Quantifying the relative contributions of aqueous phase and photochemical processes to water-soluble organic carbon formation in winter in a megacity of South China

Abstract

To identify potential formation mechanisms of water-soluble organic carbon (WSOC) and quantify their contributions to WSOC in urban Guangzhou of south China, a comprehensive campaign was carried out in winter of 2019-2020. During the campaign, WSOC, total carbon (TC), black carbon (BC), water-soluble inorganic ions (WSIIs) and fourteen elements in PM_2.5 were collected using inline instruments. Bulk PM_2.5 and size-segregated particle samples were also synchronously collected using offline instruments for analyzing the dominant chemical components including WSOC, organic carbon (OC), elemental carbon (EC) and WSIIs. In addition, gaseous pollutants (e.g., NH₃, SO₂, HNO₃, NO₂, O₃) and meteorological parameters were also measured during the same period. PM_2.5 pollution episodes during the campaign period were mainly driven by increased nitrate concentrations. The mass concentration of WSOC increased from 3.9±1.1 μg m^-3 on non-episode days to 6.8±0.6 μg m^-3 on episode days, although the mass ratio of WSOC to OC in PM_2.5 changed little (<4%). Photochemical processes dominated WSOC formation in the afternoon and aqueous phase chemical processes played the dominant role in the night, from which newly formed WSOC distributed in the condensation mode and the droplet mode, respectively. Source apportionment analysis using positive matrix factorization (PMF) model suggested that on average 35% and 65% of WSOC mass in PM_2.5 were related with the photochemical processes and aqueous phase chemical processes, respectively. Aqueous phase chemical processes were highly affected by nitrate pollution, which was closely related with O₃ pollution.