Soil and Environmental Chemistry

Dedication

Preface

Chapter 1. Elements: Their Origin and Abundance

1.1 Introduction

1.2 A Brief History of the Solar System and Planet Earth

1.3 The Composition of Earth’s Crust and Soils

1.4 The Abundance of Elements in the Solar System, Earth’s Crust, and Soils

1.5 Elements and Isotopes

1.6 Nuclear Binding Energy

1.7 Enrichment and Depletion during Planetary Formation

1.8 Planetary Accretion

1.9 The Rock Cycle

1.10 Soil Formation

1.11 Concentration Frequency Distributions of the Elements

1.12 Estimating the Most Probable Concentration and Concentration Range Using the Logarithmic Transformation

1.13 Summary

Appendix 1A Factors Governing Nuclear Stability and Isotope Abundance

Appendix 1B Nucleosynthesis

Appendix 1C Thermonuclear Fusion Cycles

Appendix 1D Neutron-Emitting Reactions that Sustain the S-Process

Appendix 1E Random Sequential Dilutions and the Law of Proportionate Effect

Appendix 1F The Estimate of Central Tendency and Variation of a Log-Normal Distribution

Chapter 2. Soil Moisture and Hydrology

2.1 Introduction

2.2 Water Resources and the Hydrologic Cycle

2.3 Water Budgets

2.4 Residence Time and Runoff Ratios

2.5 Groundwater Hydrology

2.6 Vadose Zone Hydrology

2.7 Elementary Solute Transport Models

2.8 Summary

Appendix 2A Soil Moisture Recharge and Loss

Appendix 2B The Water-Holding Capacity of a Soil Profile

Appendix 2C Predicting Capillary Rise

Appendix 2D Symbols and Units in the Derivation of the Retardation Coefficient Model of Solute Transport

Appendix 2E Symbols and Units in the Derivation of the Plate Theory Model of Solute Transport

Appendix 2F Empirical Water Characteristic Function and Unsaturated Hydraulic Conductivity

Chapter 3. Clay Mineralogy and Clay Chemistry

3.1 Introduction

3.2 Mineral Weathering

3.3 The Structure of Layer Silicates

Appendix 3A Formal Oxidation Numbers

Appendix 3B The Geometry of Pauling’s Radius Ratio Rule

Appendix 3C Bragg’s Law and X-Ray Diffraction in Layer Silicates

Appendix 3D Osmotic Model of Interlayer Swelling Pressure

Appendix 3E Experimental Estimates of Interlayer Swelling Pressure

Chapter 4. Ion Exchange

4.1 Introduction

4.2 The Discovery of Ion Exchange

4.3 Ion Exchange Experiments

4.4 Interpreting the Ion Exchange Isotherm

4.5 Summary

Appendix 4A Thermodynamic and Conditional Selectivity Coefficients

Appendix 4B Nonlinear Least Square Fitting of Exchange Isotherms

Appendix 4C Equivalent Fraction-Dependent Selectivity Coefficient for (Mg2+, Ca2+) Exchange on the Libby Vermiculite

Chapter 5. Water Chemistry

5.1 The Equilibrium Constant

5.2 Activity and the Equilibrium Constant

5.3 Modeling Water Chemistry

5.4 Summary

Appendix 5A ChemEQL Result Data File Format

Appendix 5B Validating Water Chemistry Simulations

Appendix 5C Validation Assessment for Examples 5.13 and 5.16

Appendix 5D Cinnabar Solubility in an Open System Containing the Gas Dihydrogen Sulfide

Appendix 5E Simultaneous Calcite-Apatite-Pyromorphite Solubility

Appendix 5F Simultaneous Gibbsite-Variscite Solubility

Appendix 5G Apatite Solubility as a Function of pH

Appendix 5H Effect of the Citrate on the Solubility of the Calcium Phosphate Mineral Apatite

Appendix 5I Effect of the Bacterial Siderophore Desferrioxamine B on the Solubility of the Iron Oxyhydroxide Goethite

