Fast Formation of Nitro-PAHs in the Marine Atmosphere Constrained in a Regional-Scale Lagrangian Field Experiment

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Mulder M. D., Dumanoğlu Y., Efstathiou C., Kukucka P., Matejovicova J., Maurer C., ...More

ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol.53, no.15, pp.8914-8924, 2019 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 53 Issue: 15
  • Publication Date: 2019
  • Doi Number: 10.1021/acs.est.9b03090
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.8914-8924
  • Dokuz Eylül University Affiliated: Yes


Polycyclic aromatic hydrocarbons (PAHs) and some of their nitrated derivatives, NPAHs, are seemingly ubiquitous in the atmospheric environment. Atmospheric lifetimes may nevertheless vary within a wide range, and be as short as a few hours. The sources and sinks of NPAH in the atmosphere are not well understood. With a Lagrangian field experiment and modeling, we studied the conversion of the semivolatile PAHs fluoranthene and pyrene into the 2-nitro derivatives 2-nitrofluoranthene and 2-nitropyrene in a cloud-free marine atmosphere on the time scale of hours to 1 day between a coastal and an island site. Chemistry and transport during several episodes was simulated by a Lagrangian box model i.e., a box model coupled to a Lagrangian particle dispersion model, FLEXPART-WRF. It is found that the chemical kinetic data do capture photochemical degradation of the 4-ring PAHs under ambient conditions on the time scale of hours to 1 day, while the production of the corresponding NPAH, which sustained 2-nitrofluoranthene/fluoranthene and 2-nitropyrene/pyrene yields of (3.7 +/- 0.2) and (1.5 +/- 0.1)%, respectively, is by far underestimated. Predicted levels of NPAH come close to observed ones, when kinetic data describing the reactivity of the OH-adduct were explored by means of theoretically based estimates. Predictions are also underestimated by 1-2 orders of magnitude, when NPAH/PAH yields reported from laboratory experiments conducted under high NOx conditions are adopted for the simulations. It is concluded that NPAH sources effective under low NOx conditions, are largely underestimated.