Introduction to Atmospheric Chemistry, by Daniel J. Jacob, Princeton University Press, 1999.

Copyright 1999 by Princeton University Press. All rights reserved. No part of this book may be reproduced in any form by any electronic or mechanical means (including photocopying, recording, or information storage and retrieval) without permission in writing from the publisher, except for reading and browsing via the World-Wide Web. Users are not permitted to mount this file on any network servers. For more information, send e-mail to permissions@pupress.princeton.edu .

Course instructors may request complete solutions to the problems by e-mail to the author: djj@io.harvard.edu

Errata last modified: January 14, 2004




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Foreword  


1 MEASURES OF ATMOSPHERIC COMPOSITION 1

      1.1 MIXING RATIO 1

      1.2 NUMBER DENSITY 2

      1.3 PARTIAL PRESSURE 6

PROBLEMS 10

      1.1 Fog formation 10

      1.2 Phase partitioning of water in cloud 10

      1.3 The ozone layer 10

2 ATMOSPHERIC PRESSURE 12

      2.1 MEASURING ATMOSPHERIC PRESSURE 12

      2.2 MASS OF THE ATMOSPHERE 13

      2.3 VERTICAL PROFILES OF PRESSURE AND TEMPERATURE 14

      2.4 BAROMETRIC LAW 15

      2.5 THE SEA-BREEZE CIRCULATION 18

PROBLEMS 21

      2.1 Scale height of the Martian atmosphere 21

      2.2 Scale height and atmospheric mass 21

3 SIMPLE MODELS 22

      3.1 ONE-BOX MODEL 23

      3.1.1 Concept of lifetime 23

      3.1.2 Mass balance equation 25

      3.2 MULTI-BOX MODELS 28

      3.3 PUFF MODELS 30

PROBLEMS 35

      3.1 Atmospheric steady state 35

      3.2 Ventilation of pollution from the United States 35

      3.3 Stratosphere-troposphere exchange 35

      3.4 Interhemispheric exchange 37

      3.5 Long-range transport of acidity 37

      3.6 Box vs. column model for an urban airshed 38

      3.7 The Montreal protocol 38

4 ATMOSPHERIC TRANSPORT 40

      4.1 GEOSTROPHIC FLOW 40

      4.1.1 Coriolis force 40

      4.1.2 Geostrophic balance 44

      4.1.3 The effect of friction 45

      4.2 THE GENERAL CIRCULATION 46

      4.3 VERTICAL TRANSPORT 50

      4.3.1 Buoyancy 50

      4.3.2 Atmospheric stability 52

      4.3.3 Adiabatic lapse rate 53

      4.3.4 Latent heat release from cloud formation 55

      4.3.5 Atmospheric lapse rate 57

      4.4 TURBULENCE 60

      4.4.1 Description of turbulence 61

      4.4.2 Turbulent flux 61

      4.4.3 Parameterization of turbulence 65

      4.4.4 Time scales for vertical transport 66

PROBLEMS 69

      4.1 Dilution of power plant plumes 69

      4.2 Short questions on atmospheric transport 70

      4.3 Seasonal motion of the ITCZ 71

      4.4 A simple boundary layer model 71

      4.5 Breaking a nighttime inversion 71

      4.6 Wet convection 72

      4.7 Scavenging of water in a thunderstorm 73

      4.8 Global source of methane 73

      4.9 Role of molecular diffusion in atmospheric transport 74

      4.10 Vertical transport near the surface 74

5 THE CONTINUITY EQUATION 75

      5.1 EULERIAN FORM 75

      5.1.1 Derivation 75

      5.1.2 Discretization 77

      5.2 LAGRANGIAN FORM 79

PROBLEMS 82

      5.1 Turbulent diffusion coefficient 82

6 GEOCHEMICAL CYCLES 83

      6.1 GEOCHEMICAL CYCLING OF ELEMENTS 83

      6.2 EARLY EVOLUTION OF THE ATMOSPHERE 85

      6.3 THE NITROGEN CYCLE 86

      6.4 THE OXYGEN CYCLE 90

      6.5 THE CARBON CYCLE 93

      6.5.1 Mass balance of atmospheric CO2 93

      6.5.2 Carbonate chemistry in the ocean 95

      6.5.3 Uptake of CO2 by the ocean 98

      6.5.4 Uptake of CO2 by the terrestrial biosphere 102

      6.5.5 Box model of the carbon cycle 103

PROBLEMS 105

      6.1 Short questions on the oxygen cycle 105

      6.2 Short questions on the carbon cycle 105

      6.3 Atmospheric residence time of helium 106

      6.4 Methyl bromide 106

      6.5 Global fertilization of the biosphere 108

      6.6 Ocean pH 109

      6.7 Cycling of CO2 with the terrestrial biosphere 109

      6.8 Sinks of atmospheric CO2 deduced from changes in atmospheric O2 110

      6.9 Fossil fuel CO2 neutralization by marine CaCO3 111

7 THE GREENHOUSE EFFECT 113

      7.1 RADIATION 115

      7.2 EFFECTIVE TEMPERATURE OF THE EARTH 119

      7.2.1 Solar and terrestrial emission spectra 119

