CRC Press is an imprint of the Taylor & Francis Group, an informa business Boca Raton London New York Eugene R. Weiner Second Edition Applications of Environmental Aquatic Chemistry A Practical Guide ß 2007 by Taylor & Francis Group, LLC. CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2008 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number-13: 978-0-8493-9066-1 (Hardcover) This book contains information obtained from authentic and highly regarded sources Reason- able efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The Authors and Publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www. copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC) 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Weiner, Eugene R. Applications of environmental aquatic chemistry : a practical guide / Eugene R. Weiner. 2nd ed. p. cm. Rev. ed. of: Applications of environmental chemistry / Eugene R. Weiner. 2000. Includes bibliographical references and index. ISBN 978-0-8493-9066-1 (alk. paper) 1. Environmental chemistry. 2. Water quality. I. Weiner, Eugene R. Applications of environmental chemistry. II. Title. TD193.W45 2007 628.1’68 dc22 2007048068 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com ß 2007 by Taylor & Francis Group, LLC. Contents Preface to the Second Edition Preface to the First Edition Author Chapter 1 Water Quality 1.1 Defining Environmental Water Quality 1.1.1 Water-Use Classifications and Water Quality Standards 1.1.2 Water Quality Classifications and Standards for Natural Waters 1.1.3 Setting Numerical Water Quality Standards 1.1.4 Typical Water-Use Classifications 1.1.4.1 Recreational 1.1.4.2 Aquatic Life 1.1.4.3 Agriculture 1.1.4.4 Domestic Water Supply 1.1.4.5 Wetlands 1.1.4.6 Groundwater 1.1.5 Staying Up-to-Date with Standards and Other Regulations 1.2 Sources of Water Impurities 1.2.1 Natural Sources 1.2.2 Human-Caused Sources 1.3 Measuring Impurities 1.3.1 What Impurities Are Present? 1.3.2 How Much of Each Impurity Is Present? 1.3.3 Working with Concentrations 1.3.4 Moles and Equivalents 1.3.4.1 Working with Equivalent Weights 1.3.5 Case History Example 1.3.6 How Do Impurities Influence Water Quality? Exercises Chapter 2 Contaminant Behavior in the Environment: Basic Principles 2.1 Behavior of Contaminants in Natural Waters 2.1.1 Important Properties of Pollutants 2.1.2 Important Properties of Water and Soil 2.2 What Are the Fates of Different Pollutants? 2.3 Processes That Remove Pollutants from Water 2.3.1 Natural Attenuation ß 2007 by Taylor & Francis Group, LLC. 2.3.2 Transport Processes 2.3.3 Environmental Chemical Reactions 2.3.4 Biological Processes 2.4 Major Contaminant Groups and Natural Pathways for Their Removal from Water 2.4.1 Metals 2.4.2 Chlorinated Pesticides 2.4.3 Halogenated Aliphatic Hydrocarbons 2.4.4 Fuel Hydrocarbons 2.4.5 Inorganic Nonmetal Species 2.5 Chemical and Physical Reactions in the Water Environment 2.6 Partitioning Behavior of Pollutants 2.6.1 Partitioning from a Diesel Oil Spill 2.7 Intermolecular Forces 2.7.1 Temperature Dependent Phase Changes 2.7.2 Volatility, Solubility, and Sorption 2.7.3 Predicting Relative Attractive Forces 2.8 Origins of Intermolecular Forces: Electronegativities, Chemical Bonds, and Molecular Geometry 2.8.1 Chemical Bonds 2.8.2 Chemical Bond Dipole Moments 2.8.3 Molecular Geometry and Molecular Polarity 2.8.4 Examples of Nonpolar Molecules 2.8.5 Examples of Polar Molecules 2.8.6 The Nature of Intermolecular Attractions 2.8.7 Comparative Strengths of Intermolecular Attractions 2.9 Solubility and Intermolecular Attractions Exercises Chapter 3 Major Water Quality Parameters and