Contaminant Hydrogeology

663 Pages·2017·35.86 MB·English

by  C. W. Fetter

Fetter FrontMatter.fm Page iii Tuesday, October 10, 2017 9:03 AM
Contaminant
Hydrogeology
Third Edition
C. W. Fetter
late of University of Wisconsin–Oshkosh
Thomas Boving
University of Rhode Island
David Kreamer
University of Nevada, Las Vegas
WAVELAND
PRESS, INC.
Long Grove, Illinois
Fetter FrontMatter.fm Page iv Tuesday, October 10, 2017 9:03 AM
For information about this book, contact:
Waveland Press, Inc.
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Long Grove, IL 60047-9580
[phone]
[email protected]
www.waveland.com
Copyright © 2018 by Nancy Fetter, Thomas Boving, and David Kreamer
10-digit ISBN 1-4786-3279-8
13-digit ISBN 978-1-4786-3279-5
All rights reserved. No part of this book may be reproduced, stored in a retrieval system, or transmitted
in any form or by any means without permission in writing from the publisher.
Printed in the United States of America
7 6 5 4 3 2 1
Contents
Acknowledgements and Dedication xii
Preface xiii
1 Introduction 1
1.1 Groundwater as a Resource 1
1.2 Types of Groundwater Contaminants 3
1.3 Drinking-Water Standards 16
1.4 Risk and Drinking Water 17
1.5 Sources of Groundwater Contamination 24
1.5.1 Category 1: Sources Designed to Discharge Substances 24
1.5.2 Category II: Sources Designed to Store, Treat and/or Dispose of
Substances 28
1.5.3 Category Ill: Sources Designed to Retain Substances During
Transport 35
1.5.4 Category IV: Sources Discharging Substances as a Consequence of
Other Planned Activities 35
1.5.5 Category V: Sources Providing a Conduit for Contaminated Water to
Enter Aquifers 38
1.5.6 Category VI: Naturally Occurring Sources Whose Discharge is
Created and/or Exacerbated by Human Activity 39
1.6 Relative Ranking of Groundwater-Contamination Sources and
Substances 40
1.7 Groundwater Contamination as a Long-Term Problem 42
1.8 Review of Mathematics and the Flow Equation 44
1.8.1 Derivatives 44
1.8.2 Darcy’s Law 46
1.8.3 Scalar, Vector, and Tensor Properties of Hydraulic Head and
Hydraulic Conductivity 47
1.8.4 Derivation of the Flow Equation in a Deforming Medium 49
1.8.5 Mathematical Notation 51
References 52
Problems 55
iii
iv Contents
2 Mass Transport in Saturated Media 56
2.1 Introduction 56
2.2 Transport by Concentration Gradients 56
2.3 Transport by Advection 61
2.4 Mechanical Dispersion 63
2.5 Hydrodynamic Dispersion 65
2.6 Derivation of the Advection-Dispersion Equation for Solute
Transport 66
2.7 Diffusion versus Dispersion 68
2.8 Moment Analysis 70
2.9 Analytical Solutions of the Advection-Dispersion Equation 75
2.9.1 Methods of Solution 75
2.9.2 Boundary and Initial Conditions 76
2.9.3 One-Dimensional Step Change in Concentration
(First-Type Boundary) 77
2.9.4 One-Dimensional Continuous Injection into a Flow Field
(Second-Type Boundary) 78
2.9.5 Third-Type Boundary Condition 82
2.9.6 One-Dimensional Slug Injection into a Flow Field 82
2.9.7 Continuous Injection into a Uniform Two-Dimensional
Flow Field 83
2.9.8 Slug Injection into a Uniform Two-Dimensional Flow Field 88
2.10 Effects of Transverse Dispersion 92
2.11 Tests to Determine Dispersivity Values 93
2.11.1 Laboratory Tests 93
2.11.2 Quantifying Dispersivity in the Field 96
2.11.3 Single-Well Tracer Test 97
2.12 Scale Effect of Dispersion 98
2.13 Stochastic Models of Solute Transport 103
2.13.1 Introduction 103
2.13.2 Stochastic Descriptions of Heterogeneity 104
2.13.3 Stochastic Approach to Solute Transport 106
2.14 Regression Analysis of Relationship between Apparent Longitudinal
Dispersivity and Field Scale 107
2.15 Deterministic Models of Solute Transport 109
2.16 Transport in Fractured Media 117
2.17 Summary 124
Chapter Notation 124
References 126
Problems 131
3 Transformation, Retardation, and Attenuation of Solutes 133
3.1 Introduction 133
