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PREFACE xi
INSTRUMENTAL METHOD ACRONYMS xiv
COMMON HYPHENATED INSTRUMENTAL METHOD ABBREVIATIONS xv
ABBREVIATED PERIODIC TABLE OF THE ELEMENTS xvi
CHAPTER 1 SUMMARY OF THE HISTORY OF SOIL CHEMISTRY 1
1.1 The 19th Century 3
1.2 The End of the 19th and the Beginning of the 20th Century 8
1.3 The 20th Century 11
1.4 The End of the 20th and the Beginning of the 21st Century 14
1.5 Conclusion 15
Problems 15
References 16
Bibliography 18
CHAPTER 2 SOIL BASICS PART I: LARGE FEATURES 19
2.1. Horizonation 28
2.2 Peds 33
2.3 Soil Color 36
2.4 Soil Naming 38
2.5 The Landscape 39
2.6 Relationship of Large Features to Soil Chemistry, Soil Analysis, and Instrumentation 40
2.7 Conclusions 42
Problems 42
References 43
Bibliography 43
CHAPTER 3 SOIL BASICS PART II: MICROSCOPIC TO ATOMIC ORBITAL DESCRIPTION OF SOIL CHEMICAL CHARACTERISTICS 44
Soil Components Independent 45
3.1 Soil Solids 45
Soil Components Interacting 53
3.2. Bonding Considerations 53
Soil Components in Combination 58
3.3 Surface Features 58
3.4 Energy Considerations 60
3.5 Reaction Paths 61
3.6 Steric Factors 62
3.7 Rate Factors 62
3.8 All Factored Together 63
3.9 Micelles 63
3.10 Coated Surfaces 63
3.11 Conclusions 65
Problems 65
References 66
Bibliography 67
CHAPTER 4 SOIL BASICS PART III: THE BIOLOGICAL AND ORGANIC COMPONENTS IN SOIL 68
Biota of Soil 69
4.1 Animals 69
4.2 Plants 71
4.3 Microorganisms 75
Biological and Organic Chemicals of Soil 79
4.4 Biochemical 79
4.5 Bioorganic 81
4.6 Organic Compounds 81
4.7 Analysis 87
4.8 Conclusions 89
Problems 90
References 90
Bibliography 92
Web Sites 92
CHAPTER 5 SOIL BASICS PART IV: THE SOIL AIR AND SOIL SOLUTION 93
5.1 Soil Air 94
5.2 Water 95
5.3 Solubility 98
5.4 Elements in Solution 99
5.5 Dissolved Gases 99
5.6 Compounds in Solution 100
5.7 Inorganic Ions in Solution 102
5.8 Organic Ions in Solution 104
5.9 Soil pH 105
5.10 The Soil Solution around Particles 106
5.11 Distribution between Soil Solids and Soil Solution 106
5.12 Oxidative and Reductive Reactions in the Soil Solution 108
5.13 Measuring Soil Water 109
5.14 Conclusion 112
Problems 112
References 113
Bibliography 114
CHAPTER 6 SPECIATION 115
6.1 Cations 118
6.2 Anions 123
6.3 Isolation of Species 128
6.4 Sampling, Sample Storage, and Speciation 129
6.5 Conclusions 130
Problems 131
References 131
Bibliography 134
CHAPTER 7 SOIL AND SOIL SOLUTION SAMPLING, SAMPLE TRANSPORT, AND STORAGE 135
7.1 Field Sampling 136
7.2 Sampling Cropped Land 147
7.3 Environmental Sampling 148
7.4 Other Environmental Sampling Situations 148
7.5 Sample Transport and Storage 148
7.6 Laboratory Sampling 149
7.7 Sampling the Soil Solution 153
7.8 Conclusions 155
Problems 156
References 157
Bibliography 158
CHAPTER 8 DIRECT AND INDIRECT MEASUREMENT IN SOIL ANALYSIS 159
8.1 Direct Measurements 160
8.2 Mediated Direct Measurement 166
8.3 Indirect Soil Measurements 168
8.4 Destructive Soil Analysis Methods 170
8.5 Soil Solution 171
8.6 Soil Solids 171
8.7 Conclusions 172
Problems 173
References 173
Bibliography 174
CHAPTER 9 ELECTRICAL MEASUREMENTS 175
9.1 The Basic Electrochemical Cell 177
9.2 Electricity Generation in Soil 177
9.3 Potentiometry (Electrodes in Soil Measurements) 178
9.4 Voltammetry 187
9.5 Electrical Conductivity 187
9.6 Time-Domain Reflectometry 188
9.7 Porous Block 189
9.8 Other Methods 189
9.9 Conclusions 189
Problems 190
References 190
Bibliography 192
CHAPTER 10 TITRIMETRIC MEASUREMENTS 193
10.1 Soil Titration 195
10.2 Titration of Soil pH 197
10.3 Organic Matter 200
10.4 Ammonia 200
10.5 Kjeldahl: Organic Nitrogen 202
10.6 Nitrite and Nitrate 203
10.7 Carbonate Determination 204
10.8 Halogen Ion Determination 205
10.9 pH-Stat Titrations 206
10.10 Conclusions 207
Problems 207
References 208
CHAPTER 11 EXTRACTION OF INORGANICS 209
11.1 Extraction Equipment 210
11.2 Water as a Soil Extractant 211
11.3 Acid Extractants 218
11.4 Extractants for Basic Soils 222
