Formation pathways of organic aerosols over a tropical coastal atmosphere

Abstract

The characteristics of non-refractory submicron aerosols (NR-PM1), focusing on organic aerosols, are examined over a tropical coastal location, Thumba, in southern peninsular India. The measurements were carried out using an aerosol chemical speciation monitor during 2017–2021. The results indicated organic aerosols as the major component (67–85%) in the NR-PM1 mass loading during all seasons. Positive matrix factorization (PMF) analysis on the OA mass spectra yielded two factors resolving Hydrocarbon-like organic aerosols (HOA) and Oxygenated organic aerosols (OOA), with the major contribution to OA coming from OOA (mass fraction >50%) during all the seasons. Examination of the diurnal variations revealed the daytime enhancement in OOA and sulfate mass fractions, indicating photochemical production overwhelming the dilution at the surface due to local atmospheric boundary layer expansion. The OOA mass concentration showed a good correlation (R > 0.5) with odd oxygen (O3+NO2) and with an increase in oxygen-to-carbon ratio (ΔO:C = 0.11 to 0.35 with Δodd oxygen = 60 μg m−3 for different seasons) (i.e., increased oxidation degree of OA) signifying the dominance of photochemistry and subsequent enhanced atmospheric oxidative capacity in OOA formation. Interestingly, the aerosol liquid water content (ALWC) doubled during the nighttime (>40 μg m−3) compared to the daytime (<20 μg m−3) in different seasons, indicating the combined impact of varying submicron aerosol composition and ambient relative humidity. Since highly humid (relative humidity >85%) conditions prevail over this tropical coastal station, especially during the nighttime, the role of aqueous-phase formation of OA is also examined. It was found that less oxidized/less-hygroscopic OA were prevalent during the nighttime, resulting in lower aqueous-phase OA processing. During all the seasons, the hygroscopicity of organics (кorganics) reached as high as > 0.22 and was mainly driven by photochemical processing rather than aqueous-phase chemistry. These results highlight the importance of the OA formation pathways in affecting their hygroscopic properties over the tropical atmosphere.