Methods of Soil Analysis. Part 3. Chemical Methods (Soil Science Society of America Book Series, No. 5)

A thorough presentation of analytical methods for characterizing soil chemical properties and processes, Methods, Part 3 includes chapters on Fourier transform infrared, Raman, electron spin resonance, x-ray photoelectron, and x-ray absorption fine structure spectroscopies, and more.Also Methods of Soil Analysis. Part 1. Physical and Mineralogical Methods - ISBN 0891188118 Minerals in Soil Environments, 2nd Edition - ISBN 0891187871The American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America are prominent international scientific societies headquartered in Madison, Wisconsin. The Societies specialize in peer-reviewed, high-quality science titles for a wide variety of audiences.Some of the many areas we publish in Methods and Management-Crop Development and Improvement-Agrosystem Management and the Global Food Crisis-Environmental Conservation and Climatology 00 0 Half-Title Page Series Page Title Page Copyright Page CONTENTS FOREWORD PREFACE CONTRIBUTORS Conversion Factors for SI and non-SI Units 1 Chapter 1 Sampling Introduction Variation of Soils Sampling Plans Judgment Sample Simple Random Sample Stratified Random Sample Systematic Sample Sources of Errors Subsampling Composite Samples References 2 Chapter 2 Quality Assurance and Quality Control Scope Sampling Physical Testing Chemical Testing Policy Statement Authority Goal Responsibility Definitions Quality Assurance Quality Control Defensibility Traceability Quality Assurance Manual Standard Operating Procedures Organization Analytical Methods Record Keeping Training Facilities Instruments and Equipment Data Management Documentation Assessment Internal External Proficiency Testing Quality Control Definitions Test Portion Replicate Duplicates Spiked (or Fortified) Samples Quality Control Check Samples Laboratory Control Samples Standard Reference Materials Control Charts Precision Reproducibility Accuracy Bias Statistical Process Control Statistics Control Charts Outliers Precision Precision of the Analysis Evaluating Sources of Imprecision Repeatability and Reproducibility Accuracy True Value Bias Contamination Blind Duplicates and Split Samples Scenario One Scenario Two Calibration Range of Analysis Method Detection Limit Limit of Quantitation Limit of Linearity Linear versus Quadratic Calibration Curves References 3 Chapter 3 Dissolution for Total Elemental Analysis Sources of Error in Dissolution of Solids Principles Digestion with Aqua Regia and Hydrofluoric Acid Digestion with Hydrofluoric, Perchloric and Sulfuric Acids Fusion with Alkali Carbonate Fusion with Sodium Peroxide Microwave Digestion Safety Notes Method for Preparation of Samples Special Apparatus Procedure Comments Method for Digestion with Aqua Regia and Hydrofluoric Acid in a Closed Vessel Special Apparatus Reagents Procedure Comments Method for Digestion with Hydrofluoric, Sulfuric, and Perchloric Acids Special Apparatus Reagents Procedure Comments Method for Pretreatment of Soils High in Ferric Oxide and Manganese Dioxide Special Apparatus Reagents Procedure Method for Fusion with Sodium Carbonate Special Apparatus Reagents Procedure Comments Method for Sodium Peroxide Fusion Special Apparatus Reagents Procedure Comments Method for Decomposition with Microwave Digestion Special Apparatus Reagents Procedure Comments References 4 Chapter 4 Atomic Absorption and Flame Emission Spectrometry Principles Comparison of Techniques Instrumentation Light Sources Atomization Systems Optical System Sensitivity and Detection Limits Interferences Nonspectral Interferences Spectral Interferences Sample Preparation Soil Digests Soil Solutions and Soil Extracts Specialized Sample Introduction Methods Hydride Generation