ENVIRONMENTAL SOIL & WATER CHEMISTRY
PRINCIPLES AND APPLICATION


By
Bill Evangelou

JOHN WILEY & SONS, INC., NEW YORK


Preface

For the past fifteen years I have been involved in educating undergraduate and graduate students in the field of soil/water chemistry. Early in my teaching/research career students in the colleges of agriculture in the field of soils had primarily a farming background. With the passing of time, however, this type of student declined dramatically in numbers and most universities and Colleges across the country established environmental science units in some form or another. Some of these units represented reorganization of Soil Science Departments, Forestry Departments, etc., while others represented independent Environmental or Natural Resources Departments. Similar reorganization took place or is currently taking place in Geology and Engineering schools. This field reorganization created a need for new textbooks with new emphasis in examining soil and water as natural resources. In my view, as of now we have not succeeded in introducing an appropriate textbook on the subject of soil and water chemistry to cover the needs of this new type of student.

This book is designed to serve as a beginning Textbook for college seniors and beginning graduate students in environmental sciences tailored specifically for the disciplines of Soil Science, Environmental Science, Agricultural Engineering, Environmental Engineering and Environmental Geology.

The textbook contains reviews of all the necessary fundamental principles of chemistry required for understanding soil/water chemistry/quality and soil/water treatments of chemically polluted soils and waters, e.g., heavy-metal contaminated soil/water, acid drainage, revegetation of disturbed lands, restoration of sodic soils and brackish waters, etc. The purpose of the book is to educate college seniors and beginning graduate students in the toxicity, chemistry and control of pollutants in the soil/water environment and on application of such knowledge to environmental restoration. Special emphasis is placed at the educational level at which the book is written so that it is understood by seniors and beginning graduate students majoring in environmental science.

The book consists of two major sections, principles and application. Each section covers several major subject areas. The principles section covers the subject areas of I. WATER CHEMISTRY AND MINERAL SOLUBILITY, II. SOIL MINERALS AND SURFACE CHEMICAL PROPERTIES and III. ELECTROCHEMISTRY AND KINETICS. The application section covers the subject areas of IV. AGRICULTURAL CHEMICAL POLLUTION AND ITS CONTROL, V. COLLOIDS AND TRANSPORT PROCESSES IN SOILS, VI. LAND DISTURBANCE POLLUTION AND ITS CONTROL, VII. USES OF ANTHROPOGENIC/INDUSTRIAL BYPRODUCTS and VIII. SOIL AND WATER: QUALITY AND TREATMENT TECHNOLOGIES. Each subject area contains one to three chapters.


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TABLE OF CONTENTS

INTRODUCTION

PRINCIPLES

I. WATER CHEMISTRY AND MINERAL SOLUBILITY

CHAPTER 1

PHYSICAL CHEMISTRY OF WATER AND SOME OF ITS CONSTITUENTS

1.1 Elements of Nature
1.1.1 Light metals
1.1.2 Heavy metals
1.1.3 Nonmetals or metalloids
1.2 Chemical Bonding
1.3 Review on Chemical Units
1.4 Basic Information on Water Chemistry
1.4.1 Physical states and properties of water
1.4.2 Effects of temperature, pressure and dissolved salts
1.4.3 Hydration
1.5 Chemical Properties of Water
1.6 Bronsted-Lowry and Lewis Definitions of Acids and Bases
1.6.1 Weak monoprotic acids
1.6.2 Weak polyprotic acids
1.6.3 Titration curve
1.6.4 Environmental water buffers
1.6.5 Open and closed systems

CHAPTER 1-SHADED SECTION

ACID-BASE CHEMISTRY PROBLEMS
Examples of Monoprotic Acid-Base Chemistry
Examples of Polyprotic Acid-Base Chemistry

