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Application of environmental aquatic chemistry
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. 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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. [...]... arise most frequently in the work of an environmental professional Environmental chemists and students of environmental chemistry should also find the book valuable as a general-purpose reference ß 2007 by Taylor & Francis Group, LLC Author Eugene R Weiner, PhD is professor emeritus of chemistry at the University of Denver, Colorado In 1965 he joined the University of Denver’s faculty From 1967 to 1992,... contain 0.173 mg of sodium What is the concentration in mg=L of sodium in the sample? Answer: 0:173 mg 1000 mL Â ¼ 3:79 mg=L or 3:79 ppm 45:6 mL L (Note that 3.79 ppm means all of the following: 3.79 g of sodium in 106 g of solution, or 3.79 3 10À3 g (3.79 mg) of sodium in 103 g (1 L) of solution, or 3.79 3 10À6 g (3.79 mg) of sodium per gram of solution.) * Operationally, 1 mole of any pure element... g=mol 2:00 g Moles of Ca(OCl)2 in 2:00 g ¼ ¼ 0:014 mol 142:9 g=mol (2) Equation 1.3 indicates that 2 moles of HOCl are formed from 1 mole of Ca(OCl)2 Therefore 2 3 0.014 mol ¼ 0.028 moles of HOCl are formed from 2.00 g of Ca(OCl)2 (3) Half of the HOCl dissociates to OClÀ, resulting in 0.014 moles of HOCl and 0.014 moles of OClÀ (4) MW of HOCl ¼ 1.0 þ 16.0 þ 35.4 ¼ 52.4 g=mol MW of OClÀ ¼ 16.0 þ 35.4... (1) Determine the number of moles in 2.00 g of Ca(OCl)2 (2) Determine the moles of HOCl formed by 2.00 g of Ca(OCl)2, if no further dissociation occurred (3) Determine the moles of HOCl and OClÀ in the water after complete dissociation (Equation 1.4) (4) Determine the weight of HOCl and OClÀ in the water (5) Calculate the ppm of HOCl þ OClÀ in 1050 L of water Answer: (1) MW of Ca(OCl)2 ¼ 40.1 þ 2316.0... molecules=cc3) Moles of a pollutant gas per liter of air (mol=L) Partial pressure of pollutant gas Mole fraction of pollutant gas With so many definitions of gas concentrations in common use, it clearly is useful to be able to convert gas concentrations from one set of units to another The rules of thumb box below illustrate the principles for converting between the two different units of air pollutant... weight of NO3 33 Â 10À3 g=L ¼ 0:53 Â 10À3 mol=L or 0:53 mmol=L 62:0 g=mol Each mole of NO3 contains 1 mole of N and 3 moles of O Therefore, 0.53 mmol=L of NO3 contains 0.53 mmol=L of N 0:53 Â 10À3 mol N=L Â 14 g N=mol ¼ 7:4 Â 10À3 g NO3 N=L This sample does not exceed the federal standard of 10 mg NO3–N=L and the source is in compliance EXAMPLE 5 USING MOLES, PPM, AND MG/L TOGETHER 2.00 g of the disinfectant... Some of the analytical methods used are gas and ion chromatography, mass spectroscopy, optical emission and absorption spectroscopy, electrochemical probes, and immunoassay testing 1.3.2 HOW MUCH OF EACH IMPURITY IS PRESENT? The amount of impurity is found by quantitative chemical analysis of the water sample The amount of impurity can be expressed in terms of total mass (e.g., ‘‘There are 15 tons of. .. soils through which they flow The number of drinking water contaminants regulated by the United States Government has increased from about five in 1940 to over 150 in 1999 There are two distinct spheres of interest for an environmental professional, the ever-changing, constructed sphere of regulations and the comparatively stable sphere of the natural environment Much of the regulatory sphere is bounded... sample (abbreviated as mol=L), moles of impurity per kilogram of sample (mol=kg), or as equivalents of impurity per liter (eq=L) or kilogram (eq=kg) of sample Moles per liter are related to the number of impurity molecules, rather than the mass of impurity Because chemical reactions involve one-on-one molecular interactions, regardless of the mass of the reacting molecules, moles are best for chemical calculations,... wastes The environmental sphere is bounded by the innate behavior of chemicals of concern While this book focuses on the environmental sphere, it makes an excursion into a small part of the regulatory sphere in Chapter 1, where the rationale for stream classifications and standards and the regulatory definition of water quality are discussed This book is intended to be a guide and reference for professionals . arise most frequently in the work of an environmental professional. Environmental chemists and students of environmental chemistry should also find the book. 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