John wiley sons environmental organic chemistry

ENVIRONMENTAL ORGANIC CHEMISTRY Second Edition ENVIRONMENTAL ORGANIC CHEMISTRY Second Edition Rene P Schwarzenbach Philip M Gschwend Dieter M Imboden @WILEY-INTERSCIENCE A JOHN WILEY & SONS, INC., PUBLICATION This text is printed on acid-free paper @ Copyright 02003 by John Wiley & Sons, Inc All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Section I07 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 1923, (978) 750-8400, fax (978) 750-4744, or on the web at www.copyright.com Requests to the Publisher for 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products and services please contact our Customer Care Department within the U S at 877-762-2974, outside the U S at 17-572-3993 or fax 17-572-4002, Wiley also publishes its books in a variety of electronic formats Some content that appears in print, however, may not be available in electronic format Libray of Congress Cataloging-in-PublicationData Is Available ISBN 0-47 1-35750-2 Printed in the United States of America 10 V CONTENTS Preface xi PART I Introduction General Topic and Overview 1.1 1.2 1.3 Introduction / Assessing Organic Chemicals in the Environment: The Needs and the Tasks / What Is This Book All About? / An Introduction to Environmental Organic Chemicals 2.1 2.2 2.3 2.4 Partitioning: Molecular Interactions and Thermodynamics 3.3 3.4 3.5 3.6 13 Introduction / 14 The Makeup of Organic Compounds / 14 Classification, Nomenclature, and Examples of Environmental Organic Chemicals / Questions and Problems / PART I1 Equilibrium Partitioning Between Gaseous, Liquid, and Solid Phases 3.1 3.2 Introduction / 59 Molecular Interactions Determining the Partitioning of Organic Compounds Between Different Phases / 59 Using Thermodynamic Functions to Quantify Molecular Energies / 73 Using Thermodynaimc Functions to Quantify Equilibrium Partitioning / 84 Using Partition Constants/Coefficientsto Assess the Equilibrium Distribution of Neutral Organic Compounds in Multiphase Systems / 93 Questions and Problems / 95 55 57 vi Vapor Pressure 4.1 4.2 4.3 4.4 4.5 97 Introduction / 98 Theoretical Background / 98 Molecular Interactions Governing Vapor Pressure / 110 Availability of Experimental Vapor Pressure Data and Estimation Methods / 118 Questions and Problems / 126 Activity Coefficient and Solubility in Water 5.1 5.2 5.3 5.4 5.5 5.6 Introduction / 135 Thermodynamic Considerations / 135 Molecular Interpretation of the Excess Free Energy of Organic Compounds in Aqueous Solutions / 142 Effect of Temperature and Solution Composition on Aqueous Solubility and Activity Coefficient / 154 Availability of Experimental Data; Methods for Estimation of Aqueous Activity Coefficient and Aqueous Solubility / 172 Questions and Problems / 175 Air-Organic Solvent and Air-Water Partitioning 6.1 6.2 6.3 6.4 6.5 7.6 213 Introduction / 214 Thermodynamic Considerations / 214 Comparison of Different Organic Solvent-Water Systems / 16 The n-Octanol-Water Partition Constant / 223 Dissolution of Organic Compounds in Water from Organic Liquid Mixtures-Equilibrium Considerations (Advanced Topic) / 235 Questions and Problems / 239 Organic Acids and Bases: Acidity Constant and Partitioning Behavior 8.1 8.2 8.3 181 Introduction / 182 Thermodynamic Considerations / 183 Air-Organic Solvent Partitioning / 185 Air-Water Partitioning / 197 Questions and Problems / 208 Organic Liquid-Water Partitioning 7.1 7.2 7.3 7.4 7.5 133 Introduction / 246 Thermodynamic Considerations / 246 Chemical Structure and Acidity Constant / 256 245 vii 8.4 8.5 8.6 Availability of Experimental Data; Methods for Estimation ofAcidity Constants 1261 Aqueous Solubility and Partitioning Behavior of Organic Acids and Bases 1268 Questions and Problems 1272 Sorption I: General Introduction and Sorption Processes Involving Organic Matter 9.1 Introduction I 277 9.2 Sorption Isotherms, Solid-Water Distribution Coefficients (Kid),and the Fraction Dissolved V),; / 280 9.3 Sorption of Neutral Organic Compounds from Water to Solid-Phase Organic Matter (POM) / 29 9.4 Sorption of Neutral Compounds to "Dissolved" Organic Matter (DOM) I 14 9.5 Sorption of Organic Acids and Bases to Natural Organic Matter (NOM) I 32 9.6 Questions and Problems / 326 10 Sorption 11: Partitioning to Living Media - Bioaccumulation and Baseline Toxicity 10.1 10.2 10.3 10.4 10.5 10.6 10.7 275 331 Introduction 1333 Partitioning to Defined Biomedia 1335 Bioaccumulation in Aquatic Systems I 349 Bioaccumulation in Terrestrial Systems / 36 I Biomagnification 1366 Baseline Toxicity (Narcosis) / 374 Questions and Problems I 381 11 Sorption 111: Sorption Processes Involving Inorganic Surfaces 387 11.1 Introduction I 389 11.2 Adsorption of Nonionic Organic Compounds to Inorganic Surfaces from Air I 39 11.3 Sorption of Nonionic Organic Compounds to Inorganic Surfaces in Water 1408 11.4 Adsorption of Ionized Organic Compounds from Aqueous Solutions to Charged Mineral Surfaces / 417 11.5 Surface Reactions of Organic Compounds (Advanced Topic) I 441 11.6 Questions and Problems I 448 viii Part I11 Transformation Processes 459 12 Thermodynamics and Kinetics of Transformation Reactions 12.1 12.2 12.3 12.4 12.5 461 Introduction / 462 Thermodynamics of Transformation Reactions / 463 Kinetic Aspects of Transformation Reactions / 468 Well-Mixed Reactor or One-Box Model / 482 Questions and Problems / 486 13 Chemical Transformations I: Hydrolysis and Reactions Involving Other Nucleophilic Species 489 13.1 Introduction, Overview / 49 13.2 Nucleophilic Substitution and Elimination at Saturated Carbon Atoms / 495 13.3 Hydrolytic Reactions of Carboxylic and Carbonic Acid Derivatives / 13 13.4 Hydrolytic Reactions of Phosphoric and Thiophosphoric Acid Esters / 536 13.5 Effects of Dissolved Metal Species and of Mineral Oxide Surfaces on Hydrolytic Reactions (Advanced Topic) / 540 13.6 Questions and Problems / 546 14 Chemical Transformations 11: Redox Reactions 14.1 14.2 14.3 14.4 555 Introduction, Overview / 556 Thermodynamic Considerations of Redox Reactions / 559 Reaction Pathways and Kinetics of Redox Reactions / 580 Questions and Problems / 602 15 Direct Photolysis 611 Introduction / 13 Some Basic Principles of Photochemistry / 14 Light Absorption by Organic Chemicals in Natural Waters / 627 Quantum Yield and Rate of Direct Photolysis / 641 Effects of Solid Sorbents (Particles, Soil Surfaces) on Direct Photolysis / 649 15.6 Questions and Problems / 650 15.1 15.2 15.3 15.4 15.5 16 Indirect Photolysis: Reactions with Photooxidants in Natural Waters and in the Atmosphere 16.1 Introduction / 656 16.2 Indirect Photolysis in Surface Waters / 658 655 ix 16.3 Indirect Photolysis in the Atmosphere (Troposphere)Reactions with Hydroxyl Radical (HO') / 672 16.4 Questions and Problems I 683 17 Biological Transformations 17.1 17.2 17.3 17.4 17.5 17.6 17.7 687 Introduction / 689 Some Important Concepts about Microorganisms 1694 Biochemical Strategies of Microbial Organic Chemists / 702 Rates of Biotransformations:Uptake / 734 Rates of Biotransformations: Microbial Growth / 739 Rates of Biotransformations: Enzymes / 750 Questions and Problems I 7 PART IV Modeling Tools: Transport and Reaction 775 18 Transport by Random Motion 18.1 Introduction: Advection and Diffusion / 779 18.2 Random Motion I 780 18.3 Random Motion at the Molecular Level: Molecular Diffusion Coefficients / 798 18.4 Diffusion in Porous Media / 15 18.5 Other Random Transport Processes in the Environment / 825 18.6 Questions and Problems / 828 777 19 Transport Through Boundaries 19.1 The Role of Boundaries in the Environment / 835 19.2 Bottleneck Boundaries / 839 19.3 Wall Boundaries 1848 19.4 Diffusive Boundaries / 866 19.5 Spherical Boundaries (Advanced Topic) / 871 19.6 Questions and Problems / 883 833 20 Air-Water