11.5 Microwave-Assisted Extraction 224
11.6 Ultrasonic Extraction 225
11.7 Sequential Extraction 225
11.8 Ion Exchange Resin Extractions 226
11.9 Surfactants 227
11.10 Conclusion 227
Problems 227
References 228
Bibliography 230
CHAPTER 12 EXTRACTION OF ORGANICS 231
12.1 Sampling Handling before Extraction 235
12.2 Extraction Equipment 235
12.3 Soil Organic Matter Extraction Solvents 243
12.4 Cleanup 247
12.5 Conclusion 250
Problems 250
References 251
Bibliography 252
CHAPTER 13 CHROMATOGRAPHY 254
13.1 Fundamentals of Chromatography 256
13.2 Gas Chromatography 257
13.3 High-Performance Liquid Chromatography 264
13.4 Thin-Layer Chromatography 265
13.5 Electrophoresis 267
13.6 Identification of Compounds Separated by Chromatographic Procedures 268
13.7 Quantification 270
13.8 Conclusion 271
Problems 271
References 272
Bibliography 273
CHAPTER 14 SPECTROSCOPY AND SPECTROMETRY 274
14.1 Spectral Overlap 275
14.2 Noise 276
14.3 The Visible Region 277
14.4 Ultraviolet Region 278
14.5 Infrared Spectroscopy 280
14.6 Nuclear Magnetic Resonance 286
14.7 Mass Spectrometry 287
14.8 Atomic Spectroscopy 288
14.9 Color Measurement: The Spectrophotometer 292
14.10 Regression Analysis 296
14.11 Relationship to the Original Sample 296
14.12 X-ray Diffraction 297
14.13 X-ray Fluorescence 297
14.14 Remote Sensing 299
14.15 Conclusion 299
Problems 300
References 300
Bibliography 303
CHAPTER 15 HYPHENATED METHODS IN SOIL ANALYSIS 304
15.1 Sample Preparation 307
15.2 Sample Destroyed 307
15.3 Nondestructive Methods 313
15.4 Triple Hyphenated Methods 314
15.5 Conclusions 316
Problems 316
References 317
Bibliography 318
INDEX 320
CHAPTER 2
Soil Basics Part I
Large Features
Soil is vastly more complex than simply ground-up rock. It contains solid inorganic and organic components in various stages of decomposition and disintegration, an aqueous solution of elements, inorganic and organic ions and molecules, and a gaseous phase containing nitrogen, oxygen, carbon dioxide, water, argon, methane, and other gases. In addition, it contains a large and varied population of macro-, meso-, and microscale animals, plants, and microorganisms. If any of these components is missing, it is not soil!
The solid portion of soil is composed of inorganic sand, silt, clay, and organic matter (OM), which interact to produce the large soil features1 (i.e., peds, profiles, pedons, and landscapes). These features, not considering rock, are discussed in this chapter. In Chapter 3, components smaller than rock, which soil scientists define as those inorganic particles smaller than 2.00 mm in diameter, are discussed. Geologic features and gravel, stones and rock, and other substances are not discussed.
Large soil components consisting of sand, silt, clay, and OM are peds, profiles, pedons, and landscapes. Peds are formed by the aggregation of sand, silt, and clay particles to form larger (secondary) soil structures that result from the action of the soil forming factors (see Figure 2.2, Figure 2.3, Figure 2.4, Figure 2.5, Figure 2.6, Figure 2.7, and Figure 2.8). Profiles develop in the loose material on the earth's surface, the regolith, and are composed of horizons of varying texture, structure, color, bulk density, and other properties. The relationship between the soil and the regolith is illustrated in Figure 2.1. Typically, horizons are, as the name implies, horizontal and are of varying thickness. A pedon is the smallest unit that can be considered “a soil” and consists of all horizons from the soil surface to the underlying geologic strata. An area consisting of similar pedons is called a polypedon.
Figure 2.1. The relationship between soil horizons, the regolith, and the underlying rock.
Figure 2.2. An example of an Alfisol; this is the Seitz soil series, the state soil of Colorado [2].
Figure 2.3. An example of a Mollisol; this is the Drummer soil series, which is the state soil of Illinois [2].