CHAPTER 2

SOLUTION/MINERAL-SALT CHEMISTRY
2.1 Introduction
2.1.1 Mineral solubility
2.1.2 Ion pair/complex effects
2.1.3 Role of hydroxide on metal solubility
2.1.4 Solubility diagrams
2.2 Specific Conductance
2.3 Acidity/Alkalinity
2.3.1 Alkalinity speciation
2.3.2 Neutralization potential
2.3.3 Alkalinity contribution by CaCO3
2.4 Chelates

CHAPTER 2-SHADED SECTION

ITERATION EXAMPLE

SPECIAL NOTE

Congruent and Incongruent Dissolution
Metal-Hydrolysis
Simultaneous Mineral Equilibria
Solution Complexes and Mineral Solubility
EC Example

 

 

 

 

 

 

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II. SOIL MINERALS AND SURFACE CHEMICAL PROPERTIES

CHAPTER 3

SOIL MINERALS AND THEIR SURFACE PROPERTIES
3.1 Composition and Structure of Soil Minerals
3.2 Aluminosilicate Minerals

CHAPTER 3-SHADED SECTIONS

SOIL MINERAL TERMS AND DEFINITIONS
BRIEF DEFINITIONS AND DISCUSSION
GENERAL RULES OF BONDING IN SOIL MINERAL STRUCTURES
RULES EXPLAINING CATION-ANION COORDINATION
HOW ARE LAYER SILICATES DIFFERENTIATED
CLAY MINERAL GROUPS IMPORTANT IN SOILS
PRIMARY MINERAL CLASSIFICATION BASED ON STRUCTURAL ARRANGEMENT
3.3 Metal-Oxides
3.4 Soil Organic Matter
3.4.1 Humic substances
3.4.2 Reactions among humic substances, clays and metals
3.4.3 Mechanisms of complex formation
3.5 Clay Mineral Surface Charge
3.5.1 Permanent structural charge
3.5.2 Variable charge
3.6 Soil/Mineral Titrations
3.6.1 Conductimetric titrations
3.6.2 Potentiometric titrations
3.7 Soil and Soil Solution Components
3.8 Role of Soil/Minerals in Controlling Water Chemistry

CHAPTER 4

SORPTION AND EXCHANGE REACTIONS
4.1 Sorption Processes
4.1.1 Surface functional groups
4.2 Adsorption/Sorption Models
4.2.1 Freundlich equilibrium approach
4.2.2 Langmuir equilibrium approach.
4.2.3 Surface complexation models
4.3 Exchange Reactions
4.3.1 Homovalent cation exchange
4.3.2 Heterovalent cation exchange
4.3.3 Quantity/intensity practical uses of exchange reactions
4.3.4 Ternary exchange systems
4.3.5 Influence of anions
4.3.6 Exchange reversibility

CHAPTER 4-SHADED SECTIONS

ADSORPTION ON A SURFACE FRACTION BASIS
RELATIONSHIP BETWEEN ExCa AND CRCa
RELATIONSHIP BETWEEN ExNa AND SAR
CATION SELECTIVITY
Q/I JUSTIFICATION

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III. ELECTROCHEMISTRY AND KINETICS

CHAPTER 5

REDOX CHEMISTRY
5.1 Definitions
5.2 Role of Redox Chemistry on Metal Solubility
5.3 General Information
5.4 Stability Diagrams
5.5 Importance of Redox Chemistry in Environmental Chemistry
5.6 How do you measure Redox?
5.7 Eh Measurements

CHAPTER 6

PYRITE OXIDATION CHEMISTRY
6.1 Introduction
6.2 Characterization
6.3 Pyrite Oxidation Mechanisms
6.4 Bacterial Pyrite Oxidation
6.5 Electrochemistry and Galvanic Effects
6.6 Bacterial Oxidation of Fe2+
6.7 Surface Mechanisms
6.8 Carbonate Role on Pyrite Oxidation
6.9 Mn- and Fe-oxides
6.10 Prediction of Acid Mine Drainage Potential
6.10.1 Potential acidity
6.10.2 Acid base accounting
6.10.3 Simulated weathering

