Source apportionment of volatile organic compounds during paddy-residue burning season in north-west India reveals large pool of photochemically formed air toxics.

Paddy-residue burning is associated with poor air quality in north-west India during October-November every year. However, till date a quantitative study of its contribution to ambient volatile organic compounds (VOCs) using highly time-resolved measurements within the region has been lacking. Several VOCs like benzene are carcinogenic and also fuel formation of secondary pollutants such as secondary organic aerosol (SOA) and ozone. Here, we undertake quantitative source-apportionment using a PMF source-receptor model on a high-quality in-situ measured dataset of 54 VOCs in Punjab, India, and validate the model results using source profiles. The contribution of the seven most dominant sources to the total VOC mass concentrations were: daytime photochemistry and biogenic VOCs (BVOCs) (26%), followed by solid-fuel usage and waste-disposal (18%), traffic (two-wheeler 14% and four-wheeler 10%), photochemically aged biomass burning (17%), industries and solvent usage (9%), and fresh paddy residue burning (6%). Ozone production potential was dominated by solid fuel usage and waste disposal (25%), followed by traffic (two-wheeler 11% and four-wheeler 12%), BVOCs and photooxidation products (21%), photochemically aged biomass burning (16%), industries & solvent usage (9%) and fresh paddy residue burning (6%). SOA production was dominated by traffic (two-wheeler 26% and four-wheeler 28%) followed by solid fuel usage and waste disposal (22%), photochemically aged biomass burning emissions (15%) with minor contribution from industries & solvents (6%), fresh paddy residue burning (2%) and photochemistry and biogenic VOCs (1%). Comparisons with global emission inventories REASv3.2.1 and EDGARv4.3.2, showed both overestimate the industry and solvent source. Further, EDGARv4.3.2 underestimated the traffic source whereas paddy residue burning emissions are absent in REASv3.2.1. Although the overall mass contribution of paddy-residue burning emissions isn't high, our results show that health-relevant compounds emitted directly and formed photochemically from biomass burning sources active at this time are majorly responsible for the unhealthy air.

Thermodynamical framework for effective mitigation of high aerosol loading in the Indo-Gangetic Plain during winter.

The Indo-Gangetic Plain (IGP) experiences severe air pollution every winter, with ammonium chloride and ammonium nitrate as the major inorganic fractions of fine aerosols. Many past attempts to tackle air pollution in the IGP were inadequate, as they targeted a subset of the primary pollutants in an environment where the majority of the particulate matter burden is secondary in nature. Here, we provide new mechanistic insight into aerosol mitigation by integrating the ISORROPIA-II thermodynamical model with high-resolution simultaneous measurements of precursor gases and aerosols. A mathematical framework is explored to investigate the complex interaction between hydrochloric acid (HCl), nitrogen oxides (NOx), ammonia (NH3), and aerosol liquid water content (ALWC). Aerosol acidity (pH) and ALWC emerge as governing factors that modulate the gas-to-particle phase partitioning and mass loading of fine aerosols. Six "sensitivity regimes" were defined, where PM1 and PM2.5 fall in the "HCl and HNO3 sensitive regime", emphasizing that HCl and HNO3 reductions would be the most effective pathway for aerosol mitigation in the IGP, which is ammonia-rich during winter. This study provides evidence that precursor abatement for aerosol mitigation should not be based on their descending mass concentrations but instead on their sensitivity to high aerosol loading.

Assessing the costs of ozone pollution in India for wheat producers, consumers, and government food welfare policies.

We assess wheat yield losses occurring due to ozone pollution in India and its economic burden on producers, consumers, and the government. Applying an ozone flux-based risk assessment, we show that ambient ozone levels caused a mean 14.18% reduction in wheat yields during 2008 to 2012. Furthermore, irrigated wheat was particularly sensitive to ozone-induced yield losses, indicating that ozone pollution could undermine climate-change adaptation efforts through irrigation expansion. Applying an economic model, we examine the effects of a counterfactual, "pollution-free" scenario on yield losses, wheat prices, consumer and producer welfare, and government costs. We explore three policy scenarios in which the government support farmers at observed levels of either procurement prices (fixed-price), procurement quantities (fixed-procurement), or procurement expenditure (fixed-expenditure). In pollution-free conditions, the fixed-price scenario absorbs the fall in prices, thus increasing producer welfare by USD 2.7 billion, but total welfare decreases by USD 0.24 billion as government costs increase (USD 2.9 billion). In the fixed-procurement and fixed-expenditure scenarios, ozone mitigation allows wheat prices to fall by 38.19 to 42.96%. The producers lose by USD 5.10 to 6.01 billion, but the gains to consumers and governments (USD 8.7 to 10.2 billion) outweigh these losses. These findings show that the government and consumers primarily bear the costs of ozone pollution. For pollution mitigation to optimally benefit wheat production and maximize social welfare, new approaches to support producers other than fixed-price grain procurement may be required. We also emphasize the need to consider air pollution in programs to improve agricultural resilience to climate change.