Exchange 887 Introduction / 889 Measurement of Air-Water Transfer Velocities I 896 Air-Water Exchange Models 1906 Air-Water Exchange in Flowing Waters I 92 Influence of Surface Films and Chemical Reactions on Air-Water Exchange (Advanced Topic) / 929 20.6 Questions and Problems 1939 20.1 20.2 20.3 20.4 20.5 X 21 BoxModels 945 21.1 21.2 21.3 1.4 Principles of Modeling / 947 One-Box Models / 955 Two-Box Models / 982 Dynamic Properties of Linear Multidimensional Models (Advanced Topic) / 991 1.5 Questions and Problems / 1000 22 Models in Space and Time 22.1 22.2 22.3 22.4 22.5 One-Dimensional Diffusion /Advection / Reaction Models / 1006 Turbulent Diffusion / 1019 Horizontal Diffusion: Two-Dimensional Mixing / 1030 Dispersion (Advanced Topic) / 1038 Questions and Problems / 1044 Part V Environmental Systems and Case Studies 23 Ponds, Lakes, and Oceans 23.1 23.2 23.3 23.4 23.5 1051 1101 Transport and Reaction in Rivers / 1102 Turbulent Mixing and Dispersion in Rivers / 1120 A Linear TransportReaction Model for Rivers / 1130 Questions and Problems / 1141 25 Groundwater 25.1 25.2 25.3 25.4 1049 Linear One-Box Models of Lakes, Ponds, and Oceans / 1054 The Role of Particles and the Sediment-Water Interface / 1059 Two-Box Models of Lakes / 1075 One-Dimensional Continuous Lake Models (Advanced Topic)/ 1082 Questions and Problems / 1093 24 Rivers 24.1 24.2 24.3 24.4 1005 1147 Groundwater Hydraulics / 1148 Time-Dependent Input into an Aquifer (Advanced Topic) / 1160 Sorption and Transformations / 1170 Questions and Problems / 1179 Appendix 1185 Bibliography 1213 Index (Subject Index, Compound Index, List of Illustrative Examples) 1255 1300 Compound Index I-Naphthylamine T8.2 Naphthaten-I -ylamine acidity constant of corresponding T8.2 acid Hammett susceptibility factor Q8.5 Naptalam decadic molar extinction E15 I coefficients, calculated electronic absorption spectrum FI5 I 544 N-Naphthalen-I-yl-phthalamic acid influence of metals on hydrolysis 544 rate and mechanism Nitrilotriacetic acid NTA decadic molar absorption FI5.1, coefficient P15.3 E21.1 exchange constant T11.2 water-aluminosilicate surface (KNAC.EDA) molecular diffusivity in air F18.9 octanol-water partition constant T10.2 (Bis-carboxymethyl-amino)-acetic acid characteristic biodegradation rate E21.1 constants one-electron reduction potential T14.4 characteristic concentration in a E21.1 Swiss lake rate constant with hydroxyl radical F16.3 reaction rate constant with variable E21.2 input, calculation of reaction rate for second order E21.3 reaction rate constant, calculation of reaction rate for variable reaction E21.2 rate constant, calculation of total reaction rate constant in a lake, E2I.I calculation of polarizability T5.5 rate constant with hydroxyl radical F16.7 in troposphere reaction quantum yield of direct T15.7 photolysis reduction potentials of single F14.9 electron steps reduction rates with sulfide and F14.7 DOM refractive index T3.1 biodegradation to catechol E l 7.9 polarizability T5.5 salting constant, seawater T5.7 value of K Z ~ M and V',, TI 7.7 3-Nitrophenol 3-Nitro-phenol acidity constant and resonance F8.4 structures F8.6 salting constant, seawater T5.7 4-Nitrophenol T13.2 4-Nitro-phenol acidity constant and resonance F8.4 P20.6 structures acidity constant, calculation E8.2 air-water partition constant P20.6 decadic molar absorption F15.5 coefficient decadic molar absorption F15.5 coefficient of anion direct photolysis rate at near surface E15.3 and in water body, calculation relative reduction rates in different F14.10 reduction media direct photolysis rate of anion at E15.3 near surface and in water body, calculation 24-h-averaged total specific light T15.6 absorption rate, calculations relative reduction rates in different systems formation by enzymatic hydrolysis 707 of paraoxon decadic molar absorption T15.4 coefficients standard enthalpy and standard T4.2 entropy of evaporation polarizability T5.5 reactant in binary actinometer 648 standard reduction potential T14.3, F14.4 para-Nitroacetophenone PNAP 631 -(4-Nitro-phenyl)-ethanone T15.4, specific light absorption rate at wavelength and total, calculations F15.9 specific light absorption rate, 63 calculation example specific light absorption rate, F15.10 seasonal and latitudinal variations total specific light absorption rate, E15.2 calculation 3-Nitroaniline 3-Nitro-phenylamine biological organic phases-water TI0.2 partition coefficients octanol-water partition constant T10.2 4-Nitroaniline T8.2 4-Nitro-phenylamine acidity constant of corresponding T8.2 acid parameters for indirect photolysis P16.2 with carbonate radical para-Nitroanisole PNA 648 I-Methoxy-4-nitro-benzene reactant in binary actinometer 648 Nitro-benzene NB T14.3 Nitro-benzene absorbance spectrum of light E15.1 biological organic phases-water TI0.2 partition coefficients value of K;MM and V',,, TI 7.7 water saturated, mole fraction T5.I product in parathion hydrolysis T13.2 reaction rate constant with hydroxyl radical F16.7 in troposphere rate constant with singlet oxygen FI 6.5 reaction quantum yield of direct T15.7 photolysis 3-Nitrobenzene sulfonic acid P13.10 methyl ester 3-Nitro-benzenesulfonic acid methyl ester rate constant of neutral hydrolysis P13 I0 reaction quantum yield of direct TI5 photolysis of anion 4-Nitrobenzene sulfonic acid P13.10 methyl ester 4-Nitro-benzenesulfonic acid methyl ester rate constant of neutral hydrolysis P13.10 4-Nitrophenyl N-p henyl 528 carbamate Phenyl-carbamic acid 4-nitro-phenyl ester hydrolysis reaction pathway 528 3-Nitro-benzoic acid 3-Nitro-benzoic acid acidity constant F8.6 4-Nitrobenzoic acid 4-Nitro-benzoic acid acidity constant T8.I F8.6 T8.1 acidity constant at different T8.3 temperatures 2-Nitrophenol T8.1 2-Nitro-phenol acidity constant T8.I P20.6 acidity constant at different T8.3 temperatures air-water partition constant P20 salting constant, seawater T5.7 rate constants of hydrolysis reaction T13.11 4-Nitrophenyl N-methyl528 N-phenyl carbamate Methyl-phenyl-carbamic acid 4-nitro-phenyl ester hydrolysis reaction pathway 528 rate constant of base catalyzed P13.6 hydrolysis rate constants of hydrolysis reaction T13.1 I 4-Nitrophenyl N,N-dimethyl T13.11 carbamate Dimethyl-carbamic acid 4-nitro-phenyl ester rate constants of hydrolysis reaction T13.11 Compound Index 3-Nitrophenyl N-phenyl E13.6 carbamate Phenyl-carbarnic acid 3-nitro-phenyl ester rate constant of base catalyzed E13.6 hydrolysis 3-Nitro-phenylacetic acid (3-Nitro-phenyl)-aceticacid acidity constant F8.6 F8.6 Nitropropane F16.3 1-Nitro-propane rate constant with hydroxyl radical F16.3 4-Nonylphenol-ethyleneglycol ether F2.16 2-(4-Nonyl-phenoxy)-ethanol a biodegradation product 39 NTA s e e Nitrilotriacetic acid water saturated, mole fraction T5.1 4-Nitro-pyridine T8.2 4-Nitro-pyridine acidity constant of corresponding T8.2 acid molecular diffusivity in air T20.5 411.7 2-Nitrotoluene 1-Methyl-2-nitro-benzene exchange constant T11.2 water-aluminosilicate surface transfer velocities in air, in water T20.5, and overall at two wind speeds F20.7 (KNACEDA) 3-Nitrotoluene E16.3 1-Methyl-3-nitro-benzene T11.2 exchange constant water-aluminosilicate surface (KNAC.EDA) indirect photolysis half-life by E16.3 hydroxyl radical in troposphere, calculation of CNitrotoIuene 1-Methyl-4-nitro-benzene exchange constant TII.2 water-aluminosilicate surface (KNAC,EDA) reaction quantum yield of direct T15.7 photolysis molecular diffusivity in water T20.5 Schmidt number in water T20.5 Octanal Octanal salting constant, seawater T5.7 n-Octane E5.2 Octane activity coefficients in six organic T6.1 solvents air-quartz partition constant and F3.7 dispersive vdW parameter air-solvent partition constants for six T6.1 organic solvents aqueous solution data T5.3 solvent-water