CHAPTER 7

REACTION KINETICS IN SOIL-WATER SYSTEMS
7.1 Introduction
7.2 Rate Laws
7.2.1 First-Order
7.2.2 Second-Order
7.2.3 Zero-Order
7.3 Application of Rate Laws
7.3.1 Pseudo-first-order reactions
7.3.2 Reductive and oxidative dissolution
7.3.3 Oxidative precipitation or reductive precipitation
7.3.4 Effect of ionic strength on kinetics
7.3.5 Determining reaction rate-order
7.4 Other Kinetic Models
7.5 Enzyme-Catalyzed Reactions
7.5.1 Noncompetitive inhibition, Michaelis-Menten steady-state
7.5.2 Competitive inhibition
7.5.3 Uncompetitive inhibition
7.5.4 Competitive/uncompetitive inhibition
7.6 Factors Controlling Reaction Rates
7.6.1 Temperature influence

CHAPTER 7-SHADED SECTION

DERIVATION OF THE NONCOMPETITIVE EQUATION
DERIVATION OF COMPETITIVE INHIBITION
DERIVATION OF UNCOMPETITIVE INHIBITION
COMPETITIVE/UNCOMPETITIVE INHIBITION

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APPLICATIONS

 

IV. AGRICULTURAL CHEMICAL POLLUTION AND ITS CONTROL

CHAPTER 8

NITROGEN, PHOSPHORUS AND PESTICIDES
8.1 Nitrogen
8.1.1 Nitrogen chemistry
8.1.2 Nitrogen and the environment products
8.1.3 Nitrogen management
8.2 Phosphorus
8.2.1 Phosphorus chemistry
8.2.2 Phosphorus and the environment
8.2.3 Phosphorus management
8.3 Pesticides
8.3.1 Pesticide chemistry
8.3.2 Pesticides and the environment
8.3.3 Pesticide management
 

V. COLLOIDS AND TRANSPORT PROCESSES IN SOILS

CHAPTER 9

SOIL COLLOIDS AND WATER SUSPENDED SOLIDS
9.1 Introduction
9.2 Factors Affecting Colloid Behavior and Importance
9.2.1 Colloid dispersion or flocculation
9.2.2 Zeta potential
9.3 Flocculation and Settling Rates
9.4 Flocculants

CHAPTER 10

WATER AND SOLUTE TRANSPORT PROCESSES
10.1 Water Mobility
10.2 Soil Dispersion-Saturated Hydraulic Conductivity
10.3 Solute Mobility
10.4 Miscible Displacement

CHAPTER 11

THE CHEMISTRY AND MANAGEMENT OF SALT-AFFECTED SOILS AND BRACKISH WATERS
11.1 Introduction
11.1.1 Osmotic effect
11.1.2 Specific ion effect
11.1.3 Physico-chemical effect
11.2 Salts and Sources
11.2.1 High sodium
11.2.2 SAR, ESP parameters
11.2.3 SAR-ESP relationships
11.2.4 Adverse effects of Na+ in the soil-water environment
11.2.5 Brine chloride and bromide
11.2.6 Heavy metals
11.2.7 Boron
11.2.8 Alkalinity
11.3 Management of Brine Disposal
11.3.1 Reclamation of salt-affected soils
11.3.2 Brine evaluation prior to disposal
 

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VI. LAND DISTURBANCE POLLUTION AND ITS CONTROL

CHAPTER 12

ACID DRAINAGE PREVENTION AND HEAVY METAL REMOVAL TECHNOLOGIES
12.1 Introduction
12.2 Mechanisms of Acid Drainage Control
12.2.1 Precipitation
12.2.2 Redox Potential
12.3 Acid Drainage Prevention Technologies
12.3.1 Alkaline materials
12.3.2 Phosphate
12.3.3 Anoxic limestone drains
12.3.4 Hydrology
12.3.5 Microencapsulation technologies
12.3.6 Organic waste
12.3.7 Bactericides
12.3.8 Wetlands
12.3.9 Inundation
12.4 Neutralization Technologies
12.4.1 Calcium Bases
12.4.2 Sodium and potassium bases
12.4.3 Ammonia
 