Sources, sinks, and chemistry of Stabilized Criegee Intermediates in the Indo-Gangetic Plain.

Night-time oxidation significantly affects the atmospheric concentration of primary and secondary air pollutants but is poorly constrained over South Asia. Here, using a comprehensively measured and unprecedented set of precursors and sinks of Stabilized Criegee Intermediates (SCI), in the summertime air of the Indo-Gangetic Plain (IGP), we investigate the chemistry, and abundance in detail. This study reports the first summertime levels from the IGP of ethene, propene, 1-butene, cis-2-butene, trans-2-butene, 1-pentene, cis-2-pentene, trans-2-pentene, and 1-hexene and their possible roles in SCI chemistry. Ethene, propene, and 1-butene were the highest ambient alkenes in both the summer and winter seasons. Applying chemical steady-state to the measured precursors, the average calculated SCI concentrations were 4.4 (±3.6) × 103 molecules cm-3, with Z-CH3CHOO (55 %) as the major SCI. Z-RCHOO (35 %) and α-pinene derived PINOO (34 %) were identified as the largest contributors to SCI with a 7.8 × 105 molecules cm-3 s-1 production rate. The peak SCI occurred during the evenings. For all SCI species, the loss was dominated (>50 %) by unimolecular decomposition or reactions with water vapor or water vapor dimer. Pollution events influenced by crop burning resulted in significantly elevated SCI production (2.1 times higher relative to non-polluted periods) reaching as high as (7.4 ± 2.5) × 105 molecules cm-3 s-1. Among individual SCI species, Z-CH3CHOO was highest in all the plume events measured accounting for at least ~41 %. Among alkenes, trans-2-butene was the highest contributor to P(SCI) in plume events ranging from 22 to 32 %. SCIs dominated the night-time oxidation of sulfur dioxide with rates as high as 1.4 (±1.1) × 104 molecules cm-3 s-1 at midnight, suggesting that this oxidation pathway could be a significant source of fine mode sulfate aerosols over the Indo-Gangetic Plain, especially during summertime biomass burning pollution episodes.

Replacing the greater evil: Can legalizing decentralized waste burning in improved devices reduce waste burning emissions for improved air quality?

Open waste burning emissions constitute a significant source of air pollution affecting human health in India. In regions where cleaner fuels have displaced solid biofuel usage, open waste burning is rapidly becoming one of the largest sources of airborne human class-I-carcinogens and particulate matter. As the establishment of waste management infrastructure in rural India is likely to take years, we explore whether health-relevant emissions can be reduced by legalizing the burning of dry non-biodegradable waste in improved devices. We measure the emission factors of 76 VOCs, CH4, CO, and CO2 from different types of waste burned in two different improved devices, a burn basket and a local water heater. Based on our experiments, we create four "what-if" intervention scenarios to assess the improvement of air quality due to the emission reductions that can be accomplished by four management strategies. We find that substituting the traditional, more polluting water heating fuels with dry plastic waste across rural India can reduce primary emissions (e.g., -29 Ggy-1 for benzene) and ozone formation potential (-2960 Ggy-1) from open waste burning. When dry waste is used in lieu of more polluting fuels, and its burning serves a purpose, the net class-I-carcinogen benzene emissions, would be halved compared to the present. The change in emissions for the class-I carcinogen 1,3-butadiene would become net negative. This happens because the emissions avoided when part of the solid biofuel currently used in rural India is replaced by plastic waste (4.1 (1.2-4.1) Ggy-1) exceed the waste burning emissions of this compound (3 (1.2-3.7) Ggy-1) by so much, that residential sector emission reductions offset all waste burning emissions including those of landfill fires. Our study demonstrates that India's air quality can be improved by permitting and promoting the use of dry packaging waste in lieu of traditional biofuels and by promoting improved burning devices.

