Variability of polycyclic aromatic hydrocarbons and their oxidative derivatives in wintertime Beijing, China

Ambient particulate matter (PM) can contain a mix of different toxic species derived from a wide variety of sources. This study quantifies the diurnal variation and nocturnal abundance of 16 polycyclic aromatic hydrocarbons (PAHs), 10 oxygenated PAHs (OPAHs) and 9 nitrated PAHs (NPAHs) in ambient PM in central Beijing during winter. Target compounds were identified and quantified using gas chromatography-time-of-flight mass spectrometry (GC-Q-ToF-MS). The total concentration of PAHs varied between 18 and 297 ngm-3 over 3 h daytime filter samples and from 23 to 165 ngm-3 in 15 h night-time samples. The total concentrations of PAHs over 24 h varied between 37 and 180 ngm-3 (mean: 97±43 ngm-3). The total daytime concentrations during high particulate loading conditions for PAHs, OPAHs and NPAHs were 224, 54 and 2.3 ngm-3, respectively. The most abundant PAHs were fluoranthene (33 ngm-3), chrysene (27 ngm-3), pyrene (27 ngm-3), benzo[a]pyrene (27 ngm-3), benzo[b]fluoranthene (25 ngm-3), benzo[a]anthracene (20 ngm-3) and phenanthrene (18 ngm-3). The most abundant OPAHs were 9,10-anthraquinone (18 ngm-3), 1,8-naphthalic anhydride (14 ngm-3) and 9-fluorenone (12 ngm-3), and the three most abundant NPAHs were 9-nitroanthracene (0.84 ngm-3), 3-nitrofluoranthene (0.78 ngm-3) and 3-nitrodibenzofuran (0.45 ngm-3). Σ PAHs and Σ OPAHs showed a strong positive correlation with the gas-phase abundance of NO, CO, SO2 and HONO, indicating that PAHs and OPAHs can be associated with both local and regional emissions. Diagnostic ratios suggested emissions from traffic road and coal combustion were the predominant sources of PAHs in Beijing and also revealed the main source of NPAHs to be secondary photochemical formation rather than primary emissions. PM2.5 and NPAHs showed a strong correlation with gas-phase HONO. 9- Nitroanthracene appeared to undergo a photodegradation during the daytime and showed a strong positive correlation with ambient HONO (R D 0:90, P