Handbook of Geochemistry

Geochemistry is concerned with the laws governing the distribution of the chemical elements and their isotopes throughout the Earth. As a concept it has been recognized for 130 years but it has grown into a separate Earth science during this century. Geochemistry has mutual links with many neighbouring disciplines. Its present field of activity is determined by many problems of broad interest and by the availability of methods. Several exterior influences have recently developed. Thus, nuclear physics and its specific measuring techniques made isotope geochem­ istry possible, while space research has stimulated the development of cosmochem­ istry. Except a few "standard" materials as Gland W 1 there is no other rock on earth whose composition is as well known as that of meteorites colliding with our planet on their cosmic course. Biochemistry is linked with the rapidly developing new branch of organic geochemistry. Our discipline has moved forward in step with the advancement of analytical chemistry. When optical and X-ray spectrochemical analysis came into use and with the discovery of natural and artificial radio-activity, many new elements were identified. With the development of spectrophotometers, radiation counters and nuclear sources over the last 20 years, a flood of analytical data on geological sub­ jects has been released, and we ought to make use of it.

1 The Discovery of the Chemical Elements. The History of Geochemistry. Definitions of Geochemistry.- I. The Discovery of the Chemical Elements.- II. The History of Geochemistry.- III. Definitions of Geochemistry.- References.- 2 Crystal Chemistry.- I. The Geometrical Framework of Crystal Structures.- a) The Lattice Constants of the Unit Cell and the Space Group.- b) The Content of the Unit Cell.- c) The Positions of the Atoms and their Parameters.- II. Some Geometrical Problems of Crystal Structures Not Related to Space Group Symmetry.- III. The Effective Radii of Atoms and Ions.- IV. The Chemical Bonds in Crystals.- a) Covalent Bond.- b) Metallic Bond.- c) Ionic Bond.- d) Van der Waals’ Bond.- e) Crystal Field- and Ligand Field-Theory.- f) Semiconductors.- g) Hydrogen Bond.- V. The Theoretical Treatment of Ionic Crystals.- VI. Polymorphism.- VII. Isomorphism.- VIII. Crystal Chemistry of Real Crystals.- a) Effects of the Heat Content of Crystals.- b) Solid Solutions (Mixed Crystals).- IX. Diffusion and Reactions in the Solid State.- References.- 3 Thermodynamics Used in Geochemistry.- I. Perfect Gases and Perfect Solutions.- II. The Equilibrium Constant.- III. Fugacity and Activity.- IV. The Laws of Thermodynamics.- a) Internal Energy.- b) The First Law.- c) Enthalpy.- d) Heat Capacity.- e) Entropy.- f) The Second Law.- g) The Third Law.- V. Free Energy.- VI. Electrode Potentials.- VII. Solutions.- VIII. The Phase Rule.- Symbols.- References.- 4 Meteorite Composition.- I. Introduction.- II. Meteorite Classification.- a) Classification of Stone Meteorites.- 1. Classification of Achondrites.- 2. Classification of Chondrites.- b) Classification of Stony-Iron Meteorites.- c) Classification of Iron Meteorites.- III. Chemical Composition of Meteorites.- a) Chemical Composition of Stone Meteorites.- b) Chemical Composition of Stony-Iron Meteorites.- c) Chemical Composition of Iron Meteorites.- IV. Mineralogical Composition of Meteorites.- References.- 5 Cosmic Abundances.- I. Introduction.- II. Cosmic Abundances.- III. The Bulk Composition of the Earth.- IV. Other Applications of Cosmic Abundances.- References.- 6 Geophysical Aspects of Structure and Composition of the Earth and the Earth Crust.