partition constants for T7.I five solvents standard enthalpies of vaporization T6.3 and of water-air transfer water saturated, mole fraction T5.1 salting constant, seawater T5.7 4-Nitrophenyl N-phenyl 528 carbamate Phenyl-carbarnic acid 4-nitro-phenyl ester rate constants of hydrolysis reaction T13.11 Nonanal Nonanal salting constant, seawater T5.7 n-Nonane Nonane air-quartz partition constant and F3.7 dispersive vdW parameter 4-Nonyl-phenol F2.15 4-Nonyl-phenol a biodegradation product 39 4-Nonylphenoldiethyleneglycol ether 2-[2-(4-Nonyl-phenoxy)-ethoxy]-ethanol a biodegradation product 39 n-Octanol 182 Octan-1-01 activity coefficients of five solutes T6.1 in octanol standard enthalpies of vaporization T6.3 and of water-air transfer 1-Octylamine F11.13 Octylarnine free energy change of cation of ion F11.14 exchange on montmorillonite Olive oil contaminated with benzene from E6.1 air, calculations solvent fitting coefficients for air-olive oil partition constant i Oxadiazon T6.2 F2.24 herbicide F2.24 Oxalic acid T11.4 Oxalic acid reaction of anion with mineral T11.4 surfaces Oxirane F16.3 Oxirane rate constant with hydroxyl radical F16.3 2-0x0-pent-4-enoic acid 700 2-0x0-pent-4-enoic acid formation by enzymatic degradation 700 of 2-hydroxymuconic acid semialdehyde Oxygen Oxygen air-water overall transfer velocity F20.9 and oil film thickness molecular diffusivity at different T20.3 temperatures molecular diffusivity in oil 930 oil-water distribution coefficient 930 air-octanol partition constants for T6.1 five solutes Schmidt number in water at T20.3 different temperatures as surrogate for natural organic 182 phases transfer velocity in water and wind F20.3 speed character as solvent 223 cosolute in water, effect on activity 187 coefficient molar volumes of dry and wet 186, 215 solvent F2.16 T7.2 solvent fitting coefficients for octanol-water partition constant of aqueous solution data T5.3 n-Octadecane Octadecane air-water partition constant T20.5 1-Nitropyrene F2.18 1-Nitro-pyrene fuel combustion product F2.18 solvent fitting coefficients for T6.2 air-octanol partition constant 4-Nonylphenolpolyethyleneglycol ether biodegradadation of 39 octanol-water partition constants for T7.I nine organic solutes partition constants for dry and wet F6.2 solvent rate constant with hydroxyl radical F16.3 refractive index T3.1 1301 P Palmitic acid see Hexadecanoic acid Paraoxon T13.12 Phosphoric acid diethyl ester 4-nitro-phenyl ester enzymatic hydrolysis 707 rate constants of hydrolysis reaction T13.12 Parathion F2.22 Thiophosphoric acid 0,O-diethyl ester 0'-(4-nitro-phenyl) ester insecticide and acaricide F2.22 1302 Compound Index mechanism of base catalyzed 538 hydrolysis rate constants of hvdrolvsis reaction T13.12 ~~ PCB s e e Biphenyl, polychlorinated standard enthalpy and entropy of T4.5 fusion, experimental and predicted data 2,3,4,5,6-Pentachlorobiphenyl 726 2,3.4,5.6-Pentachloro-biphenyl PCB33 s e e 2’,3,4-Trichlorobiphenyl microbial reduction catalyzed by 726 metalloenzymes PCB47 s e e 2,2’,4,4’-Tetrachlorobiphenyl Pentachlorobenzene Pentachloro-benzene biological organic phases-water T10.2 partition coefficients PCB52 see 2,2’,5,5’-Tetrachlorobiphenyl PCBlOl s e e 2,2’,4,5,5’-Pentachloro- biphenyl equilibrium bioaccumulation factor, E l I &i0, calculations PCB153 s e e 2,2’,4,4’,5,5’-Hexachloro- biphenyl octanol-water partition constant TIO.2 PCB170 see 2,2’.3,3’,4,4’.5-Heptachloro- biphenyl PCBlSO see 2,2’,3,4,4’.5,5’-Heptachloro- biphenyl PCB185 see 2,2’,3.4.5.5’,6-Heptachloro- biphenyl PCDD s e e Dibenzo-p-dioxine, polychlorinated PCDF s e e Dibenzo-furan polychlorinated Pentachloroethane T13.7 1,I I ,Z.Z-Pentachloro-ethane pelimination reaction 507 kinetic data for substitution and T13.7 elimination reactions Pentachlorophenol PCP 39 2.3.4.5.6-Pentachloro-phenol absorbance spectrum of light P15.5 absorbance spectrum of light of P15.5 anion acidic biocide 39 PCE see Tetrachloroethene acidity constant T8.1, F8.9 PCP s e e Pentachlorophenol acidity constant, calculation E8.2 Penicillin V F2.25 3,3-Dimethyl-7-0~0-6-(2-phenoxy-acetylarnin0)-4 - thia-I -aza-bicyclo[3.2.0]heptane-2-carboxylic acid antibiotic F2.25 lethal concentration vs F10.15 liposome-water distribution ratio n-octanol-water distribution ratio F8.9 and pH 2,2’,4,4’,5-Pentachloro biphenyl 2,4,5,2’,4‘-Pentachloro-biphenyl vapor pressure as function of F4.4 temperature 2,2’,4,5,5’-Pentachloro PCB I0 biphenyl distribution ratio of anion into polar FIO 14 lipids and into octanol 377 E9.3 2,4,5,2’,5’-Pentachloro-biphenyl concentration in pore water from E9.3 sediment concentration, calculation concentrations in lake water and T10.3 sediment molar volume and molecular E19.3 difhsivity in water organic carbon-water distribution E9.3 ratio, calculations partition constants E19.3 partition properties and TI 0.3 accumulation factors in aquatic organisms sediment to open water diffusion, E19.3 calculations organic carbon-water distribution F9 I ratio and oH phenolate anion as biocide 39 reaction quantum yield of direct P15.5 photolysis reaction quantum yield of direct T15.7 photolysis of anion species fractions at different pHs, E8.1 calculations Pentanal Pentanal salting constant, seawater TS n-Pentane Pentane air-teflon partition constant and F3.7 dispersive vdW parameter aqueous solution data T5.3 salting constant, seawater TS water saturated mole fraction T5.I 1-Pentanol Pentan-1-01 aqueous solution data T5.3 rate constant with hydroxyl radical F16.7 in troposphere water saturated, mole fraction T5.1 molecular diffusivity in air F18.9 2-Pentanone Pentan-2-one aqueous solution data T5.3 water saturated, mole fraction T5.1 1-Pentylamine Pentylamine free energy change of cation of ion F11.14 exchange on montmorillonite Permethrin T17.3 3-(2.2-dichloro-vinyI)-2,2-dimethyl-cyclopropane carboxylic acid 3-phenoxy-benzyl ester enzymatic hydrolysis 707 Perylene F2.13 Perylene biological organic phases-water T10.2 partition coefficients H-donor ( a ) and H-acceptor property (p) T4.3 octanol-water partition constant T10.2 Phenanthrene F2.11 Phenanthrene air-quartz and air-teflon surface E4.2 partition constants, calculations aqueous solution data T5.2, T5.3 aromatism as model compound in aquatic 950 environment, qualitative description carboxylation to phenanthrene 733 carboxylic acid concentrations in earthworm and P10.2 soil concentrations in ryegrass, yarrow P10.3 and air decadic molar absorption F15.3 coefficient H-donor (a)and H-acceptor property (p) T4.3 measured and predicted E9.2 concentrations on soils and sediments organic carbon-water partition E9.2 constant rate constant with hydroxyl radical F16.7 in troposphere reaction quantum yield of direct T15.7 photolysis Compound Index retardation factor in groundwater, E9.4 calculations transfer velocities in air, in water T20.5, and overall at two wind speeds F20.7 retardation factor in water with E9.4 cosolvent, calculations value of kX and KzMT f 7.6 salting constant, seawater T5.7 soil-water and sediment-water E9.2 distributions, calculations sorption on teflon and on quartz E l f I surfaces from air, calculations standard enthalpies of vaporization T6.3 and of water-air transfer standard enthalpy and entropy of T4.5 fusion, experimental and predicted data Phenoxyacetic acid Phenoxy-acetic acid acidity constant T8.6 T8.6 Hammett susceptibility factor T8.6 3-Phenoxy-benzylalcohol T17.3 (3-Phenoxy-phenyl)-methanol formation by enzymatic hydrolysis 707 of permethrin ~7.6 value of pmxand K i T1 vapor pressure of subcooled liquid E4.2 at given temperature, calculation N-Phenyl-[1,4]benzoquinoneimine standard enthalpy of air-plant PZ0.3 transfer Phenol F2.15 Phenol acidity constant T8.1 T8.6 F8.6 (4-lmino-cyclohexa-2,5-dienylidene)- phenyl-amine