Cold Vapor Method Solid Samples Flow Injection References 5 Chapter 5 Inductively Coupled Plasma Emission Spectrometry and Inductively Coupled Plasma-Mass Spectrometry Inductively Coupled Plasma-Atomic Emission Spectrometry and Inductively Coupled Plasma-Mass Spectrometry Instrumentation Analytical Capabilities Practical Applications Quality Control Methods Summary References 6 Chapter 6 Neutron Activation Analysis Principles Neutron Induced Reactions Neutron Capture Cross-Sections Production and Decay of Radioactive Isotopes Nuclear Decay and Detection of Radiation Equipment Neutron Sources Gamma-Ray Detectors Multichannel Analyzers General Methods Radiation Safety Preparation of Samples for Neutron Irradiation Neutron Irradiation Radioassay References 7 Chapter 7 Elemental Analysis by X-Ray Fluorescence Spectroscopy Principles Nature and Production of X-Ray Spectra Interaction of X-Rays with Matter Instrumentation Wavelength-Dispersive Spectrometers Energy Dispersive Spectrometers Advantages/Disadvantages of Wavelength-Dispersive Spectrometers and Energy-Dispersive Spectrometers Equipment Selection and Safety Analytical Capabilities Qualitative Analysis Quantitative Analysis Sample Preparation Techniques Loose Powders Pressed Pellets Fused Discs Thin Films Liquid Samples Methods for Analysis of Major Elements Preparation of Glass Discs Analysis of Minor and Trace Elements in Soil and Plant Samples Preparation of Pressed Powder Pellets Elemental Analysis of Loose Powder and Liquid Samples Other Applications References 8 Chapter 8 Liquid Chromatography Principles High-Performance Liquid Chromatography Instrumentation Columns Separation Methods Eluents (Mobile Phases) Detectors Recorders Applications Comments Ion Chromatography Instrumentation Eluent-Suppressed System Eluent-Nonsuppressed System Columns Separation Methods Eluents Detectors Recorders Applications References 9 Chapter 9 Differential Pulse Voltammetry Direct Current and Normal Pulse Polarography Direct Current Polarography Normal Pulse Polarography Differential Pulse Polarography Principles Applications Anodic Stripping Voltammetry Principles Applications Modem Voltammetric Techniques Instruments and Electrodes Instruments Indicator Electrodes General Methods Application to Soil Solutions and Natural Waters Complexation and Speciation Oxidation-Reduction Chemical Analysis Interferences and Other Problems Conclusions Acknowledgments References 10 Chapter 10 Fourier Transform Infrared and Raman Spectroscopy Theory Molecular Energy Molecular Vibrations Infrared Absorption Raman Scattering Vibrational Analysis Fourier Transform Infrared Spectrometers Principles of Operation Data Collection Spectral Processing Considerations Spectral Analysis Comparison to Raman Spectroscopy Sampling Methods Transmission Methods Self-Supporting Films Diffuse Reflectance Attenuated Total Reflectance Fourier Transform Infrared Microspectroscopy Low Temperature Studies Raman Microprobe Acknowledgments References 11 Chapter 11 Electron Spin (or Paramagnetic) Resonance Spectroscopy Theory and Principles The Resonance Phenomenon Spectral Parameters The g-Factor The ESR Experiment Instrumentation Sample Preparation Precautions, Sensitivity, Resolution Physico-Mathematical Determination and Theoretical Interpretation of Spectral Parameters Applications to Soil Systems Whole Soil Organic Paramagnetic Species in Soil Interpretation, Examples, and Comments on Electron Spin Resonance Data Paramagnetic Transition Metal Ion Complexes with Soil Organic and Mineral Materials Spin Derivatization in Soil Chemistry Electron Spin Resonance-Related Spectroscopies Electron Nuclear Double Resonance Spectroscopy Electron Spin Echo Spectroscopy Comments References 12 Chapter 12 X-Ray Photoelectron Spectroscopy X-Ray Photoelectron