- Principal Subdivision of the Earth’s Interior.- I. Inferences from Earthquakes and Earth Tides.- a) Principles of Scismic Wave Propagation.- b) The Jeffreys-Bullen Curves.- c) Interpretation of Travel-Time Curves.- d) Scismic Velocities in the Crust.- e) Scismic Velocities in Mantle and Core.- f) Travel Time and Amplitude Anomalies.- g) Inferences from free Oscillation and Earth Tides.- II. Density, Elasticity, Viscosity.- a) Theoretical Density-Scismic Velocity Relations.- b) Density Models for Earth’s Interior.- c) Gravity and Pressure within the Earth.- d) Elastic Constants.- e) Zero-Pressure Properties of the Mantle.- f) Viscous Properties.- g) Strain Energy Dissipation.- III. Gravity and Earth’s Figure.- a) Dimensions and Flattening of the Earth.- b) Low-Order Harmonics of the Geoid.- c) Gravity Anomalies.- d) Isostasy.- IV. Geomagnetism.- a) Basic Concepts.- b) The Dipole Field.- c) Non-Dipole Field and Secular Variations.- d) Magnetic Anomalies.- e) Rock Magnetism.- f) Paleomagnetism.- g) Electromagnetic Induction within the Earth.- h) Induction Anomalies.- V. The Thermal State.- a) Terrestrial Heat Flow and Volcanism.- b) Non-Radiogenic Heat.- c) Radiogenic Heat.- d) Heat Transfer.- e) Basic Equation of Heat Diffusion.- f) Thermal Balance and Temperature Distribution.- g) Melting Curves.- h) Thermal Expansion and Specific Heat.- i) Thermal Convection.- VI. Conclusions.- Symbols.- References.- 7 Composition and Abundance of Common Igeneous Rocks.- I. Nomenclature of Igneous (Magmatic) Rocks.- II. Chemical Composition of Common Igneous Rocks.- III. Rock Nomenclature and Current Trends in Igneous Petrology.- IV. Abundance of Common Intrusive Rocks.- V. Abundance of Common Volcanic Rocks.- VI. Average Composition of the Upper Continental Earth’s Crust.- References.- 8 Composition and Abundance of Common Sedimentary Rocks.- I. Nomenclature of Sedimentary Rocks.- a) Clastic Sediments and Sedimentary Rocks.- 1. Pyroclastic Deposits ― Volcanic Tuffs.- b) Chemical and Biogenic Sediments and Sedimentary Rocks.- c) Clastic Sediments and Sedimentary Rocks with Specific Chemical Constituents or Organic Residues.- II. Average Composition of Common Sedimentary Rocks.- III. Rock Nomenclature and Current Trends in Sedimentary Petrology.- IV. Abundance of Common Sediments and Sedimentary Rocks.- References.- 9 Composition and Abundance of Common Metamorphic Rock Types.- I. General Trends in Metamorphism.- II. Isochemical Series of Metamorphism.- a) Retrogressive Metamorphism.- III. Allochemical Series of Metamorphism (Metasomatism).- IV. Contact Metamorphism.- a) Spotted Slates.- b) Spotted Mica-schists.- c) Hornfels.- V. Migmatites, Anatexis, Granitization.- References.- 10 The Oceans, Streams, and Atmosphere.- I. The Oceans.- a) General Features of the Ocean Basin.- b) Salinity and Temperature of Ocean Water.- c) Water Types and Oceanic Mixing.- d) Composition of Sea Water.- e) Distribution of Elements in Sea Water.- II. Streams.- a) Discharge, Dissolved Load and Sediment Load.- b) Composition of Streams.- III. The Atmosphere.- a) The Structure of the Atmosphere.- b) Composition of the Atmosphere.- c) Atmospheric Precipitation.- References.- 11 Evaluation of Data.- I. Analytical Errors and Related Topics in Geochemistry.- a) Precision.- b) Accuracy.- c) Sensitivity.- II. Statistical Procedures.- a) Introduction.- 1. Intention.- 2. General Definitions.- 3. Definitions of Moments.- b) Propagation of Error.- c) Rules for Rounding Sample Statistics.- d) Summary Statistics ― Single Variable.- 1. Central Measures.- 2. Variance, s2 or V.