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The Atmosphere as a Chemical Reactor. Radiation (energy). Inputs. Outputs. Chemistry. Biogeochemical Cycling. Temperature Structure of the Atmosphere. from: http://www.uwsp.edu/geo/faculty/ritter/images/atmosphere/structure_ composition/atmospheric_structure.jpg.
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The Atmosphere as aChemical Reactor Radiation (energy) Inputs Outputs Chemistry Biogeochemical Cycling
Temperature Structure of the Atmosphere from: http://www.uwsp.edu/geo/faculty/ritter/images/atmosphere/structure_ composition/atmospheric_structure.jpg
Pressure Structure of the Atmosphere from: http://okfirst.ocs.ou.edu/train/meteorology/graphics/VertTP.gif
Mixing Ratio vs. Concentration • Mixing Ratio – the fraction of air by volume that is composed of a certain compound. • The fraction of N2 is 0.80 or 80% • The fraction of N2O is 3.6x10-7 or 3.6x10-5% or 360 ppbv. • Concentration (number density) – number of molecules of a specified compound contained in a fixed volume. • [N2O] at 1010 mbar = 8.86x1012 molecules/cm3 • [N2O] at 500 mbar = 4.38x1012 molecules/cm3 The atmosphere has a density of 2.69x1019 molecules/cm3at sea level
Vertical Mixing of the Troposphere • Boundary Layer – hours to days • Free Troposphere – days to weeks • Tropopause - years
Horizontal Mixing of the Troposphere from: Jacob
Kinetics Only true for elementary reactions!
Lifetime, Pseudo First Order • First order reaction: • Second order reaction:
Lifetime • Some compounds have multiple sinks • Methane chemical loss in troposphere by OH ≈ 12yrs physical deposition to the soil ≈ 100 yrs chemical loss in stratosphere ≈ 40 yrs Overall lifetime:
J Values • Photochemistry
Radical Chemistry • Radicals do the work of the chemistry in the atmosphere. • Produced by photochemical reactions and reactions by other radicals • O(3P) is a bi-radical • O(1D) is not a radical, but it is very reactive
Production of OH Radical Assume steady-state for O(1D) Production Loss
Production of OH Radical Solve for [O(1D)] Substitute into the production of OH
Coupling of NOx and HOx fast NO slow
Oxidation of Formaldehyde Maximum O3 production = 3 molecules (high NOx) Maximum HOx production = 2 molecules (high NOx) Minimum O3 production = 0 molecules (low NOx) Minimum HOx producion = -2 molecules (low NOx)
Oxidation of Methane Can oxidize NO to NO2 just like HO2 formaldehyde
O3 Production by Methane • High NOx (maximum O3 and HOx production): • Low NOx (minimum O3and HOx production):