Applications 3.1 Interactions among Water Quality Parameters 3.2 pH 3.2.1 Background 3.2.2 Defining pH 3.2.3 Acid-Base Reactions 3.2.4 Importance of pH 3.2.5 Measuring pH 3.2.6 Water Quality Criteria and Standards for pH 3.3 Oxidation–Reduction Potential 3.3.1 Background 3.4 Carbon Dioxide, Bicarbonate, and Carbonate 3.4.1 Background 3.4.2 Solubility of CO 2 in Water 3.4.3 Soil CO 2 ß 2007 by Taylor & Francis Group, LLC. 3.5 Acidit y and Alka linity 3.5.1 Background 3.5.2 Acidity 3.5.3 Alkalinity 3.5.4 Importance of Alkalinity 3.5.5 Water Quality Criteria and Standards for Alkalinity 3.5.6 Calculating Alkalinity 3.5.7 Calculating Changes in Alkalinity, Carbonate, and pH 3.6 Hardness 3.6.1 Background 3.6.2 Calculating Hardness 3.6.3 Importance of Hardness 3.7 Dissolved Oxygen 3.7.1 Background 3.8 Biological Oxygen Demand and Chemical Oxygen Demand 3.8.1 Background 3.8.2 BOD 5 3.8.3 BOD Calculation 3.8.4 COD Calculation 3.9 Nitrogen: Ammonia, Nitrite, and Nitrate 3.9.1 Background 3.9.2 Nitrogen Cycle 3.9.3 Ammonia=Ammonium Ion 3.9.4 Water Quality Criteria and Standards for Ammonia 3.9.5 Nitrite and Nitrate 3.9.6 Water Quality Criteria and Standards for Nitrate 3.9.7 Methods for Removing Nitrogen from Wastewater 3.9.7.1 Air-Stripping Ammonia 3.9.7.2 Nitrification–Denitrification 3.9.7.3 Breakpoint Chlorination 3.9.7.4 Ammonium Ion Exchange 3.9.7.5 Biosynthesis 3.10 Sulfide and Hydrogen Sulfide 3.10.1 Background 3.10.1.1 Formation of H 2 S in Detention Ponds, Wetlands, and Sewers 3.10.1.2 Typical Water Quality Criteria and Standards for H 2 S 3.10.2 Case Study 3.10.2.1 Odors of Biological Origin in Water (Mostly Hydrogen Sulfide and Ammonia) 3.10.2.2 Environmental Chemistry of Hydrogen Sulfide 3.10.2.3 Chemical Control of Odors 3.10.2.4 pH control ß 2007 by Taylor & Francis Group, LLC. 3.10.2.5 Oxidation 3.10.2.6 Eliminate Reducing Conditions Caused by Decomposing Organic Matter 3.10.2.7 Sorption to Activated Charcoal 3.11 Phosphorus 3.11.1 Background 3.11.2 Important Uses for Phosphorus 3.11.3 Phosphorous Cycle 3.11.4 Mobility in the Environment 3.11.5 Phosphorous Compounds 3.11.6 Removal of Dissolved Phosphate 3.12 Solids (Total, Suspended, and Dissolved) 3.12.1 Background 3.12.2 TDS and Salinity 3.12.3 Specific Conductivity and TDS 3.12.4 TDS Test for Analytical Reliability 3.13 Temperature Exercises Reference Chapter 4 Behavior of Metal Species in the Natural Environment 4.1 Metals in Water 4.1.1 Background 4.1.2 Mobility of Metals in the Water Environment 4.1.3 General Behavior of Dissolved Metals in Water 4.1.3.1 Hydrolysis Reactions 4.1.3.2 Hydrated Metals as Acids 4.1.4 Influence of pH on the Solubility of Metals 4.1.5 Influence of Redox Potential on the Solubility of Metals 4.1.5.1 Redox-Sensitive Metals: Cr, Cu, Hg, Fe, Mn 4.1.5.2 Redox-Insensitive Metals: Al, Ba, Cd, Pb, Ni, Zn 4.1.5.3 Redox-Sensitive Metalloids: As, Se 4.2 Metal Water Quality Standards 4.3 Case Study 1 4.3.1 Treatment of Trace Metals in Urban Stormwater Runoff 4.3.2 Behavior of Common Stormwater Pollutants under Oxidizing and Reducing Conditions 4.4 Case Study 2 4.4.1 Acid Rock Drainage 4.4.1.1 Summary of Acid Formation in Acid Rock Drainage 4.4.1.2 Non-iron Metal Sulfides Do Not Generate Acidity 4.4.1.3 Acid-Base Potential of Soil 4.4.1.4 Determining the Acid-Base Potential ß 2007 by Taylor & Francis Group, LLC. 4.5 Case Study 3 4.5.1 Identifying Metal Loss and Gain Mechanisms in a Stream Exercises References Chapter 5 Soil, Groundwater, and Subsurface Contamination 5.1 Nature of Soils 5.1.1 Soil Formation 5.1.1.1 Physical Weathering 5.1.1.2 Chemical Weathering 5.1.1.3 Secondary Mineral Formation 5.1.1.4 