Partition and adsorption of organic contaminants in environmental systems Machine generated contents note: 1 Important Thermodynamic Properties 1.1 Introduction 1 1.2 First Law of Thermodynamics 2 1.3 Second Law of Thermodynamics 3 1.4 Extensive and Intensive Properties 6 1.5 Chemical Potential 6 1.6 Chemical Potentials in Multiple Phases 7 1.7 Change in Chemical Potential with Pressure 8 1.8 Activity of a Substance: 9 1.9 Vapor Liquid and Vapor Solid Equilibria 10 2 Fundamentals of the Solution Theory 2.1 Introduction 14 2.2 Raoults Law 14 2.3 Henrys Law 18 2.4 Flory Huggins Theory 19 2.5 Variation of Activity Coefficient with Concentration 21 2.6 Molar Heat of Solution 22 2.7 Cohesive Energy Density and Solubility Parameter 27 3 Interphase Partition Equations 3.1 Partition between Two Separate Phases 30 3.2 Partition between an Organic Solvent and Water 31 3.3 Partition between a Macramolecular Phase and Water 32 3.4 Temperature Dependence of Partition Coefficient 33 3.5 Concentration Dependence of Partition Coefficient 36 4 Fundamentals of the Adsorption Theory 4.1 Introduction 39 4.2 Langmuir Adsorption Isotherm 41 4.3 Freundlich Equation 43 4.4 BET Multilayer Adsorption Theory 43 4.5 Polanyi Adsorption Potential Theory 45 4.6 Surface Areas of Solids 48 4.7 Sosteric Heat of Adsorption 50 5 Contaminant Partition and Bioconcentration 5.1 Introduction 53 5.2 Octanol Water Systems 54 5.3 Heptane Water Systems 59 5.4 Butanol Water Systems 62 5.5 Substituent Contributions to Partition Coefficients 63 5.6 Lipid Water Systems 68 5.6.1 Solubility of Solutes in Lipids 68 5.6.2 Lipid Water Partition Coefficient 72 5.7 Correlations of Partition Coefficients 77 5.8 Bioconcentration of Organic Contaminants 80 6 Adsorption of Vapors on Minerals and Other Solids 6.1 Introduction 86 6.2 Nitrogen Isotherm and Solid Surface Area 86 6.3 Micropore Volume 90 6.4 Imnproper Surface Area Measurement 92 6.5 Adsorption of Water and Organic Vapors 100 7 Contaminant Sorption to Soils and Natural Solids 7.1 Introduction 106 7.2 Background in Sorption Studies 107 7.2.1 Influences of Mineral Matter Organic Matter and Water 107 7.2.2 Soils as a Dual Sorbent for Organic Compounds 109 7.3 Sorption from Water Solution 112 7.3.1 General Equilibrium Characteristics 112 7.3.2 Effect of Soil Organic Matter versus Sediment Organic Matter 124 7.3.3 Effect of Contaminant Water Solubility 133 7.3.4 Behavior of PAHs versus Other Nonpolar Contaminants 138 7.3.5 Estimation of Sorption Coefficients for Nonpolar Contaminants 145 7.3.6 Sorption to Previouy Contaminated Soils 146 7.3.7 Deviations from Linear Sorption Isotherms 149 7.3.8 Influence of Dissolv and Suspended Natural Organic Matter 18 7.3.9 Influence of Surfactants and Microemulsions 178 7.4 Sorption from Organic Solvents 192 7.4.1 Effect of Solvent Polarity 192 7.4.2 Effects of Temperature Moisture and Contaminant Polarity 195 7.5 Sorption from Vapor Phase 200 7.5.1 General Aspects of Vapor Sorption 200 7.5.2 Influence of Moisture on Vapor Sorptiom 203 7.6 Influence of Sorption on Contaminant Activity 210 8 Contaminant Uptake by Plants from Soil and Water 8.1 Introduction 214 8.2 Background in Plant Uptake Studies 215 8.3 Theoretical Considerations 216 8.4 Uptake by Small Plant Roots from Water 220 8.5 Uptake by Plant Seedlings from Soil 223 8.6 Uptake by Root Crops from Different Soils 226 8.7 Effect of Plant Composition 228 8.8 Contaminant Levels in Aquatic Plants and Sediments 229 8.9 Time Dependence of Contaminants in Plants 231