Spectroscopy Principles X-Ray Photoelectron Spectroscopy Instrumentation Referencing Binding Energy X-Ray Photoelectron Spectroscopy Analysis Spin Orbit Splitting Satellites Multiplet Splitting Atomic Concentrations Calculations Angle Resolved X-Ray Photoelectron Spectroscopy and Depth Profile Studies Sample Preparation Sampling Handling and Treatment Recent Advances and Developments Acknowledgments References 13 Chapter 13 X-Ray Absorption Fine Structure Spectroscopy Physical Basis of X-Ray Absorption Fine Structure Synchrotrons and Beam Line Hardware Experimental and Data Analysis Extended X-Ray Absorption Fine Structure Analysis of Soil Materials Data Analysis Programs Sources of Further Information References 14 Chapter 14 Salinity: Electrical Conductivity and Total Dissolved Solids Introduction Saturation and other Aqueous Extracts Principles Apparatus Reagent Procedure Calculations Comments Electrical Conductivity of Waters and Aqueous Extracts Principles Apparatus Reagents Procedure Calculation Comments Electrical Conductivity of Saturated Soil Pastes and Determination of Soil Salinity Principles Apparatus Reagents Procedure Calculation Comments Total Dissolved Solids in Waters and Aqueous Extracts Principles Apparatus Procedure Calculation Comments References 15 Chapter 15 Carbonate and Gypsum Carbonate Total Carbonate Analysis Pressure Calcimeter Method Gravimetric Method Simple Titrimetric Procedure Volumetric Calcimeter Method Gravimetric Method for Loss of Carbon Dioxide Acetic Acid Dissolution Method Carbonate Reactivity Carbonate Reactivity by pH Stat Carbonate Reactivity by a Manometric Procedure Active Carbonate Carbonate Equilibria-Solid Phase Principles Reaction Rates Extraction of Soil Water for Carbonate Equilibrium Determinations Gypsum Method References 16 Chapter 16 Soil pH and Soil Acidity Definition of pH Significance of Soil pH Values Presence of Free Acids Presence of Aluminum Ions Presence of Hydroxy-Aluminum Presence of Calcium Carbonate Presence of Sodium Carbonate Factors Which Affect Soil pH The Effect of Dilution Salt Content Carbon Dioxide Content Suspension Effect Fundamentals of pH Measurement Colorimetric Determinations of pH Electrometric Measurements Electrometric Measurement of Soil pH Equipment Standardization of the Meter Electrode Problems Procedure for Soil pH Measurement Equipment and Reagents Determination-pH in Water pH in One-One Hundredth Molar Calcium Chloride pH in One Molar Potassium Chloride Alternative Methods for pH Measurement Use of Microelectrodes Use of Test Kits pH Papers References 17 Chapter 17 Lime Requirement Introduction: Definition and Importance of Lime Requirement Methods Factors Affecting Lime Requirement Nature of Soil Acidity Neutralization Sequence: Initial and Desired pH Soil Properties Analytical Considerations Lime Requirement Methods Field Estimation of Lime Requirement Soil-Lime Incubations Soil-Base Titrations Soil-Buffer Equilibrations Exchangeable Aluminum Other Lime Requirement Methods References 18 Chapter 18 Aluminum Total Aluminum Introduction Principles Fusion and Dissolution Methods for Total Aluminum Comments Alternative Procedure for Total Aluminum Exchangeable and Extractable Aluminum Extraction from Mineral Soils with Unbuffered Salts Extraction of Aluminum from Organic Matter and Organic Soils Extraction of Aluminum from Poorly Ordered Phases Sampling Aluminum in Soil Solutions Introduction In Situ Sampling with Lysimeters Extraction of Soil Samples in the Laboratory Filtration of Soil Solution Samples Chemical Speciation of Solution Aluminum Introduction Timed Spectrophotometric Assays Physicochemical Separation Methods Spectrophotometric Methods for Aluminum Analysis Introduction 8-Hydroxyquinoline-Butyl Acetate Alternate Spectrophotometric Methods Atomic