Introduction to Atmospheric Chemistry

by Jacob, Daniel J.

• ISBN13: 9780691001852
• ISBN10: 0691001855
• Format: Hardcover
• Copyright: 1999-12-21
• Publisher: Princeton Univ Pr

Summary

Atmospheric chemistry is one of the fastest growing fields in the earth sciences. Until now, however, there has been no book designed to help students capture the essence of the subject in a brief course of study. Daniel Jacob, a leading researcher and teacher in the field, addresses that problem by presenting the first textbook on atmospheric chemistry for a one-semester course. Based on the approach he developed in his class at Harvard, Jacob introduces students in clear and concise chapters to the fundamentals as well as the latest ideas and findings in the field. Jacob's aim is to show students how to use basic principles of physics and chemistry to describe a complex system such as the atmosphere. He also seeks to give students an overview of the current state of research and the work that led to this point. Jacob begins with atmospheric structure, design of simple models, atmospheric transport, and the continuity equation, and continues with geochemical cycles, the greenhouse effect, aerosols, stratospheric ozone, the oxidizing power of the atmosphere, smog, and acid rain. Each chapter concludes with a problem set based on recent scientific literature. This is a novel approach to problem-set writing, and one that successfully introduces students to the prevailing issues. This is a major contribution to a growing area of study and will be welcomed enthusiastically by students and teachers alike.

