Chemistry of the Climate System

Preface......Page 8
Prologue......Page 10
List of principal symbols......Page 12
Contents......Page 14
1.1 Air and atmosphere - a multiphase and multi-component system......Page 20
1.2 Chemistry and environmental research......Page 25
1.3.1 From Antiquity to the Renaissance: Before the discovery of the air composition......Page 31
1.3.2 Discovery of the air and water composition......Page 35
1.3.3 Discovery of trace substances in air......Page 39
1.3.4 Dust and acid rain: Air pollution......Page 41
2 Chemical evolution......Page 46
2.1.1 Origin of elements, molecules and the earth......Page 47
2.1.2 Origin of organic bonded carbon......Page 56
2.1.2.1 What is organic chemistry?......Page 57
2.1.2.2 Origin of carbon......Page 59
2.1.3 Origin of nitrogen......Page 65
2.2 Evolution of the atmosphere......Page 67
2.2.1.1 Volcanic gases......Page 68
2.2.1.2 Gases occluded and produced from rocks......Page 71
2.2.1.3 The pre-biological primitive atmosphere......Page 76
2.2.2.1 Origin of life......Page 81
2.2.2.2 The rise of oxygen and ozone: Biogeochemical evolution......Page 86
2.2.2.3 Photosynthesis: Non-equilibrium redox processes......Page 93
2.2.2.4 A short history of understanding of photosynthesis......Page 100
2.2.2.5 The carbon and oxygen pools and global cycling......Page 104
2.2.2.6 Life limits by catastrophic events: Mass extinction......Page 112
2.3 The earth’s energy sources......Page 113
2.3.1.1 The sun and its radiation output......Page 114
2.3.1.2 Solar radiation transfer through the atmosphere......Page 115
2.3.2 Absorption and emission of light......Page 121
2.3.2.1 Absorption (Lambert-Beer law)......Page 122
2.3.2.2 Emission (Planck’s law and Stefan-Boltzmann’s law)......Page 123
2.3.3 Terrestrial radiation and radiation budget......Page 125
2.3.4 Geothermal energy......Page 127
2.3.5.1 Wind energy......Page 129
2.3.5.3 Bioenergy......Page 130
2.3.5.4 Comparison among earth’s energy sources - potential for humans......Page 133
2.3.6 Abiogenic versus biogenic formation of “fossil fuels”......Page 135
2.4 The biosphere and global biogeochemical cycles......Page 136
2.4.1 Biosphere and the noosphere......Page 137
2.4.2 Biogeochemical cycling: The principles......Page 142
2.4.3 Global biogeochemical cycles......Page 146
2.4.3.1 Nitrogen......Page 147
2.4.3.2 Sulfur......Page 151
2.4.3.3 Chlorine......Page 155
2.4.4 What is the role of life in earth’s climate system?......Page 160
2.5 The hydrosphere and the global water cycle......Page 164
2.5.1 Water: Physical and chemical properties......Page 165
2.5.1.1 Water structure: Hydrogen bond......Page 166
2.5.1.2 Water as solvent......Page 169
2.5.1.3 Water properties in relation to the climate system......Page 170
2.5.2 Hydrologic cycle and the climate system......Page 171
2.5.3 Atmospheric water......Page 174
2.5.3.1 Water vapor......Page 176
2.5.3.2 Clouds......Page 178
2.5.3.3 Haze, mist and fog......Page 181
2.5.3.4 Precipitation......Page 182
2.5.4 Dew, frost, rime and interception......Page 184
2.5.5 Soil water and groundwater: Chemical weathering......Page 186
2.5.6 Surface water: Rivers and lakes......Page 187
2.5.7 The oceans......Page 189
2.6.1 Source characteristics......Page 191
2.6.2.1 Vegetation and microorganisms (soils and waters)......Page 192
2.6.2.2 Animals......Page 195
2.6.3 The ocean as source......Page 197
2.6.4.1 Soil dust......Page 200