product of oxidative coupling of F14.19 aniline oxidation acidity constant and resonance F8.3 structur air-water partition constant 198 T20.5 aqueous solution data T5.2, T5.3 H-donor ( a )and H-acceptor property (j3) T4.3 Hammett constant for ortho T8.7 substitution Phenyl sulfide Benzenethiol nucleophilicity in water TZ3.3 N-Phenyl-l,4F14.19 phenylenediamine N-Phenyl-benzene-I ,4-diamine product of oxidative coupling of F14.19 aniline oxidation Phenylacetic acid Phenyl-acetic acid acidity constant T8.6 F8.6 T8.6 Hammett susceptibility factor T8.6, F8.7 Hammett susceptibility factor T8.6, F8.7 molecular diffusivity in air T20.5 rate constant with hydroxyl radical F f 6.3 molecular diffusivity in water T20.5 nucleophilicity of phenolate in water 499 polarizability T5.5 radicals of oxidation and products of F14.18 coupling rate constant with hydroxyl radical F16.3 rate constant with hydroxyl radical F16.7 in troposphere salting constant, seawater T5.7 Schmidt number in water T20.5 solvent-water partition constants for T7.I five solvents standard enthalpies of vaporization T6.3 and of water-air transfer standard enthalpy and standard T4.2 entropy of evaporation Phenyl N-methyl-N-phenyl P13.6 carbamate Methyl-phenyl-carbamic acid phenyl ester rate constant of base catalvzed PZ3.6 hydrolysis 5-Phenyl-pentanoic acid F17.4 5-Phenyl-pentanoic acid f!-oxidation and degradation to F f 7.4 3-phenyl-propionic acid 3-Phenyl-propionic acid 3-Phenyl-propionic acid acidity constant T8.6 nucleophilicity in water 499 Phorate P13.11 Dithiophosphoric acid 0,O-diethyl ester S-ethylsulfanylmethyl ester rate constants of hvdrolvsis P13.11 Phosphoric acid diethyl P13.9 3-bromophenyl ester Phosphoricacid 3-bromo-phenyl ester diethyl ester rate constant of base catalyzed PI 3.9 hydrolysis Phosphoric acid diethyl P13.9 3-chlorophenyl ester Phosphoric acid 3-chloro-phenyl ester diethyl ester rate constant of base catalyzed Pf3.9 hydrolysis Phosphoric acid diethyl P13.9 3-methoxyphenyl ester Phosphoric acid diethyl ester 3-methoxy-phenyl ester rate constant of base catalyzed P13.9 F14.19 hydrolysis 2-Phenoxy-phenol F14.18 2-Phenoxy-phenol product of oxidative coupling of F14.18 phenol oxidation 4-Phenoxy-phenol F14.18 4-Phenoxy-phenol product of oxidative coupling of F14.18 phenol oxidation standard enthalpy and standard T4.2 entropy of evaporation 1303 T8.6 formation by degradation of F f 7.4 5-Phenyl-pentanoic acid Hammett susceptibility factor T8.6, F8.7 Phenylamine s e e Aniline Phosphoric acid diethyl P13.9 3-methylyphenyl ester Phosphoric acid diethyl ester 3-methyl-phenyl ester rate constant of base catalysed P13.9 hydrolysis Phosphoric acid diethyl P13.9 3-nitrophenyl ester Phosphoric acid diethyl ester 3-nitro-phenyl ester rate constant of base catalyzed PZ3.9 hydrolysis Phosphoric acid diethyl P13.9 4-acetylphenyl ester Phosphoric acid 4-acetyl-phenyl ester diethyl ester rate constant of base catalyzed PI 3.9 hydrolysis Phosphoric acid diethyl P13.9 4-bromopbenyl ester Phosphoric acid 4-bromo-phenyl ester diethyl ester rate constant of base catalyzed P13.9 hydrolysis Phosphoric acid diethyl 4-chlorophenyl ester P13.9 Phosphoric-acid-4-chloro-phenyl ester diethyl ester rate constant of base catalyzed P13.9 hydrolysis Phosphoric acid diethyl P13.9 4-cyanophenyl ester Phosphoric acid 4-cyano-phenyl ester diethyl ester rate constant of base catalyzed PZ3.9 hydrolysis Phosphoric acid diethyl P13.9 4-ethylyphenyl ester Phosphoric acid diethyl ester 4-ethyl-phenyl ester rate constant of base catalyzed P13.9 hydrolysis 1304 Compound Index Phosphoric acid diethyl P13.9 4-methoxyphenyl ester Phosphoric acid diethyl ester 4-rnethoxy-phenyl ester rate constant of base catalyzed P13.9 hydrolysis Phosphoric acid diethyl P13.9 4-nitrophenyl ester Phosphoric acid diethyl ester 4-nitro-phenyl ester rate constant of base catalyzed P13.9 hvdrolvsis a Phosphoric acid diethyl phenyl ester Phosphoric acid diethyl ester phenyl ester rate constant of base catalyzed P13.9 hydrolysis o-Phthalic acid o-PA E8.1 Phthalic acid reaction of anion with mineral T11.4 surfaces sorption on goethite PI I.12 acidity constants E8 I species fractions at different pHs, E8 I calculations 1,2-Phthalic acid s e e o-Phthalic acid Picolinate PHP F13.21 Pyridine-2-carboxylic acid phenyl ester oxide surface catalyzed hydrolysis F13.21, F13.22 acidity constant of corresponding T8.3 acid at different temperatures T17.3 N-(3.4-Dichloro-phenyI)-propionarnide enzymatic hydrolysis 707 1-Propanol Propan-1-01 as cosolvent T5.8 T5.8 2-Propanol F18.9 Propan-2-01 molecular diffusivity in air F18.9 Propionic acid T17.3 Propionic acid p13*9 formation by enzymatic hydrolysis 707 ofpropanii Phthalates F2.17 production rate, usage as plasticizer 42 Piperidine T8.2 Piperidine acidity constant of corresponding T8.2 acid Propanil n-Propylbenzene Propyl-benzene aqueous solution data T5.3 salting constant, seawater T5.7 standard enthalpy and standard T4.2 entropy of evaporation water saturated, mole fraction T5.1 Purine F16.3 7H-Purine rate constant with hydroxyl radical F16.3 Pyrene F2.13 Pyrene black carbon-water distribution E9.3 coefficient Propachlor 501 2-Chloro-N-isopropyl-N-phenyl-acetamide reaction with nucleophiles 501 Propane F2.3 Propane bond angles F2.3 value of pmax and K,M TI 7.6 T4.3 Hammett susceptibility factor of T8.6 corresponding acid nucleophilicity in water 499 rate constant with hydroxyl radical F16.3 reactant in binary actinometer 648 solvent-water partition constants for P.1 five solvents Pyrimidine F16.3 Pyrirnidine rate constant with hydroxyl radical F16.3 Pyrrole F16.7 1H-Pyrrole rate constant with hydroxyl radical F16.7 in troposphere Pyruvate 2-0x0-propionic acid standard redox potential T14.2 concentrations in ryegrass, yarrow P 10.3 and air Tetracycl0[3.2.0.O~~'.O~~~]heptane dissolved organic carbon-water F9.14 distribution coefficient for different organic matters Fishtine and structural parameters T4.4 for estimating vapor pressure organic carbon- and black 304 carbon-water distribution coefficients F2.17 H-donor ( a )and H-acceptor property (B) Q PNAP see para-Nitroacetophenone Preventol pesticide 42 conjugated x-electron system 30 concentration in pore water from E9.3 sediment concentration, calculation H-donor ( a )and H-acceptor property (p) Polychlorinated PCDF F2.15 dibenzo-furans environmental source and fate 41 Pyridine F2.11 Pyridine acidity constant of corresponding T8.2 acid T8.6 rate constant with hydroxyl radical F16.7 in troposphere PNA see para-Nitroanisol Polychlorinated PCDD F2.15 dibenzo-(1,4]-dioxins environmental source and fate 41 value of kax and KrM T17.6 T4.3 organic carbon-water distribution E9.3 ratio, calculations reaction quantum yield of direct T15.7 photolysis Quadricyclane P13.11 rate constants in water at various P 13.11 PHS Quartz as bipolar surface sorbent for 71 sorbates of different polarity Quaternary ammonium salts cationic surfactants F2.18 F2.18 Quinoline 48.5 Quinoline acidity constant of corresponding Q8.5 acid distribution to huniic acid and pH F9.18 Hammett susceptibility factor QS.5 refractive index T3.1 sorption isotherm of cation on F l l natural solid salting constant, seawater T5 value of kax and K,M T17.6 sorption isotherm to kaolinite in F11.6 aqueous solution R standard enthalpies of vaporization T6.3 and of water-air transfer Radon Radon profile of lake for vertical turbulent F22.8 diffusivity calculations 1029 standard enthalpy and entropy of T4.5 fusion, experimental and predicted data standard enthalpy of air-plant P10.3 transfer profile of the bottom of the north PZ2.6 atlantic 1305 Compound Index transfer velocity in water and wind F20.3 speed 2,3,7,8-TCDD see 2,3,7,8-Tetrachloro-dibenzo[l,4]dioxin concentrations in lake water and T10.3 