9780231124409

Geochemistry

by
  • ISBN13:

    9780231124409

  • ISBN10:

    0231124406

  • Edition: 2nd
  • Format: Hardcover
  • Copyright: 2003-11-01
  • Publisher: Columbia Univ Pr

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Summary

Written expressly for undergraduate and graduate geologists, this book focuses on how geochemical principles can be used to solve practical problems. The attention to problem-solving reflects the authors'belief that showing how theory is useful in solving real-life problems is vital for learning. The book gives students a thorough grasp of the basic principles of the subject, balancing the traditional equilibrium perspective and the kinetic viewpoint. The first half of the book considers processes in which temperature and pressure are nearly constant. After introductions to the laws of thermodynamics, to fundamental equations for flow and diffusion, and to solution chemistry, these principles are used to investigate diagenesis, weathering, and natural waters. The second half of the book applies thermodynamics and kinetics to systems undergoing changes in temperature and pressure during magmatism and metamorphism. This revised edition incorporates new geochemical discoveries as examples of processes and pathways, with new chapters on mineral structure and bonding and on organic matter and biomarkers. Each chapter has worked problems, and the authors assume that the student has had a year of college-level chemistry and a year of calculus. Praise for the first edition "A truly modern geochemistry book.... Very well written and quite enjoyable to read.... An excellent basic text for graduate level instruction in geochemistry." -- Journal of Geological Education "An up-to-date, broadly conceived introduction to geochemistry.... Given the recent flowering of geochemistry as an interdisciplinary science, and given the extent to which it now draws upon the fundamentals of thermodynamics and kinetics to understand earth and planetary processes, this timely and rigorous [book] is welcome indeed." -- Geochimica et Cosmochimica Acta

Author Biography

Harry Y. McSween, Jr.: University of Tennessee, Knoxville Steven M. Richardson: Winona State University Maria E. Uhle: University of Tennessee, Knoxville

