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Monitoring Chemical Climate Change in America The Case for Ammonia V. Bowersox, C. Lehmann, B. Larson Acknowledge – R. Claybrooke NADP Program Office Air and Rain– the Beginnings of a Chemical Climatology by Robert Angus Smith (1872) “When the sulphuric acid increases more rapidly than the ammonia, the rain becomes acidic.” Ammonia/Ammonium Trends Methods: trends period: 1985 through 2002 applied Seasonal Kendall Trend Test meteorological seasons (Dec-Feb, etc.) applied four NADP data completeness criteria to accept/reject a season & a site calculated Sen’s Estimator to quantify trends Ammonia/Ammonium Trends Results: 139 sites met completeness criteria for the 18-year trends period Ammonium Increasing • 124 (89.2%) sites • 58 (41.7%) significant (p<0.05) Ammonium Decreasing • 15 (10.8%) sites • 2 (1.4%) significant Sulfate, Nitrate & Ammonium Trends Results: Sulfate Ammonium Nitrate Up Sig | Down Sig 7 0 | 132 106 124 58 | 15 2 70 23 | 69 17 Chemical Climate: SO4/NH4/NH3/NO3/HNO3 Inorganic SO4 has low volatility & reacts readily with NH3 to form stable salts • (NH4)2SO4 : NH4/SO4 = 1.00 • (NH4)3H(SO4)2 : NH4/SO4 = 0.75 • (NH4)HSO4 : NH4/SO4 = 0.50 • H2SO4 : NH4/SO4 = 0.00 Ammonia-rich environment: NH4/SO4>1.00 (Seinfeld, Saxena,Tanner,etal.) Chemical Climate: SO4/NH4/NH3/NO3/HNO3 NH4/NH3/NO3/HNO3 : distribution between aerosol & gas phases depends on SO4, T, TD, PHNO3, PNH3 Ammonia-excess: NH4-[(SO4+NO3+Cl) - (base cations)] > 0 (Blanchard, etal., 2000, JAWMA) Monitoring Chemical Climate Change in America The Case for Ammonia NH4 increased at ~90% (42% significant) of sites & SO4 decreased at ~95% (76% significant) of sites between 1985 and 2002. These trends, accompanied by locally significant changes in NO3, have increased the ammoniaexcess, altering the SO4/NH4/NH3/NO3/HNO3 chemistry in air and precipitation in the United States. Monitoring Chemical Climate Change in America The Case for Ammonia The NADP provides a long-term high-quality database for studying our chemical climate.