3.2 Classification of Chemical Reactions 134
Contents v
3.3 Sorption Processes 134
3.4 Equilibrium Surface Reactions 135
3.4.1 Linear Sorption Isotherm 135
3.4.2 Freundlich Sorption Isotherm 138
3.4.3 Langmuir Sorption Isotherm 140
3.4.4 BET Sorption 142
3.4.5 Polanyi–Dubinin–Manes (PDM) Sorption Isotherm 143
3.4.6 Effect of Equilibrium Retardation on Solute Transport 144
3.5 Nonequilibrium (Kinetic) Sorption Models 148
3.6 Sorption of Hydrophobic (Organic) Compounds 153
3.6.1 Introduction 153
3.6.2 Partitioning onto Soil or Aquifer Organic Carbon 154
3.6.3 Estimating K from K Data 155
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3.6.4 Estimating K from Solubility Data 156
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3.6.5 Estimating K from Molecular Structure 161
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3.6.6 Quantitative Structure-Property Relationships 163
3.6.7 Multiple Solute Effects 165
3.7 Homogeneous Reactions 168
3.7.1 Introduction 168
3.7.2 Chemical Equilibrium 168
3.7.3 Chemical Kinetics 168
3.8 Radioactive Decay 170
3.9 Biodegradation 171
3.10 Colloidal Transport 176
3.10.1 Colloid Attachment/Detachment and Straining Theory 179
3.11 Summary 187
Chapter Notation 187
References 189
Problems 195
4 Flow and Mass Transport in the Vadose Zone 198
4.1 Introduction 198
4.2 Soil as a Porous Medium 199
4.3 Soil Colloids 200
4.4 The Electrostatic Double Layer 200
4.5 Salinity Effects on Hydraulic Conductivity of Soils 202
4.6 Flow of Water in the Unsaturated Zone 203
4.6.1 Soil-Water Potential 204
4.6.2 Soil-Water Characteristic Curves 204
4.6.3 Hysteresis 210
4.6.4 Construction of a Soil-Water-Retention Curve 211
4.6.5 Measurement of Soil-Water Potential 213
4.6.6 Unsaturated Hydraulic Conductivity 214
4.6.7 Buckingham Flux Law 218
4.6.8 Richards Equation 219
vi Contents
4.7 Liquid Mass Transport in the Unsaturated Zone 220
4.8 Equilibrium Models of Mass Transport 221
4.9 Nonequilibrium Models of Mass Transport 224
4.10 Anion Exclusion 225
4.11 Preferential Flowpaths in the Vadose Zone 229
4.12 Vapor Phase Transport 233
4.12.1 Gaseous Diffusion 233
4.12.2 Gaseous Advection 238
4.12.3 Effusion (Knudsen flow) 239
4.12.4 Combinations of Vapor Transport Processes 239
4.12.5 Other Environmental Factors 239
4.13 Summary 241
Chapter Notation 241
References 243
Problems 246
5 Multiphase Flow 247
5.1 Introduction 247
5.2 Basic Concepts 248
5.2.1 Saturation Ratio 248
5.2.2 Interfacial Tension and Wettability 249
5.2.3 Capillary Pressure 250
5.2.4 Relative Permeability 253
5.2.5 Darcy’s Law For Two-Phase Flow 257
5.2.6 Fluid Potential and Head 258
5.3 Migration of Light Nonaqueous Phase Liquids (LNAPLs) 262
5.4 Capillary and Bond Numbers 267
5.5 Partitioning Interwell Tracer Tests 269
5.6 Volatilization of NAPLs 271
5.7 Vapor Density 277
5.8 Measurement of the Thickness of a Floating Product 278
5.9 Effect of the Rise and Fall of the Water Table on the Distribution of
LNAPLs 287
5.10 Migration of Dense Nonaqueous Phase Liquids (DNAPLs) 290
5.10.1 Relative Mobility 290
5.10.2 Vadose Zone Migration 292
5.10.3 Vertical Movement in the Saturated Zone 294
5.10.4 Horizontal Movement in the Saturated Zone 296
5.10.5 DNAPL Flow in Fracture Systems 301
5.10.6 Dissolution of DNAPL 303
5.11 Monitoring for LNAPLs and DNAPLs 305
5.12 Summary 308
Chapter Notation 309
References 310
Problems 315
Contents vii
6 Inorganic Chemicals in Groundwater 316
6.1 Introduction 316
6.2 Units of Measurement and Concentration 316
6.3 Chemical Equilibrium and the Law of Mass Action 317
6.4 Oxidation-Reduction Reactions 320
6.5 Relationship between pH and Eh 323
6.5.1 pH 323
6.5.2 Relationship of Eh and pH 325
6.5.3 Eh-pH Diagrams 326
6.5.4 Calculating Eh-pH Stability Fields 328
6.6 Metal Complexes and Facilitated Particle Transport 338
6.6.1 Hydration of Cations 338
