutants through existing technologies of greener transport fleets over India. Large scale conversion of the vehicle fleets as explored here can lead to a substantial reduction of air pollution and fewer lives lost

RTEII : A new high-resolution (0.1° × 0.1°) road transport emission inventory for India of 74 speciated NMVOCs, CO, NOx, NH3, CH4, CO2, PM2.5 reveals massive overestimation of NOx and CO and missing nitromethane emissions by existing inventories

21 of 30 most polluted cities for particulate matter (PM2.5) are in India, yet the distribution, identity and emissions of volatile organic compounds (VOCs) from traffic, which are PM2.5 and ozone precursors, remain unknown. Here, we measured emission factors (EFs) of 74 VOCs from a range of Indian vehicle-technology and fuel types. When combined with 0.1 ° × 0.1 ° spatially resolved activity data for the year 2015, toluene (137 ± 39 Gg yr1), isopentane (111 ± 38 Ggyr−1), and acetaldehyde (41 ± 6 Ggyr−1) were top 3-VOC emissions. Petrol-2-wheelers and LPG-3-wheelers emitted the highest VOCs (EFs> 50 gVOC/L) and had highest secondary pollutant formation potential, so their replacement with electric vehicles would improve air quality. EDGARv4.3.2 and REASv.2.1 emission inventories overestimated total road sector emitted VOCs due to obsolete EFs and activity data, in particular over-estimating ethene, propene, ethyl benzene, 2,2- dimethyl butane, CO, NOx while significantly under-estimating acetaldehyde. Nitromethane emissions were missing from previous inventories and with isocyanic acid and benzene contributed significantly to toxic emissions (summed total ~41 ± 4 Ggyr−1). Knowledge of key VOCs emitted from the world's third largest road-network provides critical new data for mitigating secondary pollutant formation over India and will enable more accurate modelling of atmospheric composition over South Asia

Significant emissions of dimethyl sulfide and monoterpenes by big-leaf mahogany trees : Discovery of a missing dimethyl sulfide source to the atmospheric environment

Biogenic volatile organic compounds exert a strong influence on regional air quality and climate through their roles in the chemical formation of ozone and fine-mode aerosol. Dimethyl sulfide (DMS), in particular, can also impact cloud formation and the radiative budget as it produces sulfate aerosols upon atmospheric oxidation. Recent studies have reported DMS emissions from terrestrial sources; however, their magnitudes have been too low to account for the observed ecosystem-scale DMS emission fluxes. Big-leaf mahogany (Swietenia macrophylla King) is an agroforestry and natural forest tree known for its high-quality timber and listed under the Convention on International Trade in Endangered Species (CITES). It is widely grown in the American and Asian environments (>2.4 million km2 collectively). Here, we investigated emissions of monoterpenes, isoprene and DMS as well as seasonal carbon assimilation from four big-leaf mahogany trees in their natural outdoor environment using a dynamic branch cuvette system, high-sensitivity proton transfer reaction mass spectrometer and cavity ring-down spectrometer. The emissions were characterized in terms of environmental response functions such as temperature, radiation and physiological growth phases including leaf area over the course of four seasons (summer, monsoon, post-monsoon, winter) in 2018-2019. We discovered remarkably high emissions of DMS (average in post-monsoon: ĝ1/419 ng g-1 leaf dry weight h-1) relative to previous known tree DMS emissions, high monoterpenes (average in monsoon: ĝ1/415 μg g-1 leaf dry weight h-1, which is comparable to oak trees) and low emissions of isoprene. Distinct linear relationships existed in the emissions of all three BVOCs with higher emissions during the reproductive phase (monsoon and post-monsoon seasons) and lower emissions in the vegetative phase (summer and winter seasons) for the same amount of cumulative assimilated carbon. Temperature and PAR dependency of the BVOC emissions enabled formulation of a new parameterization for use in global BVOC emission models. Using the measured seasonal emission fluxes, we provide the first estimates for the global emissions from mahogany trees which amount to circa 210-320 Gg yr-1 for monoterpenes, 370-550 Mg yr-1 for DMS and 1700-2600 Mg yr-1 for isoprene. Finally, through the results obtained in this study, we have been able to discover and identify mahogany as one of the missing natural sources of ambient DMS over the Amazon rainforest as well. These new emission findings, indication of seasonal patterns and estimates will be useful for initiating new studies to further improve the global BVOC terrestrial budget

Non-methane hydrocarbon (NMHC) fingerprints of major urban and agricultural emission sources for use in source apportionment studies