Absorption and Inductively Coupled Plasma Optical Emission Spectrometry Atomic Absorption and Atomic Emission Spectrometry Plasma Emission and Plasma Mass Spectrometry Alternative Methods for Aluminum Analysis X-Ray Fluorescence Spectrometry Titrimetric Methods References 19 Chapter 19 Lithium, Sodium, Potassium, Rubidium, and Cesium General Introduction Properties of the Alkali Metals Mineralogy of Alkali Elements in Soils Potassium Sodium Lithium, Rubidium, and Cesium Analytical Methods for the Alkali Metals Analysis for Total Alkali Elements Hydrofluoric Acid Digestion for Total Alkali Elements Measurement of Soil Potassium Exchangeable Potassium Nonexchangeable Potassium Mineral Potassium Analyses Soil Tests for Potassium Mehlich 1 Extraction Mehlich 3 Extraction Ammonium Acetate Extractable Potassium Morgan Extraction Modified Morgan Extraction Ammonium Bicarbonate-Diethylenetriamine Pentaacetic Acid Extraction Exchangeable and Soluble Sodium Introduction Procedure Lithium, Rubidium, and Cesium Introduction Procedure for Extractable Lithium or Rubidium References 20 Chapter 20 Beryllium, Magnesium, Calcium, Strontium, and Barium Properties of Alkaline-Earth Metals Mineralogy and Distribution of Beryllium, Magnesium, Calcium, Strontium, and Barium in Rocks and Soils Total Elemental Magnesium, Calcium, Strontium, Barium, and Beryllium Introduction Digestion Methods Analysis by Atomic Absorption Spectroscopy Analysis by Inductively Coupled Plasma-Atomic Emission Spectrometry X-Ray Fluorescence Suspended Solids by Inductively Coupled Plasma-Atomic Emission Spectrometry Ion Beam Partitioning of Alkaline-Earth Metals in Soils Introduction Soluble Extractable/Exchangeable Fraction Availability Indices Analytical Methods Introduction Atomic Absorption Spectrophotometry Inductively Coupled Plasma Electrothermal Atomic Absorption Flame Emission Photometry Ion Chromatography Titrimetric Permanganate Method Colorimetric References 21 Chapter 21 Boron Principles and Concepts in Boron Chemistry Boron Chemistry in Aqueous Media Boron Adsorption-Desorption by Soil Constituents Boron Extraction Methods Total Boron in Soil-Fusion Method Boron Availability Assessment for Plant Uptake Boron Determination Colorimetric Methods Potentiometric Methods Inductively Coupled Plasma Spectrometry References 22 Chapter 22 Silicon Silicon in Soils Principles of Analyses Sample Preparation for Total Silicon: Lithium Tetraborate Fusion Sample Preparation for Total Silicon: Acid Digestion Silicon Determination by Light Absorption Spectrometry Yellow Silicomolybdic Acid Procedure Blue Silicomolybdous Acid Procedure References 23 Chapter 23 Iron Principal Forms of Soil Iron Total Iron Introduction Decomposition of Sample (Sodium Carbonate Fusion) Decomposition of Sample (Hydrofluoric Acid/Perchloric Acid/Sulfuric Acid Digestion) Decomposition of Sample (Hydrofluoric Acid Digestion) Selective Extraction Procedures Introduction Total "Free" Iron Oxide "Active" or "Amorphous" Iron Oxide Organically Bound Iron Water-Soluble and Exchangeable Iron Availability Indices Introduction Diethylenetriaminepentaacetic Acid (DTPA) Soil Test Procedure for DTPA-Extractable Iron Procedure for Ammonium Bicarbonate-DTPA Extractable Iron Atomic Absorption Spectroscopy Principles Special Apparatus Reagents Procedure Colorimetric Determination of Ferrous Iron and Ferric Iron by the 1,10-Phenanthroline Method Principles Special Apparatus Reagents Procedure References 24 Chapter 24 Manganese Introduction Analysis Instrumental Approaches-Introduction Inductively Coupled Argon Plasma Emission Spectroscopy Atomic Absorption Colorimetric (Periodate) Method Availability Indices Background Method for Water-Soluble Manganese Exchangeable Manganese Double Acid (Hydrochloric Acid + Sulfuric Acid)-Extractable