Atmospheric aerosol chemistry and source apportionment of PM10 using stable carbon isotopes and PMF modelling during fireworks over Hyderabad, southern India

Abstract

This study examined the influence of fireworks on atmospheric aerosols over the Southern Indian city of Hyderabad during festival of Diwali using mass closure, stable carbon isotopes and the EPA-PMF model. Identification of chemical species in day and night time aerosol samples for 2019 and 2020 Diwali weeks showed increased concentrations of NH4+, NO3−, SO42−, K+, organic carbon (OC), Ba, Pb and Li, which were considered as tracers for fireworks. PM10 source apportionment was done using inorganic (trace elements, major ions) and carbonaceous (organic and elemental carbon; OC & EC) constituents, along with stable isotopic compositions of TC and EC. K+/Na+ ∼1 and K+nss/OC > 0.5 indicated contribution from fireworks. High NO3−, NH4+, Na+, Cl− and SO42− suggested the presence of deliquescent salts NaCl, NH4NO3 and (NH4)2SO4. TAE/TCE >1 suggested H+ exclusion, indicating possible presence of H2SO4 and NH4HSO4 in the aerosols. Ba, Pb, Sb, Sr and Fe increased by 305 (87), 12 (11), 12 (3), 3 (2) and 3 (4) times on Diwali nights, compared to pre-Diwali of 2019 (2020), and are considered as metallic tracers of fireworks. δ13CTC and δ13CEC in aerosols closely resembled that of diesel and C3 plant burning emissions, with meagre contribution from firecrackers during Diwali period. The δ13CEC was relatively depleted than δ13CTC and δ13COC. For both years, δ13COC-EC (δ13COC - δ13CEC) were positive, suggesting photochemical aging of aerosols during long-range transport, while for pre-Diwali 2019 and post-Diwali 2020, δ13COC-EC were negative with high OC/EC ratio, implying secondary organic aerosols formation. High toluene during Diwali week contributed to fresh SOA formation, which reacted with precursor 12C, leading to 13C depletions. Eight-factored EPA-PMF source apportionment indicated highest contribution from residue/waste burning, followed by marine/dust soil and fireworks, while least was contributed from solid fuel/coal combustion.