Composition and size distribution of airborne particulate PAHs and oxygenated PAHs in two Chinese megacities

• Size-resolved PAHs and OPAHs in China were measured.
• 4-/5-ring PAHs dominate in winter, while 5-/6-ring PAHs dominate in summer.
• BaP/BeP ratios indicate current atmosphere of China more oxidative.
• PAHs and OPAHs in 2013 decreased by 50–90% compared to those in 2003

Concentrations and compositions of PAHs and oxygenated PAHs (OPAHs) in four size ranges of ambient particles (< 1.1, 1.1–3.3, 3.3–9.0 and > 9.0 μm) collected in Xi'an and Guangzhou, two megacities of China, during the winter and summer of 2013 were measured and compared with those in 2003. The TSP-equivalent concentrations of Σ14PAHs in Xi'an and Guangzhou are 57 ± 20 and 18 ± 23 ng m− 3 in winter, 5–10 times higher than those in summer. PAHs in both cities are dominated by 5- and 6-ring congeners in summer. In contrast, they are dominated by 4- and 5-ring congeners in winter, probably due to enhanced gas-to-particle phase partitioning of the semi-volatile PAHs. TSP-equivalent Σ7OPAHs during winter are 54 ± 15 and 23 ± 32 ng m− 3 in Xi'an and Guangzhou and dominated by 5-ring OPAHs.Size distribution results showed that the fine modes (< 3.3 μm) of PAHs and OPAHs in both cities are dominated by 4- and 5-ring congeners in winter and 5- and 6-ring congeners in summer. Relative abundances of 3-ring PAHs and OPAHs increased along with an increase in particle sizes, accounting for from about 1% of the total PAHs or OPAHs in the smallest particles (< 1.1 μm) to > 90% of the total in the largest particles (> 9.0 μm). The toxicity of PAH assessment indicated that atmospheric particles in Xi'an and Guangzhou during winter are much more toxic than those during summer and fine particles are more toxic than coarse particles. Compared to those in 2003, fine particulate PAHs and OPAHs in both cities during winter decreased by 50–90%, most likely due to the replacement of coal by natural gas in the country.