In complex atmospheric emission environments such as urban agglomerates, multiple sources control the ambient chemical composition driving air quality and regional climate. In contrast to pristine sites, where reliance on single or a few chemical tracers is often adequate for resolving pollution plumes and source influences, the comprehensive chemical fingerprinting of sources using nonmethane hydrocarbons (NMHCs) and the identification of suitable tracer molecules and emission ratios becomes necessary. Here, we characterise and present chemical fingerprints of some major urban and agricultural emission sources active in South Asia, such as paddy stubble burning, garbage burning, idling vehicular exhaust and evaporative fuel emissions. A total of 121 whole air samples were actively collected from the different emission sources in passivated air sampling steel canisters and then analysed for 49 NMHCs (22 alkanes, 16 aromatics, 10 alkenes and one alkyne) using thermal desorption gas chromatography flame ionisation detection. Several new insights were obtained. Propane was found to be present in paddy stubble fire emissions (8 %), and therefore, for an environment impacted by crop residue fires, the use of propane as a fugitive liquefied petroleum gas (LPG) emission tracer must be done with caution. Propene was found to be ∼ 1.6 times greater (by weight) than ethene in smouldering paddy fires. Compositional differences were observed between evaporative emissions of domestic LPG and commercial LPG, which are used in South Asia. While the domestic LPG vapours had more propane (40 ± 6 %) than n-butane (19 ± 2 %), the converse was true for commercial LPG vapours (7 ± 6 % and 37 ± 4 %, respectively). Isoprene was identified as a new tracer for distinguishing paddy stubble and garbage burning in the absence of isoprene emissions at night from biogenic sources. Analyses of source-specific inter-NMHC molar ratios revealed that toluene/benzene ratios can be used to distinguish among paddy stubble fire emissions in the flaming (0.38 ± 0.11) and smouldering stages (1.40 ± 0.10), garbage burning flaming (0.26 ± 0.07) and smouldering emissions (0.59 ± 0.16), and traffic emissions (3.54 ± 0.21), whereas i-pentane = npentane can be used to distinguish biomass burning emissions (0.06 1.46) from the petrol-dominated traffic and fossil fuel emissions (2.83 4.13). i-butane = n-butane ratios were similar (0.20 0.30) for many sources and could be used as a tracer for photochemical ageing. In agreement with previous studies, i-pentane, propane and acetylene were identified as suitable chemical tracers for petrol vehicular and evaporative emissions, LPG evaporative and vehicular emissions and flaming-stage biomass fires, respectively. The secondary pollutant formation potential and human health impact of the sources was also assessed in terms of their hydroxyl radical (OH) reactivity (s-1), ozone formation potential (OFP; gO3/gNMHC) and fractional benzene, toluene, ethylbenzene and xylenes (BTEX) content. Petrol vehicular emissions, paddy stubble fires and garbage fires were found to have a higher pollution potential (at = 95 % confidence interval) relative to the other sources studied in this work. Thus, many results of this study provide a new foundational framework for quantitative source apportionment studies in complex emission environments

Structural and electrical properties of CuAlMo thin films prepared by magnetron sputtering

The structural and electrical properties of a low resistivity CuAlMo thin film resistor material were investigated. The thin films were grown on Al2O3 and glass substrates by direct current (dc) magnetron sputtering. The key electrical properties of sheet resistance, temperature coefficient of resistance (TCR) and resistance stability were investigated as a function of sputtering pressure and post-deposition heat treatment time and temperature. A low sputtering pressure range of 0.13 to 0.40 Pa produced CuAlMo films with sheet resistance in the range 0.1 to 0.2 Ω/□ and resistance stability of 0.45 to 0.65% with a TCR of − 90 ppm/°C which could be shifted to zero following annealing in air at 425 °C. Films grown at higher sputtering pressures of 0.53 to 0.80 Pa had increased sheet resistance in the range 0.4 to 0.6 Ω/□ and inferior stability of 0.8 to 1.7% with a more negative TCR of − 110 to − 180 ppm/°C which could not be shifted to zero following annealing. The stability of the films grown at 0.13 and 0.40 Pa could be further improved to < 0.25% with heat treatment, due to the formation of a protective aluminium oxide layer. A minimum dwell time of 3 h at 425 °C was required to stabilise the films and set the electrical properties

Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument

We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCIs) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the aforementioned campaigns is caused at least partially by SCIs. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCIs, the background OH concentration can be removed through the addition of sulfur dioxide. SCIs also add to the previously underestimated production rate of sulfuric acid. An average estimate of the SCI concentration of similar to 5.0 x 10(4) molecules cm(-3) (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCIs, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere.Peer reviewe

Identifying Criegee intermediates as potential oxidants in the troposphere

Abstract and poster presented at the AGU Fall meeting, San Francisco 2015.Criegee intermediates (CI) are formed during the ozonolysis of unsaturated compounds and have been intensively studied in the last few years due to their possible role as oxidants in the troposphere. Stabilised CI (SCI) are now known to react very rapidly, k(298 K) = 10-12 to 10-10 cm3 molecule-1 s-1, with a large number of trace gases (SO2, NO2, organic acids, water dimers). Still, it remains challenging to assess their effective oxidative capacity, as CI chemistry is complex, spans a large range of rate coefficients for different SCI conformers reacting with water dimers and trace gases, and in addition no reliable measurement technique able to detect ambient SCI concentrations is currently available. In this study, we examine the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns, aided by literature data, to estimate the abundance of SCI in the lower troposphere. The budget of SCI is analyzed using four different approaches: 1) based on an observed yet unexplained H2SO4 production; 2) from the measured concentrations of unsaturated volatile organic compounds (VOC); 3) from OH reactivity measurements; 4) from the unexplained production rate of OH. A SCI concentration range between 5 x 103 and 2 x 106 molecule cm-3 is calculated for the two environments. The central weighted estimate of the SCI concentration over the boreal forest of ~ 5 x 104 molecules cm-3 implies a significant impact on the conversion of SO2 into H2SO4. In addition, we present measurements obtained using our inlet pre-injector laser-induced fluorescence assay by gas expansion technique (IPI-LIF-FAGE) for the above-mentioned campaigns. A recent laboratory study performed with the same instrumental setup showed that the IPI-LIF-FAGE system is sensitive to the detection of the OH formed from unimolecular decomposition of SCI. Building on these measurements, the background OH (OHbg) measured during the two field campaigns is investigated in comparison with many other trace gases to assess if the observations in controlled conditions are transferable to ambient conditions

Identifying Criegee intermediates as potential oxidants in the troposphere

Discussion started 24/10/16We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCI) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the afore-mentioned campaigns is caused at least partially by SCI. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. The background OH concentration also complements the previously underestimated production rate of sulfuric acid and is consistent with its scavenging through the addition of sulphur dioxide. A central estimate of the SCI concentration of ~ 5 × 104 molecules cm−3 (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCI, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere

Tropospheric Ozone Assessment Report: present-day tropospheric ozone distribution and trends relevant to vegetation

This Tropospheric Ozone Assessment Report (TOAR) on the current state of knowledge of ozone metrics of relevance to vegetation (TOAR-Vegetation) reports on present-day global distribution of ozone at over 3300 vegetated sites and the long-term trends at nearly 1200 sites. TOAR-Vegetation focusses on three metrics over vegetation-relevant time-periods across major world climatic zones: M12, the mean ozone during 08:00–19:59; AOT40, the accumulation of hourly mean ozone values over 40 ppb during daylight hours, and W126 with stronger weighting to higher hourly mean values, accumulated during 08:00–19:59. Although the density of measurement stations is highly variable across regions, in general, the highest ozone values (mean, 2010–14) are in mid-latitudes of the northern hemisphere, including southern USA, the Mediterranean basin, northern India, north, north-west and east China, the Republic of Korea and Japan. The lowest metric values reported are in Australia, New Zealand, southern parts of South America and some northern parts of Europe, Canada and the USA. Regional-scale assessments showed, for example, significantly higher AOT40 and W126 values in East Asia (EAS) than Europe (EUR) in wheat growing areas (p < 0.05), but not in rice growing areas. In NAM, the dominant trend during 1995–2014 was a significant decrease in ozone, whilst in EUR it was no change and in EAS it was a significant increase. TOAR-Vegetation provides recommendations to facilitate a more complete global assessment of ozone impacts on vegetation in the future, including: an increase in monitoring of ozone and collation of field evidence of the damaging effects on vegetation; an investigation of the effects on peri-urban agriculture and in mountain/upland areas; inclusion of additional pollutant, meteorological and inlet height data in the TOAR dataset; where not already in existence, establishing new region-specific thresholds for vegetation damage and an innovative integration of observations and modelling including stomatal uptake of the pollutant