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ISBN 10: 1405121424
ISBN 13: 978-1405121422
Author: Kula Misra
INTRODUCTION TO Geochemistry
This book is intended to serve as a text for an introductory course in geochemistry for undergraduate/ graduate students with at least an elementary-level background in earth sciences, chemistry, and mathematics. The text, containing 83 tables and 181 figures, covers a wide variety of topics – ranging from atomic structure to chemical and isotopic equilibria to modern biogeochemical cycles – which are divided into four interrelated parts: Crystal Chemistry; Chemical Reactions (and biochemical reactions involving bacteria); Isotope Geochemistry (radiogenic and stable isotopes); and The Earth Supersystem, which includes discussions pertinent to the evolution of the solid Earth, the atmosphere, and the hydrosphere.
In keeping with the modern trend in the field of geochemistry, the book emphasizes computational techniques by developing appropriate mathematical relations, solving a variety of problems to illustrate application of the mathematical relations, and leaving a set of questions at the end of each chapter to be solved by students. However, so as not to interrupt the flow of the text, involved chemical concepts and mathematical derivations are separated in the form of boxes. Supplementary materials are packaged into ten appendixes that include a standard-state (298.15 K, 1 bar) thermodynamic data table and a listing of answers to selected chapter-end questions.
Introduction to Geochemistry Principles and Applications 1st Table of contents:
1 Introduction
1.1 Units of measurement
1.1.1 The SI system of units
1.1.2 Concentration units for solutions
1.2 The Geologic Time Scale
1.3 Recapitulation
1.4 Questions
PART I CRYSTAL CHEMISTRY
2 Atomic Structure
2.1 Historical development
2.1.1 Discovery of the electron
2.1.2 The Rutherford–Bohr atom
2.1.3 Wave mechanics
2.2 The working model
2.2.1 Quantum numbers
2.2.2 Energy levels of the atomic orbitals
2.3 The ground state electron configuration of elements
2.3.1 Filling atomic orbitals with electrons: the Aufbau principle
2.3.2 The Periodic Table
2.3.3 Transition elements
2.4 Chemical behavior of elements
2.4.1 Ionization potential and electron affinity
2.4.2 Classification of elements
2.5 Summary
2.6 Recapitulation
2.7 Questions
3 Chemical Bonding
3.1 Ionic bonding
3.1.1 Ionic radii
3.1.2 Coordination number and radius ratio
3.1.3 Lattice energy of ideal ionic crystals
3.2 Crystal structures of silicate minerals
3.3 Ionic substitution in crystals
3.3.1 Goldschmidt’s rules
3.3.2 Ringwood’s rule
3.4 Crystal-field theory
3.4.1 Crystal-field stabilization energy
3.4.2 Nickel enrichment in early-formed magmatic olivine
3.4.3 Colors of transition-metal complexes
3.5 Isomorphism, polymorphism, and solid solutions
3.5.1 Isomorphism
3.5.2 Polymorphism
3.5.3 Solid solutions
3.6 Covalent bonding
3.6.1 Valence bond theory versus molecular orbital theory
3.6.2 Covalent radii
3.6.3 Hybridization of atomic orbitals
3.6.4 Sigma (σ), pi (π), and delta (δ) molecular orbitals
3.6.5 The degree of ionic character of a chemical bond: Electronegativity
3.7 Metallic bonds
3.8 Van der Waals bonds
3.9 Hydrogen bond
3.10 Comparison of bond types
3.11 Goldschmidt’s classification of elements
3.12 Summary
3.13 Recapitulation
3.14 Questions
PART II CHEMICAL REACTIONS
4 Basic Thermodynamic Concepts
4.1 Chemical equilibrium
4.1.1 Law of Mass Action – equilibrium constant (Keq )
4.1.2 Le Chatelier’s principle
4.2 Thermodynamic systems
4.2.1 Attributes of a thermodynamic system
4.2.2 State functions
4.2.3 The Gibbs phase rule
4.2.4 Equations of state