Enhanced secondary aerosol formation driven by excess ammonia during fog episodes in Delhi, India.

The Indo-Gangetic Plain (IGP) has high wintertime fine aerosol loadings that significantly modulate the widespread fog formation and sustenance. Here, we investigate the potential formation of secondary inorganic aerosol driven by excess ammonia during winter fog. Physicochemical properties of fine aerosols (PM1 and PM2.5) and trace gases (HCl, HONO, HNO3, SO2, and NH3) were simultaneously monitored at hourly resolution using Monitor for AeRosols and Gases in Ambient air (MARGA-2S) for the first time in India. Results showed that four major ions, i.e., Cl-, NO3-, SO42-, and NH4+ contributed approximately 97% of the total measured inorganic ionic mass. The atmosphere was ammonia-rich in winter and ammonium was the dominant neutralizer with aerosol neutralization ratio (ANR) close to unity. The correlation between ammonium and chloride was ≥0.8, implying the significant formation of ammonium chloride during fog in Delhi. Thermodynamical model ISORROPIA-II showed the predicted PM1 and PM2.5 pH to be 4.49 ± 0.53, and 4.58 ± 0.48 respectively which were in good agreement with measurements. The ALWC increased from non-foggy to foggy periods and a considerable fraction of fine aerosol mass existed in the supermicron size range of 1-2.5 µm. The sulfur oxidation ratio (SOR) of PM1, PM2.5 reached up to 0.60, 0.75 in dense fog and 0.74, 0.87 when ambient RH crossed a threshold of 95%, much higher than non-foggy periods (with confidence level of ≥95%) pointing to enhanced formation of secondary aerosol in fog.

Quantitative Assessment of Nitrous Oxide Levels in Room Air of Operation Theaters and Recovery Area: An Observational Study.

BACKGROUND: Nitrous oxide has been used during surgical anesthesia for many years. However, information about occupational exposure and related risks due to N2O exposure to the health care personnel in India are still poorly understood. Here, we measured the residual N2O levels during the working time of operation theatre room air in our tertiary care hospital. MATERIAL AND METHODS: The air samples were collected from different anesthesia exposure zones on different days for quantitative analysis of available N2O in the room air in respective areas. Nitrous oxide concentrations in the ambient air were also measured to compare outdoor and indoor levels. OBSERVATIONS AND RESULTS: Nitrous oxide mixing ratios were found to be 65.61 ± 0.05 ppm, 281.63 ± 0.43 ppm, and 165.42 ± 0.42 ppm in elective surgical theatres of the hospital on three different days whereas in emergency operation theatres of the same hospital levels of N2O were 166.75 ± 0.07 ppm, 510.19 ± 0.30 ppm and 2443.92 ± 0.64 ppm during same period. In elective pediatric surgical theatres levels of N2O were found to be 1132.55 ± 0.70 ppm and 362.21 ± 0.13 ppm on two days of reading respectively. Outdoor levels of N2O in contrast found 0.32 ± 0.01 ppm and was lower by a factor of 1000. CONCLUSION: We observed the very high ambient concentration of N2O in the surgical theatre's environment (up to 2443 ppm) and recovery areas (up to 50 ppm). It was 5 to 50 times higher ambient concentration of N2O than REL in OT area and 200-7000 times higher ambient concentration of N2O than outdoor ambient air in all surgical theaters other than CTVS OTs.

Probing wintertime air pollution sources in the Indo-Gangetic Plain through 52 hydrocarbons measured rarely at Delhi & Mohali.