sediment Ronnel 542 Thiophosphoric acid 0,O-dimethyl ester 0’-(2,4,5-trichIoro-phenyl) ester influence of metals on hydrolysis 542 rate and mechanism TCE see Trichloro-ethene concentrations in water, sediment E10.4 and mussel 2,4,5-TCP see 2,4,5-TrichlorophenoI equilibrium bioaccumulation factor, EIO I K,%i0,calculations E10.2 S 2,4,6-TCP see 2,4,6-TrichlorophenoI food chain concentrations and F10.9 biomagnification in trout Salicylic acid T11.4 2-Hydroxy-benzoic acid microbial oxidation to catechol 699 Teflon Poly-tetrafluoro-ethene as nonpolar surface sorbent for F 3.7 sorbates of different polarity fugacites in water, sediment and F10.8 biolipid a-Terpinene P16.3 p-Cymene rate constant with hydroxyl radical P16.3 in troposphere fugacities in air and pasture, EI0.5 equilibrium concentration in pasture, calculations reaction of anion with mineral T11.4 surfaces Sarin F2.22 Isopropyl-methylphosphono-fluoridoate nerve poison F2.22 Semiquinone SQ 568 Semiquinone intermediate in redox reaction 568 Stearic acid see Octadecanoic acid tram-Stilbene 1,l’-(E)-Ethene-I,2-diyl-dibenzene decadic molar absorption F15.2 coefficient Styrene F2.13 Vinyl-benzene decadic molar absorption F15.2 coefficient rate constant with hydroxyl radical F16.7 in troposphere Sucrose 2-(3,4-Dihydroxy-2,5-bis-hydroxymethyltetrahydro-furan-2-yloxy)-6-hydroxymethyl- tetrahydro-pyran-3,4,5-triol molecular diffusivity in water Fl8 I0 Sulcotrion Q8.7 2-(2-Chloro-4-methanesulfonyl-benzoyl)cyclohexane-I 3-dione acidity constant Q8.7 Sulfadiazine F2.20 4-Arnino-N-(4.6-dimethyl-pyrimidin-2-yl) benzenesulfonamide therapeutical drug F2.20 Sulfomethuron F2.20 2-[(4.6-Dimethyl-pyrimidin-2-ylcarbamoyl)- sulfamoyll-benzoic acid herbicide F2.20 Sulfur hexafluoride Sulfur hexafluoride transfer velocity in water and wind FZ0.3 speed T TBT see Tributyltin 1,2,3,4-TCDD see 1,2,3,4-Tetrachloro-dibenzo[l,4]dioxin 1,2,3,7-TCDD see 1.2,3,7-Tetrachloro-dibenzo[l,4]dioxin fugacities and activities in water, E10.4 sediment and mussel, calculations Tetrahromo-methane T14.3 Tetrabromo-methane standard reduction potential T14.3, F14.4 fugacities in arctic terrestrial food F10.12 chain partition constants for octanol, air, E10.4 0rg.C and lipids with water 1,1,2,2-TetrachloroT13.7 1-fluoroethane 1,1,2,2-Tetrachloro-l -fluoro-ethane kinetic data for substitution and T13.7 elimination reactions 3,3’,4,4’-Tetrachloroazobenzene partition properties and TI 0.3 accumulation factors in aquatic organisms saturation concentration in water E10.4 standard enthalpies of vaporization T6.3 and of water-air transfer 459 Bis-(3,4-dichloro-phenyl)-diazene highly toxic reaction product in soils 459 1,2,3,4-Tetrachlorobenzene P10.1 1,2,3,4-Tetrachloro-benzene bioaccumulation factor of soybean PIO.I leaves and roots to water biological organic phases-water TI0.2 partition coefficients octanol-water partition constant T10.2 polarizability T5.5 1,2,4,5-TetrachIorobenzene 1,2,4,5-Tetrachloro-benzene fugacities in air and terrestrial food FIO.11 chain P9.5 standard enthalpy of air-lipid T10.5 transfer standard enthalpy of air-pasture E10.5 transfer standard enthalpy of air-plant 363 transfer 1,2,3,4-TetrachloroF16.7 dibenzo[1,4jdioxin 1,2,3,4-Tetrachloro-dibenzo[ 1.4ldioxin rate constant with hydroxyl radical FI 6.7 in troposphere P16.3 1,2,3,7-Tetrachloro -dibenzo[1,4]dioxin P5.5 Freundlich isotherm parameters P9.5 1,2,3,7-Tetrachloro-dibenzo[l.4]dioxin organic carbon-water partition P9.5 constant 2,3,7,8-Tetrachloro TCDD 41 dibenzo[1,4jdioxin 2,3,7,8-Tetrachloro-dibenzo[l.4]dioxin concentrations in air, soil, grass and P10.4 E10.3 milk polarizability T5.5 2,2’,5,5’-Tetrachlorobiphenyl PCBS2 2,5,2,5’-Tetrachloro-biphenyl air-lipid partition coefficient T10.5 air-octanol partition constant E10.5 air-plant equilibrium coefficient E l 0.3 aqueous solution data T5.Z bioconcentration factor in E l I phytoplankton biomagnification factors from T10.6 pasture to animal fat concentrations in air and in pasture E10.5 concentrations in air, pasture and T10.5 milk rate constant with hydroxyl radical P16.3 in trooosDhere L standard enthalpy of evaporation P10.4 1,1,1,2-TetrachIoroethane 1,l,I 2-Tetrachloro-ethane H-donor (a) and H-acceptor property (B) T13.7 T4.3 kinetic data for substitution and T13.7 elimination reactions 1,1,2,2-Tetrachloroethane 32,2-Tetrachloro-ethane @elimination reaction T13.2 T13.2 1306 Compound Index pelimination reaction 510 kinetic data for substitution and T13.7 elimination reactions polarizability T5.5 Tetrachloroethene PCE F2.2 1,I ,2,2-Tetrachloro-ethene air-water partition constant T20.5 aqueous solution data T5.2, T5.3 as air pollutant in cyclohexane at E6.1 "C, calculations as model compound in different 947 one-box model calculations as terminal electron acceptor 729 bond angles F2.3 characteristic amount, input and B21.2 output data of a Swiss lake concentration in air over a Swiss B21.2 lake concentrations in a river at different P20.4 flow distances Fishtine and structural parameters T4.4 for estimating vapor pressure formation by microbial reduction of 726 hexaxhloroethane by heme proteins H-donor ( a )and H-acceptor property (p) T4.3 soil surface-air equilibrium, E11.2 calculations standard enthalpies of vaporization T6.3 and of water-air transfer transfer velocities in air, in water T20.5, and overall at two wind speeds F20.7 two-box lake model (stratification), E21.5 calculations E21.6 two-box lake model with stratification and mixing periods, ca 1cu1ations water saturated, mole fraction T5.1 Tetrachloromethane CT Tetrachloro-methane aqueous solution data T5.3 H-donor ( a ) and H-acceptor property (p) rate constant with hydroxyl radical F16.3 rate constant with hydroxyl radical F16.7 in troposphere reactant of a higly toxic reaction 459 product in landfills reduction to trichloroethene by 704 metallo-enzymes relative rates of reduction by three F14.17 metals salting constant, seawater T5 Schmidt number in water T20.5 1,2,4,5-Tetramethylbenzene TeMB 292 1,2,4,5-TetramethyI-benzene Fishtine and structural parameters T4.4 for estimating vapor pressure T4.3 standard enthalpy and standard E4 I entropy of fusion, calculations kinetic data for substitution and T13.7 elimination reactions E4.1 vapor pressure at given temperatures, calculation Thioacetic acid Thioacetic acid acidity constant T8.I pathways of reduction to various F14.14 products T8.1 Thiometon T13.12 Dithiophosphoric acid S-(2-ethylsulfanyl-ethyl) ester 0.0-dimethyl ester rate constants of hydrolysis reaction T13.12 polarizability T5.5 reduction by heme proteins to the 726 trichloro-methyl radical salting constant, seawater T5.7 polarizability T5.5 P4.3 Tetrahydrofuran E16.3 Tetrahydro-furan indirect photolysis half-life by El 6.3 hydroxyl radical in troposphere, calculation of vapor pressures at four P4.1 temperatures one-box lake model with variable B21.2 input, calculations product of reductive 557 dihalo-elimination reaction of HCE 1,l,I ,2-Tetrafluoro-ethane world production rate, major use T2.4 relative rates of reduction in F14.16 different media pathways of reduction by zinc F14.15 l,l,l,Z-Tetrafluoroethane vapor pressure as function of F4.4 temperature one-box lake model, calculations B21.2 overall air-water exchange velocity P21.2 retardation by sorption in E25.6 groundwater system vapor pressures at six temperatures P4.3 organic carbon-water distribution F9.7 and quality of solid molecular diffusivity in water T20.5 one-dimensional vertical lake 1091 model, numerical calculations with MASAS value of /*maxand KLMTI 7.6 major use T2.4 molecular diffusivity in air T20.5 one-dimensional vertical lake F23.7 model, calculated vs measured values for Greifensee standard reduction potential T14.3, F14.4 microbial reduction to chloroform 721 microbial