Figure 2.4. An example of an Ultisol; this is the Bama Series, which is the state soil of Alabama [2].
Figure 2.5. An example of a Spodosol; the Kalkaska soil series, the state soil of Michigan (single-grain structure in horizon C means that all the sand particles act independently of each other) [2].
Figure 2.6. An example of an Aridisol; the Casa Grande soil series, the state soil of Arizona.
Figure 2.7. An example of a Andisol; this is the Bonner soil series, found in northern Idaho, eastern Washington, and western Montana [3].
Figure 2.8. An example of a Vertisol; this is the Lualualei series, which is found in Hawaii [2].
Soil features, texture, peds, profiles, and other properties and materials go together in different ways to form different soils. Soil scientists in the United States classify soils into 12 orders, some of which are illustrated in Figure 2.2, Figure 2.3, Figure 2.4, Figure 2.5, Figure 2.6, Figure 2.7, and Figure 2.8. The orders are differentiated by their characteristics, which are a result of the action of the soil forming factors: climate, parent material, topography, biota, and time, which all interact during soil formation. Climate, moisture, and temperature determine the biota, as well as a soil's age, and whether it can develop in a certain locality. The soil parent material will be acted upon by other factors but will in turn provide the minerals needed for plant growth and other biological activity.
Consideration of the larger components of soil might seem like a strange place to start a discussion of soil chemistry, analysis, and instrumental methods. However, these larger structures can and do affect the chemistry of a soil. For instance, in many cases, the larger features control the movement of air and water in soil. Sandy textured soils will have higher infiltration and percolation rates than clayey soils. The same can be said for soils with good, strong structure, versus soils with poor or weak structure. As water moves into soil, it displaces air and, as it moves out, air replaces it. Thus, soil with poor or slow infiltration and percolation will have generally lower oxygen contents. This directly affects soil aeration and thus its oxidation–reduction status.
Infiltration and percolation rates also determine which salts have been leached out of the soil. For instance, high infiltration and percolation rates leach calcium and magnesium out of soil and they become acidic. Where calcium and magnesium are not leached out, the soils are neutral or basic. Thus, the type and amount of salts present will affect a soil's pH, which will in turn affect the solubility and availability of both natural and contaminating inorganic and organic compounds.
The species of components present will also be affected by oxidation–reduction, and pH. For example, iron is primarily in the Fe3+ (oxidized) or the Fe2+ (reduced) state depending on the oxidation–reduction potential of the soil. Speciation, which depends, in part, on the oxygen status of soil, is of environmental concern because some species are more soluble, such as Fe2+, and are thus more biologically available than others. The occurrence of a specific species is related to the chemistry occurring in a soil, which is related to its features. Thus, large features must be taken into consideration when studying soil chemistry and when developing analytical and instrumental methods.
The most striking large feature of soil is the occurrence of distinct horizons. For the analytical chemist, three soil horizonation conditions exist: (1) high-rainfall areas that typically have tree or tall grass vegetation and extensive horizon development, (2) low-rainfall and desert areas with sparse and desert vegetation and little horizon development, and (3) areas with rainfall between these extremes will have variable vegetation and horizonation. It is not possible to draw sharp boundaries between these areas because local conditions such as rainfall frequency, time of year, and intensity of rainfall dramatically affect the climate in transition areas. Each of these situations presents unique challenges to the analytical chemist.
Parent material salts are dissolved when water falls on soil. These salts are leached into and eventually out of the soil. Plants grow, produce biomass, exude OM (including acids), die, and thus add OM to both the soil surface and subsurface. Silica and alumina, which are relatively immobile, slowly dissolve and are eluted into the lower areas of a developing soil. OM is decomposed, mixed by organisms, and leached into the soil. As this process continues, horizons develop in the soil parent material and, eventually, a recognizable soil profile is produced (see Figure 2.1, Figure 2.2, Figure 2.3, Figure 2.4, Figure 2.5, Figure 2.6, Figure 2.7, Figure 2.8, and Figure 2.9). The depth of the soil and the number and type of horizons that develop depends on the soil forming factors, the most active of which are climate and biota, although parent material, as mentioned earlier, is also important [1,2].
Figure 2.9. Soil structure and its most common location in a soil profile. Platy structure can be found in any horizon. Subangular and angular blocky structures can be found both higher and lower in the profile than indicated.
Soil parent material is not always derived from the underlying rock. In some cases, rock is covered by other geologic materials deposited by ice (glacial till), water (alluvium), wind (loess), gravity (colluvium), or a combination of these transporting agents. A more complete list of transporting agents and the geomorphic features they form is given in Table 2.1. Once deposited, these materials become the parent material from which soil develops.
TABLE 2.1. Soil Parent Material Transporting Agents, The Name of the Material, and the Geomorphic Features They Forma
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