During wintertime, the Indo-Gangetic Plain suffers from severe air pollution affecting several hundred million people. Here we present unprecedented measurements and source analyses of 52 NMHCs (25 alkanes, 16 aromatics, 10 alkenes and one alkyne) in the cities of Delhi and Mohali (300 km north of Delhi) during wintertime (Dec 2016-Jan 2017). NMHCs were measured using a thermal desorption gas chromatograph equipped with flame ionisation detectors with data traceable to WMO standards. The ten most abundant NMHCs that were measured were the same at both Delhi and Mohali: propane, n-butane, acetylene, ethane, toluene, i-butane, ethene, i-pentane, benzene and propene and accounted for >50% of total measured NMHC mass concentration (137 ± 5.8 µg m-3 in Mohali and 239 ± 7.7 µg m-3 in Delhi). Ambient NMHCs and calculated hydroxyl radical reactivity were approximately twice as high in Delhi relative to Mohali, and 2-12 times higher than most other mega-cities, except Lahore and Karachi. Using chemical source signatures, traffic and LPG usage emissions were identified as the major contributor of these reactive NMHCs at both sites during nighttime, with additional minor contributions of garbage burning in Mohali, and evaporative fuel and biomass burning emissions in Delhi. Comparison of NMHC/CO and NMHC/C2H2 ratios over Mohali and Delhi, to other cities, suggested gasoline/petrol-fuelled vehicles were major NMHC emitters within the traffic source. The data from both Mohali and Delhi suggest that a large fraction of the fleet comprised vehicles with older emission control in both Mohali and Delhi. Analyses revealed poor representation of propene, ethene and trimethylbenzenes in the emission inventory (EDGARv4.3.2) over Mohali and Delhi. This study provides key data and new insights into the sources of reactive NMHCs (lifetime < few days) that drive regional wintertime pollution through direct effects and the formation of secondary pollutants.

Gridded 1 km × 1 km emission inventory for paddy stubble burning emissions over north-west India constrained by measured emission factors of 77 VOCs and district-wise crop yield data.

Every year in the post-monsoon season, ~1.7 billion tons of paddy stubble is burnt openly in the Indo-Gangetic Plain (IGP) producing persistent smog and air quality deterioration that affects the entire IGP. Information concerning the identity, amounts and spatial distribution of volatile organic compounds (VOCs) which drive ozone and aerosol formation is still largely unknown as existing global emission inventories have poor VOC speciation and rely on limited satellite overpasses for mapping burnt areas. Here, emission factors (EFs) of 77 VOCs were measured from paddy fire smoke and combined with 1 km × 1 km stubble burning activity constrained by annual crop production yields and detected fires to compile a new gridded emission inventory for 2017. Our results reveal a large source of acetaldehyde (37.5 ± 9.6 Ggy-1), 2-furaldehyde (37.1 ± 12.5 Ggy-1), acetone (34.7 ± 13.6 Ggy-1), benzene (9.9 ± 2.8 Ggy-1) and isocyanic acid (0.4 ± 0.2 Ggy-1) that are not accounted for by existing emission inventories (GFED, GFAS, FINv2.1). During October-November, these emissions (346 ± 65 Ggy-1 NMVOC; 38 ± 8 Ggy-1 NOx; 16 ± 4 Ggy-1 NH3; 129 ± 9 Ggy-1 PM2.5; 22,125 ± 3674 Ggy-1 GHG CO2 equivalents) are more than 20 times larger than corresponding emissions from traffic and municipal waste burning over north-west India. Mitigation of this source alone can therefore yield massive air-quality climate co-benefits for more than 500 million people.

Season-wise analyses of VOCs, hydroxyl radicals and ozone formation chemistry over north-west India reveal isoprene and acetaldehyde as the most potent ozone precursors throughout the year.

The north-west Indo-Gangetic Plain is the agricultural cereal-basket of India owing to its prolific wheat and rice production. Surface ozone pollution is of growing concern over it, yet no detailed year-round in-situ measurements of its most reactive precursors, particularly the volatile organic compounds (VOCs) are available from this region. Here, using the first year-long continuous measurements of 23 major VOCs, ozone, NOx, CO and their atmospheric oxidation products from a regionally representative site in north-west India, we evaluated speciated OH reactivities (OHR), ozone formation potential (OFP) and ozone production regimes (OPR) across all seasons. The average seasonal OHR ranged from 14 s-1 (winter) to 21.5 s-1 (summer). We provide the first estimate of OH radical mixing ratios varying between 0.06 and 0.37 ppt in different seasons for the peak daytime hours in this region. Recycling via HO2+NO was the most important pathway contributing to >85% of the OH production throughout the year. Contrary to satellite derived proxies and chemical transport models which predict NOx sensitive OPR, we show it to be strongly sensitive to both VOCs and NOx (>90% days in a year). Remarkably for densely populated regions, isoprene and acetaldehyde collectively accounted for ~30-50% of the total OFP in all seasons. Biogenic emissions of isoprene (reaching 12.9 mg/m2/h) and high acetaldehyde from anthropogenic and photochemical sources were observed for all seasons. Monitoring and control of isoprene and acetaldehyde are therefore urgently required for efforts focused on mitigating surface ozone pollution in this demographically important region of the world.

