Soil and Water Chemistry

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ISBN: 9780849312588 | 0849312582
Cover: Hardcover
Copyright: 10/29/2003

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Traditionally the study of chemical principles as they relate to soil has been limited to the field of agronomics. Soil and Water Chemistry: An Integrative Approach, stands alone because it balances agricultural and environmental perspectives in its analysis of the chemical properties and processes that affect organic and inorganic soil substances.Written for soil science practitioners, researchers, and students, this book provides a comprehensive treatment of soil composition and reactions. Topics include: clay mineralogy, soil organic matter, mineral weathering and stability, ion speciation, solubility, ion exchange, adsorption, oxidation-reduction, acidity, alkalinity, and salinity. Each chapter concludes with numerous exercises that emphasize concepts and have practical, real-world applications.

Chapter 1 The Soil Chemical Environment: An Overview

(34)

1.1 Phases and Chemical Processes in Soil

(5)

1.1.1 Intraphase Soil Processes

(1)

1.1.2 Interphase Soil Processes

(2)

1.2 Elements in the Soil Environment: Their Concentrations and Important Species

(8)

1.3 Units and Conversions

(5)

1.4 Heterogeneity of Soil Chemical Characteristics

(12)

1.4.1 Descriptive Statistical Properties

(2)

1.4.2 Geostatistics

(22)

1.4.2.1 Variograms

(4)

1.4.2.2 Interpolation by Kriging

(3)

1.5 Exercises

(3)

References

(1)

Chapter 2 Soil Minerals

(66)

2.1 Chemical Bonds

(3)

2.2 Pauling's Rules

(5)

2.3 Crystal Structure

(2)

2.4 Silicate Classes

(11)

2.4.1 Nesosilicates

(2)

2.4.2 Sorosilicates

(1)

2.4.3 Cyclosilicates

(1)

2.4.4 Inosilicates

(1)

2.4.5 Phyllosilicates

(4)

2.4.6 Tectosilicates

(3)

2.5 Clay Mineralogy

(24)

2.5.1 Division 1:1 Phyllosilicate Minerals

(4)

2.5.2 Division 2:1 Phyllosilicate Minerals

(15)

2.5.2.1 Pyrophyllite Group

(3)

2.5.2.2 Smectite Group

(6)

2.5.2.3 Vermiculite Group

(1)

2.5.2.4 Mica and Illite Groups

(1)

2.5.2.5 Chlorite Group

(2)

2.5.2.6 Interstratified Layer Silicates

(2)

2.6 Hydrous Metal Oxides

(10)

2.6.1 Hydrous Aluminum Oxides

(3)

2.6.2 Hydrous Iron Oxides

(3)

2.6.3 Hydrous Manganese Oxides

(2)

2.6.4 Allophane and Imogolite

(2)

2.7 X-Ray Diffraction Analysis

(8)

2.7.1 Principles

(3)

2.7.2 Clay Mineral Characterization

(5)

2.8 Exercises

(2)

References

100

(1)

Chapter 3 Chemical Weathering

101

(28)

3.1 Hydrolysis and Oxidation

101

(4)

3.2 Balancing Chemical Reactions

105

(4)

3.3 Mineral Stability: Primary Silicates in the Sand- and Silt-Sized Fractions

109

(2)

3.4 Mineral Stability: Clay-Sized Fraction

111

(2)

3.5 Weathering and Formation Characteristics of the Phyllosilicates

113

(11)

3.5.1 Mica

113

(7)

3.5.2 Chlorite

120

(2)

3.5.3 Vermiculite

122

(1)

3.5.4 Smectite

123

(1)

3.6 General Weathering Scheme for the Phyllosilicates

124

(1)

3.7 Exercises

125

(2)

References

127

(2)

Chapter 4 Organic Matter in Soil

129

(54)

4.1 Determination of Soil Organic Carbon Concentrations

131

(2)

4.2 Organic Functional Groups: A Review

133

(7)

4.3 Nonhumic Substances

140

(15)

4.3.1 Carbohydrates

140

(3)

4.3.2 Nitrogen, Sulfur, and Phosphorus Compounds

143

(7)

4.3.3 Lipids

150

(2)

4.3.4 Lignins

152

(3)

4.4 Humic Substances

155

(23)

4.4.1 Genesis of Humic Substances

157

(6)

4.4.2 Chemical and Structural Characteristics of Humic Substances

163

(44)

4.4.2.1 Elemental Content

163

(4)

