Particulate-bound alkyl nitrate pollution and formation mechanisms in Beijing, China

Abstract. Fine particulate matter (PM2.5) samples were collected between November 2020 and October 2021 at the Minzu University of China in Beijing, and the n-alkyl nitrate concentrations in the PM2.5 samples were determined to investigate n-alkyl nitrate pollution and formation mechanisms. C9–C16 n-alkyl nitrate standards were synthesized, and the n-alkyl nitrate concentrations in PM2.5 were determined by gas chromatography triple quadrupole mass spectrometry. Temporal trends in and correlations between particulate-bound n-alkyl nitrate, ozone, PM2.5, and nitrogen dioxide concentrations were investigated to assess the relationships between particulate-bound n-alkyl nitrate concentrations and gas-phase homogeneous reactions in the photochemical process and speculate the particulate-bound n-alkyl nitrates' formation mechanisms. The n-alkyl nitrate concentrations in the PM2.5 samples were 9.67–2730 pg m−3, and the mean was 578 pg m−3. The n-alkyl nitrate homologue group concentrations increased as the carbon chain length increased; i.e., long-chain n-alkyl nitrates contributed more than short-chain n-alkyl nitrates to the total n-alkyl nitrate concentrations in PM2.5. The n-alkyl nitrate concentrations clearly varied seasonally and diurnally, the concentrations decreasing in the order winter > spring > autumn > summer and the mean concentrations being higher at night than in the day. The particulate-bound n-alkyl nitrate and ozone concentrations significantly negatively correlated despite gas-phase alkyl nitrate and ozone concentrations previously being found to positively correlate. This indicated that long-chain alkyl nitrates may not be produced during gas-phase homogeneous reactions. The particulate-bound n-alkyl nitrate concentrations followed the same trends as and significantly positively correlated with the PM2.5 and nitrogen dioxide concentrations. Nitrogen dioxide is an important contributor of nitrates in particulate matter. This indicated that particulate-bound n-alkyl nitrates may form through non-homogeneous reactions between alkanes and nitrates on particulate matter surfaces. As secondary pollutants, particulate-bound alkyl nitrates are important components of PM2.5 during haze events and strongly affect haze pollution and atmospheric visibility.