ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-10-21895-2010 The influence of gas-particle partitioning and surface-atmosphere exchange on ammonia during BAQS-Met Ellis R. A. 1 Murphy J. G. 1 Markovic M. Z. 1 VandenBoer T. C. 1 Makar P. A. 2 Brook J. 2 Mihele C. 2 Department of Chemistry, University of Toronto, 80 St. George St., Toronto, ON, M6P 2S1, Canada Environment Canada, Science and Technology Branch, Air Quality Research Division, 4905 Dufferin St., Toronto, ON, M3H 5T4, Canada 20 09 2010 10 9 21895 21929 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys-discuss.net/10/21895/2010/acpd-10-21895-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/10/21895/2010/acpd-10-21895-2010.pdf

The Border Air Quality and Meteorology study (BAQS-Met) was an intensive field campaign conducted in Southwestern Ontario during the summer of 2007. The focus of BAQS-Met was determining the causes of the formation of ozone and fine particulate matter (PM<sub>2.5</sub>), and of the regional significance of trans-boundary transport and lake breeze circulations on that formation. Fast (1 Hz) measurements of ammonia were acquired using a Quantum Cascade Laser Tunable Infrared Differential Absorption Spectrometer (QC-TILDAS) at the Harrow supersite. Measurements of PM<sub>2.5</sub> ammonium, sulfate and nitrate were made using an Ambient Ion Monitor Ion Chromatograph (AIM-IC) with hourly time resolution.The median mixing ratio of ammonia was 2.5 ppb, with occasional high spikes at night resulting from local emissions. Measurements were used to assess major local emissions of NH<sub>3</sub>, diurnal profiles and gas-particle partitioning. The measurements were compared with results from A Unified Regional Air-quality Modelling System (AURAMS). While the fraction of total ammonia (NH<sub>x</sub>≡NH<sub>3</sub> + NH<sub>4</sub><sup>+</sup>) observed in the gas phase peaks between 0.1 and 0.8, AURAMS tended to predict fractions of either less than 0.05 or greater than 0.8. The model frequently predicted acidic aerosol, in contrast withobservations whereinNH<sub>x</sub> always exceeded the observed equivalents of sulfate. One explanation for our observations is that the net flux of ammonia from the land surface to the atmosphere increases when aerosol sulfate is present, effectively buffering the mixing ratio of gas phase ammonia, a process not included in the model. We explore the impact of a bi-directional flux parameterization on the predicted gas-particle partitioning of atmospheric ammonia.

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