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

• Main Authors: A. Elzein, R. E. Dunmore, M. W. Ward, J. F. Hamilton, A. C. Lewis
• Format: Article
• Language: English
• Published: Copernicus Publications 2019-07-01
• Series: Atmospheric Chemistry and Physics
• Online Access: https://www.atmos-chem-phys.net/19/8741/2019/acp-19-8741-2019.pdf
• ISSN: 1680-7316; 1680-7324

<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&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span> over 3&thinsp;h daytime filter samples and from 23 to 165&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span> in 15&thinsp;h night-time samples. The total concentrations of PAHs over 24&thinsp;h varied between 37 and 180&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span> (mean: <span class="inline-formula">97±43</span>&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>). The total daytime concentrations during high particulate loading conditions for PAHs, OPAHs and NPAHs were 224, 54 and 2.3&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>, respectively. The most abundant PAHs were fluoranthene (33&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>), chrysene (27&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>), pyrene (27&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>), benzo[a]pyrene (27&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>), benzo[b]fluoranthene (25&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>), benzo[a]anthracene (20&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>) and phenanthrene (18&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>). The most abundant OPAHs were 9,10-anthraquinone (18&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>), 1,8-naphthalic anhydride (14&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>) and 9-fluorenone (12&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>), and the three most abundant NPAHs were 9-nitroanthracene (0.84&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>), 3-nitrofluoranthene (0.78&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>) and 3-nitrodibenzofuran (0.45&thinsp;ng&thinsp;m<span class="inline-formula">⁻³</span>). <span class="inline-formula">∑</span>PAHs and <span class="inline-formula">∑</span>OPAHs showed a strong positive correlation with the gas-phase abundance of NO, CO, <span class="inline-formula">SO₂</span> 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. <span class="inline-formula">PM_2.5</span> 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 (<span class="inline-formula"><i>R</i>=0.90</span>, <span class="inline-formula"><i>P</i> <i>&lt;</i> 0.001</span>). 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<span class="inline-formula">⁻⁵</span> to 10<span class="inline-formula">⁻³</span> (risk per million people ranges from 26 to 2053 cases per year).</p>