Regional budgets for nitrogen oxides from continental sources: Variations of rates for oxidation and deposition with season and distance from source regions


  • J. William Munger,

  • Song-Miao Fan,

  • Peter S. Bakwin,

  • Mike L. Goulden,

  • Allen. H. Goldstein,

  • Albert S. Colman,

  • Steven C. Wofsy


Measurements of nitrogen deposition and concentrations of NO, NO2, NOy (total oxidized N), and O3 have been made at Harvard Forest in central Massachusetts since 1990 to define the atmospheric budget for reactive N near a major source region. Total (wet plus dry) reactive N deposition for the period 1990–1996 averaged 47 mmol m−2 yr−1 (126 μmol m−2 d−1, 6.4 kg N ha−1 yr−1), with 34% contributed by dry deposition. Atmospheric input adds about 12% to the N made available annually by mineralization in the forest soil. The corresponding deposition rate at a distant site, Schefferville, Quebec, was 20 mmol m−2 d−1 during summer 1990. Both heterogeneous and homogeneous reactions efficiently convert NOx to HNO3 in the boundary layer. HNO3 is subsequently removed rapidly by either dry deposition or precipitation. The characteristic (e-folding) time for NOx oxidation ranges from 0.30 days in summer, when OH radical is abundant, to ∼1.5 days in the winter, when heterogeneous reactions are dominant and O3 concentrations are lowest. The characteristic time for removal of NOx oxidation products (defined as NOy minus NOx) from the boundary layer by wet and dry deposition is ∼1 day, except in winter when it decreases to 0.6 day. Biogenic hydrocarbons contribute to N deposition through formation of organic nitrates but are also precursors of reservoir species, such as peroxyacetylnitrate, that may be exported from the region. A simple model assuming pseudo first-order rates for oxidation of NOx, followed by deposition, predicts that 45% of NOx in the northeastern U.S. boundary layer is removed in 1 day during summer and 27% is removed in winter. It takes 3.5 and 5 days for 95% removal in summer and winter, respectively.