Manganese Diethylenetriaminepentaacetic Acid-Extractable Manganese Easily Reducible Manganese Selective Dissolution of Manganese Oxides from Soils and Sediments Total Manganese by Atomic Absorption or Inductively Coupled Plasma Emission Spectroscopy Total Manganese, Direct Soil Analyses by Inductively Coupled Plasma Emission Spectroscopy Total Manganese by the Colorimetric Method References 25 Chapter 25 Chromium Soil Handling The Problem Method Digestion Methods for Total Chromium in Soils and Plants s-Diphenylcarbazide Method for Determining Soluble Chromium(VI) Reaction Mechanism and Conditions Interference in s-Diphenylcarbazide Chromium (VI) Test Oxidative Preparation of Samples for s-Diphenylcarbazide Test Oxidation of Organic Ligands Oxidation of Chromium (III) to Chromium (VI) Alternative Methods for Chromium (III), Chromium (VI), and Total Chromium in Solution Recommended Procedures for Determination of Chromium Chromium(VI) Standards Chromium Standards Digestion of Soil Materials for Chromium Analysis Chromium Oxidizable by Hypochlorite Determination of Exchangeable and Total Chromium{VI) in Soils Extraction of Labile Chromium(III) Determination of Chromium (VI) in Solutions Oxidation of Organic Ligands Binding Chromium (III) Oxidation of Inorganic Chromium (III) with Cerium (IV) Methods for Studying Soil Redox Using Chromium as a Redox Tool Standard Chromium Net Oxidation Test Total Chromium(VI) Reducing Capacity Available Reducing Capacity for Chromium (VI) Soil Reducing Intensity for Chromium(VI) References 26 Chapter 26 Copper and Zinc Forms and Concentrations of Copper and Zinc in Soils Available Copper and Zinc Forms in Soils Soil Properties versus Deficiencies of Copper and Zinc Development of Copper and Zinc Soil Tests Availability Indices Overview of Copper and Zinc Soil Tests Soil Sample and Extractant Preparation Diethylenetriaminepentaacetic Acid-Triethanolamine Method Diethylenetriaminepentaacetic Acid-NH4HC03 Method Mehlich-I (Double Acid) Method Mehlich-III Method Dilute Hydrochloric Acid Method Total Copper and Zinc Hydrofluoric, Nitric, Perchloric, and Sulfuric Acid Method References 27 Chapter 27 Molybdenum and Cobalt General Principles Total Molybdenum Principles Method Comments Availability Indexes for Molybdenum Principles Method Comments Method Comments Total Cobalt Principles Method Comments Availability Index for Cobalt Acknowledgments References 28 Chapter 28 Nickel, Cadmium, and Lead Sampling and Sample Preparation Total Nickel, Cadmium, and Lead Principles United States Environmental Protection Agency SW-846, Method 3050: Digestion with Nitric Acid and Hydrochloric Acid in a Conical Beaker on a Hot Plate Digestion with Nitric Acid and Perchloric Acid in a Block Digester Digestion with Hydrogen Peroxide, Hydroflouric Acid, Nitric Acid, and Perchloric Acid in Teflon Beakers on a Hot Plate Selective Extraction of Nickel, Cadmium, and Lead from Soils Principles Plant Available Fractions of Nickel, Cadmium, and Lead Principles Diethylenetriaminepentaacetic Acid Method Ammonium Bicarbonate-Diethylenetriaminepentaacetic Acid Method One-Tenth Molar Hydrochloric Acid Method Double Acid (Mehlich I) Method Mehlich III Method Analytical Determination of Nickel, Cadmium, and Lead Atomic Absorption Spectrophotometry Inductively Coupled Plasma Atomic Emission Spectrophotometry Separation and Concentration Method for Atomic Absorption Spectrometry or Inductively Coupled Plasma Atomic Emission Spectrometry Acknowledgments References 29 Chapter 29 Mercury Total Mercury in Soils and Sediments Introduction Principles of Total Mercury Analysis Total Mercury Method Total Mercury in Soil Extracts, Leachates, and Water Samples Introduction Principles Manual Method for Determination of Dissolved, Suspended, and Total Mercury Automated