Table of Contents

Preface	xi
Measures of Atmospheric Composition	3	(11)
Mixing Ratio	3	(1)
Number Density	4	(4)
Partial Pressure	8	(6)
Further Reading	11	(1)
Problems	11	(1)
Fog Formation	11	(1)
Phase Partitioning of Water in Cloud	11	(1)
The Ozone Layer	11	(3)
Atmospheric Pressure	14	(10)
Measuring Atmospheric Pressure	14	(1)
Mass of the Atmosphere	14	(2)
Vertical Profiles of Pressure and Temperature	16	(2)
Barometric Law	18	(3)
The Sea-Breeze Circulation	21	(3)
Problems	22	(1)
Scale Height of the Martian Atmosphere	22	(1)
Scale Height and Atmospheric Mass	22	(2)
Simple Models	24	(18)
One-Box Model	25	(5)
Concept of Lifetime	25	(2)
Mass Balance Equation	27	(3)
Multibox Models	30	(3)
Puff Models	33	(9)
Problems	36	(1)
Atmospheric Steady State	36	(1)
Ventilation of Pollution from the United States	37	(1)
Stratosphere-Troposphere Exchange	37	(2)
Interhemispheric Exchange	39	(1)
Long-Range Transport of Acidity	39	(1)
Box versus Column Model for an Urban Airshed	40	(1)
The Montreal Protocol	40	(2)
Atmospheric Transport	42	(37)
Geostrophic Flow	42	(6)
Coriolis Force	42	(4)
Geostrophic Balance	46	(2)
The Effect of Friction	48	(1)
The General Circulation	48	(5)
Vertical Transport	53	(10)
Buoyancy	53	(2)
Atmospheric Stability	55	(1)
Adiabatic Lapse Rate	56	(2)
Latent Heat Release from Cloud Formation	58	(2)
Atmospheric Lapse Rate	60	(3)
Turbulence	63	(16)
Description of Turbulence	64	(1)
Turbulent Flux	64	(3)
Parameterization of Turbulence	67	(3)
Time Scales for Vertical Transport	70	(1)
Further Reading	71	(1)
Problems	71	(1)
Dilution of Power Plant Plumes	71	(1)
Short Questions on Atmospheric Transport	72	(1)
Seasonal Motion of the ITCZ	73	(1)
A Simple Boundary Layer Model	74	(1)
Breaking a Nighttime Inversion	74	(1)
Wet Convection	75	(1)
Scavenging of Water in a Thunderstorm	76	(1)
Global Source of Methane	76	(1)
Role of Molecular Diffusion in Atmospheric Transport	77	(1)
Vertical Transport near the Surface	78	(1)
The Continuity Equation	79	(8)
Eulerian Form	79	(5)
Derivation	79	(2)
Discretization	81	(3)
Lagrangian Form	84	(3)
Further Reading	85	(1)
Problems	85	(1)
Turbulent Diffusion Coefficient	85	(2)
Geochemical Cycles	87	(28)
Geochemical Cycling of Elements	87	(2)
Early Evolution of the Atmosphere	89	(1)
The Nitrogen Cycle	90	(4)
The Oxygen Cycle	94	(3)
The Carbon Cycle	97	(18)
Mass Balance of Atmospheric CO2	97	(1)
Carbonate Chemistry in the Ocean	97	(3)
Uptake of CO2 by the Ocean	100	(4)
Uptake of CO2 by the Terrestrial Biosphere	104	(1)
Box Model of the Carbon Cycle	105	(2)
Further Reading	107	(1)
Problems	107	(1)
Short Questions on the Oxygen Cycle	107	(1)
Short Questions on the Carbon Cycle	108	(1)
Atmospheric Residence Time of Helium	108	(1)
Methyl Bromide	109	(2)
Global Fertilization of the Biosphere	111	(1)
Ocean pH	111	(1)
Cycling of CO2 with the Terrestrial Biosphere	112	(1)
Sinks of Atmospheric CO2 Deduced from Changes in Atmospheric O2	113	(1)
Fossil Fuel CO2 Neutralization by Marine CaCO3	113	(2)
The Greenhouse Effect	115	(31)
Radiation	118	(3)
Effective Temperature of the Earth	121	(5)
Solar and Terrestrial Emission Spectra	121	(1)
Radiative Balance of the Earth	122	(4)
Absorption of Radiation by the Atmosphere	126	(7)
Spectroscopy of Gas Molecules	126	(2)
A Simple Greenhouse Model	128	(3)
Interpretation of the Terrestrial Radiation Spectrum	131	(2)
Radiative Forcing	133	(5)
Definition of Radiative Forcing	133	(2)
Application	135	(2)
Radiative Forcing and Surface Temperature	137	(1)
Water Vapor and Cloud Feedbacks	138	(2)
Water Vapor	138	(2)
Clouds	140	(1)
Optical Depth	140	(6)
Further Reading	142	(1)
Problems	142	(1)
Climate Response to Changes in Ozone	142	(1)
Interpretation of the Terrestrial Radiation Spectrum	143	(1)
Jupiter and Mars	144	(1)
The ``Faint Sun'' Problem	144	(1)
Planetary Skin	145	(1)
Absorption in the Atmospheric Window	145	(1)
Aerosols	146	(11)
Sources and Sinks of Aerosols	146	(2)
Radiative Effects	148	(9)
Scattering of Radiation	148	(2)
Visibility Reduction	150	(1)
Perturbation to Climate	151	(3)
Further Reading	154	(1)
Problems	155	(1)
Residence Times of Aerosols	155	(1)
Aerosols and Radiation	155	(2)
Chemical Kinetics	157	(7)
Rate Expressions for Gas-Phase Reactions	157	(2)
Bimolecular Reactions	157	(1)
Three-Body Reactions	158	(1)
Reverse Reactions and Chemical Equilibria	159	(1)
Photolysis	160	(1)
Radical-Assisted Reaction Chains	161	(3)
Further Reading	163	(1)
Stratospheric Ozone	164	(36)
Chapman Mechanism	164	(7)
The Mechanism	164	(2)
Steady-State Solution	166	(5)
Catalytic Loss Cycles	171	(8)
Hydrogen Oxide Radicals (HOx)	171	(1)
Nitrogen Oxide Radicals (NOx)	172	(5)
Chlorine Radicals (ClOx)	177	(2)
Polar Ozone Loss	179	(8)
Mechanism for Ozone Loss	181	(2)
PSC Formation	183	(2)
Chronology of the Ozone Hole	185	(2)
Aerosol Chemistry	187	(13)
Further Reading	191	(1)
Problems	191	(1)
Shape of the Ozone Layer	191	(1)
The Chapman Mechanism and Steady State	191	(1)
The Detailed Chapman Mechanism	192	(1)
HOx-Catalyzed Ozone Loss	193	(1)
Chlorine Chemistry at Midlatitudes	193	(2)
Partitioning of Cly	195	(1)
Bromine-Catalyzed Ozone Loss	196	(1)
Limitation of Antarctic Ozone Depletion	197	(1)
Fixing the Ozone Hole	198	(1)
PSC Formation	199	(1)
Oxidizing Power of the Troposphere	200	(31)
The Hydroxyl Radical	201	(4)
Tropospheric Production of OH	201	(2)
Global Mean OH Concentration	203	(2)
Global Budgets of CO and Methane	205	(2)
Cycling of HOx and Production of Ozone	207	(5)
The OH Titration Problem	207	(1)
CO Oxidation Mechanism	207	(3)
Methane Oxidation Mechanism	210	(2)
Global Budget of Nitrogen Oxides	212	(3)
Global Budget of Tropospheric Ozone	215	(1)
Anthropogenic Influence on Ozone and OH	216	(15)
Further Reading	219	(1)
Problems	219	(1)
Sources of CO	219	(1)
Sources of Tropospheric Ozone	220	(1)
Oxidizing Power of the Atmosphere	221	(2)
OH Concentrations in the Past	223	(1)
Acetone in the Upper Troposphere	223	(2)
Transport, Rainout, and Chemistry in the Marine Upper Troposphere	225	(2)
Bromine Chemistry in the Troposphere	227	(1)
Nighttime Oxidation of NOx	228	(1)
Peroxyacetylnitrate (PAN) as a Reservoir for NOx	229	(2)
Ozone Air Pollution	231	(14)
Air Pollution and Ozone	231	(2)
Ozone Formation and Control Strategies	233	(7)
Ozone Production Efficiency	240	(5)
Further Reading	242	(1)
Problems	242	(1)
NOx- and Hydrocarbon-Limited Regimes for Ozone Production	242	(1)
Ozone Titration in a Fresh Plume	243	(2)
Acid Rain	245	(12)
Chemical Composition of Precipitation	245	(4)
Natural Precipitation	245	(1)
Precipitation over North America	246	(3)
Sources of Acids: Sulfur Chemistry	249	(1)
Effects of Acid Rain	250	(2)
Emission Trends	252	(5)
Problems	253	(1)
What Goes Up Must Come Down	253	(1)
The True Acidity of Rain	253	(1)
Aqueous-Phase Oxidation of SO2 by Ozone	253	(1)
The Acid Fog Problem	254	(1)
Acid Rain: The Preindustrial Atmosphere	255	(2)
Numerical Solutions to Problems	257	(2)
Appendix. Physical Data and Units	259	(2)
Index	261