Appraisal of regional haze event and its relationship with PM2.5 concentration, crop residue burning and meteorology in Chandigarh, India.

Air pollution affects not only the air quality in megacities but also in medium and small-sized cities due to rapid urbanization, industrialization, and other anthropogenic activities. From October 28, 2015 to November 3, 2015, the Indo-Gangetic Plains region, including Chandigarh encountered an episode of poor visibility during the daytime. The daily average PM2.5 concentration reached 191 µg/m3, and visibility reduced by ∼2.2 times in the Chandigarh region. PM2.5 concentration was found around 4 times higher than a non-haze day and more than 3 times higher than National Ambient Air Quality Standards for 24 h. A significant correlation between PM2.5 and CO (r: 0.87) during the haze period indicated similarity in their emission sources; which was attributed to the burning of solid organic matter. Further, satellite data and back-trajectory analysis of air masses showed large-scale rice stubble burning in the agricultural fields, adjoining to the city areas. The transboundary movement of air masses below 500 m and meteorological conditions played a major role in building the pollution load in the Chandigarh region. Moreover, the enhanced concentration of biomass burning tracers, i.e., organic carbon (∼3.8 times) and K+ ions (2∼ times) in PM2.5 and acetonitrile (∼2.3 times) in ambient air was observed during the haze event. The study demonstrates how regional emissions and meteorological conditions can affect the air quality in a city; which can be useful for proper planning and mitigation policies to minimize high air pollution episodes.

Gridded Emissions of CO, NO x, SO2, CO2, NH3, HCl, CH4, PM2.5, PM10, BC, and NMVOC from Open Municipal Waste Burning in India.

Accurate emission inventories serve as critical inputs for air quality and climate models but are poorly constrained over India. We present a new municipal open waste burning emission inventory from India (OWBEII), at a resolution of 0.1° × 0.1°. Out of the 216 (201-232) Tg y-1 of waste produced in the year 2015, 68 (45-105) Tg y-1 was burned in the open. To determine emissions from waste burning, emission factors of 59 non-methane volatile organic compounds (NMVOCs), CH4, CO2, CO, and NO x were measured from garbage fires in rural and urban sites in India. The NMVOC emissions from open waste burning of 1.4-2 Tg y-1 increase India's total anthropogenic NMVOC budget by 8-12%, while BC emissions (40-110 Ggy-1) increase the total anthropogenic BC emissions by 8-12%. Open waste burning in India emits 3-7 Tg y-1 of CO and 58-130 Tg y-1 of CO2. Emissions increase the total anthropogenic CO and CO2 in the MIX-Asia inventory by 4-11% and 2-6%, respectively. Open waste burning may affect atmospheric OH reactivity and ozone formation rates downwind of urban centers through the emission of other highly reactive compounds such as acetaldehyde (20-320 Gg y-1), propene (50-170 Gg y-1), and ethene (50-190 Gg y-1) and is s source of carcinogenic benzene (30-280 Gg y-1).

Contribution of post-harvest agricultural paddy residue fires in the N.W. Indo-Gangetic Plain to ambient carcinogenic benzenoids, toxic isocyanic acid and carbon monoxide.

