Stevenson F.J. Humus chemistry: genesis, composition, reactions (New York; Chichester, 1994).

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043 | | Институт углехимии и химического материаловедения CO РАН (В 2010 г. институт отделился от Института угля (065)) | Кемерово

1 Organic Matter in Soils: Pools, Distribution, Transformations, and Function ................................ 1 Pools of Organic Matter in Soils ............................. 1 Organic Matter (Humus) Content of Soils ...................... 6 Decomposition Processes and Ages of Organic Matter .......... 11 Function of Organic Matter in Soil .......................... 14 Organic Matter and Sustainable Agriculture .................. 19 Environmental Significance of Humic Substances .............. 19 Summary ..................................................... 20 References .................................................. 21 2 Extraction, Fractionation, and General Chemical Composition of Soil Organic Matter .......................... 24 Brief Historical Review ..................................... 24 Associations of Organic Matter in Soil ...................... 34 Extraction Methods .......................................... 34 Fractionations Based on Solubility Characteristics .......... 41 Purification ................................................ 45 Classification and Distribution of Dissolved Organic С (DOC) ....................................................... 51 Comparison of Soil Humic Substances with Those of Other Environments ................................................ 54 Physical Fractionation of Organic Matter .................... 54 Summary ..................................................... 55 References .................................................. 56 3 Organic Forms of Soil Nitrogen .............................. 59 Fractionation of Soil N ..................................... 59 Nitrogen in Humic and Fulvic Acids .......................... 66 Biochemical N Compounds ..................................... 71 Biomass N ................................................... 89 Natural Variations in N Isotope Abundance ................... 90 l5N-NMR Spectroscopy ........................................ 90 Stability of Soil Organic N ................................. 90 Summary ..................................................... 91 References .................................................. 92 4 Native Fixed Ammonium and Chemical Reactions of Organic Matter with Ammonia and Nitrite ............................. 96 Levels of Native Fixed NH₄⁺ in Soils ........................ 96 The C/N Ratio .............................................. 100 Chemical Reactions of NH₃ and NO₂^- with Organic Matter ..... 102 Summary .................................................... 110 References ................................................. 111 5 Organic Phosphorus and Sulfur Compounds .................... 113 The C/N/P/S Ratio .......................................... 113 Soil Organic P ............................................. 115 Soil Organic S ............................................. 128 Summary .................................................... 137 References ................................................. 137 6 Soil Carbohydrates ......................................... 141 Significance of Soil Carbohydrates ......................... 142 Structure and Classification ............................... 142 State in the Soil .......................................... 144 Quantitative Determination of Soil Carbohydrates ........... 154 Summary .................................................... 163 References ................................................. 164 7 Soil Lipids ................................................ 166 Lipid Content of Soil Humus ................................ 166 Function in Soil ........................................... 171 Composition ................................................ 175 Summary .................................................... 185 References ................................................. 185 8 Biochemistry of the Formation of Humic Substances .......... 188 Major Pathways of Humus Synthesis .......................... 188 The Lignin Theory .......................................... 191 The Polyphenol Theory ...................................... 197 Sugar-Amine Condensation ................................... 206 Scheme for the Formation of Humic Substances ............... 208 Summary .................................................... 209 References ................................................. 210 9 Reactive Functional Groups ................................. 212 Elemental Content .......................................... 212 Methods of Functional Group Analysis ....................... 214 Distribution of Oxygen-Containing Functional Groups ........ 226 Diagenetic Transformations ................................. 231 Summary .................................................... 234 References ................................................. 234 10 Structural Components of Humic and Fulvic Acids as Revealed by Degradation Methods ............................ 236 Experimental Approaches .................................... 236 Hydrolysis Methods ......................................... 238 Reductive Cleavage ......................................... 240 Oxidative Methods .......................................... 248 Miscellaneous Chemical Approaches .......................... 254 Thermal Methods ............................................ 255 Summary .................................................... 256 References ................................................. 