Internally Mixed Sea Salt, Soot, and Sulfates at Macao, a Coastal City in South China

Abstract

ABSTRACT Direct observation of the mixing state of aerosol particles in a coastal urban city is critical to understand atmospheric processing and hygroscopic growth in humid air. Morphology, composition, and mixing state of individual aerosol particles from Macao, located south of the Pearl River Delta (PRD) and 100 km west of Hong Kong, were investigated using scanning electron microscopy (SEM) and transmission electron microscopy coupled with energy-dispersive X-ray spectrometry (TEM/EDX). SEM images show that soot and roughly spherical particles are prevalent in the samples. Based on the compositions of individual aerosol particles, aerosol particles with roughly spherical shape are classified into coarse Na-rich and fine S-rich particles. TEM/EDX indicates that each Na-rich particle consists of a Na-S core and NaNO3 shell. Even in the absence of heavy pollution, the marine sea salt particles were completely depleted in chloride, and Na-related sulfates and nitrates were enriched in Macao air. The reason could be that SO2 from the polluted PRD and ships in the South China Sea and NO2 from vehicles in the city sped up the chlorine depletion in sea salt through heterogeneous reactions. Fresh soot particles from vehicular emissions mainly occur near curbside. However, there are many aged soot particles in the sampling site surrounded by main roads 200 to 400 m away, suggesting that the fresh soot likely underwent a quick aging. Overall, secondary nitrates and sulfates internally mixed with soot and sea salt particles can totally change their surface hygroscopicity in coastal cities. IMPLICATIONS This study of compositional changes in mixed marine aerosols and anthropogenic pollutants underscores the importance of aerosol mixing states with regard to their role in visibility, climate, as well as health inhalation. Almost all sea salt particles in Macao air were depleted in chloride but enriched in Na-related sulfates and nitrates through heterogeneous atmospheric reactions. Most soot particles are aggregated with or encapsulated by S-rich particles, suggesting that the fresh soot particles likely underwent a quick aging. Future climate model should consider the mixing states of sea salt and soot particles in the atmosphere of the China coast.