Seasonal variations in aerosol acidity and its driving factors in the eastern Indo-Gangetic Plain: A quantitative analysis

This study employs ISORROPIA-II for the evaluation of aerosol acidity and quantification of contributions from chemical species and meteorological parameters to acidity variation in the Indian context. PM2.5 samples collected during summer (April-July 2018), post-monsoon (September-November 2018), and winter (December 2018-January 2019) from a rural receptor location in the eastern Indo-Gangetic Plain (IGP) were analyzed for ionic species, water-soluble organic carbon (WSOC), and organic and elemental carbon (OC, EC) fractions. This was followed by estimation of the in situ aerosol pH and liquid water content (LWC) using the forward mode of ISORROPIA-II, which is less sensitive to measurement uncertainty compared to the reverse mode, for a K+-Ca2+Mg2+-NH4+-Na+-SO42--NO3--Cl--H2O system. Aerosol pH was moderately acidic (summer: 2.93 +/- 0.67; post-monsoon: 2.67 +/- 0.23; winter: 3.15 +/- 0.34) and was most sensitive to SO42- and total ammonium (TNH3) variation. The LWC of aerosol showed an increasing trend from summer (16.6 +/- 13.6 mu g m(-3)) through winter (32.9 +/- 10.4 mu g m(-3)). With summer as the baseline, the largest changes in aerosol pH during the other seasons was driven by SO42- (Delta pH: 0.70 to 0.82 units), followed by TNH3 (Delta pH: +0.25 to +0.38 units) with K+ and temperature being significant only during winter (Delta pH: +0.51 and + 0.46 units, respectively). The prevalent acidity regime provided three major insights: i) positive summertime Cl- depletion (49 +/- 20%) as a consequence of SO42- substitution increased aerosol pH by 0.03 +/- 0.20 units and decreased LWC by 2.4 +/- 5.9 mu g m(-3); ii) the rate of strong acidity (H-str(+)) neutralization and the [H-str(+)]/[SO42-] molar ratio suggested the existence of bounded acidity in ammonium-rich (winter) conditions; and iii) significant correlations between LWC, WSOC, and secondary organics during post-monsoon and winter pointed towards a possible indirect role of WSOC in enhancing LWC of aerosol, thereby increasing pH. Given the inability of proxies such as H-str(+) and charge ratios to accurately represent aerosol pH as demonstrated here, this study emphasizes the need for rigorous thermodynamic model-based evaluation of aerosol acidity in the Indian scenario.