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.

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.

Characterization of atmospheric trace gases and water soluble inorganic chemical ions of PM1 and PM2.5 at Indira Gandhi International Airport, New Delhi during 2017-18 winter.

Water soluble inorganic chemical ions of PM1 and PM2.5 and atmospheric trace gases were monitored simultaneously on hourly resolution at Indira Gandhi International Airport (IGIA), Delhi during 8 December 2017-10 February 2018. Monitoring was made by MARGA (Monitoring AeRosol and Gases in ambient Air) under winter fog experiment (WIFEX) program of the Ministry of Earth Sciences (MoES), Government of India. The result based on the analysis of the data so generated reveals that Cl-, NH4+, NO3- and SO42- were dominant ions in order which collectively constituted 96.8 and 97.3% of the of the total measured ionic mass in PM1 and PM2.5 respectively. Their overall average concentrations in PM1 were 19.5 ± 19.7, 18.4 ± 10.5, 16.6 ± 8.7 and 10.3 ± 5.7 µg/m3 and in PM2.5 were 36.0 ± 33.9, 32.7 ± 17.2, 28.5 ± 13.6 and 19.9 ± 13.9 µg/m3. Average concentrations of HCl, HNO3, HNO2, SO2 and NH3 trace gases were 0.7 ± 0.3, 2.7 ± 1.1, 6.6 ± 4.7, 22.0 ± 12.3 and 25.7 ± 9.1 µg/m3 respectively. Weather parameters along with low mixing height played significant role in the occurrence of high concentration of these chemical species. NH4+ was the prime neutralizer of the acidic components and mostly occurred in (NH4)2SO4/NH4HSO4, NH4NO3 and NH4Cl molecular forms. Major sources of these chemical species were fossil fuel combustion in aviation activity and transportation, coal burning in thermal power plants, industrial processes and emissions from biomass burning and agro-based activity. The quality of air with respect to PM2.5 always remained deteriorated. It became alarming during low visibility period mainly due to high concentration of Cl-, NO3-, SO42- and NH4+. Both meteorological and chemical processes interactively fed each other which occasionally resulted in fog development and visibility degradation. The knowledge gained by this study will help in simulation of atmospheric processes which lead to fog development and dispersal in the Delhi region.

Characterization and source identification of PM2.5 and its chemical and carbonaceous constituents during Winter Fog Experiment 2015-16 at Indira Gandhi International Airport, Delhi.

Data on mass concentration of PM2.5 and its carbonaceous and water soluble inorganic chemical ions were compiled through sampling of PM2.5 at Indira Gandhi International Airport, Delhi during Dec. 16, 2015-Feb. 15, 2016 under Winter Fog Experiment (WIFEX) program of the Ministry of Earth Sciences (MoES) and analysing the samples. The data so generated were interpreted in terms of their variation on different time scales and apportioning their sources. It is found that mass concentration of PM2.5 averaged over the whole period of observation was 198.6±55.6. The concentration of organic carbon (OC) and elemental carbon (EC) was 24.7±9.4 and 11.7±4.7µg/m3 respectively with no any trend of increase or decrease over the observational period. SO42-, Cl- and NO3- dominated over other anions with their overall average concentration 34.0±23.1, 32.7±16.1 and 13.3±8.7µg/m3 respectively. Among cations, NH4+ showed highest concentration with an average value of 21.0±10.6µg/m3. Variation of daily average mass concentration of these parameters over the period of observation matched well with the variation of PM2.5 mass concentration indicating thereby to be the major contributors to the PM2.5 mass. NH4+ mostly occurred as NH4Cl and NH4NO3 and poorly as (NH4)2SO4 or NH4HSO4. H+ ion mostly occurred as H2SO4 and occasionally as HNO3. Carbonaceous aerosols and NO3- were mainly generated from fossil-fuel combustion. NH4+ and anthropogenic Cl- were mostly generated by biomass burning. The source of SO42- was found to be industries and thermal power plants. Continental Ca2+ and Mg2+ originated from thermal power plants and soil dust.