4.4.2.2 Functional Groups and Structural Components

167

(6)

4.4.2.3 Molecular Mass and Configuration

173

(5)

4.5 Exercises

178

(2)

References

180

(3)

Chapter 5 Soil Water Chemistry

183

(72)

5.1 Nature of Water

183

(2)

5.2 Ion Hydration

185

(3)

5.3 Electrolyte Solutions

188

(7)

5.4 Hydrolysis of Cations

195

(3)

5.5 Lowry-Brønsted Acids and Bases

198

(9)

5.6 Complex Ions and Ion Pairs

207

(9)

5.6.1 Stability of Soluble Complexes

208

(3)

5.6.2 The Irving and Williams Series

211

(1)

5.6.3 Metal-Fulvate Interactions

212

(4)

5.7 The Ion Association Model

216

(7)

5.8 Ion Speciation in Soil Solution

223

(4)

5.8.1 Acid Soil Solution

224

(1)

5.8.2 Alkaline Soil Solution

225

(2)

5.9 Qualitative Aspects of Ion Speciation

227

(5)

5.10 Soil Water Sampling Methodologies

232

(6)

5.10.1 In Situ Soil Water Sampling

232

(4)

5.10.2 Ex Situ Soil Water Sampling

236

(2)

5 11 Methods of Chemical Analysis: Elemental Analysis

238

(10)

5.11.1 Atomic Spectrometry

238

(8)

5.11.1.1 Flame Atomic Absorption Spectrophotometry

238

(5)

5.11.1.2 Atomic Emission Spectrometry

243

(1)

5.11.1.3 Graphite Furnace Atomic Absorption Spectrophotometry

243

(2)

5.11.1.4 Hydride Generation Atomic Absorption Spectrophotometry

245

(1)

5.11.2 Inductively Coupled (Argon) Plasma Spectrometry

246

(2)

5.12 Exercises

248

(3)

References

251

(4)

Chapter 6 Mineral Solubility

255

(56)

6.1 Mineral Solubility: Basic Principles

255

(8)

6.1.1 Mineralogical Controls on Ion Activities in Soil Solutions

257

(3)

6.1.2 The Ion Activity Product and Relative Saturation

260

(3)

6.2 Application of Mineral Solubility Principles: Impediments

263

(6)

6.2.1 The Estimation of Standard Free Energies of Formation

264

(4)

6.2.2 Metastability and the Step Rule

268

(1)

6.3 The Deviation of KSp from KdjS

269

(5)

6.3.1 Poorly Crystalline and Microcrystalline Solids

269

(2)

6.3.2 Solid Solutions

271

(3)

6.4 Mineral Solubility and Solution Composition

274

(2)

6.5 Stability Diagrams

276

(26)

6.5.1 Activity Diagrams

277

(3)

6.5.2 Activity Ratio Diagrams

280

(3)

6.5.3 The Temperature Dependence of the Equilibrium Constant

283

(7)

6.5.4 In Situ Stabilization: Observed and Predicted Transformations of Metallic Lead in Alkaline Soil

290

(7)

6.5.5 Predominance Diagrams

297

(5)

6.6 Predicting Solution Composition

302

(3)

6.7 Exercises

305

(3)

References

308

(3)

Chapter 7 Surface Chemistry and Adsorption Reactions

311

(88)

7.1 Surface Functional Groups and Complexes

311

(11)

7.1.1 Inorganic Soil Particle Surfaces and the Source of Charge

313

(8)

7.1.2 Surface Complexes

321

(1)

7.2 The Solid-Solution Interface: A Microscopic View

322

(12)

7.2.1 Surface Charge Density

322

(5)

7.2.2 Points of Zero Charge

327

(3)

7.2.3 The Electric Double-Layer

330

(4)

7.3 Quantitative Description of Adsorption

334

(30)

7.3.1 The Adsorption Isotherm

335

(13)

7.3.2 Linear Partition Theory

348

(10)

7.3.3 Adsorption Kinetics and Desorption Hysteresis

358

(6)

7.4 Specific Retention of Metals and Ligands

364

(6)

7.5 Ligand Effects on Metal Adsorption

370

(3)

7.6 Organic Surface Functional Groups and Organic Molecular Retention Mechanisms

373

(4)

7.6.1 Organic Surface Functional Groups

373

(1)

7.6.2 Molecular Retention Mechanisms

373

(4)

7.7 Surface Complexation Models

377

(17)

7.7.1 The Nonelectrostatic Model

380

(6)