Procedure for Determination of Total Mercury Organic Mercury Compounds General Comments References 30 Chapter 30 Selenium and Arsenic General Introduction Selenium Introduction Total Selenium in Soil Total Selenium and Selenium Species in Soil Solutions and Water Extracts of Soil Selenium Availability Arsenic Introduction Total Arsenic in Soil Total Arsenic and Arsenic Species in Soil Solutions and Water Extracts of Soil Availability Indices of Soil Arsenic Acknowledgments References 31 Chapter 31 Bromine, Chlorine, & Fluorine General Introduction Bromine Introduction Direct Potentiometric Method Microdiffusion Method Ion Chromatography Chlorine Introduction Principles Potentiometric Titration Method Direct Potentiometric Method Automatic Titration Method Mercury(II) Thiocyanate Method Ion Chromatography Fluorine Introduction Principles Total Fluorine Soluble Fluorine Measurement of Fluorine in Solution Other Available Methods for Determination of Bromine, Chlorine, and Fluorine References 32 Chapter 32 Phosphorus Total Phosphorus Principles Special Apparatus Methods Comments Total Organic Phosphorus Principles Special Apparatus Methods Comments Fractionation of Soil Phosphorus Fractionation of Inorganic Phosphorus Fractionation of Organic Phosphorus Availability Indices General Principles Methods Buffering Indices Principles Methods Comments Phosphorus Determination Principles Special Apparatus Colorimetric Methods Other Methods References 33 Chapter 33 Sulfur General Introduction Total Sulfur Wet Chemical Methods Automated Instrumental Methods Comments Inorganic Sulfate Principles Methods Comments Organic Sulfur Hydriodic Acid-Reducible Sulfur Carbon-Bonded Sulfur Availability Indices Extraction of Sulfate-Sulfur Extraction of Organic Sulfur References 34 Chapter 34 Total Carbon, Organic Carbon, and Organic Matter General Information Total Carbon Introduction Total Carbon by Dry Combustion Total Carbon by Wet Combustion Organic Carbon Introduction Organic Carbon as Calculated from Total Carbon Determinations Wet and Dry Combustion Techniques for Direct Measurement of Organic Carbon in Calcareous Soils Organic Carbon in Soil Extracts Rapid Dichromate Oxidation Techniques Comparison of Methods for Determining Organic Carbon Organic Matter Introduction Calculation of Organic Matter Content Direct Estimation of Organic Matter Expression of Soil Organic Matter Content Acknowledgments References 35 Chapter 35 Organic Matter Characterization Introduction Extraction of Soil Organic Matter Extraction and Purification of Humic Substances Extraction and Purification of Soil Polysaccharides Fractionation of Soil Organic Matter Fractionation of Humic Substances Fractionation of Polysaccharides Density Fractionation of Soil Organic Matter Characterization of Humic Substances Characterization by Chemical Methods Characterization by Spectroscopic Methods Measurements of Physical Properties Other Techniques Characteristics of Soil Polysaccharides Determination of Monosaccharide Composition Future Developments Acknowledgment References 36 Chapter 36 Extraction of Organic Chemicals Sampling and Preservation Liquid Samples Solid Samples Extraction Procedures Purge and Trap Solvent Extraction Extract Cleanup Gel Permeation Chromatography Other Cleanup Procedures "Bound" Pesticide Residues Matrix and Surrogate Spiking Solutions Conclusions Acknowledgments References 37 Chapter 37 Nitrogen-Total Dumas Methods Kjeldahl Methods General Pretreatment of Sample Digestion of Sample Determination of Ammonium in Digest Regular Kjeldahl Method Special Apparatus Reagents Procedure Comments Ammonia Electrode Modification of Kjeldahl Method Special Apparatus Reagents Procedure Comments Hydrofluoric Acid Modification of Kjeldahl Method to Include Fixed Ammonium Special Apparatus