257 11 Characterization of Soil Organic Matter by NMR Spectroscopy and Analytical Pyrolysis ...................... 259 Theory of Nuclear Magnetic Resonance Spectroscopy (NMR) .... 259 Techniques for ^l3C-NMR Spectroscopy ........................ 263 ^l3C-NMR Spectroscopic Analysis of Humic and Fulvic Acids ...................................................... 265 ^l3C-NMR Spectroscopic Analysis of Soil Organic Matter In Situ ....................................................... 272 ^lH-NMR Spectroscopy ........................................ 274 ^l5N-NMR Spectroscopy ....................................... 276 ³¹P-NMR Spectroscopy ....................................... 277 Analytical Pyrolysis ....................................... 277 Summary .................................................... 281 References ................................................. 281 12 Structural Basis of Humic Substances ....................... 285 General Considerations ..................................... 286 Type Structures for Humic and Fulvic Acids ................. 287 Unique Feature of Humic Substances in Seawater ............. 294 A Simplified Structural Representation of Soil Humic Substances ................................................. 294 Summary .................................................... 301 References ................................................. 301 13 Spectroscopic Approaches ................................... 303 Ultraviolet (UV) and Visible Regions ....................... 304 Infrared (IR) Spectroscopy ................................. 307 Electron Spin Resonance (ESR) Spectroscopy ................. 317 Fluorescence Spectroscopy .................................. 322 Summary .................................................... 322 References ................................................. 323 14 Colloidal Properties of Humic Substances ................... 325 The Colloidal State ........................................ 325 Molecular Weights and Particle Sizes ....................... 326 Morphological Features by Electron Microscopy .............. 339 Structural Evaluation by X-Ray Diffraction ................. 341 Small-Angle X-Ray Scattering ............................... 342 Size Evaluation by Gel Filtration .......................... 343 Summary .................................................... 347 References ................................................. 348 15 Electrochemical and Ion-Exchange Properties of Humic Substances ................................................. 350 Acidic Nature of Humic and Fulvic Acids .................... 351 Selectivity of Humic Substances for Exchange Cations ....... 367 Contribution of Organic Matter to the Cation-Exchange Capacity (CEC) of the Soil ................................. 367 Coagulation of Humic Substances by Polyelectrolytes ........ 372 Electrophoresis ............................................ 373 Oxidation-Reduction Potential .............................. 374 Summary .................................................... 375 References ................................................. 375 16 Organic Matter Reactions Involving Metal Ions in Soil ...... 378 Properties of Metal-Organic Matter Complexes ............... 379 Significance of Chelation Reactions in Soil ................ 381 Forms of Transition Metal Ions in Soil ..................... 384 Biochemical Compounds as Chelating Agents .................. 388 Trace Metal Interactions with Humic Substances ............. 394 Summary .................................................... 401 References ................................................. 401 17 Stability Constants of Metal Complexes with Humic Substances ................................................. 405 General Considerations ..................................... 405 Modeling Approaches ........................................ 408 Summary .................................................... 427 References ................................................. 427 18 Clay-Organic Complexes and Formation of Stable Aggregates ................................................. 429 Nature of Clay Colloids .................................... 429 Adsorption of Defined Organic Compounds by Clay ............ 431 Naturally Occurring Clay-Organic Complexes ................. 439 Role of Organic Matter in Forming Stable Aggregates in Soil ....................................................... 445 Soil Wettability ........................................... 449 Summary .................................................... 450 References ................................................. 450 19 Organic Matter Reactions Involving Pesticides in Soil ...... 453 Humus Chemistry in Relation to Pesticide Behavior .......... 455 Adsorption Mechanisms ...................................... 462 Relative Affinities of Pesticides for Soil Organic Matter ..................................................... 469 Summary .................................................... 469 References ................................................. 469 20 Role of Organic Matter in Pedogenic Processes .............. 472 Weathering of Rocks and Minerals ........................... 473 Neogenesis of Minerals ..................................... 477 Translocation of Mineral Matter and Horizon Differentiation ............................................ 478 Organic Matter and Soil Classification ..................... 483 Paleohumus ................................................. 485 Effects of Acidic Inputs (Acid Rain) on Pedogenic Processes .................................................. 485 Summary .................................................... 486 References ................................................. 486 Index ......................................................... 489