4.2.5 Kinds of thermodynamic systems and processes
4.3 Laws of thermodynamics
4.3.1 The first law: conservation of energy
4.3.2 The second law: the concept and definition of entropy (S)
4.3.3 The fundamental equation: the first and second laws combined
4.3.4 The third law: the entropy scale
4.4 Auxiliary thermodynamic functions
4.4.1 Enthalpy (H)
4.4.2 Heat capacity (Cp, Cv )
4.4.3 Gibbs free energy (G)
4.4.4 Computation of the molar free energy of a substance at T and P (G PT)
4.5 Free energy change of a reaction at T and P (ΔG PR,T)
4.5.1 Computation of ΔG 1R,T
4.5.2 Evaluation of the volume integral
4.5.3 General equation for, ΔG PR, T
4.6 Conditions for thermodynamic equilibrium and spontaneity in a closed system
4.7 Metastability
4.8 Computation of simple P–T phase diagrams
4.8.1 Procedure
4.8.2 The Clapeyron equation
4.9 Thermodynamic data tables
4.10 Summary
4.11 Recapitulation
4.12 Questions
5 Thermodynamics of Solutions
5.1 Chemical potential
5.1.1 Partial molar properties
5.1.2 Definition of chemical potential (μ)
5.1.3 Expression for free energy in terms of chemical potentials
5.1.4 Criteria for equilibrium and spontaneous change among phases of variable composition
5.1.5 Criteria for equilibrium and spontaneous change for a reaction
5.1.6 The Gibbs–Duhem equation
5.2 Variation of chemical potential (μiα) with temperature, pressure, and composition
5.2.1 Temperature dependence of chemical potential
5.2.2 Pressure dependence of chemical potential
5.2.3 Dependence of chemical potential on composition: the concept of activity
5.3 Relationship between Gibbs free energy change and equilibrium constant for a reaction
5.4 Gases
5.4.1 Pure ideal gases and ideal gas mixtures
5.4.2 Pure nonideal gases: fugacity and fugacity coefficient
5.4.3 Nonideal gas mixtures
5.5 Ideal solutions involving condensed phases
5.5.1 Mixing properties of ideal solutions
5.5.2 Raoult’s Law
5.5.3 Henry’s Law
5.5.4 The Lewis Fugacity Rule
5.5.5 Activities of constituents in ideal solutions
5.6 Nonideal solutions involving condensed phases
5.7 Excess functions
5.8 Ideal crystalline solutions
5.8.1 Application of the mixing-on-sites model to some silicate minerals
5.8.2 Application of the local charge balance model to some silicate minerals
5.9 Nonideal crystalline solutions
5.9.1 General expressions
5.9.2 Regular solution
5.10 Summary
5.11 Recapitulation
5.12 Questions
6 Geothermometry and Geobarometry
6.1 Tools for geothermobarometry
6.2 Selection of reactions for thermobarometry
6.3 Dependence of equilibrium constant on temperature and pressure
6.4 Univariant reactions and displaced equilibria
6.4.1 Al2SiO5 polymorphs
6.4.2 Garnet–rutile–Al2SiO5 polymorph–ilmenite–quartz (GRAIL) barometry
6.4.3 Garnet–plagioclase–pyroxene–quartz (GAPES and GADS) barometry
6.5 Exchange reactions
6.5.1 Garnet–clinopyroxene thermometry
6.5.2 Garnet–biotite (GABI) thermometry
6.5.3 Magnetite–ilmenite thermometry and oxygen barometry
6.6 Solvus equilibria
6.7 Uncertainties in thermobarometric estimates
6.8 Fluid inclusion thermobarometry
6.9 Summary
6.10 Recapitulation
6.11 Questions
7 Reactions Involving Aqueous Solutions
7.1 Water as a solvent
7.2 Activity–concentration relationships in aqueous electrolyte solutions
7.2.1 Activity coefficient of a solute
7.2.2 Standard state of an aqueous solute
7.2.3 Estimation of activity coefficients of solutes
7.3 Dissociation of acids and bases
7.4 Solubility of salts
7.4.1 The concept of solubility
7.4.2 Solubility product
7.4.3 Saturation index
7.4.4 Ion pairs
7.4.5 Aqueous complexes of ore metals
7.5 Dissociation of H2CO3 acid – the carbonic acid system
7.5.1 Open system
7.5.2 Closed system