reduction to 721 trichloroethene concentration change in river due to E24.2 flow time and air exchange standard Gibbs energy P12.1 Henry constant P12 I microbial reduction catalyzed by F17.10 cobalamin characteristic times of air-water E24.2 exchange in river, two flow regimes Thiophenol F2.20 Benzenethiol acidity constant T8.I chemical intermediate F2.20 solid-water distribution and organic F9.7 carbon content of solid TNT see 2,4,6-Trinitrotoluene standard reduction potential T14.3, F14.4 Toluene F2.13 Toluene activity coefficients in six organic T6.1 solvents water saturated, mole fraction T5.1 activity coefficients of five solutes T6.I in toluene 2,3,4,6-Tetrachlorophenol 2,3,4,6-Tetrachloro-phenol addition to fumarate 730 standard enthalpy of air-water P8.2 transfer 1,1,2,3-Tetrachloro-propene , I ,2.3-Tetrachloro-propene Tetrachloroethene PCE F2.2 I ,Z,Z-TetrachIoro-ethene change of a time-variable input in E25.6 well due to sorption in groundwater system 767 air-solvent partition constants for six T6.1 organic solvents air-teflon and air-quartz partition F3.7 constants and dispersive vdW parameter air-toluene partition constants for T6.1 five solutes air-water partition constant 198 aqueous solution data T5.3 Compound Index value of K M M and TmaxTI 7.7 biological organic phases-water TI0.2 partition coefficients kinetic data for substitution and T13.7 elimination reactions enzymatic addition to fumarate 704 molecular diffusivity, calculation of E20.3 H-donor ( a )and H-acceptor property (j?) overall transfer velocity at wind EZ0.3 speed, calculation of Summary of models and T23.8 measurements in Lake Superior polarizability T5.5 two-box coupled waterkediment T23.7 system in Lake Superior T4.3 methylbenzene-water partition T7.1 constants for nine organic solutes microbial oxidation to 717 cis-1,2-dihydroxy-3-methyIcyclohexa-3,s-diene refractive index T3.1 relative rates of reduction in F14.16 different media molecular diffusivity in water FI 8.I Schmidt number in water at E20.3 different temperatures, calculation of octanol-water partition constant T10.2 seawater-air flux, calculation of E20 I molecular diffusivity in air F18.9 polarizability T5.5 rate constant with hydroxyl radical F16.7 in troposphere salting constant, seawater T5.7 solvent-water partition constants for T7.1 five solvents standard enthalpies of vaporization T6.3 and of water-air transfer standard enthalpy and standard T4.2 entropy of evaporation value of KrMM and V,, TI 7.7 value of hx and K M TI 7.6 water saturated, mole fraction T5.1 Toluene-4-sulfonic acid Toluene-4-sulfonic acid T8.l acidity constant T8.1 anion as hardener and stabilizer F 2.20 uptake by organisms 738 TPT see Triphenyltin 1,2,3-TrCB see 1,2,3-Trichlorobenzene 1,2,4-TrCB see 1,2,4-Trichlorobenzene Trichlorfon F2.22 (2.2,2-Trichloro-l-hydroxy-ethyl)-phosphonic acid dimethyl ester insecticide F2.22 Trichloroacetic acid F2.17 Trichloro-acetic acid presence in the environment by 42 direct input and by hydrolysis of esters rate constant with hydroxyl radical F16.3 1,2,3-Trichlorobenzene 1.2.3-Trichloro-benzene lethal body burden (LBB) for fish E1 0.6 2,4,6-Triaminotoluene TAT F14.6 2-Methyl-benzene-I ,3,5-triamine endproduct in TNT reduction F14.6 1,1,2-Tribromoethane T13.7 l,I,Z-Tribromo-ethane kinetic data for substitution and T13.7 elimination reactions T13.7 concentration in arctic ocean E20.1 Henry constant E20 I Henry constant in seawater E20.1 Henry constant in seawater, E20 I temperature dependence 1065 3,4,2'-Trichloro-biphenyl concentrations, inputs and outputs in T23.4 Lake Superior one-box three phase model in Lake 1068 Superior one-box two phase model in Lake 1065 Superior physico-chemical properties 723.4 surface mixed sediment layer model 1065 in Lake Superior two-box waterkediment model in 1079 Lake Superior 2,4,4'-Trichlorobiphenyl 2,4.4'-Trichloro-biphenyl aqueous solution data T5.2 standard enthalpies of vaporization T6.3 and of water-air transfer l,l,l-Trichloroethane TrCE l,l,l-Trichloro-ethane concentration in air EZ0.I T13.7 concentration in arctic ocean E20 I density E20.2 evaporation time, calculation of E20.2 H-donor (a) and H-acceptor property (p) T4.3 Henry constant E20.1 Henry constant in seawater EZO I polarizability T5.5 Henry constant in seawater, E20.1 temperature dependence theoretical bioaccumulation E10.6 potential (TBP) in fish, calculations kinetic data for substitution and T13.7 elimination reactions volume fraction in fish membrane E10.6 lipids, calculations 1,3,5-TrCB see 1,3,5-TrichIorobenzene Tribromo-methane Tribromo-methane concentration in air E20.1 standard reduction potential T14.3, F14.4 Tributyltin TBT 325 humic acid-water distribution ratio F9.19 and pH Tricapryline Octanoic acid 2-octanoyloxy-I -octanoyloxymethyl-ethyl ester Tricapryline-water vs F10.4 octanol-water partition 2',3,4-Trichlorobiphenyl PCB33 1,2,4-Trichlorobenzene F16.7 1,2,4-Trichloro-benzene air-water partition constant T20.5 molecular diffusivity in air T20.5 molecular diffusivity in water 720.5 rate constant with hydroxyl radical F16.7 in troposphere Schmidt number in water 720.5 transfer velocities in air, in water T20.5, and overall at two wind speeds F20.7 P9.4 1,3,5-Trichlorobenzene 1,3,5-Trichloro-benzene biological organic phases-water T10.2 partition coefficients octanol-water partition constant T10.2 polarizability T5.5 major use T2.4 molecular diffusivity, calculation of EZ0.3 overall transfer velocity at wind E20.3 speed, calculation of rate constant with hydroxyl radical F16.3 rate constant with hydroxyl radical FI 6.7 in troposphere salting constant, seawater T5.7 saturation pressure of pure liquid E20.2 Schmidt number in water at E20 different temperatures, calculation seawater-air flux, calculation of E20, I typical concentration in air P6.3 typical concentration in Arctic P6.3 surface waters 1307 1308 Compound Index 1,1,2-Trichloroethane T13.7 ,I ,2-Trichloro-ethane E16.3 indirect photolysis half-life by hydroxyl radical in troposphere, calculation of kinetic data for substitution and T13.7 elimination reactions rate constant with hydroxyl radical F16.3 Trichloroethene TCE F14.15 ,I,2-Trichloro-ethene aqueous solution data T5.3 transfer velocities in air, in water T20.5, and overall at two wind speeds ~ Trichloromethane E5.3 Trichloro-methane activity coefficients of four organic T3.2 solutes in trichloromethane air-teflon partition constant and F3.7 dispersive vdW parameter co-metabolic degradation with El 7.8 methane diffusion from groundwater to E19.2 atmosphere, calculations diffusion plus advection from ,522.4 groundwater to atmosphere, calculations formation by microbial reduction of 721 tetrachloroethene H-donor ( a )and H-acceptor property (p) temperature dependence of B18.4 molecular diffusivity in water aqueous solution data T5.2, T5.3 formation by microbial reduction of 721 tetrachloromethane H-donor (a)and H-acceptor property (p) T4.3 kinetic data for substitution and T13.7 elimination reactions molecular diffusivity in water P18.4 polarizability T5.5 T4.3 rate constant with hydroxyl radical F16.3 microbial oxidation to 717 trichloro-oxirane rate constant with hydroxyl radical F16.7 in troposphere molar volume, calculations 804 T18.3 refractive index T3.I salting constant, seawater T5 molecular diffusivity in water, 813 calculations pathways of reduction by zinc F14.15 product in tetrachloroethane T13.2 /?