Seasonal variation, air-water exchange, and multivariate source apportionment of polycyclic aromatic hydrocarbons in the coastal area of Dalian, China

Abstract

The concentrations and seasonal variations of polycyclic aromatic hydrocarbons (PAHs) in air and seawater dissolved samples from the coastal area of Dalian were investigated, as well as their air-water exchanges. The average concentrations of PAHs were 27.5 ± 14.6 ng/m³ and 49.5 ± 20.5 ng/L in the air and water, respectively. Phenanthrene was the dominant congener in both air and water dissolved phase. Seasonality was discovered in the air with the concentrations higher in winter than in summer, but not in the water dissolved phase. Air-water exchange trends also displayed apparent seasonality with 3-4 ring PAHs generally being volatilization or equilibrium in summer but deposition in winter, which highlighted the important influence of temperature on the air-water exchange direction of PAHs. The air-water exchange fluxes of individual PAH congeners ranged from -24331 to 6541 ng/m²/d, and the highest deposition and volatilization fluxes both appeared at the industrial areas, which emphasized the influence of point source emission to the magnitude of air-water diffusion flux of PAHs. Multivariate source apportionment approaches, including principle component analysis, diagnostic ratios, and positive matrix factorization, were conducted, which suggested that PAHs in water originated from multiple sources. Frequent port transport correlated vehicle/ship emission rather than coal combustion may be the primary contributor of PAHs to the coastal air and water.

Keywords: Air; Air-water exchange; PAHs; Seasonal variations; Seawater; Source apportionment.