7.7.2 Electrostatic Effects on Adsorption

386

(18)

7.7.2.1 The Constant Capacitance Model

387

(4)

7.7.2.2 The Modified Triple Layer Model

391

(3)

7.8 Exercises

394

(3)

References

397

(2)

Chapter 8 Cation Exchange

399

(46)

8.1 Cation Exchange: A Beginning for Soil Chemistry

399

(2)

8.2 Qualitative Aspects of Cation Exchange

401

(3)

8.3 Cation Exchange Capacity and Exchange Phase Composition

404

(5)

8.3.1 Exchange Phase Composition

404

(3)

8.3.2 Methods of Measuring the Cation Exchange Capacity

407

(2)

8.3.2.1 Ammonium Acetate (pH 7 or 8.2)

407

(1)

8.3.2.2 Cation Exchange Capacity of Arid Land Soils

408

(1)

8.3.2.3 Cation Exchange Capacity of Acid Soils

409

(1)

8.3.2.4 Unbuffered Salt Extraction

409

(1)

8.4 Quantitative Description of Cation Exchange

409

(31)

8.4.1 Cation Exchange Selectivity

410

(14)

8.4.1.1 Kerr Selectivity Coefficient

410

(2)

8.3.1.2 Vanselow Selectivity Coefficient

412

(4)

8.4.1.3 Rothmund and Kornfeld Selectivity Coefficient

416

(2)

8.4.1.4 Gapon Selectivity Coefficient

418

(2)

8.4.1.5 Gaines and Thomas Selectivity Coefficient

420

(1)

8.4.1.6 Davies Selectivity Coefficient

421

(1)

8.4.1.7 Regular Solution Model

422

(2)

8.4.2 Exchange Isotherms and Preference

424

(6)

8.4.3 Exchange Equilibrium Constant

430

(10)

8.5 Exercises

440

(2)

References

442

(3)

Chapter 9 Oxidation-Reduction Reactions in Soils

445

(28)

9.1 The Electron Activity

446

(3)

9.2 Redox Potential Measurements

449

(5)

9.3 Redox Status in Soils

454

(5)

9.3.1 Reduction-Oxidation Sequences in Soils

455

(3)

9.3.2 Redox Zones

458

(1)

9.4 pe-pH Predominance Diagrams

459

(12)

9.4.1 Construction of pe-pH Diagrams: The Cr-H20 System

460

(4)

9.4.2 Examples of pe-pH Diagrams for Redox-Sensitive Elements

464

(10)

9.4.2.1 Iron and Manganese

465

(2)

9.4.2.2 Selenium

467

(2)

9.4.2.3 Arsenic

469

(2)

9.5 Exercises

471

(1)

References

472

(1)

Chapter 10 Acidity in Soil Materials

473

(26)

10.1 The Measurement of Soil Solution pH

474

(3)

10.1.1 The pH Electrode System

474

(2)

10.1.2 Soil Solution pH

476

(1)

10.2 Chemical and Biochemical Processes that Influence Soil Solution pH

477

(6)

10.3 Acid-Neutralizing Capacity and the Quantification of Soil Acidity

483

(1)

10.4 Neutralization of Soil Acidity

484

(4)

10.5 Acid Generation and Management in Mine Spoils: The Oxidation of Pyrite

488

(7)

10.5.1 Acid Generation and Neutralization in Pyritic Wastes

488

(4)

10.5.2 Pyritic Mine Spoil Reclamation: Case Study

492

(3)

10.6 Exercises

495

(2)

References

497

(2)

Chapter 11 Soil Salinity and Sodicity

499

(24)

11.1 Sources of Salts

500

(1)

11.2 Diagnostic Characteristics of Saline and Sodic Soils

501

(3)

11.3 Irrigation Water Quality Parameters and Relationships

504

(2)

11.4 Genesis, Management, and Reclamation of Salt-Affected Soils

506

(13)

11.4.1 Saline Soils

507

(4)

11.4.2 Sodic Soils

511

(7)

11.4.2.1 Classification of Sodic Soils

511

(2)

11.4.2.2 Flocculation and Dispersion in Colloidal Suspensions

513

(3)

11.4.2.3 Genesis and Management of Sodic Soils

516

(2)

11.4.3 Sodic Mine Spoil Reclamation

518

(1)

11.5 Exercises

519

(2)

References

521

(2)

Index

523

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Soil and Water Chemistry

Summary

Table of Contents

Supplemental Materials