2.6.4.2 Sea salt......Page 203
2.6.4.3 Volcanism and emanation......Page 204
2.6.4.4 Lightning......Page 209
2.6.4.5 Biomass burning......Page 211
2.6.4.6 Atmospheric chemistry: Secondary sources......Page 217
2.6.5 Anthropogenic sources......Page 220
2.6.5.1 Fossil fuel use: The energy problem......Page 221
2.6.5.2 Agriculture: The food problem......Page 228
2.6.5.3 Land-use change and deforestation: The population problem......Page 231
2.7 Emission of atmospheric substances......Page 234
2.7.1.1 Ammonia (NH3)......Page 238
2.7.1.2 Dinitrogen monoxide (N2O)......Page 241
2.7.1.3 Nitrogen monoxide (NO)......Page 242
2.7.2.1 Sulfur dioxide (SO2)......Page 244
2.7.2.2 Reduced sulfur compounds (H2S, DMS, COS)......Page 247
2.7.3.1 Carbon dioxide (CO2)......Page 249
2.7.3.2 Carbon monoxide (CO)......Page 250
2.7.3.3 Methane (CH4)......Page 252
2.7.3.4 Non-methane volatile organic compounds (NMVOC)......Page 253
2.8 The human problem: A changing earth system......Page 257
2.8.1 Humans historic perspective: From the past into the future......Page 259
2.8.2 Changing chemical composition of the atmosphere: Variations and trends.......Page 264
2.8.2.1 Fundamentals: Why concentration fluctuates?......Page 267
2.8.2.2 SO2, NO2 and dust: Classic for local to regional up-scaling......Page 269
2.8.2.3 CO2: The fossil fuel era challenge......Page 273
2.8.2.4 CH4 and N2O: Permanent agricultural associates......Page 283
2.8.2.5 Halogenated organic compounds: Sit out problem......Page 287
2.8.2.6 CO: The biomass burning problem......Page 289
2.8.2.7 O3: Locally believed to be solved but regional unsolved......Page 291
2.8.2.8 H2O2: Mysterious......Page 301
2.8.2.9 OH: The key oxidant......Page 304
2.8.2.10 H2: Light but problematic......Page 306
2.8.3.1 The carbon budget......Page 307
2.8.3.2 The CO2-carbonate system......Page 312
2.8.3.3 Atmospheric CO2 residence time......Page 322
2.8.4 Global sustainable chemistry......Page 325
2.8.4.1 Growth and equilibrium (stationary state)......Page 326
2.8.4.2 Man-made carbon cycling: Air capture and CO2 cycling......Page 328
3 Climate, climate change and the climate system......Page 340
3.1 Climate and climatology: A historical perspective......Page 342
3.2 Climate and the climate system......Page 347
3.3 Chemical weather and climate......Page 350
3.4 Climate change and variability......Page 353
4 Fundamentals of physico-chemistry in the climate system......Page 364
4.1 Physical basics......Page 365
4.1.1.1 Fluid characteristics......Page 366
4.1.1.2 The gas laws......Page 367
4.1.1.3 Mean free path and number of collisions between molecules......Page 371
4.1.1.4 Viscosity......Page 374
4.1.1.5 Diffusion......Page 375
4.1.2 Units for chemical abundance: Concentrations and mixing ratios......Page 376
4.1.3 Thermodynamics: The equations of state......Page 380
4.1.4 Equilibrium......Page 385
4.1.5 Steady state......Page 387
4.2 Chemical reactions......Page 390
4.2.1 Kinetics: The reaction rate constant......Page 391
4.2.2 Radicals......Page 398
4.2.3 Photochemistry: The photolysis rate constant......Page 399
4.2.4 Oxidation and reduction (the redox processes)......Page 404
4.2.5.1 Environmental relevance of acidity......Page 409
4.2.5.2 Acid-base theories......Page 410
4.2.5.3 Atmospheric acidity......Page 414
4.2.5.4 pH averaging......Page 420
4.3 Multiphase processes......Page 421
4.3.1 Aerosols, clouds and precipitation: The climate multiphase system......Page 424