Chapter 6. Natural Organic Matter and Humic Colloids

6.1 Introduction

6.2 Soil Carbon Cycle

6.3 Soil Carbon

6.4 Dissolved Organic Carbon

6.5 Humic Substances

6.6 Humic Colloids

6.7 Summary

Appendix 6A Hydroxamate and Catecholamide Siderophore Moieties

Appendix 6B Surface Microlayers

Appendix 6C Humic Oxygen Content and Titratable Weak Acids

Appendix 6D Hydrophobic and Hydrophilic Colloids

Chapter 7. Acid-Base Chemistry

7.1 Introduction

7.2 Principles of Acid-Base Chemistry

7.3 Sources of Environmental Acidity and Basicity

7.4 Atmospheric Gases

7.5 Ammonia-Based Fertilizers and Biomass Harvesting

7.6 Charge Balancing in Plant Tissue and the Rhizosphere

7.7 Mechanical Properties of Clay Colloids and Soil Sodicity

7.8 Exchangeable Acidity

7.9 Summary

Appendix 7A Buffer Index

Appendix 7B Converting Mass Fraction to Sum-of-Oxides Composition

Appendix 7C Saturation Effect: Atmospheric Conversion of Sulfur Trioxide to Sulfuric Acid

Appendix 7D Bicarbonate and Carbonate Reference Levels

Appendix 7E Calculating the pH of a Sodium Carbonate Solution

Appendix 7F Calculating the Aqueous Carbon Dioxide Concentration in a Weak Base Solution

Appendix 7G Ion Exchange Isotherm for Asymmetric (Ca2+, Al3+) Exchange

Appendix 7H The Effect of (Na+, Ca2+) Exchange on the Critical Coagulation Concentration of Montmorillonite

Appendix 7I Predicting Changes in SAR by Water Chemistry Simulation

Chapter 8. Redox Chemistry

8.1 Introduction

8.2 Redox Principles

8.3 Interpreting Redox Stability Diagrams

8.4 Microbial Respiration and Electron Transport Chains

8.5 Summary

Appendix 8A Assigning Formal Oxidation Numbers

Appendix 8B Converting (pe, pH) Redox Coordinates into (E_H, pH) Coordinates

Appendix 8C Limitations in the Measurement of the Environmental Reduction Potential Using Platinum ORP Electrodes

Chapter 9. Adsorption and Surface Chemistry

9.1 Introduction

9.2 Mineral and Organic Colloids as Environmental Adsorbents

9.3 The Adsorption Isotherm Experiment

9.4 Hydrophobic and Hydrophilic Colloids

9.5 Interpreting the Adsorption Isotherm Experiment

9.6 Variable-Charge Mineral Surfaces

9.7 The Adsorption Envelope Experiment: Measuring pH-Dependent Ion Adsorption

9.8 Valence Bond Model of Proton Sites

9.9 Surface Complexes

9.10 Summary

Appendix 9A Particle Sedimentation Rates in Water: Stokes’s Law

Appendix 9B Linear Langmuir Expression

Appendix 9C Hydrolysis Model of Proton Sites

Chapter 10. Risk Assessment

10.1 Introduction

10.2 The Federal Risk Assessment Paradigm

10.3 Dose-Response Assessment

10.4 Exposure Pathway Assessment

10.5 Intake Estimates

10.6 Risk Characterization

10.7 Exposure Mitigation

10.8 Summary

Appendix 10A Chemical- and Site-Specific Factors that May Affect Contaminant Transport by Surface Water

Appendix 10B Chemical- and Site-Specific Factors that May Affect Contaminant Transport by Groundwater

Appendix 10C Chemical- and Site-Specific Factors that May Affect Contaminant Transport Involving Soils or Sediments

Appendix 10D Chemical- and Site-Specific Factors that May Affect Contaminant Transport Involving Air and Biota

Appendix 10E Water Ingestion Equation

Appendix 10F Soil Ingestion Equation

Appendix 10G Food Ingestion Equation

Appendix 10H Air Inhalation Equation

Appendix 10I Hazard Index—Cumulative Noncarcinogenic Risk

Appendix 10J Cumulative Target Risk—Cumulative carcinogenic Risk

References

Index