Table of Contents

Preface to the Second Edition xv
ONE INTRODUCING CONCEPTS IN GEOCHEMICAL SYSTEMS 1(11)
Overview
1(1)
What Is Geochemistry?
1(3)
Historical Overview
1(2)
Beginning Your Study of Geochemistry
3(1)
Geochemical Variables
4(1)
Geochemical Systems
4(1)
Thermodynamics and Kinetics
5(1)
An Example: Comparing Thermodynamic and Kinetic Approaches
5(4)
Notes on Problem Solving
9(1)
Suggested Readings
10(1)
Problems
10(2)
TWO HOW ELEMENTS BEHAVE 12(23)
Overview
12(1)
Elements, Atoms, and the Structure of Matter
12(12)
Elements and the Periodic Table
12(1)
The Atomic Nucleus and Isotopes
13(5)
The Basis for Chemical Bonds: The Electron Cloud
18(2)
Size, Charge, and Stability
20(2)
Elemental Associations
22(2)
Bonding
24(8)
Perspectives on Bonding
24(2)
Structural Implications of Bonding
26(6)
Retrospective on Bonding
32(1)
Summary
32(1)
Suggested Readings
32(2)
Problems
34(1)
THREE A FIRST LOOK AT THERMODYNAMIC EQUILIBRIUM 35(21)
Overview
35(1)
Temperature and Equations of State
35(2)
Work
37(1)
The First Law of Thermodynamics
37(2)
Entropy and the Second Law of Thermodynamics
39(3)
Entropy and Disorder
42(1)
Reprise: The Internal Energy Function Made Useful
42(2)
Auxiliary Functions of State
44(3)
Enthalpy
44(1)
The Helmholtz Function
45(1)
Gibbs Free Energy
45(2)
Cleaning Up the Act: Conventions for E, H, F, G, and S
47(1)
Composition as a Variable
48(4)
Components
48(3)
Changes in E, H, F, and G Due to Composition
51(1)
Conditions for Heterogeneous Equilibrium
52(1)
The Gibbs-Duhem Equation
53(1)
Summary
53(1)
Suggested Readings
54(1)
Problems
55(1)
FOUR HOW TO HANDLE SOLUTIONS 56(23)
Overview
56(1)
What Is a Solution?
56(6)
Crystalline Solid Solutions
57(3)
Amorphous Solid Solutions
60(1)
Melt Solutions
60(2)
Electrolyte Solutions
62(1)
Gas Mixtures
62(1)
Solutions That Behave Ideally
62(4)
Solutions That Behave Nonideally
66(2)
Activity in Electrolyte Solutions
68(3)
The Mean Salt Method
69(1)
The Debye-Hückel Method
69(2)
Solubility
71(5)
The Ionic Strength Effect
74(1)
The Common Ion Effect
74(1)
Complex Species
75(1)
Summary
76(1)
Suggested Readings
76(1)
Problems
77(2)
FIVE DIAGENESIS: A STUDY IN KINETICS 79(15)
Overview
79(1)
What Is Diagenesis?
79(1)
Kinetic Factors in Diagenesis
80(7)
Diffusion
80(5)
Advection
85(2)
Kinetics of Mineral Dissolution and Precipitation
87(5)
The Diagenetic Equation
92(1)
Summary
92(1)
Suggested Readings
92(1)
Problems
93(1)
SIX ORGANIC MATTER AND BIOMARKERS: A DIFFERENT PERSPECTIVE 94(17)
Overview
94(1)
Organic Matter in the Global Carbon Cycle
94(2)
Organic Matter Production and Cycling in the Oceans
96(1)
Fate of Primary Production: Degradation and Diagenesis
96(2)
Factors Controlling Accumulation and Preservation
98(5)
Preservation by Sorption
98(1)
Degradation in Oxic Environments
99(1)
Diagenetic Alteration
99(4)
Chemical Composition of Biologic Precursors
103(2)
Carbohydrates
103(1)
Proteins
103(1)
Lipids
104(1)
Lignin
105(1)
Biomarkers
105(1)
Application of Biomarkers to Paleoenvironmental Reconstructions
106(2)
Alkenone Temperature Records
106(1)
Amino Acid Racemization
107(1)
Summary
108(1)
Suggested Readings
109(1)
Problems
110(1)
SEVEN CHEMICAL WEATHERING: DISSOLUTION AND REDOX PROCESSES 111(26)
Overview
111(1)
Fundamental Solubility Equilibria
111(8)
Silica Solubility
111(1)
Solubility of Magnesias Silicates
112(2)
Solubility of Gibbsite
114(1)
Solubility of Aluminosilicate Minerals
115(4)
Rivers as Weathering Indicators
119(2)
Agents of Weathering
121(3)
Carbon Dioxide
121(1)
Organic Acids
122(2)
Oxidation-Reduction Processes
124(9)