4.3.2 Gas-liquid equilibrium (Henry equilibrium)......Page 426
4.3.3 Properties of droplets......Page 428
4.3.3.1 Vapor pressure change: The Kelvin equation......Page 429
4.3.3.2 Surface tension and surface active substances......Page 431
4.3.3.3 Vapor pressure lowering: Raoult’s law......Page 432
4.3.3.4 Freezing point depression......Page 434
4.3.4 Gas-to-particle formation: Homogeneous nucleation......Page 435
4.3.5 Atmospheric aerosols and properties of aerosol particles......Page 440
4.3.6 Formation of cloud droplets: Heterogeneous nucleation......Page 447
4.3.7.1 Mass transfer: General remarks......Page 448
4.3.7.2 Adsorption......Page 454
4.3.7.3 Surface chemistry: Kinetics of heterogeneous chemical reaction......Page 455
4.3.7.4 Mass transfer into the droplet with chemical reaction......Page 457
4.4 Atmospheric removal: Deposition processes......Page 461
4.4.1 Dry deposition......Page 462
4.4.2 Wet deposition......Page 468
4.5 Characteristic times: Residence time, lifetime and turnover time......Page 470
5.1.1 The principles of chemistry in the climate system......Page 478
5.1.2 Substances in the climate system......Page 481
5.2 Hydrogen......Page 483
5.3 Oxygen......Page 484
5.3.1 Atomic, molecular oxygen and ozone: O, O2 and O3 (Ox)......Page 486
5.3.2.1 Atmosphere, free of trace species......Page 490
5.3.2.2 Atmosphere with trace species......Page 493
5.3.3 Reactive oxygen species II: RO, RO2 and ROOH......Page 497
5.3.4 Water and the hydrated electron: H2O and H2O- (ea-q)......Page 500
5.3.5 Aqueous phase oxygen chemistry......Page 509
5.3.5.1 From dioxygen to peroxide (O2 chemistry)......Page 511
5.3.5.2 From ozone to hydroxyl (O3 and O1 chemistry)......Page 518
5.3.6 Multiphase oxygen chemistry......Page 522
5.3.6.1 Historical remarks......Page 523
5.3.6.2 Hydrogen peroxide......Page 525
5.3.6.3 Ozone......Page 528
5.3.7 Stratospheric oxygen chemistry......Page 530
5.4 Nitrogen......Page 535
5.4.1 Thermolysis of nitrogen: Formation of NO......Page 536
5.4.2 Ammonia (NH3)......Page 537
5.4.4.1 Gas phase chemistry......Page 538
5.4.4.2 Aqueous phase and interfacial chemistry......Page 543
5.4.5 Organic nitrogen compounds......Page 554
5.4.5.1 Amines and nitriles......Page 555
5.4.5.2 Organic NOx compounds......Page 556
5.5 Sulfur......Page 557
5.5.1 Sulfides (H2S, CS2, COS, RSH): Reduced sulfur......Page 560
5.5.2 Oxides and oxoacids: SO2, H2SO3, SO3, H2SO4......Page 564
5.5.2.2 Aqueous sulfur chemistry......Page 565
5.5.3 Multiphase sulfur chemistry......Page 573
5.6 Phosphorus......Page 574
5.7 Carbon......Page 577
5.7.1 Elemental carbon and soot......Page 578
5.7.2 C1 chemistry: CO, CO2, CH4, CH3OH, HCHO, HCOOH......Page 580
5.7.3 C2 chemistry: C2H2, C2H4, C2H6, C2H5OH, CH3CHO, CH3COOH, (COOH)2......Page 585
5.7.4 Alkenes, ketones and aromatic compounds......Page 591
5.7.5 Is the atmospheric fate of complex organic compounds predictable?......Page 593
5.8 Halogens (Cl, Br, F and I)......Page 594
5.8.1 Gas phase chemistry......Page 595
5.8.2 Aqueous and interfacial chemistry......Page 598
5.9 Other elements......Page 602
6 Final remark......Page 604
A.1 List of acronyms and abbreviations found in literature......Page 608
A.2 Quantities, units and some useful numerical values......Page 613
A.3 The geological timescale......Page 617
A.4 Biography......Page 618
References......Page 630
Author index......Page 710
Subject index......Page 714