Reagents Procedure Comments Permanganate-Reduced Iron Modification of Kjeldahl Method to Include Nitrate and Nitrite Special Apparatus Reagents Procedure Comments Salicylic Acid-Thiosulfate Modification of Kjeldahl Method to Include Nitrate and Nitrite Special Apparatus Reagents Procedure Comments Regular Kjeldahl Method Using a Block Digester Special Apparatus Reagents Procedure Comments Other Methods Acknowledgments References 38 Chapter 38 Nitrogen-Inorganic Forms Methods for Determination of Inorganic Nitrogen in Soils Extraction of Exchangeable Ammonium and Nitrate and Nitrite Introduction Method Determination of Ammonium, Nitrate, and Nitrite in Soil Extracts Steam-Distillation Methods Microdiffusion Methods Colorimetric Methods Ion-Selective Electrodes Determination of Nonexchangeable Ammonium Introduction Principles Method Calculations Comments References 39 Chapter 39 Nitrogen-Organic Forms Introduction Recovery of Various Forms of Nitrogen as Ammonia by Steam-Distillation Procedures Principles Method Comments Colorimetric Method for Amino Acid-Nitrogen Principles Method Comments Colorimetric Method for Amino Sugars Principles Method Comments References 40 Chapter 40 Cation Exchange Capacity and Exchange Coefficients Introduction Origin of Charges on Soil Particles Historical Review of Cation Exchange Capacity Methods Criteria for Selection of Cation Exchange Capacity Methodology Cation Exchange Selectivity Coefficients Problems in Measurement of Cation Exchange Capacity Presence of Soluble Salts and Carbonates Effect of Cation and Anion Type pH Effects and the Use of Buffered Solutions Ionic Strength Effects and Removal of Entrained Electrolyte Cation Exchange Capacity of Soils Containing Salts, Carbonates or Zeolites Introduction Method Cation Exchange Capacity of All Other Soils Compulsive Exchange Method Unbuffered Salt Extraction Method Ammonium Acetate (pH 7) Method Summation of Cations (Effective Cation Exchange Capacity) Measurement of Selectivity Coefficients Introduction Use of Homoionic Clay Fractions to Determine the Vanselow Selectivity Coefficient Acknowledgments References 41 Chapter 41 Charge Analysis of Soils and Anion Exchange Source of Surface Charge Constant Charge Variable Charge Charge/Potential Relationships Counterion Adsorption Specific versus Indifferent Inner-Sphere versus Outer-Sphere Stern Model Solid Particle versus Embathing Solution Points of Zero Charge Measurement of Surface Charge Point of Zero Net Charge Introduction Apparatus Reagents Procedure Calculations Comments Point of Zero Salt Effect Introduction Batch Method (Discontinuous) Backtitration Method Automatic Potentiometric Titration (Continuous) Calculations Comments Point of Zero Net Proton Charge Constant Charge Density Apparatus Reagents Procedure Calculations Comments References 42 Chapter 42 Redox Measurements of Soils Theory Application of Redox Measurements Construction of Platinum Electrodes Cleaning and Testing Electrodes Field Installation Field Measurement of Redox Potential Reliability of Field Redox Measurements Retrieval of Electrodes at End of Study Controlled Redox Potential Studies References 43 Chapter 43 Kinetic Methods and Measurements Batch Techniques Tube Technique Stirred-Batch Reactors Effects of Mixing Disadvantages Advantages Flow Methods Continuous Flow Methods Apparatus Fluidized Bed Reactor Stopped-Flow Technique Analyses of Rate Data Collected from Batch and Flow Techniques Integrated Rate Equations and Graphical Assessment Initial Rate Method Least Squares Techniques Example of Data Analyses Using Initial Rate and Integrated Rate Experiments Relaxation Methods Background Pressure-Jump Relaxation References 44 Chapter 44 Equilibrium Modeling in Soil Chemistry Mathematical Basis of Chemical Equilibrium Models Modeling