Thermodynamic Conventions for Redox Systems
124(3)
Eh-pH Diagrams
127(2)
Redox Systems Containing Carbon Dioxide
129(2)
Activity-Activity Relationships: The Broader View
131(2)
Summary
133(1)
Suggested Readings
134(2)
Problems
136(1)
EIGHT THE OCEANS AND ATMOSPHERE AS A GEOCHEMICAL SYSTEM 137(32)
Overview
137(1)
Composition of the Oceans
137(4)
A Classification of Dissolved Constituents
137(2)
Chemical Variations with Depth
139(2)
Composition of the Atmosphere
141(2)
Carbonate and the Great Marine Balancing Act
143(9)
Some First Principles
143(5)
Calcium Carbonate Solubility
148(3)
Chemical Modeling of Seawater: A Summary
151(1)
Global Mass Balance and Steady State in the Oceans
152(7)
Examining the Steady State
152(2)
How Does the Steady State Evolve?
154(1)
Box Models
154(4)
Continuum Models
158(1)
A Summary of Ocean-Atmosphere Models
158(1)
Gradual Change: The History of Seawater and Air
159(7)
Early Outgassing and the Primitive Atmosphere
159(5)
The Rise of Oxygen
164(2)
Summary
166(1)
Suggested Readings
166(2)
Problems
168(1)
NINE TEMPERATURE AND PRESSURE CHANGES: THERMODYNAMICS AGAIN 169(19)
Overview
169(1)
What Does Equilibrium Really Mean?
169(1)
Determining When a System Is in Equilibrium
169(3)
The Phase Rule
170(1)
Open versus Closed Systems
171(1)
Changing Temperature and Pressure
172(4)
Temperature Changes and Heat Capacity
172(2)
Pressure Changes and Compressibility
174(2)
Temperature and Pressure Changes Combined
176(1)
A Graphical Look at Changing Conditions: The Clapeyron Equation
176(1)
Reactions Involving Fluids
177(2)
Raoult's and Henry's Laws: Mixing of Several Components
179(1)
Standard States and Activity Coefficients
179(2)
Solution Models: Activities of Complex Mixtures
181(1)
Thermobarometry: Applying What We Have Learned
182(2)
Summary
184(1)
Suggested Readings
185(1)
Problems
186(2)
TEN PICTURING EQUILIBRIA: PHASE DIAGRAMS 188(18)
Overview
188(1)
GX2 Diagrams
188(2)
Derivation of T-X2 and P-X2 Diagrams
190(1)
T-X2 Diagrams for Real Geochemical Systems
191(5)
Simple Crystallization in a Binary System: CaMgSi2O6-CaAl2Si2O8
192(1)
Formation of a Chemical Compound in a Binary System: KAlSi2O6-SiO2
193(1)
Solid Solution in a Binary System: NaAlSi3O8-CaAl2Si2O8
194(1)
Unmixing in a Binary System: NaAlSi3O8-KAlSi3O8
195(1)
Thermodynamic Calculation of Phase Diagrams
196(1)
Binary Phase Diagrams Involving Fluids
197(2)
P-T Diagrams
199(2)
Systems with Three Components
201(1)
Summary
201(3)
Suggested Readings
204(1)
Problems
205(1)
ELEVEN KINETICS AND CRYSTALLIZATION 206(21)
Overview
206(1)
Effect of Temperature on Kinetic Processes
206(2)
Diffusion
208(2)
Nucleation
210(6)
Nucleation in Melts
211(3)
Nucleation in Solids
214(2)
Growth
216(3)
Interface-Controlled Growth
216(2)
Diffusion-Controlled Growth
218(1)
Some Applications of Kinetics
219(4)
Aragonite less than=> Calcite: Growth as the Rate-Limiting Step 220
Iron Meteorites: Diffusion as the Rate-Limiting Step
220(2)
Bypassing Theory: Controlled Cooling Rate Experiments
222(1)
Bypassing Theory Again: Crystal Size Distributions
223(1)
Summary
223(1)
Suggested Readings
224(2)
Problems
226(1)
TWELVE THE SOLID EARTH AS A GEOCHEMICAL SYSTEM 227(36)
Overview
227(1)
Reservoirs in the Solid Earth
227(6)
Composition of the Crust
227(2)
Composition of the Mantle
229(2)
Composition of the Core
231(2)
Fluxes in the Solid Earth
233(4)
Cycling between Crust and Mantle
233(3)
Heat Exchange between Mantle and Core
236(1)
Fluids and the Irreversible Formation of Continental Crust
236(1)
Melting in the Mantle
237(6)
Thermodynamic Effects of Melting
