PM2.5 acidity at a background site in the Pearl River Delta region in fall-winter of 2007-2012

Abstract

Based on field observations and thermodynamic model simulation, the annual trend of PM2.5 acidity and its characteristics on non-hazy and hazy days in fall-winter of 2007-2012 in the Pearl River Delta region were investigated. Total acidity ([H(+)](total)) and in-situ acidity ([H(+)](in-situ)) of PM2.5 significantly decreased (F-test, p < 0.05) at a rate of -32 ± 1.5 nmol m(-3)year(-1) and -9 ± 1.7 nmol m(-3) year(-1), respectively. The variation of acidity was mainly caused by the change of the PM2.5 component, i.e., the decreasing rates of [H(+)](total) and [H(+)](in-situ) due to the decrease of sulfate (SO4(2-)) exceeded the increasing rate caused by the growth of nitrate (NO3(-)). [H(+)](total), [H(+)](in-situ) and liquid water content on hazy days were 0.9-2.2, 1.2-3.5 and 2.0-3.0 times those on non-hazy days, respectively. On hazy days, the concentration of organic matter (OM) showed significant enhancement when [H(+)](in-situ) increased (t-test, p < 0.05), while this was not observed on non-hazy days. Moreover, when the acidity was low (i.e., R = [NH4(+)]/(2 × [SO4(2-)]+[NO3(-)])>0.6), NH4NO3 was most likely formed via homogenous reaction. When the acidity was high (R ≤ 0.6), the gas-phase formation of NH4NO3 was inhibited, and the proportion of NO3(-) produced via heterogeneous reaction of N2O5 became significant.

Keywords: Haze; Nitrate; PM(2.5) acidity; Secondary organic carbon; Sulfate.