Metal-Ligand-Surface Interactions Metal-Organic Ligand Interactions Adsorption Models Thermochemical Data Data Sources Nonideality Corrections Geochemical Equilibrium Models Used in Soil Chemistry GEOCHEM SOILCHEM MINTEQ MINEQL+ C-Salt FITEQL Examples of Equilibrium Computations Speciation Calculation with GEOCHEM-PC Validation of Equilibrium Models Methods of Validation Modeling Limitations Equilibrium Conditions Thermochemical Data Adsorption Modeling Future Trends in Equilibrium Modeling References 45 SUBJECT INDEX Sampling / Roger G. Peterson and Lyle D. Calvin -- Quality assurance and quality control / E.J. Klesta, Jr. and J.K. Bartz -- Dissolution for total elemental analysis / L.R. Hossner -- Atomic absorption and flame emission spectrometry / Robert J. Wright and Tomasz I. Stuczynski -- Inductively coupled plasma emission spectrometry and inductively coupled plasma-mass spectroscopy / Parviz N. Soltanpour [and others] -- Neutron activation analysis / Philip A. Helmke -- Elemental analysis by x-ray fluorescence spectroscopy / A.D. Karathanasis and Ben F. Hajek -- Liquid chromatography / M.A. Tabatabai and W.T. Frankenberger, Jr. -- Differential pulse voltammetry / Larry M. Shuman -- Fourier transform infrared and Raman spectroscopy / C.T. Johnston and Y.O. Aochi -- Electron spin (or paramagnetic) resonance spectroscopy / Nicola Senesi -- X-ray photoelectron spectroscopy / R.K. Vempati, T.R. Hess, and D.L. Cocke -- X-ray absorption fine structure spectroscopy / Scott Fendorf and Donald L. Sparks -- Salinity: electrical conductivity and total dissolved solids / J.D. Rhoads -- Carbonate and Gypsum / Richard H. Loeppert and Donald L. Suarez -- Soil pH and soil acidity / Grant W. Thomas -- Lime requirement / J. Thomas Sims -- Aluminum / Paul M. Bertsch and Paul R. Bloom -- Lithium, Sodium, Potassium, Rubidium, and Cesium / Philip A. Helmke and Donald L. Sparks -- Beryllium, Magnesium, Calcium, Strontium, and Barium / Donald L. Suarez -- Boron / R. Keren -- Silicon / R. Lewis Jones and Gary B. Dreher -- Iron / Richard L. Loeppert and W.P. Inskeep -- Manganese / R.P. Gambrell -- Chromium / Richmond J. Bartlett and Bruce R. James -- Copper and Zinc / Stewart T. Reed and D.C. Martens -- Molybdenum and Cobalt / John L. Sims -- Nickel, Cadmium, and lead / Michael C. Amacher -- Mercury / James G. Crock -- Selenium and Arsenic / P.M. Huang and Roger Fujii -- Bromine, Chlorine, and Fluorine / W.T. Frankenberger, Jr. [and others] -- Phosphorus / Shiou Kuo -- Total Carbon, organic Carbon, and organic matter / Darrell W. Nelson and Lee E. Sommers -- Organic matter characterization / Roger S. Swift -- Extraction of organic chemicals / Brij L. Sawhney -- Nitrogen-total / John M. Bremner -- Nitrogen-inorganic forms / R.L. Mulvaney -- Nitrogen / F.J. Stevenson -- Cation exchange capacity and exchange coefficients / Malcolm E. Sumner and William P. Miller -- Charge analyses of soils and Anion exchange / Lucian W. Zelazny, Liming He, and An M. Vanwormhoudt -- Redox measurements of soils / W.H. Patrick, Jr., R.P. Gambrell, and S.P. Faulkner -- Kinetic methods and measurements / Donald L. Sparks [and others] -- Equilibrium modeling in soil chemistry / S.V. Mattigod and J.M. Zachara Pt. 1. Physical And Mineralogical Methods -- Pt. 2. Microbiological And Biochemical Properties / Editorial Committee, R.w. Weaver, Chair ... [et Al.] ; Managing Editor, S.h. Mickelson -- Pt. 3. Chemical Methods / Editorial Committee, D.l. Sparks ... [et Al.] ; Managing Editor, J.m. Bartels -- Pt. 4. Physical Methods / Editorial Committee, Gaylon S. Campbell ... [et Al.] ; Managing Editor, Lisa Al-amoodi Arnold Klute, Editor. Pt. 1 Is A Reprint Of Pt. 1 Of The 2nd Ed., Originally Published In 1986 As No. 9, Pt. 1 Of The Series Agronomy. Includes Bibliographical References And Indexes.