6.6.2 Complexation 339
6.6.3 Organic Complexing Agents 341
6.6.4 Facilitated Particle Transport 341
6.7 Chemistry of Nonmetallic Inorganic Contaminants 343
6.7.1 Fluoride 343
6.7.2 Chlorine and Bromine 344
6.7.3 Sulfur 344
6.7.4 Nitrogen 346
6.7.5 Arsenic 347
6.7.6 Selenium 348
6.7.7 Phosphorus 350
6.8 Chemistry of Metals 350
6.8.1 Beryllium 350
6.8.2 Strontium 350
6.8.3 Barium 351
6.8.4 Vanadium 351
6.8.5 Chromium 351
6.8.6 Cobalt 353
6.8.7 Nickel 353
6.8.8 Molybdenum 353
6.8.9 Copper 354
6.8.10 Silver 354
6.8.11 Zinc 354
6.8.12 Cadmium 354
6.8.13 Mercury 356
6.8.14 Lead 356
6.8.15 Rare Earth Elements 358
6.9 Radioactive Isotopes 358
6.9.1 Introduction 358
6.9.2 Adsorption of Cationic Radionuclides 359
6.9.3 Uranium 360
6.9.4 Thorium 363
6.9.5 Radium 364
viii Contents
6.9.6 Radon 367
6.9.7 Tritium 368
6.10 Geochemical Zonation 368
6.11 Summary 371
Chapter Notation 372
References 372
Problems 375
7 Organic Compounds in Groundwater 376
7.1 Introduction 376
7.2 Physical Properties of Organic Compounds 376
7.3 Organic Structure and Nomenclature 378
7.3.1 Hydrocarbon Classes 378
7.3.2 Aromatic Hydrocarbons 382
7.4 Petroleum and Coal Tar 383
7.4.1 Petroleum Distillates 383
7.4.2 Coal Tar 389
7.4.3 Groundwater contamination associated with petroleum products and
coal tar 390
7.5 Functional Groups 395
7.5.1 Organic Halides 395
7.5.2 Alcohols 395
7.5.3 Ethers 395
7.5.4 Aldehydes and Ketones 399
7.5.5 Carboxylic and Sulfonic Acids 400
7.5.6 Esters 402
7.5.7 Phenols 404
7.5.8 Organic Compounds Containing Nitrogen 405
7.5.9 Organic Compounds Containing Sulfur and Phosphorus 408
7.5.10 Emerging Contaminants 410
7.6 Degradation of Organic Compounds 415
7.6.1 Introduction 415
7.6.2 Degradation of Hydrocarbons 415
7.6.3 Degradation of Chlorinated Hydrocarbons 418
7.6.4 Degradation of Organic Pesticides 425
7.6.5 Degradation of Gasoline Compounds 427
7.7 Field Studies of Biological Degradation of Organic Molecules 428
7.8 Analysis of Organic Compounds in Groundwater 428
7.9 Fingerprinting Petroleum Distillates and Coal Tar 434
7.10 Summary 442
References 442
Problems 447
Contents ix
8 Site Characterization—Groundwater and Soil Monitoring 450
8.1 Introduction 450
8.2 Noninvasive Measures 452
8.2.1 Interpretation of Aerial Photography and Remote Sensing 452
8.2.2 The Use of Surface Geophysical Techniques for Site
Characterization 453
8.2.3 Rapid Noninvasive Field Surveys and Screening 455
8.3 Minimally Invasive Soil Monitoring 456
8.3.1 Soil Vapor Monitoring—Introduction 456
8.3.2 Methods of Soil Gas Monitoring 457
8.3.3 Soil Water Sampling—Introduction 458
8.3.4 Suction Lysimeters 458
8.3.5 Installation of Suction Lysimeters 460
8.3.6 Phyto-screening 461
8.4 Invasive Methods - Monitoring Well Design 462
8.4.1 General Information 462
8.4.2 Monitoring Well Casing 464
8.4.3 Monitoring Well Screens 472
8.4.4 Naturally Developed and Filter-Packed Wells 473
8.4.5 Annular Seal 474
8.4.6 Protective Casing 475
8.4.7 Screen Length and Setting 476
8.4.8 Summary of Monitoring Design for Single Screened Wells 479
8.4.9 Multiple-level Wells and Multilevel Devices for Groundwater
Monitoring 479
8.5 Installation of Monitoring Wells 485
8.5.1 Decontamination Procedures 485
8.5.2 Methods of Drilling 486
8.5.3 Drilling in Contaminated Soil 494
8.5.4 Sample Collection of Solid Material During Drilling 494
8.5.5 Installation of Monitoring Wells 498
8.5.6 Monitoring Well Development 503
8.5.7 Record Keeping During Monitoring Well Construction 507
8.5.8 Monitoring Well and Borehole Abandonment 507
8.6 Well Sampling 509
8.6.1 Introduction 509
8.6.2 Fluid Level and Pressure Measurement 509
8.6.3 Well Purging 510
8.6.4 Well-Sampling Devices 510
8.6.5 Methods of Collecting a Groundwater Sample Without Drilling a
Well 514
8.6.6 Low-Flow Purging of Monitoring Wells 516
8.6.7 Sampling Frequency 518