      7.2.2 Radiative balance of the Earth 121

      7.3 ABSORPTION OF RADIATION BY THE ATMOSPHERE 123

      7.3.1 Spectroscopy of gas molecules 123

      7.3.2 A simple greenhouse model 126

      7.3.3 Interpretation of the terrestrial radiation spectrum 128

      7.4 RADIATIVE FORCING 130

      7.4.1 Definition of radiative forcing 131

      7.4.2 Application 132

      7.4.3 Radiative forcing and surface temperature 134

      7.5 WATER VAPOR AND CLOUD FEEDBACKS 136

      7.5.1 Water vapor 136

      7.5.2 Clouds 137

      7.6 OPTICAL DEPTH 138

PROBLEMS 141

      7.1 Climate response to changes in ozone 141

      7.2 Interpretation of the terrestrial radiation spectrum 141

      7.3 Jupiter and Mars 142

      7.4 The "faint Sun" problem 142

      7.5 Planetary skin 143

      7.6 Absorption in the atmospheric window 143

8 AEROSOLS 144

      8.1 SOURCES AND SINKS OF AEROSOLS 144

      8.2 RADIATIVE EFFECTS 146

      8.2.1 Scattering of radiation 146

      8.2.2 Visibility reduction 148

      8.2.3 Perturbation to climate 148

PROBLEMS 153

      8.1 Residence times of aerosols 153

      8.2 Aerosols and radiation 153

9 CHEMICAL KINETICS 155

      9.1 RATE EXPRESSIONS FOR GAS-PHASE REACTIONS 155

      9.1.1 Bimolecular reactions 155

      9.1.2 Three-body reactions 155

      9.2 REVERSE REACTIONS AND CHEMICAL EQUILIBRIA 157

      9.3 PHOTOLYSIS 158

      9.4 RADICAL-ASSISTED REACTION CHAINS 159

10 STRATOSPHERIC OZONE 162

      10.1 CHAPMAN MECHANISM 162

      10.1.1 The mechanism 162

      10.1.2 Steady-state solution 164

      10.2 CATALYTIC LOSS CYCLES 169

      10.2.1 Hydrogen oxide radicals (HOx) 169

      10.2.2 Nitrogen oxide radicals (NOx) 170

      10.2.3 Chlorine radicals (ClOx) 176

      10.3 POLAR OZONE LOSS 178

      10.3.1 Mechanism for ozone loss 180

      10.3.2 PSC formation 181

      10.3.3 Chronology of the ozone hole 184

      10.4 AEROSOL CHEMISTRY 186

PROBLEMS 190

      10.1 Shape of the ozone layer 190

      10.2 The Chapman mechanism and steady state 190

      10.3 The detailed Chapman mechanism 191

      10.4 HOx-catalyzed ozone loss 192

      10.5 Chlorine chemistry at mid-latitudes 192

      10.6 Partitioning of Cly 193

      10.7 Bromine-catalyzed ozone loss 194

      10.8 Limitation of antarctic ozone depletion 195

      10.9 Fixing the ozone hole 196

      10.10 PSC formation 198

11 OXIDIZING POWER OF THE TROPOSPHERE 199

      11.1 THE HYDROXYL RADICAL 200

      11.1.1 Tropospheric production of OH 200

      11.1.2 Global mean OH concentration 201

      11.2 GLOBAL BUDGETS OF CO AND METHANE 204

      11.3 CYCLING OF HOx AND PRODUCTION OF OZONE 206

      11.3.1 OH titration 206

      11.3.2 CO oxidation mechanism 207

      11.3.3 Methane oxidation mechanism 209

      11.4 GLOBAL BUDGET OF NITROGEN OXIDES 211

      11.5 GLOBAL BUDGET OF TROPOSPHERIC OZONE 215

      11.6 ANTHROPOGENIC INFLUENCE ON OZONE AND OH 217

PROBLEMS 220

      11.1 Sources of CO 220

      11.2 Sources of tropospheric ozone 220

      11.3 Oxidizing power of the atmosphere 221

      11.4 OH concentrations in the past 223

      11.5 Acetone in the upper troposphere 224

      11.6 Transport, rainout, and chemistry in the marine upper troposphere 225

      11.7 Bromine chemistry in the troposphere 227

      11.8 Nighttime oxidation of NOx 229

      11.9 Peroxyacetylnitrate (PAN) as a reservoir for NOx 230

12 OZONE AIR POLLUTION 232

      12.1 AIR POLLUTION AND OZONE 232

      12.2 OZONE FORMATION AND CONTROL STRATEGIES 234

      12.3 OZONE PRODUCTION EFFICIENCY 241

PROBLEMS 244

      12.1 NO x - and hydrocarbon-limited regimes for ozone production 244

      12.2 Ozone titration in a fresh plume 245

13 ACID RAIN 247

      13.1 CHEMICAL COMPOSITION OF PRECIPITATION 247

      13.1.1 Natural precipitation 247

      13.1.2 Precipitation over North America 248

      13.2 SOURCES OF ACIDS: SULFUR CHEMISTRY 251

      13.3 EFFECTS OF ACID RAIN 253

      13.4 EMISSION TRENDS 254

PROBLEMS 256

      13.1 What goes up must come down 256

      13.2 The true acidity of rain 256

      13.3 Aqueous-phase oxidation of SO2 by ozone 256

      13.4 The acid fog problem 257

      13.5 Acid rain: the preindustrial atmosphere 258

NUMERICAL SOLUTIONS TO PROBLEMS 259

INDEX 261