Roles of Plants and Soil Organisms 5.2 Soil Profiles 5.2.1 Soil Horizons 5.2.2 Successive Steps in the Typical Development of a Soil and Its Profile (Pedogenesis) 5.3 Organic Matter in Soil 5.3.1 Humic Substances 5.3.2 Some Properties of Humic Materials 5.3.2.1 Binding to Dissolved Species 5.3.2.2 Light Absorption 5.4 Soil Zones 5.4.1 Air in Soil 5.5 Contaminants Become Distributed in Water, Soil, and Air 5.5.1 Volatilization 5.5.2 Sorption 5.6 Partition Coefficients 5.6.1 Air–Water Partition Coefficient (Henry’s Law) 5.6.2 Soil–Water Partition Coefficient 5.6.3 Determining K d Experimentally 5.6.4 Role of Soil Organic Matter 5.6.5 Octanol–Water Partition Coefficient, K ow 5.6.6 Estimating K d Using Measured Solubility or K ow 5.7 Mobility of Contaminants in the Subsurface 5.7.1 Retardation Factor 5.7.2 Effect of Biodegradation on Effective Retardation Factor 5.7.3 A Model for Sorption and Retardation 5.7.4 Soil Properties 5.8 Particulate Transport in Groundwater: Colloids 5.8.1 Colloid Particle Size and Surface Area 5.8.2 Particle Transport Properties 5.8.3 Electrical Charges on Colloids and Soil Surfaces 5.8.3.1 Electrical Double Layer 5.8.3.2 Adsorption and Coagulation ß 2007 by Taylor & Francis Group, LLC. 5.9 Case Study: Clearing Muddy Ponds 5.9.1 Pilot Jar Tests 5.9.1.1 Jar Test Procedure with Alum Coagulant 5.9.1.2 Jar Test Procedure with Gypsum Coagulant Exercises References Chapter 6 General Properties of Nonaqueous Phase Liquids and the Behavior of Light Nonaqueous Phase Liquids in the Subsurface 6.1 Types and Properties of Nonaqueous Phase Liquids 6.2 General Characteristics of Petroleum Liquids, the Most Common LNAPL 6.2.1 Types of Petroleum Products 6.2.2 Gasoline 6.2.3 Middle Distillates 6.2.4 Heavier Fuel Oils and Lubricating Oils 6.3 Behavior of Petroleum Hydrocarbons in the Subsurface 6.3.1 Soil Zones and Pore Space 6.3.2 Partitioning of Light Nonaqueous Phase Liquids in the Subsurface 6.3.3 Processes of Subsurface Migration 6.3.4 Petroleum Mobility Through Soils 6.3.5 Behavior of LNAPL in Soils and Groundwater 6.3.6 Summary: Behavior of Spilled LNAPL 6.3.7 Weathering of Subsurface Contaminants 6.3.8 Petroleum Mobility and Solubility 6.4 Formation of Petroleum Contamination Plumes 6.4.1 Dissolved Contaminant Plume 6.4.2 Vapor Contaminant Plume 6.5 Estimating the Amount of LNAPL Free Product in the Subsurface 6.5.1 How LNAPL Layer Thickness in the Subsurface Affects LNAPL Layer Thickness in a Well 6.5.1.1 Effect of Soil Texture on LNAPL in the Subsurface and in Wells 6.5.1.2 Effect of Water Table Fluctuations on LNAPL in the Subsurface and in Wells 6.5.1.3 Effect of Water Table Fluctuations on LNAPL Measurements in Wells 6.6 Estimating the Amount of Residual LNAPL Immobilized in the Subsurface 6.6.1 Subsurface Partitioning Loci of LNAPL Fuels 6.7 Chemical Fingerprinting of LNAPLs 6.7.1 First Steps in Chemical Fingerprinting of Fuel Hydrocarbons 6.7.2 Identifying Fuel Types ß 2007 by Taylor & Francis Group, LLC. 6.7.3 Age-Dating Fuel Spills 6.7.3.1 Gasoline 6.7.3.2 Changes in BTEX Ratios Measured in Groundwater 6.7.3.3 Diesel Fuel 6.8 Simulated Distillation Curves and Carbon Number Distribution Curves References Chapter 7 Behavior of Dense Nonaqueous Phase Liquids in the Subsurface 7.1 DNAPL Properties 7.2 DNAPL Free Product Mobility 7.2.1 DNAPL in the Vadose Zone 7.2.2 DNAPL at the Water Table 7.2.3 DNAPL in the Saturated Zone 7.3 Testing for the Presence of DNAPL 7.3.1 Contaminant Concentrations in Groundwater and Soil That Indicate the Proximity of DNAPL 7.3.2 Calculation Method for Assessing Residual DNAPL in Soil 7.4 Polychlorinated Biphenyls 7.4.1 Background 