Recent trends in gas-phase ammonia and PM2.5 ammonium in the Southeast United States.

UNLABELLED: Ammonia measurements from the Southeastern Aerosol Research and Characterization (SEARCH) study network were analyzed for trends over 9 yr (2004-2012) of observations. Total ammonia concentrations, defined as the sum of gas-phase ammonia and fine particle ammonium, were found to be decreasing by 1-4% yr(-1) and were qualitatively consistent with ammonia emission estimates for the SEARCH states of Alabama, Georgia, Mississippi, and Florida. On the other hand, gas-phase ammonia mixing ratios were found to be slightly rising or steady over the region, leading to the observation that the gas-phase fraction of total ammonia has steadily increased over 2004-2012 as a result of declining emissions of the strong acid precursor species sulfur dioxide (SO2) and nitrogen oxides (NOx) and consequent reduced partitioning of ammonia to the fine particle phase. Because gas-phase ammonia is removed from the atmosphere more rapidly than fine particle ammonium, an increase in the gas-phase fraction of total ammonia may result in shifted deposition patterns as more ammonia is deposited closer to sources rather than transported downwind in fine particles. Additional long-term measurements and modeling studies are needed to determine if similar transitions of total ammonia to the gas phase are occurring outside of the Southeast and to assess if these changes are impacting plants and ecosystems near major ammonia sources. Unusually high ammonia concentrations observed in 2007 in the SEARCH measurements are hypothesized to be linked to emissions from wildfires that were much more prevalent across the Southeast during that year due to elevated temperatures and widespread drought. Although wildfires are currently estimated to be a relatively small fraction (3-10%) of total ammonia emissions in the Southeast, the projected increased incidence of wildfires in this region as a result of global climate change may lead to this source's increased importance over the rest of the 21st century. IMPLICATIONS: Ammonia concentrations from the Southeastern Aerosol Research and Characterization study (SEARCH) network are analyzed over the 9-yr period 2004-2012. Total ammonia (gaseous ammonia+PM2.5 ammonium) concentrations declined at a rate of 1-4% yr(-1), consistent with U.S. Environmental Protection Agency (EPA) emission estimates for the Southeast United States, but the fraction of ammonia in the gas phase has risen steadily (+1-3% yr(-1)) over the time period. Declining emissions of SO2 and NOx resulting from imposed air quality regulations have resulted in decreased atmospheric strong acids and less ammonia partitioning to the particle phase, which may impact the amount and overall pattern of ammonia deposition.