Effect of Biomass Burning on PM2.5 Composition and Secondary Aerosol Formation During Post‐Monsoon and Winter Haze Episodes in Delhi

Delhi metropolitan area suffers from extreme haze during the post‐monsoon and winter season, impacting climate, public health, and economy. We used a high‐resolution time‐of‐flight aerosol mass spectrometer (HR‐ToF‐AMS) and aethalometer at two urban locations in Delhi to capture non‐refractory PM2.5 (NR‐PM2.5) and black carbon (BC) during the post‐monsoon and winter season of 2019–2020. Four haze periods with high composition based‐PM2.5 (C‐PM2.5 = NR‐PM2.5 + BC) concentration and distinct chemical composition were identified, during all of which organics dominated but with varying contribution (∼[50%–70%] of C‐PM2.5). Biomass burning organic aerosol (BBOA) was dominant in all periods (∼[31%–45%] of OA), but the majority of it was highly aged ∼(45%–50%) with high O/C (0.71 and 0.46 at the two sites), formed most likely through rapid dark oxidation of freshly emitted and partially oxidized BBOA. High polycyclic aromatic hydrocarbons (PAH) signals in the fresh BBOA mass spectra suggest incomplete combustion activities such as open biomass burning emissions as major source. During an agricultural burning event in north‐western India, we estimated that ∼(44%–53%) of total C‐PM2.5 (combined contribution of aged BBOA and oxygenated OA) measured in Delhi was influenced by long‐range transported biomass burning emissions. During winter, secondary inorganics constituted a significant fraction apart from organics ∼(48%–55%), mainly in the form of ammonium nitrate (NH4NO3; up to ∼[19%–25%] of C‐PM2.5) and ammonium sulfate (NH4SO4; up to ∼[27%–38%]). Enhanced formation of NH4NO3 and related‐secondary organic aerosol (SOA) were linked to nighttime oxidation of BBOA, while NH4SO4 and related‐SOA were linked to heterogeneous aqueous phase oxidation under high RH conditions (>90%).