7.6 Acidity and alkalinity of a solution
7.7 pH buffers
7.8 Dissolution and precipitation of calcium carbonate
7.8.1 Solubility of calcite in pure water
7.8.2 Carbonate equilibria in the CaCO3–CO2–H2O system
7.8.3 Factors affecting calcite solubility
7.8.4 Abiological precipitation of calcium carbonate in the oceans
7.8.5 Biological precipitation of calcium carbonate in the oceans
7.8.6 Carbonate compensation depth
7.9 Chemical weathering of silicate minerals
7.9.1 Mechanisms of chemical weathering
7.9.2 Solubility of Silica
7.9.3 Equilibria in the system K2O–Al2O3–SiO2–H2O
7.10 Summary
7.11 Recapitulation
7.12 Questions
8 Oxidation–Reduction Reactions
8.1 Definitions
8.2 Voltaic cells
8.2.1 Zinc–hydrogen cell
8.2.2 Standard hydrogen electrode and standard electrode potential
8.2.3 Zinc–copper cell
8.2.4 Electromotive series
8.2.5 Hydrogen–oxygen fuel cell
8.3 Relationship between free energy change (ΔGr) and electrode potential (E) – the Nernst equati
8.4 Oxidation potential (Eh)
8.5 The variable pe
8.6 Eh–pH stability diagrams
8.6.1 Stability limits of surface water
8.6.2 Procedure for construction of Eh–pH diagrams
8.6.3 Geochemical classification of sedimentary redox environments
8.7 Role of microorganisms in oxidation–reduction reactions
8.7.1 Geochemically important microorganisms
8.7.2 Examples of oxidation–reduction reactions mediated by microorganism
8.8 Oxidation of sulfide minerals
8.8.1 Mediation by microorganisms
8.8.2 Oxidation of pyrite
8.8.3 Acid mine drainage
8.8.4 Bioleaching
8.8.5 Biooxidation
8.8.6 Biofiltration
8.9 Oxygen fugacity
8.9.1 Oxygen buffers
8.9.2 Oxygen fugacity–sulfur fugacity diagrams
8.10 Summary
8.11 Recapitulation
8.12 Questions
9 Kinetics of Chemical Reactions
9.1 Rates of chemical reactions (R): basic principles
9.1.1 Elementary and overall reactions
9.1.2 Rate–law expression
9.1.3 Integrated rate equations for elementary reactions
9.1.4 Principle of detailed balancing
9.1.5 Sequential elementary reactions
9.1.6 Parallel elementary reactions
9.2 Temperature dependence of rate constants
9.2.1 The Arrhenius equation – activation energy
9.2.2 Transition states
9.3 Relationship between rate and free energy change of an elementary reaction (ΔGr)
9.4 Catalysts
9.4.1 Homogeneous catalysis
9.4.2 Heterogeneous catalysis
9.5 Mass transfer in aqueous solutions
9.5.1 Advection–diffusion equation
9.5.2 The temperature dependence of diffusion coefficient
9.6 Kinetics of geochemical processes – some examples
9.6.1 Diffusion-controlled and surface-controlled reaction mechanisms
9.6.2 Dissolution and precipitation of calcite in aqueous solutions
9.6.3 Dissolution of silicate minerals
9.7 Summary
9.8 Recapitulation
9.9 Questions
PART III ISOTOPE GEOCHEMISTRY
10 Radiogenic Isotopes
10.1 Radioactive decay
10.1.1 Abundance and stability of nuclides
10.1.2 Mechanisms of radioactive decay
10.2 Principles of radiometric geochronology
10.2.1 Decay of a parent radionuclide to a stable daughter
10.2.2 Basic equation for radiometric age determination
10.2.3 Decay series
10.3 Selected methods of geochronology
10.3.1 Rubidium–strontium system
10.3.2 Samarium–neodymium system
10.3.3 Uranium–thorium–lead system
10.3.4 Rhenium–osmium system
10.3.5 Potassium (40K)–argon (40Ar) method
10.3.6 Argon (40Ar)–argon (39Ar) method
10.3.7 Carbon-14 method
10.4 Isotope ratios as petrogenetic indicators
10.4.1 Strontium isotope ratios
10.4.2 Neodymium isotope ratios
10.4.3 Combination of strontium and neodymium isotope ratios
10.4.4 Osmium isotope ratios
10.5 Summary
10.6 Recapitulation
10.7 Questions
11 Stable Isotopes
11.1 Isotopic fractionation
11.1.1 Causes of isotopic fractionation
11.1.2 Mechanisms of isotopic fractionation
