CONTENTS 1 MEASURES OF ATMOSPHERIC COMPOSITION
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1 i CONTENTS 1 MEASURES OF ATMOSPHERIC COMPOSITION MIXING RATIO NUMBER DENSITY PARTIAL PRESSURE 6 PROBLEMS Fog formation Phase partitioning of water in cloud The ozone layer 10 2 ATMOSPHERIC PRESSURE MEASURING ATMOSPHERIC PRESSURE MASS OF THE ATMOSPHERE VERTICAL PROFILES OF PRESSURE AND TEMPERATURE BAROMETRIC LAW THE SEA-BREEZE CIRCULATION 18 PROBLEMS Scale height of the Martian atmosphere Scale height and atmospheric mass 21 3 SIMPLE MODELS ONE-BOX MODEL Concept of lifetime Mass balance equation MULTI-BOX MODELS PUFF MODELS 30 PROBLEMS Atmospheric steady state Ventilation of pollution from the United States Stratosphere-troposphere exchange Interhemispheric exchange Long-range transport of acidity Box vs. column model for an urban airshed The Montreal protocol 38 4 ATMOSPHERIC TRANSPORT GEOSTROPHIC FLOW Coriolis force Geostrophic balance The effect of friction THE GENERAL CIRCULATION VERTICAL TRANSPORT Buoyancy Atmospheric stability 52
2 ii Adiabatic lapse rate Latent heat release from cloud formation Atmospheric lapse rate TURBULENCE Description of turbulence Turbulent flux Parameterization of turbulence Time scales for vertical transport 66 PROBLEMS Dilution of power plant plumes Short questions on atmospheric transport Seasonal motion of the ITCZ A simple boundary layer model Breaking a nighttime inversion Wet convection Scavenging of water in a thunderstorm Global source of methane Role of molecular diffusion in atmospheric transport Vertical transport near the surface 74 5 THE CONTINUITY EQUATION EULERIAN FORM Derivation Discretization LAGRANGIAN FORM 79 PROBLEMS Turbulent diffusion coefficient 82 6 GEOCHEMICAL CYCLES GEOCHEMICAL CYCLING OF ELEMENTS EARLY EVOLUTION OF THE ATMOSPHERE THE NITROGEN CYCLE THE OXYGEN CYCLE THE CARBON CYCLE Mass balance of atmospheric CO Carbonate chemistry in the ocean Uptake of CO 2 by the ocean Uptake of CO 2 by the terrestrial biosphere Box model of the carbon cycle 103 PROBLEMS Short questions on the oxygen cycle Short questions on the carbon cycle Atmospheric residence time of helium Methyl bromide Global fertilization of the biosphere Ocean ph Cycling of CO 2 with the terrestrial biosphere Sinks of atmospheric CO 2 deduced from changes in atmospheric O Fossil fuel CO 2 neutralization by marine CaCO 3 111
3 7 THE GREENHOUSE EFFECT RADIATION EFFECTIVE TEMPERATURE OF THE EARTH Solar and terrestrial emission spectra Radiative balance of the Earth ABSORPTION OF RADIATION BY THE ATMOSPHERE Spectroscopy of gas molecules A simple greenhouse model Interpretation of the terrestrial radiation spectrum RADIATIVE FORCING Definition of radiative forcing Application Radiative forcing and surface temperature WATER VAPOR AND CLOUD FEEDBACKS Water vapor Clouds OPTICAL DEPTH 138 PROBLEMS Climate response to changes in ozone Interpretation of the terrestrial radiation spectrum Jupiter and Mars The faint Sun problem Planetary skin Absorption in the atmospheric window 143 iii 8 AEROSOLS SOURCES AND SINKS OF AEROSOLS RADIATIVE EFFECTS Scattering of radiation Visibility reduction Perturbation to climate 148 PROBLEMS Residence times of aerosols Aerosols and radiation CHEMICAL KINETICS RATE EXPRESSIONS FOR GAS-PHASE REACTIONS Bimolecular reactions Three-body reactions REVERSE REACTIONS AND CHEMICAL EQUILIBRIA PHOTOLYSIS RADICAL-ASSISTED REACTION CHAINS STRATOSPHERIC OZONE CHAPMAN MECHANISM The mechanism Steady-state solution 164
4 iv 10.2 CATALYTIC LOSS CYCLES Hydrogen oxide radicals (HO x ) Nitrogen oxide radicals (NO x ) Chlorine radicals (ClO x ) POLAR OZONE LOSS Mechanism for ozone loss PSC formation Chronology of the ozone hole AEROSOL CHEMISTRY 186 PROBLEMS Shape of the ozone layer The Chapman mechanism and steady state The detailed Chapman mechanism HO x -catalyzed ozone loss Chlorine chemistry at mid-latitudes Partitioning of Cl y Bromine-catalyzed ozone loss Limitation of antarctic ozone depletion Fixing the ozone hole PSC formation OXIDIZING POWER OF THE TROPOSPHERE THE HYDROXYL RADICAL Tropospheric production of OH Global mean OH concentration GLOBAL BUDGETS OF CO AND METHANE CYCLING OF HO X AND PRODUCTION OF OZONE OH titration CO oxidation mechanism Methane oxidation mechanism GLOBAL BUDGET OF NITROGEN OXIDES GLOBAL BUDGET OF TROPOSPHERIC OZONE ANTHROPOGENIC INFLUENCE ON OZONE AND OH 217 PROBLEMS Sources of CO Sources of tropospheric ozone Oxidizing power of the atmosphere OH concentrations in the past Acetone in the upper troposphere Transport, rainout, and chemistry in the marine upper troposphere Bromine chemistry in the troposphere Nighttime oxidation of NO x Peroxyacetylnitrate (PAN) as a reservoir for NO x OZONE AIR POLLUTION AIR POLLUTION AND OZONE OZONE FORMATION AND CONTROL STRATEGIES OZONE PRODUCTION EFFICIENCY 241 PROBLEMS 244
5 v 12.1 NO x - and hydrocarbon-limited regimes for ozone production Ozone titration in a fresh plume ACID RAIN CHEMICAL COMPOSITION OF PRECIPITATION Natural precipitation Precipitation over North America SOURCES OF ACIDS: SULFUR CHEMISTRY EFFECTS OF ACID RAIN EMISSION TRENDS 254 PROBLEMS What goes up must come down The true acidity of rain Aqueous-phase oxidation of SO 2 by ozone The acid fog problem Acid rain: the preindustrial atmosphere 258 NUMERICAL SOLUTIONS TO PROBLEMS 259 INDEX 261
A B C D PROBLEMS Dilution of power plant plumes. z z z z
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