7.4.2 Environmental Behavior 7.4.3 Analysis of PCBs 7.4.4 Case Study: Mistaken Identification of PCB Compounds References Chapter 8 Biodegradation and Bioremediation of LNAPLs and DNAPLs 8.1 Biodegradation and Bioremediation 8.2 Basic Requirements for Biodegradation 8.3 Biodegradation Processes 8.3.1 Case Study 8.3.1.1 Passive (Intrinsic) Bioremediation of Fuel LNAPLs: California Survey 8.4 Natural Aerobic Biodegradation of NAPL Hydrocarbons 8.5 Determining the Extent of Bioremediation of LNAPL 8.5.1 Using Chemical Indicators of the Rate of Intrinsic Bioremediation 8.5.2 Hydrocarbon Contaminant Indicator 8.5.3 Electron Acceptor Indicators 8.5.4 Dissolved Oxygen Indicator 8.5.5 Nitrate Plus Nitrite Denitrification Indicator 8.5.6 Metal Reduction Indicators: Manganese (IV) to Manganese (II) and Iron (III) to Iron (II) 8.5.7 Sulfate Reduction Indicator 8.5.8 Methanogenesis (Methane Formation) Indicator ß 2007 by Taylor & Francis Group, LLC. 8.5.9 Redox Potential and Alkalinity as Biodegradation Indicators 8.5.9.1 Using Redox Potentials to Locate Anaerobic Biodegradation within the Plume 8.5.9.2 Using Alkalinity to Locate Anaerobic Biodegradation within the Plume 8.6 Bioremediation of Chlorinated DNAPLs 8.6.1 Reductive Dechlorination of Chlorinated Ethenes 8.6.2 Reductive Dechlorination of Chlorinated Ethanes 8.6.3 Case Study: Using Biodegradation Pathways for Source Identification References Chapter 9 Behavior of Radionuclides in the Water and Soil Environment 9.1 Introduction 9.2 Radionuclides 9.2.1 A Few Basic Principles of Chemistry 9.2.1.1 Matter and Atoms 9.2.1.2 Elements 9.2.2 Properties of an Atomic Nucleus 9.2.2.1 Nuclear Notation 9.2.3 Isotopes 9.2.4 Nuclear Forces 9.2.5 Quarks, Leptons, and Gluons 9.2.6 Radioactivity 9.2.6.1 a Emission 9.2.6.2 b Emission 9.2.6.3 g Emission 9.2.7 Balancing Nuclear Equations 9.2.8 Rates of Radioactive Decay 9.2.8.1 Half-Life 9.2.9 Radioactive Decay Series 9.2.10 Naturally Occurring Radionuclides 9.3 Emissions and Their Properties 9.4 Units of Radioactivity and Absorbed Radiation 9.4.1 Activity 9.4.2 Absorbed Dose 9.4.3 Dose Equivalent 9.4.4 Unit Conversion Tables 9.4.4.1 Converting between Units of Dose Equivalent and Units of Activity (Rems to Picocuries) 9.5 Naturally Occurring Radioisotopes in the Environment 9.5.1 Case Study: Radionuclides in Public Water Supplies 9.5.2 Uranium 9.5.2.1 Uranium Geology 9.5.2.2 Uranium in Water ß 2007 by Taylor & Francis Group, LLC. [...]... 10 .4 .11 .2 Ultraviolet Disinfection Treatment 10 .4 .11 .3 Membrane Filtration Water Treatment 10 .5 Ion Exchange 10 .5 .1 Why Do Solids in Nature Carry a Surface Charge? 10 .5.2 Cation- and Anion-Exchange Capacity (CEC) 10 .5.3 Exchangeable Bases: Percent Base Saturation 10 .5.4 CEC in Clays and Organic Matter 10 .5.4 .1 CEC in Clays 10 .5.4.2 CEC in Organic Matter 10 .5.5 Rates of Cation Exchange 10 .6 Indicators of. .. Laboratory Reported Results 10 .10 Case Study: Water Quality Profile of Groundwater in Coal-Bed Methane Formations 10 .10 .1 Geochemical Explanation for the Stiff Patterns ß 2007 by Taylor & Francis Group, LLC 10 .10 .1. 1 10 .10 .1. 2 10 .10 .1. 3 10 .10 .1. 