238(1)
Types of Melting Behavior
238(2)
Causes of Melting
240(3)
Differentiation in Melt-Crystal Systems
243(5)
Fractional Crystallization
243(3)
Chemical Variation Diagrams
246(1)
Liquid Immiscibility
247(1)
The Behavior of Trace Elements
248(7)
Trace Element Fractionation during Melting and Crystallization
248(3)
Compatible and Incompatible Elements
251(4)
Volatile Elements
255(4)
Crust and Mantle Fluid Compositions
255(3)
Mantle and Crust Reservoirs for Fluids
258(1)
Cycling of Fluids between Crust and Mantle
259(1)
Summary
259(1)
Suggested Readings
260(2)
Problems
262(1)
THIRTEEN USING STABLE ISOTOPES 263(23)
Overview
263(1)
Historical Perspective
263(1)
What Makes Stable Isotopes Useful?
264(2)
Mass Fractionation and Bond Strength
266(1)
Geologic Interpretations Based on Isotopic Fractionation
266(15)
Thermometry
266(4)
Isotopic Evolution of the Oceans
270(1)
Fractionation in the Hydrologic Cycle
271(4)
Fractionation in Geothermal and Hydrothermal Systems
275(3)
Fractionation in Sedimentary Basins
278(1)
Fractionation among Biogenic Compounds
278(1)
Isotopic Fractionation around Marine Oil and Gas Seeps
279(2)
Summary
281(1)
Suggested Readings
282(2)
Problems
284(2)
FOURTEEN USING RADIOACTIVE ISOTOPES 286(27)
Overview
286(1)
Principles of Radioactivity
286(4)
Nuclide Stability
286(1)
Decay Mechanisms
287(1)
Rate of Radioactive Decay
288(2)
Decay Series and Secular Equilibrium
290(1)
Geochronology
290(9)
Potassium-Argon System
291(1)
Rubidium-Strontium System
292(2)
Samarium-Neodymium System
294(1)
Uranium-Thorium-Lead System
294(3)
Extinct Radionuclides
297(1)
Fission Tracks
298(1)
Geochemical Applications of Induced Radioactivity
299(3)
Neutron Activation Analysis
299(1)
40Argon-39Argon Geochronology
300(1)
Cosmic-Ray Exposure
301(1)
Radionuclides as Tracers of Geochemical Processes
302(8)
Heterogeneity of the Earth's Mantle
302(2)
Magmatic Assimilation
304(2)
Subduction of Sediments
306(1)
Isotopic Composition of the Oceans
307(1)
Degassing of the Earth's Interior to Form the Atmosphere
308(2)
Summary
310(1)
Suggested Readings
310(2)
Problems
312(1)
FIFTEEN STRETCHING OUR HORIZONS: COSMOCHEMISTRY 313(30)
Overview
313(1)
Why Study Cosmochemistry?
313(1)
Origin and Abundance of the Elements
314(4)
Nucleosynthesis in Stars
314(2)
Cosmic Abundance Patterns
316(2)
Chondrites as Sources of Cosmochemical Data
318(2)
Cosmochemical Behavior of Elements
320(3)
Controls on Cosmochemical Behavior
320(1)
Chemical Fractionations Observed in Chondrites
321(2)
Condensation of the Elements
323(4)
How Equilibrium Condensation Works
323(3)
The Condensation Sequence
326(1)
Evidence for Condensation in Chondrites
327(1)
Infusion of Matter from Outside the Solar System
327(3)
Isotopic Diversity in Meteorites
327(2)
A Supernova Trigger?
329(1)
The Discovery of Stardust in Chondrites
330(1)
The Most Volatile Materials: Organic Compounds and Ices
330(2)
Extraterrestrial Organic Compounds
330(1)
Ices-The Only Thing Left
331(1)
A Time Scale for Creation
332(1)
Estimating the Bulk Compositions of Planets
333(7)
Some Constraints on Cosmochemical Models
333(2)
The Equilibrium Condensation Model
335(1)
The Heterogeneous Accretion Model
336(1)
The Chondrite Mixing Model
336(3)
Planetary Models: Cores and Mantles
339(1)
Summary
340(1)
Suggested Readings
341(1)
Problems
342(1)
Appendix A: Mathematical Methods 343(5)
Appendix B: Finding and Evaluating Geochemical Data 348(3)
Appendix C: Numerical Values of Geochemical Interest 351(2)
Glossary 353(6)
Index 359

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