Atmospheric Chemistry: Air Pollution and Global Warming Summary of materials related to University of Washington course Atm S 458 Air Pollution Chemistry taught Autumn 2014 by Professor Joel Thornton compiled by Michael C. McGoodwin (MCM). Content last updated 1/15/2015 Table of Contents Introduction ................................................................................................................................................. 3 A Little Light Physics .................................................................................................................................... 5 Blackbody Radiation ................................................................................................................................. 5 Planck’s Distribution Formula or Law..................................................................................................... 5 Wien’s Displacement Law ....................................................................................................................... 6 Stefan-Boltzmann Law ........................................................................................................................... 7 Solar Spectrum and Earth Irradiance ........................................................................................................ 7 Divisions of Visible Light: ....................................................................................................................... 9 Divisions of Ultraviolet UV.................................................................................................................... 10 Divisions of Infrared IR ........................................................................................................................ 10 Selected Topics in General Atmospheric Science ......................................................................................... 11 Major Subdivisions of Atmospheric Sciences ............................................................................................ 11 Atmospheric Layers and Relation to Temperature (including the Boundary Layer) .................................... 11 Troposphere (0 to 6–20 km) .................................................................................................................. 12 The Atmospheric Boundary Layer in the Troposphere and its Diurnal Variation .................................... 12 Stratosphere (6–20 km to ~50–55 km) .................................................................................................. 13 Mesosphere (~50–55 km to 80–85 km) .................................................................................................. 13 Thermosphere (80–85 km to 690 km) and Ionosphere (60–300 km) ....................................................... 14 Exosphere (690 km to 10,000 km) ....................................................................................................... 14 Pressure, Flows, and Fronts .................................................................................................................... 14 Ideal Gas Law ...................................................................................................................................... 15 Partial Pressure and Manometers ......................................................................................................... 15 Atmospheric Pressure Variation with Altitude (or Geopotential Height) .................................................. 15 Upper Level Atmospheric Pressures and Flows ..................................................................................... 19 Atmospheric Chemistry .............................................................................................................................. 22 Review of QM Electron Orbitals and Configurations ................................................................................. 22 Principle Quantum Number n .............................................................................................................. 22 Angular Momentum quantum numbers ℓ , m , and s ............................................................................ 22 Chemical Composition of Earth’s Atmosphere: Overview .......................................................................... 33 Chemical Evolution of Earth’s Atmosphere and the Organisms Influencing This .................................... 33 Composition of the Modern Atmosphere (Selected) ................................................................................ 35 Specific Elements and Compounds in the Atmosphere ............................................................................. 36 Nitrogen and the Nitrogen Cycle ........................................................................................................... 36 Oxygen: Allotropes O2 and Ozone O3, Ions, and Radicals; Sources and Sinks of O2 ................................ 38 Water Vapor H20 .................................................................................................................................. 41 Carbon Dioxide CO2 ............................................................................................................................. 42 Methane CH4 ....................................................................................................................................... 45 Carbon Monoxide CO ........................................................................................................................... 46 Sulfur Dioxide SO2 ............................................................................................................................... 46 Nitric Oxide NO, Nitrogen Dioxide NO2, and Combined Nitrogen Oxides NOx .......................................... 47 Lead Pb as an Environmental Pollutant ................................................................................................ 48 Hazardous Organic Compounds ........................................................................................................... 48 Overview of Urban Air Pollution ............................................................................................................... 49 Types of Air Pollution by Atmospheric or Geographic Region ................................................................. 49 Trends in US Air Quality 1990 to 2010 .................................................................................................... 50 London-type Smog .................................................................................................................................. 51 Photostationary-State Ozone, Night vs. Day in the Background Troposphere, and PAN ............................. 52 Photochemical Smog (PC Smog) ............................................................................................................... 53 Page 1 of 141 AtmChemSummary_AtmS458_MCM_Fall2014.docx 15 Jan 2015 Initiation of PC O3 Production ........................................................................................................... 54 Propagation of PC O3 Production ....................................................................................................... 54 The NOx Cycle ................................................................................................................................... 55 Termination of PC O3 Production ....................................................................................................... 55 Ozone Isopleth and PO3 ..................................................................................................................... 56 The Most Important Ozone-Related ROGs Found in a 1987 Southern CA study .................................. 57 Isoprene and Terpenes ...................................................................................................................... 57 Ozone from Alcohols Including Oxygenated Fuels .............................................................................. 58 Photochemical Oxidation of CO ......................................................................................................... 58 Aerosol Particles in the Global and Polluted Atmosphere .......................................................................... 59 Particle Sizes Defined ........................................................................................................................ 59 Empiric Modes of Aerosol Distribution .............................................................................................. 60 Sources and Compositions ................................................................................................................ 61 Processes Affecting Particle Size and Evolution .................................................................................. 64 Removal Processes ............................................................................................................................ 66 Particle Morphology and Shape ......................................................................................................... 66 Health Effects of Aerosol Particles ..................................................................................................... 66 Effects of Meteorology on Air Pollution ..................................................................................................... 68 Forces Influencing Horizontal Winds ................................................................................................