Size-segregated airborne fine (PM2.1) and coarse (PM>2.1) particulates were measured in an urban environment over central Indo-Gangetic plain in between 2015 and 2018 to get insights into its nature, chemistry and sources. Mean (±1σ) concentration of PM2.1 was 98 (±76) μgm-3 with a seasonal high during winter (DJF, 162 ± 71 μgm-3) compared to pre-monsoon specific high in PM>2.1 (MAMJ, 177 ± 84 μgm-3) with an annual mean of 170 (±69) μgm-3. PM2.1 was secondary in nature with abundant secondary inorganic aerosols (20% of particulate mass) and water-soluble organic carbon (19%) against metal enriched (25%) PM>2.1, having robust signature of resuspensions from Earth's crust and road dust. Ammonium-based neutralization of particulate acidity was essentially in PM2.1 with an indication of predominant H2SO4 neutralization in bisulfate form compared to Ca2+ and Mg2+-based neutralization in PM>2.1. Molecular distribution of n-alkanes homologues (C17-C35) showed Cmax at C23 (PM2.1) and C18 (PM>2.1) with weak dominance of odd-numbered n-alkanes. Carbon preference index of n-alkanes was close to unity (PM2.1: 1.4 ± 0.3; PM>2.1: 1.3 ± 0.4). Fatty acids (C12-C26) were characterized with predominance of even carbon with Cmax at n-hexadecanoic acid (C16:0). Low to high molecular weight fatty acid ratio ranged from 2.0 (PM>2.1) to 5.6 (PM2.1) with vital signature of anthropogenic emissions. Levoglucosan was abundant in PM2.1 (758 ± 481 ngm-3) with a high ratio (11.6) against galactosan, emphasizing robust contribution from burning of hardwood and agricultural residues. Receptor model resolves secondary aerosols and biomass burning emissions (45%) as the most influential sources of PM2.1 whereas, crustal (29%) and secondary aerosols (29%) were found responsible for PM>2.1; with significant variations among the seasons.
Abundance of fine particulate-bound 16 priority polycyclic aromatic hydrocarbons (PAHs) was investigated to ascertain its sources and potential carcinogenic health risks in Varanasi, India. The city represents a typical urban settlement of South Asia having particulate exposure manyfold higher than standard with reports of pollution induced mortalities and morbidities. Fine particulates (PM2.5) were monitored from October 2019 to May 2020, with 32% of monitoring days accounting ≥100 μgm-3 of PM2.5 concentration, frequently from November to January (99% of monitoring days). The concentration of 16 priority PAHs varied from 24.1 to 44.6 ngm-3 (mean: 33.1 ± 3.2 ngm-3) without much seasonal deviations. Both low (LMW, 56%) and high molecular weight (HMW, 44%) PAHs were abundant, with Fluoranthene (3.9 ± 0.4ngm-3) and Fluorene (3.5 ± 0.3ngm-3) emerged as most dominating PAHs. Concentration of Benzo(a)pyrene (B(a)P, 0.5 ± 0.1ngm-3) was lower than the national standard as it contributed 13% of total PAHs mass. Diagnostic ratios of PAH isomers indicate predominance of pyrogenic sources including emissions from biomass burning, and both from diesel and petrol-driven vehicles. Source apportionment using receptor model revealed similar observation of major PAHs contribution from biomass burning and fuel combustion (54% of source contribution) followed by coal combustion for residential heating and cooking purposes (44%). Potential toxicity of B[a]P equivalence ranged from 0.003 to 1.365 with cumulative toxicity of 2.13ngm-3. Among the PAH species, dibenzo[h]anthracene contributed maximum toxicity followed by B[a]P, together accounting 86% of PAH induced carcinogenicity. Incremental risk of developing cancer through lifetime exposure (ILCR) of PAHs was higher in children (3.3 × 10-4) with 56% contribution from LMW PAHs, primarily through ingestion and dermal contact. Adults in contrast, were more exposed to inhale airborne PAHs with cumulative ILCR of 2.2 × 10-4. However, ILCR to PM2.5 exposure is probably underestimated considering unaccounted metal abundance thus, require source-specific control measures.