11.1.3 Fractionation factor
11.1.4 The delta (δ) notation
11.1.5 Calculation of the fractionation factor from δ values
11.2 Types of isotopic fractionation
11.2.1 Equilibrium isotope effects
11.2.2 Kinetic isotope effects
11.3 Stable isotope geothermometry
11.3.1 Oxygen isotope geothermometry
11.3.2 Sulfur isotope geothermometry
11.4 Evaporation and condensation processes
11.4.1 Evaporation of ocean water
11.4.2 Condensation of water vapor
11.4.3 Meteoric water line
11.5 Source(s) of water in hydrothermal fluids
11.6 Estimation of water: rock ratios from oxygen isotope ratios
11.7 Sulfur isotopes in sedimentary systems
11.7.1 Bacterial sulfate reduction (BSR)
11.7.2 Thermochemical sulfate reduction (TSR)
11.7.3 Sulfur isotopic composition of seawater sulfate through geologic time
11.7.4 Open versus closed sedimentary systems with respect to sulfate and sulfide
11.7.5 Sulfur isotope ratios of sulfides in marine sediments
11.8 Mass-independent fractionation (MIF) of sulfur isotopes
11.9 Iron isotopes: geochemical applications
11.9.1 Fractionation of iron isotopes
11.9.2 Abiotic versus biotic precipitation of Fe minerals in banded iron formations
11.10 Summary
11.11 Recapitulation
11.12 Questions
PART IV THE EARTH SUPERSYSTEM
12 The Core–Mantle–Crust System
12.1 Cosmic perspective
12.1.1 The Big Bang: the beginning of the universe
12.1.2 Nucleosynthesis: creation of the elements
12.1.3 The Solar System
12.1.4 Meteorites
12.1.5 Solar System abundances of the elements
12.1.6 Origin of the Solar System: the planetesimal model
12.2 Evolution of the Earth
12.2.1 The internal structure of the Earth
12.2.2 Bulk Earth composition
12.2.3 The primary geochemical differentiation of the proto-Earth: formation of the Earth’s core a
12.2.4 Formation and growth of the Earth’s crust
12.3 Generation and crystallization of magmas
12.3.1 Geochemical characteristics of primary magmas
12.3.2 Behavior of trace elements during partial melting of source rocks
12.3.3 Behavior of trace elements during magmatic crystallization
12.3.4 Chemical variation diagrams
12.3.5 Rare earth elements
12.4 Geochemical discrimination of paleotectonic settings of mafic volcanic suites
12.4.1 Tectonomagmatic discrimination diagrams
12.4.2 Spider diagrams
12.5 Summary
12.6 Recapitulation
12.7 Questions
13 The Crust–Hydrosphere–Atmosphere System
13.1 The present atmosphere
13.1.1 Temperature and pressure distribution in the atmosphere
13.1.2 Photochemical reactions in the atmosphere
13.1.3 The Ozone layer in the stratosphere
13.1.4 Composition of the atmosphere
13.2 Evolution of the Earth’s atmosphere over geologic time
13.2.1 Origin of the atmosphere
13.2.2 A warm Archean Earth: the roles of carbon dioxide and methane
13.2.3 Oxygenation of the atmosphere
13.2.4 The Great Oxidation Event (GOE)
13.2.5 A model for the evolution of the atmosphere
13.2.6 The Phanerozoic atmosphere
13.3 Air pollution: processes and consequences
13.3.1 Depletion of stratospheric ozone – the “ozone hole”
13.3.2 Smogs
13.3.3 Acid deposition
13.3.4 Greenhouse gases and global warming
13.4 The hydrosphere
13.4.1 Composition of modern seawater
13.4.2 Mass balance of dissolved constituents in seawater
13.5 Evolution of the oceans over geologic time
13.5.1 Origin of the oceans
13.5.2 Oxidation state of the oceans
13.5.3 Composition of the oceans
13.6 Geosphere–hydrosphere–atmosphere–biosphere interaction: global biogeochemical cycles
13.6.1 The carbon cycle
13.6.2 The oxygen cycle
13.6.3 The nitrogen cycle
13.6.4 The sulfur cycle
13.6.5 The phosphorus cycle
13.7 Summary
13.8 Recapitulation
13.9 Questions
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