- 3. Moments, Semi-Invariants.- 4. Standardized Variable.- e) Summary Statistics ― Two or More Variables.- 1. Correlation Coefficient, Covariance.- 2. Sample and Dispersion Matrices.- 3. Closed Array Data.- 4. Ratio Correlation.- f) Properties of Some Probability Density Functions.- 1. Normal (Gauss-Laplace) Law.- 2. Lognormal (Galton) Law.- 3. Binomial Law.- 4. Poisson Law.- g) Assumption of Randomness and Normality.- 1. General.- 2. Hypothesis that a Sample has a Normally Distributed Parent Population.- h) Estimation.- 1. Confidence Interval for Mean ?.- 2. Confidence Interval for Sum (or Difference) of Means ?1 and ?2.- 3. Confidence Interval for Variance ?2.- 4. Confidence Interval for Correlation Coefficient r.- 5. Confidence Interval for Mean of Binomial Distribution.- i) Tests of Hypothesis.- 1. General.- 2. Hypothesis that ? is Equal to Some Numerical Value (Population Variance Unknown).- 3. Hypothesis that ?2 is Equal to Some Numerical Value.- 4. Hypothesis that Two Samples have the Same Population Variance.- 5. Hypothesis that Two Samples have the Same Population Mean.- 6. Hypothesis that Several Samples have the Same Population Variance (BAR-LETT’S Test).- 7. Hypothesis that the Population Correlation Coefficient ? is Equal to Some Numerical Value.- 8. Hypothesis that a Sample of Enumeration Data is from a Binomial Population of Probability ?0.- k) Analysis of Variance.- 1. General.- 2. Single Factor with Replication.- 3. Two Factor Crossed with Replication.- 4. Two Factor Nested, with Replication.- l) Linear Regression.- 1. General.- 2. Analysis of Regression (Test of Independence of Two Variables).- 3. Analysis of Regression (Test of Linearity).- III. Interpretation of Chemical Analysis of Silicates.- a) Calculation of Atomic Proportion.- b) Significance of Oxygen.- c) Interpretation of the Analysis of a Complex Silicate.- d) Calculation of the Igneous Norm of a Rock.- e) Metamorphic and Plutonic Norm Calculation.- 1. Introduction.- 2. Minerals of the Mesonorm.- 3. Principles of Calculation.- 4. Calculation Procedure (Mesonorm).- 5. Epinorm.- Appendix 1. Areas of the Normal Curve (from DIXON and MASSEY, 1951).- 2. Values of t (from DIXON and MASSEY, 1951).- 3. Percentiles of the x2 Distribution (from DIXON and MASSEY, 1951).- 4. (a) F Distribution, Upper 5% Points, (b) F Distribution, Upper 1% Points (from DIXON and MASSEY, 1951).- 5. Conversion Tables, Weight Per Cent to Gram-Atoms × 104.- References.- 12 Tables.- 1. Physical Constants.- 2. Periodic System.- 3. Table of Relative Atomic Weights.- 4. Table of Isotopic Abundance and Relative Atomic Weights.- 5. Naturally Occurring Radioactive Elements.- 6. Electronic Configuration of the Elements in Their Normal States.- 7. The Effective Radii of Atoms.- 8. Table of the Effective Radii of Ions.- 9. Ionization Potentials for Elements in the Atomic State.- 10. Electronegativity Values.- 11. Molar Volumes and Densities of Minerals.- 12. The Theoretical Composition of Some Silicate Minerals in Cation Percentage.- 13. The Theoretical Composition of Some Silicate Minerals in Weight Percentage.- 14. The Theoretical Composition of Some Non-silicate Minerals in Weight Percentage.- 15. The Theoretical Composition of Some Ore Minerals in Weight Percentage.- 16. Astronomical Constants.- 17. Solar Dimensions.- 18. Dimensions of the Planets and the Moon.- 19. Earth’s Dimensions.- 20. Earth’s Interior, Masses and Dimensions of the Principle Subdivisions.- 21. The Surface Areas of the Earth.- 22. Geological Time-scales.- 23. Measures, Units and Conversion Factors.- References.- Author Index.