<p><strong>Abstract.</strong> Ambient particulate matter (PM) can contain a mix of different toxic species derived from a wide variety of sources. This study quantifies the variation in diurnal 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 ng m<sup>−3</sup> over 3 h daytime filter samples and from 23 to 165 ng m<sup>−3</sup> in 15 h night-time samples. The total concentrations of PAHs over 24 h varied between 37 and 180 ng m<sup>−3</sup> (mean: 97 ng m<sup>−3</sup>). The total daytime concentrations during high particulate loading conditions for PAHs, OPAHs and NPAHs were 224, 54, and 2.3 ng m<sup>−3</sup>, respectively. The most abundant PAHs were fluoranthene (33 ng m<sup>−3</sup>), chrysene (27 ng m<sup>−3</sup>), pyrene (27 ng m<sup>−3</sup>), benzo(a)pyrene (27 ng m<sup>−3</sup>), benzo[b]fluoranthene (25 ng m<sup>−3</sup>), benzo[a]anthracene (20 ng m<sup>−3</sup>) and phenanthrene (18 ng m<sup>−3</sup>). 9,10-Anthraquinone (18 ng m<sup>−3</sup>), 1,8 Naphthalic anhydride (14 ng m<sup>−3</sup>) and 9-Fluorenone (12 ng m<sup>−3</sup>) were the three major OPAHs species, while 9-Nitroanthracene (0.84 ng m<sup>−3</sup>), 3-Nitrofluoranthene (0.78 ng m<sup>−3</sup>) and 3-Nitrodibenzofuran (0.45 ng m<sup>−3</sup>) were the three most abundant NPAHs. ∑PAHs and ∑OPAHs showed a strong positive correlation with the gas phase abundance of NO, CO, SO<sub>2</sub>, 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 for PAHs in Beijing, and also revealed the dominant source of NPAHs was secondary photochemical formation rather than primary emissions. PM<sub>2.5</sub> and NPAHs showed a strong correlation with gas phase HONO. 9-Nitroanthracene appeared to undergo a photodegradation during the daytime and has shown a strong positive correlation with ambient HONO (R = 0.90, P < 0.001). The lifetime excess lung cancer risk for the species with available toxicological data (16 PAHs, 1 OPAH and 6 NPAHs) was calculated to be in the range 10<sup>−5</sup> to 10<sup>−3</sup> (risk per million people range from 26 to 2053).</p>

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 ng m −3 over 3 h daytime filter samples and from 23 to 165 ng m −3 in 15 h night-time samples. The total concentrations of PAHs over 24 h varied between 37 and 180 ng m −3 (mean: 97 ± 43 ng m −3 ). The total daytime concentrations during high particulate loading conditions for PAHs, OPAHs and NPAHs were 224, 54 and 2.3 ng m −3 , respectively. The most abundant PAHs were fluoranthene (33 ng m −3 ), chrysene (27 ng m −3 ), pyrene (27 ng m −3 ), benzo[a]pyrene (27 ng m −3 ), benzo[b]fluoranthene (25 ng m −3 ), benzo[a]anthracene (20 ng m −3 ) and phenanthrene (18 ng m −3 ). The most abundant OPAHs were 9,10-anthraquinone (18 ng m −3 ), 1,8-naphthalic anhydride (14 ng m −3 ) and 9-fluorenone (12 ng m −3 ), and the three most abundant NPAHs were 9-nitroanthracene (0.84 ng m −3 ), 3-nitrofluoranthene (0.78 ng m −3 ) and 3-nitrodibenzofuran (0.45 ng m −3 ).PAHs and OPAHs showed a strong positive correlation with the gas-phase abundance of NO, CO, SO 2 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. PM 2.5 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 = 0.90, P < 0.001). The lifetime excess lung cancer risk for those species that have available toxicological data (16 PAHs, 1 OPAH and 6 NPAHs) was calculated to be in the range 10 −5 to 10 −3 (risk per million people ranges from 26 to 2053 cases per year).

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