-elimination reaction rate constant with hydroxyl radical F16.3 rate constant with hydroxyl radical FI 6.7 in troposphere relative rates of reduction by three F14 I7 metals solvent fitting coefficients for T6.2 air-trichloromethane partition constant i T7.2 solvent fitting coefficients for trichloromethane-water partition constant of organic compounds standard enthalpies of vaporization T6.3 and of water-air transfer standard reduction potential T14.3, FI 4.4 salting constant, seawater T5.7 trichloromethane-water partition T7.1 constants for nine organic solutes standard enthalpies of vaporization T6.3 and of water-air transfer water saturated, mole fraction T5.1 standard free energy of formation P14 I standard oxidation potential T14.3, F14.4 value of K,MMand P", TI 7.7 water saturated, mole fraction T5.1 world production rate, major use T2.4 Trichloro-fluoromethane CFC-11 T2.4 Trichloro-fluoro-methane air-water partition constant T20.5 major use T2.4 molecular diffusivity in air T20.5 molecular difhsivity in water T20.5 salting constant, seawater 7'5.7 Schmidt number in water T20.5 standard enthalpies of vaporization T6.3 and of water-air transfer Trichloro-oxirane 717 2,2,3-Trichloro-oxirane formation by microbial oxidation of 717 trichloroethene 2,4,5-TrichlorophenoI 323 2,4,5-Trichloro-phenol organic carbon-water distribution F9.17 ratio and pH 2,4,6-TrichlorophenoI 2,4,6-Trichloro-phenoI acidity constant Q8.6, P8.3 Q8.6 butyl acetate-water partition P8.3 constant 3,4,5-TrichlorophenoI 3,4,5-Trichloro-phenol acidity constant 13.6 Q8.6 acidity constant, calculation E8.2 2,4,5-Trichlorophenoxy acetic 2,4,5-T acid (2,4.5-Trichloro-phenoxy)-acetic acid acidity constant F8 271 acidity constant, calculation E8.2 n-octanol-water distribution ratio F8.9, and pH and K+-concentration F8.10 3,4,5-TrichlorophenyI E13.6 N-phenyl carbamate Phenyl-carbamic acid 3,4.5-trichloro-phenyl ester rate constant of hydrolysis, E13.6 calculations Trichloromethane E5.3 Trichloro-methane fate of along Mississippi River after 1132 two peak spills, case study maximum concentration change 1132 along flow in Mississippi River, case study total mass change along flow in 1132 Mississippi River, case study Trichloromethyl radical 726 Trichloromethyl formation by microbial reduction of 726 tetrachloromethane with heme proteins Triethylphosphate T13.12 Phosphoric acid triethyl ester mechanism of base catalyzed 538 hydrolysis rate constant with hydroxyl radical F16.3 rate constants of hydrolysis reaction T13.12 Triethylamine F2.18 Triethyl-amine solvent, wetting agent F2.18 Trifluoroacetic acid Trifluoro-acetic acid acidity constant T8.I Trifluralin T8.1 F15.7 (2,6-Dinitro-4-trifluoromethyl-phenyl)- dipropyl-amide reaction pathway of direct F15.7 photolysis Trimethyl-[3-(methyl-phenylcarbamoy1oxy)-phenyl]ammonium P13.6 N,N,N-Trimethyl-3-(([methyl-(phenyl)-amino]carbony1)-oxy)benzenaminium rate constant of base catalyzed P13.6 hydrolysis Trimethylphosphate T13.2 Phosphoric acid trimethyl ester mechanism of base catalyzed 538 hydrolysis nucleophile substitution reaction T13.2 rate constant with hydroxyl radical F16.3 rate constants of hydrolysis reaction T13.12 Compound Index 1,2,3-Trimethylbenzene 1,2,3-Trimethyl-benzene polarizability T5.5 1,3,5-Trimethylbenzene Mesitylene aqueous solution data T5.2, T5.3 F16.7 Triphenylphosphate F2.22 Phosphoric acid triphenyl ester plasticizer and fire retardant F2.22 polarizability T5.5 rate constant with hydroxyl radical F16.7 in troposphere water saturated, mole fraction T S I 2,3,5-Trimethylhexane P16.3 2,3,5-Trimethyl-hexane rate constant with hydroxyl radical P16.3 in troposphere 2,4,6-Trimethylphenol 2,4,6-Trimethyl-phenol acidity constant T8.1 T8.1 bond angles F2.3 molar volume, calculation T18.3 rate constant with hydroxyl radical F16.3 1,3,5-Trinitrobenzene F11.6 1,3,5-Trinitro-benzene sorbed to clay mineral, schematic F11.8 drawing sorption isotherm to kaolinite in F11.6 aqueous solution T8.1 2,4,6-Trinitrotoluene TNT F2.18 2-Methyl-I ,3.5-trinitro-benzene exchange constant T11.2 water-aluminosilicate surface (KNACEDA) explosive 45 microbial reduction to 721 2,6-Dinitro-4-nitroso-toluene nonlinear isotherm with mineral 409 surfaces one-electron reduction potential T14.4 organic carbon-water partition P11.5 constant pathways of reduction to F14.6 triaminotoluene reaction quantum yield of direct TI5 photolysis sorption on illite from water, E11.4 calculations Trinitroglycerol 1,2,3-Tris-nitrooxy-propane explosive F2.18 rate constants of hydrolysis reaction T13.12 Triphenyltin TPT 325 humic acid-water distribution ratio F9.19 and pH U Urea F18.10 Urea molecular diffusivity in water F18.10 V Trimethylamine F2.3 Trirnethyl-amine acidity constant of corresponding T8.2 acid 2,4,6-Trinitrophenol Picric acid acidity constant T8.1 Triolein Octadec-9-enoic acid 2-octadec-9-enoyloxy-1-0ctadec-9enoyloxymethyl-ethyl ester Triolein-water vs octanol-water F10.4 partition F2.18 Vanillic acid 699 4-Hydroxy-3-rnethoxy-benzoic acid oxidative cleavage to 699 protocatechuic acid Vinyl acetate s e e Acetic acid ethenyl ester molecular diffusivity in air F18.9 molecular order in bulk and cavity 10 mono- and multilayer film on 392 mineral surfaces sorbed to clay mineral, schematic F11.8 drawing standard Gibbs energy of pure E13.1 water surface of droplets in atmospheric 889 clouds transfer velocity at evaporation 896 transfer velocity of vapor in air and F20.2 wind speed typical transfer velocity of a 893 substance in water X m-Xylene F17.11 rn-Xylene addition to fumarate 731 m/g-Xylene F2.13 m/p-Xylene air-quartz partition constant and F3.7 dispersive vdW parameter concentration in diesel fuel T19.3 Vinyl chloride VC see Chloroethene density T19.3 W dissolution from diesel fuel into E19.4 aqueous phase, calculations Water F2.3 Water acidity constant at different T8.3 temperatures molecular diffusivity in water and in T19.3 diesel fuel activity coefficients of four organic T3.2 solutes in water air phase transfer velocity and wind T20.4 speed amount adsorbed on mineral oxide F11.3 surface and relative humidity amount of in a cloud P6.2 bond angles F2.3 characteristics of lakes T23.1 characteristics of oceans T23.1 content in atmosphere 889 film renewal time in substance 908 exchange models film thickness in substance 908 exchange models flux of evaporation, annual 898 evaporation rate H-bonding structures in pure liquid F3.5 H-donor (a)and H-acceptor property (p) 2-4.3 kinematic viscosity at different T20.3, temperatures F20.6 layer thickness on mineral surface 394 and affinity to organic sorbates 1309 1310 List of Illustrative Examples Environmental Organic Chemistry, 2nd Edition Rene P Schwarzenbach, Philip M Gschwend and Dieter M Imboden Copyright 02003 John Wiley &L Sons, Inc LISTOF ILLUSTRATIVE EXAMPLES Chapter 2.1 Determining the Oxidation States of the Carbon Atoms Present in Organic Molecules Chapter Chapter 3.1 4.1 5.1 The “Soup Bowl” Problem Basic Vapor Pressure Calculations Deriving Liquid Aqueous Solubilities, Aqueous Activity Coefficients, and Excess Free Energies in Aqueous Solution from Experimental Solubility Data Evaluating the Factors that Govern the Aqueous Activity Coefficient of a Given Compound Evaluating the Effect of Temperature on Aqueous Solubilities and Aqueous Activity Coefficients Quantifying the Effect of Inorganic Salts on Aqueous Solubility and Aqueous Activity Coefficients Estimating the Solubilities and Activity Coefficients of Organic Pollutants in Organic Solvent-Water Mixtures Assessing the Contamination of Organic Liquids by Air Pollutants Evaluating the Direction of Air-Water Gas Exchange at Different Temperatures Assessing the Effect of Solution Composition on Air-Aqueous Phase Partitioning Estimating Air-Water Partition Constants by the Bond Contribution Method Evaluating the Factors that Govern the Organic Solvent-Water Partitioning of a Compound Estimating Octanol-Water Partition Constants from Structure Using the A t o d r a g m e n t Contribution Method Estimating Octanol-Water Partition Constants Based on Experimental Kiow’s of Structurally Related Compounds