3-D agricultural air quality modeling: Impacts of NH3/H2S gas–phase reactions and bi-directional exchange of NH3

Abstract

Accurately simulating the transport and fate of reduced nitrogen (NHx = ammonia (NH3) + ammonium (NH4+))- and sulfur-containing compounds emitted from agricultural activities represents a major challenge in agricultural air quality modeling. In this study, the Community Multiscale Air Quality (CMAQ) modeling system is further developed and improved by implementing 22 ammonia (NH3)/hydrogen sulfide (H2S) related gas-phase reactions and adjusting a few key parameters (e.g., emission potential) for bi-directional exchange of NH3 fluxes. Several simulations are conducted over the eastern U.S. domain at a 12-km horizontal resolution for January and July 2002 to examine the impacts of those improved treatments on air quality. The 5th generation mesoscale model (MM5) and CMAQ predict an overall satisfactory and consistent performance with previous modeling studies, especially for 2-m temperature, 2-m relative humidity, ozone (O3), and fine particulate matter (PM2.5). High model biases exist for precipitation in July and also dry/wet depositions. The updated model treatments contribute to O3, NHx, and PM2.5 by up to 0.4 ppb, 1.0 μg m−3, and 1.0 μg m−3 in January, respectively, and reduce O3 by up to 0.8 ppb and contribute to NHx and PM2.5 by up to 1.2 and 1.1 μg m−3 in July, respectively. The spatial distributions of O3 in both months and sulfur dioxide (SO2) in January are mainly affected by inline dry deposition velocity calculation. The spatial distributions of SO2 and sulfate (SO42−) in July are affected by both inline dry deposition velocity and NH3/H2S reactions. The variation trends of NH3, NHx, ammonium nitrate (NH4NO3), PM2.5 and total nitrogen (TN) are predominated by bi-directional exchange of NH3 fluxes. Uncertainties of NH3 emission potentials and empirical constants used in the bi-directional exchange scheme may significantly affect the concentrations of NHx and PM2.5, indicating that a more accurate and explicit treatment for those parameters should be considered in the future work.