VII. SOIL AND WATER: QUALITY AND TREATMENT TECHNOLOGIES

CHAPTER 13

WATER QUALITY
13.1 Introduction
13.2 Aquatic Contaminants
13.3 Toxicity Indicators
13.4 Metals
13.5 Primary Contaminants
13.5.1 Arsenic
13.5.2 Barium
13.5.3 Aluminum
13.5.4 Cadmium
13.5.5 Chromium
13.5.6 Fluoride
13.5.7 Lead
13.5.8 Mercury
13.5.9 Nitrate
13.5.10 Selenium
13.5.11 Nickel
13.5.12 Silver
15.6 Secondary Contaminants
13.6.1 Copper
13.6.2 Iron
13.6.3 Zinc
13.6.4 Foaming agents
13.6.5 Chloride
13.6.6 Color
13.6.8 Hardness
13.6.9 Manganese
13.6.10 Odor
13.6.11 pH
13.6.12 Sodium
13.6.13 Sulfate
13.6.14 Taste
13.6.15 Total dissolved solids
13.7 Microbiological MCLs
13.8 Maximum contaminant levels for turbidity
13.9 Radioactivity (radionuclides)
13.10 Ammonia
13.11 Industrial Organics
13.11.1 Benzene
13.11.2 Carbon tetrachloride
13.11.3 Chlordane
13.11.4 Chlorobenzene
13.11.5 Meta-Dichlorobenzene, Ortho-Dichlorobenzene, and Para-Dichlorobenzene
13.11.6 1,2-Dichloroethane
13.11.7 1,1-Dichloroethylene and 1,2-Dichloroethylene
13.11.8 Methylene chloride
13.11.9 Polychlorinated biphenyls
13.11.10 Tetrachloroethylene
13.11.11 Trichlorobenzene(s)
13.11.12 1,1,1-Trichloroethane
13.11.13 Trichloroethylene
13.11.14 Vinyl chloride
13.11.15 Xylene
13.12 Pesticides
13.12.1 Endrin
13.12.2 Lindane
13.12.3 Methoxychlor
13.12.4 Toxaphene
13.12.5 2,4-D (2,4-Dichlorophenoxyacetic Acid)
13.12.6 2,4,5-TP (Silver)
13.12.7 Trihalomethanes (TTHMs)
13.13 Chelators
13.13.1 EDTA
13.13.2 NTA
13.13.3 DTPA
13.13.4 DMPS
13.13.5 Citrate
13.14 Summary

CHAPTER 14

SOIL AND WATER DECONTAMINATION TECHNOLOGIES
14.1 Introduction
14.2 Methods of Soil Treatment
14.2.1 Low/high temperature treatment
14.2.2 Radio frequency heating
14.2.3 Steam stripping
14.2.4 Vacuum extraction
14.2.5 Aeration
14.2.6 Bioremediation
14.2.7 Soil flushing or washing
14.3 In-Situ Technologies
14.3.1 Surfactant enhancements
14.3.2 Cosolvents
14.3.3 Electrokinetics
14.3.4 Hydraulic and pneumatic fracturing
14.3.5 Treatment walls
14.4 Supercritical Water Oxidation
14.5 Public Community Water Systems
14.5.1 Some general information on water testing
14.5.2 Microbiological maximum contaminant levels
14.5.3 Activated carbon filtration
14.5.2 Air stripping
14.5.5 Disinfection
14.5.6 Distillation
14.5.7 Ion exchange
14.5.8 Reverse osmosis
14.6 Bottled Water
  

 

 

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