Chapter 5.2 5.3 5.4 5.5 Chapter 6.1 6.2 6.3 Chapter 6.4 7.1 7.2 7.3 7.4 Chapter 8.1 Estimating the Concentrations of Individual PCB Congeners in Water that Is in Equilibrium with an Aroclor and an Aroclor/Hydraulic Oil Mixture Assessing the Speciation of Organic Acids and Bases in Natural Waters 8.2 Estimating Acidity Constants of Aromatic Acids and Bases Using the Hammett Equation 8.3 Assessing the Air-Water Distribution of Organic Acids and Bases in a Cloud List of Illustrative Examples Chapter 9.1 9.2 9.3 9.4 Chapter 10 Chapter 11 9.5 10.1 10.2 10.3 10.4 10.5 10.6 11.1 11.2 11.3 11.4 11.5 Chapter 12 Chapter 13 11.6 11.7 12.I 12.2 12.3 13.1 13.2 13.3 13.4 Chapter 14 13.5 13.6 14.1 14.2 14.3 14.4 1311 Determining KidValues from Experimental Data Evaluating the Concentration Dependence of Sorption of Phenanthrene to Soil and Sediment POM Estimating Pore Water Concentrations in a Polluted Sediment How Much Does the Presence of 20% Methanol in the “Aqueous” Phase Affect the Retardation of Phenanthrene in an Aquifer? Evaluating the Effect of DOM on the Bioavailability of Benzo(a)pyrene Evaluating Bioaccumulation from a Colloid-Containing Aqueous Solution Estimating Equilibrium Bioaccumulation Factors from Water Estimating Equilibrium Bioaccumulation Factors from Air Calculating Fugacities or Chemical Activities to Evaluate Bioaccumulation Evaluating Air-Pasture Partitioning of PCBs Evaluating Lethal Body Burdens of Chlorinated Benzenes in Fish Estimating the Fraction of Phenanthrene Present in the Gas Phase and Sorbed to the Walls of a Vessel Sorption of Tetrachloroethene from Air to Moist and Dry Soil Gas-Particle Partitioning of Organic Compounds to Environmental Tobacco Smoke Adsorption or Absorption? Estimating the Retardation of Trinitrotoluene Transport in Groundwater Transport of Di-Isopropanol-Amine (DIPA) in Groundwater from a Sour Gas Processing Plant Estimating Dodecyl Sulfonate Sorption to Alumina at Different pHs Estimating the Adsorption of Benzoic Acid to Goethite Energetics of Syntrophic Cooperation in Methanogenic Degradation Transformation of Methyl Bromide to Methyl Chloride and Vice Versa A Benzyl Chloride Spill Into a Pond Evaluating the Thermodynamics of Hydrolysis Reactions Some More Reactions Involving Methyl Bromide 1,2-Dibromoethane in the Hypolimnion of the Lower Mystic Lake, Massachusetts Deriving Kinetic Parameters for Hydrolysis Reactions from Experimental Data Calculating Hydrolysis Reaction Times as a Function of Temperature and pH Estimating Hydrolysis Rate Constants Using the Hammett Relationship Calculating Standard Reduction Potentials from Free Energies of Formation Establishing Mass Balances for Oxygen and Nitrate in a Given System Calculating the Reduction Potential of an Aqueous Hydrogen Sulfide (H2S) Solution as a Function of pH and Total H2S Concentration Calculating Free Energies of Reaction from Half Reaction Reduction Potentials 1312 List of Illustrative Examples 14.5 Estimating Rates of Reduction of Nitroaromatic Compounds by DOM Components in the Presence of Hydrogen Sulfide Chapter 15 15.1 Determining Decadic Molar Extinction CoeScients of Organic Pollutants 15.2 Using the Screening Factor S(&) to Estimate the Total Specific Light Absorption Rate of PNAP in the Epilimnion of a Lake 15.3 Estimating the Photolysis Half-Life of a Weak Organic Acid in the Well-Mixed Epilimnion of a Lake Chapter 16 Chapter 17 Chapter 18 Chapter 19 Chapter 20 16.1 Estimating Near-Surface Hydroxyl Radical Steady-State Concentrations in Sunlit Natural Waters 16.2 16.3 17.1 17.2 17.3 17.4 Estimating the Indirect Photolysis Half-Life of Atrazine in a Shallow Pond Estimating Tropospheric Half-Lives of Organic Pollutants Is a Proposed Microbial Transformation Thermodynamically Feasible? What Products Do You Expect from the Microbial Degradation of EDB? What Products Do You Expect from the Microbial Degradation of Linuron? What Products Do You Expect from the Microbial Degradation of Vinyl Chloride in an Oxic Environment? 17.5 What Products Do You Expect from the Microbial Degradation of DDT in a Reducing Environment? 17.6 Evaluating the Biodegradation of Glycerol by Microorganisms Growing on that Substrate in a Well-Mixed Tank 17.7 Estimating the Time to Degrade a Spilled Chemical 17.8 Evaluating the CO-Metabolic Biodegradation of Trichloroethene by Microorganisms Growing on Methane in a Well-Mixed Tank 17.9 Estimating Biotransformation Rates of an Organic Pollutant in a Natural System 18.1 Estimating Molar Volumes 18.2 Estimating Molecular Diffusivity in Air Difhsivities in Water 18.3 Estimating Molecular Diffusivity in Water 18.4 Evaluating the Steady-State Flux of Benzene from Spilled Gasoline Through Soil to the Atmosphere 18.5 Interpreting Stratigraphic Profiles of Polychlorinated Naphthalenes in Lake Sediments 19.1 Vertical Exchange of Water in a Lake 19.2 Diffusion of a Volatile Compound from the Groundwater Through the Unsaturated Zone into the Atmosphere 19.3 Release of PCBs from the Historically Polluted Sediments of Boston Harbor 19.4 Dissolution of a Non-Aqueous-Phase Liquid (NAPL) into the Aqueous Phase 19.5 Desorption Kinetics of an Organic Chemical from Contaminated Sediments 20.1 Evaluating the Direction of Air-Water Exchange 20.2 Estimating Evaporation Rates of Pure Organic Liquids List of Illustrative Examples Chapter 21 Chapter 22 Chapter 23 Chapter 24 Chapter 25 1313 20.3 Estimating the Overall Air-Water Transfer Velocity from Wind Speed for Different Water Temperatures 20.4 Air-Water Exchange of Benzene in Rivers 20.5 Air-Water Exchange Enhancement for Formaldehyde and Acetaldehyde 21.1 Assessing the Behavior of Nitrilotriacetic Acid (NTA) in a Lake 21.2 How Certain Is the Degradation Rate of Nitrilotriacetic Acid (NTA) in Greifensee? (Advanced Topic) 21.3 Higher-Order Reaction of Nitrilotriacetic Acid (NTA) in Greifensee (Advanced Topic) 21.4 Fate of a Pesticide and its Decomposition Product in a Small Lake 21.5 Tetrachloroethene (PCE) in Greifensee: From the One-Box to the Two-Box Model 21.6 Dynamic Behavior of Tetrachloroethene (PCE) in Greifensee 22.1 Vertical Distribution of Dichlorodifluoromethane (CFC- 12) in a Small Lake 22.2 Vertical Turbulent Diffusion Coefficient in a Lake 22.3 A Patch of the Pesticide Atrazine Below the Surface of a Lake 22.4 Transport of a Volatile Compound From the Groundwater Through the Unsaturated Zone Into the Atmosphere-Illustrative Example 19.2 Reconsidered 23.1 A Vinyl Acetate Spill Into a Pond 24.1 Mean Flow Velocity of River G for Different Discharge Rates 24.2 Air-Water Exchange in River G 24.3 A Spill of Atrazine in River G 24.4 Turbulent Diffusion and Longitudinal Dispersion in River G 24.5 A Second Look at the Atrazine Spill in River G The Effect of Dispersion 25.1 Darcy’s Law in Groundwater Systems S 25.2 Dispersion and Advection in Groundwater System S 25.3 Infiltration of Polluted River Water into Groundwater System S 25.4 A Sudden Rise of the 2,4-Dinitrophenol Concentration in River R 25.5 Continuing the Case of 2,4-Dinitrophenol in River R 25.6 Transport of Tetrachloroethene in Groundwater System S 25.7 Infiltration of Benzylchloride into Groundwater System S .. .ENVIRONMENTAL ORGANIC CHEMISTRY Second Edition ENVIRONMENTAL ORGANIC CHEMISTRY Second Edition Rene P Schwarzenbach Philip M Gschwend Dieter M Imboden @WILEY- INTERSCIENCE A JOHN WILEY & SONS, ... Switzerland Environmental Organic Chemistry, 2nd Edition Rene P Schwarzenbach, Philip M Gschwend and Dieter M Imboden Copyright 02003 John Wiley &L Sons, Inc Part I Introduction Environmental Organic Chemistry, ... research Environmental Organic Chemistry, 2nd Edition Rene P Schwarzenbach, Philip M Gschwend and Dieter M Imboden Copyright 02003 John Wiley &L Sons, Inc Chapter AN INTRODUCTION TO ENVIRONMENTAL ORGANIC