4 Bicarbonate Anion Increase Calcium and Magnesium Cation Decrease Sodium Cation May Increase Sulfate Anion Decrease References Appendix A A Selective Dictionary... high-quality water as water in a pristine environment unaltered by human activity If the chemist is also a fisherman, she or he might regard high-quality water as a good habitat for fish and other aquatic organisms A drinking water treatment plant manager will define high-quality water as water with a minimum amount of substances that have to be removed or treated to produce safe and palatable drinking water... demonstrating that a recreation class 2 classification is appropriate shall be assigned a class 1a classification, unless a reasonable level of inquiry has failed to identify any existing class 1 uses of the water segment Class 1b—Potential primary contact: This classification shall be assigned to water segments for which no use attainability analysis has been performed demonstrating that a recreation class... Radium 9.5.3 .1 Radium in Soil 9.5.3.2 Radium in Water Radon 9.5.4 .1 Health Issues Exercises References Chapter 10 Selected Topics in Environmental Chemistry 10 .1 Agricultural Water Quality 10 .2 Sodium Adsorption Ratio 10 .2 .1 What SAR Values Are Acceptable? 10 .3 Deicing and Sanding of Roads: Controlling Environmental Effects 10 .3 .1 Methods for Maintaining Winter Highway Safety 10 .3.2 Antiskid Materials... Fecal Contamination: Coliform and Streptococci Bacteria 10 .6 .1 Background 10 .6.2 Total Coliforms 10 .6.3 Fecal Coliforms 10 .6.4 Escherichia coli 10 .6.5 Fecal Streptococci 10 .6.6 Enterococci 10 .7 Municipal Wastewater Reuse: The Movement and Fate of Microbial Pathogens 10 .7 .1 Pathogens in Treated Wastewater 10 .7.2 Transport and Inactivation of Viruses in Soils and Groundwater 10 .8 Oil and Grease 10 .8 .1. .. classified In addition, site-specific standards may be established where special conditions exist, such as where aquatic life has become acclimated to high levels of dissolved metals Each state has tables of water quality standards for each classified water body In addition to standards for environmental waters, there are separate human health-based standards for groundwater used for public drinking water... Dictionary of Water Quality Parameters and Pollutants A. 1 Introduction A. 1. 1 Water Quality Inorganic Parameters: Classified by Abundance A. 2 Alphabetical Listing of Chemical and Physical Water Quality Parameters and Pollutants Answers to Selected Chapter Exercises ß 2007 by Taylor & Francis Group, LLC ß 2007 by Taylor & Francis Group, LLC Preface to the Second Edition Much new material has been added to... Oil and Grease Analysis 10 .8.2 Silica Gel Treatment 10 .9 Quality Assurance and Quality Control in Environmental Sampling 10 .9 .1 QA/QC Has Different Field and Laboratory Components 10 .9.2 Essential Components of Field QA/QC 10 .9.2 .1 Sample Collection 10 .9.3 Field Sample Set 10 .9.3 .1 Quality Control Samples 10 .9.3.2 Blank Sample Requirements 10 .9.3.3 Field Duplicates and Spikes 10 .9.3.4 Understanding Laboratory... supply and to water delivered to the public from drinking water treatment plants Drinking water standards are chosen to protect the public health 1. 1.2 WATER QUALITY CLASSIFICATIONS FOR NATURAL WATERS AND STANDARDS The following preliminary steps, taken by a state or federal agency, are a common approach to evaluating water quality in natural waters: 1 Define in general the basic purposes for which natural . and Standards for Natural Waters 1. 1.3 Setting Numerical Water Quality Standards 1. 1.4 Typical Water-Use Classifications 1. 1.4 .1 Recreational 1. 1.4.2 Aquatic Life 1. 1.4.3 Agriculture 1. 1.4.4 Domestic. Edition Preface to the First Edition Author Chapter 1 Water Quality 1. 1 Defining Environmental Water Quality 1. 1 .1 Water-Use Classifications and Water Quality Standards 1. 1.2 Water Quality Classifications and. by Taylor & Francis Group, LLC. 10 .10 .1. 1 Bicarbonate Anion Increase 10 .10 .1. 2 Calcium and Magnesium Cation Decrease 10 .10 .1. 3 Sodium Cation May Increase 10 .10 .1. 4 Sulfate Anion Decrease References Appendix