In the north west Indo-Gangetic Plain (N.W.IGP), large scale post-harvest paddy residue fires occur every year during the months of October-November. This anthropogenic perturbation causes contamination of the atmospheric environment with adverse impacts on regional air quality posing health risks for the population exposed to high concentrations of carcinogens such as benzene and toxic VOCs such as isocyanic acid. These gases and carbon monoxide are known to be emitted from biomass fires along with acetonitrile. Yet no long-term in-situ measurements quantifying the impact of this activity have been carried out in the N.W. IGP. Using high quality continuous online in-situ measurements of these gases at a strategic downwind site over a three year period from 2012 to 2014, we demonstrate the strong impact of this anthropogenic emission activity on ambient concentrations of these gases. In contrast to the pre-paddy harvest period, excellent correlation of benzenoids, isocyanic acid and CO with acetonitrile (a biomass burning chemical tracer); (r≥0.82) and distinct VOC/acetonitrile emission ratios were observed for the post-paddy harvest period which was also characterized by high ambient concentrations of these species. The average concentrations of acetonitrile (1.62±0.18ppb), benzene (2.51±0.28ppb), toluene (3.72±0.41ppb), C8-aromatics (2.88±0.30ppb), C9-aromatics (1.55±0.19ppb) and CO (552±113ppb) in the post-paddy harvest periods were about 1.5 times higher than the annual average concentrations. For isocyanic acid, a compound with both primary and secondary sources, the concentration in the post-paddy harvest period was 0.97±0.17ppb. The annual average concentrations of benzene, a class A carcinogen, exceeded the annual exposure limit of 1.6ppb at NTP mandated by the National Ambient Air Quality Standard of India (NAAQS). We show that mitigating the post-harvest paddy residue fires can lower the annual average concentration of benzene and ensure compliance with the NAAQS. Calculations of excessive lifetime cancer risk due to benzene amount to 25 and 10 per million inhabitants for children and adults, respectively, exceeding the USEPA threshold of 1 per million inhabitants. Annual exposure to isocyanic acid was close to 1ppb, the concentration considered to be sufficient to enhance risks for cardiovascular diseases and cataracts. This study makes a case for urgent mitigation of post-harvest paddy residue fires as the unknown synergistic effect of multi-pollutant exposure due to emissions from this anthropogenic source may be posing grave health risks to the population of the N.W. IGP.

Limitation of the Use of the Absorption Angstrom Exponent for Source Apportionment of Equivalent Black Carbon: a Case Study from the North West Indo-Gangetic Plain.

Angstrom exponent measurements of equivalent black carbon (BCeq) have recently been introduced as a novel tool to apportion the contribution of biomass burning sources to the BCeq mass. The BCeq is the mass of ideal BC with defined optical properties that, upon deposition on the aethalometer filter tape, would cause equal optical attenuation of light to the actual PM2.5 aerosol deposited. The BCeq mass hence is identical to the mass of the total light-absorbing carbon deposited on the filter tape. Here, we use simultaneously collected data from a seven-wavelength aethalometer and a high-sensitivity proton-transfer reaction mass spectrometer installed at a suburban site in Mohali (Punjab), India, to identify a number of biomass combustion plumes. The identified types of biomass combustion include paddy- and wheat-residue burning, leaf litter, and garbage burning. Traffic plumes were selected for comparison. We find that the combustion efficiency, rather than the fuel used, determines αabs, and consequently, the αabs can be ∼1 for flaming biomass combustion and >1 for older vehicles that operate with poorly optimized engines. Thus, the absorption angstrom exponent is not representative of the fuel used and, therefore, cannot be used as a generic tracer to constrain source contributions.

OH reactivity measurements within a boreal forest: evidence for unknown reactive emissions.

Boreal forests emit large amounts of volatile organic compounds (VOCs) which react with the hydroxyl radical (OH) to influence regional ozone levels and form secondary organic aerosol. Using OH reactivity measurements within a boreal forest in Finland, we investigated the budget of reactive VOCs. OH reactivity was measured using the comparative reactivity method, whereas 30 individual VOCs were measured using proton transfer reaction mass spectrometry, thermal-desorption gas chromatography mass spectrometry, and liquid chromatography mass spectrometry, in August 2008. The measured OH reactivity ranged from below detection limit (3.5 s(-1)), to approximately 60 s(-1) in a single pollution event. The average OH reactivity was approximately 9 s(-1) and no diel variation was observed in the profiles. The measured OH sinks (approximately 30 species) accounted for only 50% of the total measured OH reactivity, implying unknown reactive VOCs within the forest. The five highest measured OH sinks were: monoterpenes (1 s(-1)), CO (0.7 s(-1)), isoprene (0.5 s(-1)), propanal and acetone (0.3 s(-1)), and methane (0.3 s(-1)). We suggest that models be constrained by direct OH reactivity measurements to accurately assess the impact of boreal forest emissions on regional atmospheric chemistry and climate.