Journal of Geophysical Research: Atmospheres

Variability in ammonium nitrate formation and nitric acid depletion with altitude and location over California



[1] Spatial variations in the partitioning of nitrate between gas phase nitric acid (HNO3) and particulate ammonium nitrate were observed using airborne measurements of trace gas mixing ratios, particle size distributions, and particle composition. During the Intercontinental Transport and Chemical Transformation experiment in April and May 2002 the NOAA WP-3 aircraft flew up to 8 km altitude on 11 research flights from Monterey, California. The formation of semivolatile aerosols was studied by examining the enhancement of fine-particulate ammonium nitrate and depletion of gas-phase HNO3 over the San Joaquin Valley, Los Angeles Basin, and Mojave Desert. Gas-phase particle precursors, HNO3 and ammonia (NH3), were converted to particulate ammonium nitrate at higher altitudes within the boundary layer. These particle layers were a consequence of lower ambient temperatures that caused a reduction of the dissociation constant for ammonium nitrate aerosol so that gas phase HNO3 was depleted and particle mass was formed. The resulting vertical gradients in particulate matter and HNO3 were observed in well-mixed boundary layers where other directly emitted trace gases (CO) and secondary pollutants (O3) exhibited no vertical gradients. Hence the equilibrium between the gas and particle phases occurred faster than boundary layer mixing times and chemical rather than meteorological effects were responsible for the layers of enhanced particulate matter aloft. Coincident HNO3 depletion and ammonium nitrate formation was also observed downwind from regions characterized by large agricultural NH3 emissions in the Los Angeles Basin and San Joaquin Valley.