Abstract

Nighttime concentrations of the gas phase nitrate radical (NO3) were successfully measured during a four week field campaign in an arid urban location, Reno Nevada, using long-path Differential Optical Absorbance Spectrometry (DOAS). While typical concentrations of NO3 ranged from 5 to 20 ppt, elevated concentrations were observed during a wildfire event. Horizontal mixing in the free troposphere was considerable because the sampling site was above the stable nocturnal boundary layer every night and this justified a box modeling approach. Process analysis of box model simulations showed NO3 accounted for approximately half of the loss of internal olefins, 60% of the isoprene loss, and 85% of the α-pinene loss during the nighttime hours during a typical night of the field study. The NO3 + aldehyde reactions were not as important as anticipated. On a polluted night impacted by wildfires upwind of the sampling location, NO3 reactions were more important. Model simulations overpredicted NO2 concentrations for both case studies and inorganic chemistry was the biggest influence on NO3 concentrations and on nitric acid formation. The overprediction may be due to additional NO2 loss processes that were not included in the box model, as deposition and N2O5 uptake had no significant effect on NO2 levels.

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