Applications of
ENVIRONMENTAL
CHEMISTRY
A Practical Guide
for
Environmental
Professionals
Eugene R. Weiner, Ph.D.
LEWIS PUBLISHERS
Boca Raton London New York Washington, D.C.
Copyright © 2000 CRC Press, LLC
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Library of Congress Cataloging-in-Publication Data
Weiner, Eugene R.
Applications of environmental chemistry: a practical guide for environmental
professionals / Eugene R. Weiner.
p. cm.
Includes index.
ISBN 1-56670-354-9 (alk. paper)
1. Environmental chemistry. I. Title
TD193.W45 2000
577′.194—dc21 99-087370
CIP
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Preface
“By sensible definition, any by-product of a chemical operation for which there is no profitable use is
a waste. The most convenient, least expensive way of disposing of said waste — up the chimney or
down the river — is the best.”
From American Chemical Industry — A History, by W. Haynes, Van Nostrand Publishers, 1954.
The quotation above describes the usual approach to waste disposal as it was practiced in the first
half of the 1900s. Current disposal and cleanup regulations are aimed at correcting problems caused
by such misguided advice and go further toward maintaining a nondegrading environment. Regu-
lations, such as federal and state Clean Water Acts, have set in motion a great effort to identify the
chemical components and other characteristics that influence the quality of surface and groundwaters
and the soils through which they flow. The number of drinking water contaminants regulated by
the U.S. government has increased from about 5 in 1940 to more than 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 bound by classifications and numerical standards for waters, soils,
and wastes. The environmental sphere is bound 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 serve as a guide and reference for professionals and students. It is
structured to be especially useful for those who must use the concepts of environmental chemistry
but are not chemists and do not have the time and/or the inclination to learn all the relevant
background material. Chemistry topics that are most important in environmental applications are
succinctly summarized with a genuine effort to walk the middle ground between too much and too
little information. Frequently used reference materials are also included, such as water solubilities,
partition coefficients, natural abundance of trace metals in soil, and federal drinking water standards.
Particularly useful are the frequent “rules of thumb” lists which conveniently offer ways to quickly
estimate important aspects of the topic being discussed.
Although it is often true that “a little knowledge can be dangerous,” it is also true that a little
chemical knowledge of the “right sort” can be of great help to the busy nonchemist. Although no
“practical guide” will please everyone with its choice of inclusions and omissions, I have based my
choices on the most frequently asked questions from my colleagues and on the material I find myself
looking up frequently. The main goal of this book is to offer nonchemist readers enough chemical
insight to help them contend with those environmental chemistry problems that seem to 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.
Chapter 1 outlines part of the administrative regulatory structure with which the reader, pre-
sumably, must interact. Chapter 2 offers some elementary theoretical background for those who
may need it or find it interesting. Professionals with little time to spare will find Chapters 3–7 and
the appendices of greatest interest, which is where pollutant properties and environmental applica-
tions are described.
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About the Author
Eugene R. Weiner, Ph.D., is professor emeritus of chemistry at the University of Denver, Colorado.
He joined the University of Denver’s faculty in 1965. From 1967 to 1992, Dr. Weiner was a
consultant with the U.S. Geological Survey, Water Resources Division in Denver, and has consulted
on environmental issues for many other private, state, and federal entities. After 27 years of research
and teaching environmental and physical chemistry, he joined Wright Water Engineers Inc., an
environmental and water resources engineering firm in Denver, as senior scientist.
Dr. Weiner received a B.S. degree in mathematics from Ohio University, an M.S. degree in
physics from the University of Illinois, and a Ph.D. degree in chemistry from Johns Hopkins
University. He has authored and coauthored approximately 200 research articles, books, and tech-
nical reports. In recent years, he conducted 16 short courses, dealing with the movement and fate
of contaminants in the environment, at major cities around the U.S. for the continuing education
program of the American Society of Civil Engineers.
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Table of Contents
Chapter 1 Water Quality
1.1 Defining Water Quality
Water Use Classifications and Water Quality Standards
Typical Water Use Classifications
Setting Numerical Water Quality Standards
Staying Up-to-Date With Standards and Other Regulations
1.2 Sources of Water Impurities
Natural Sources
Human-caused Sources
1.3 Measuring Impurities
What Impurities Are Present?
How Much of Each Impurity Is Present?
Working with Concentrations
How Do Impurities Influence Water Quality?
Chapter 2 Principles of Contaminant Behavior in the Environment
2.1 The Behavior of Contaminants in Natural Waters
Important Properties of Pollutants
Important Properties of Water and Soil
2.2 What Are the Fates of Different Pollutants?
2.3 Processes That Remove Pollutants from Water
Transport Processes
Environmental Chemical Reactions
Biological Processes
2.4 Major Contaminant Groups and Their Natural Pathways for Removal from Water
Metals
Chlorinated Pesticides
Halogenated Aliphatic Hydrocarbons
Fuel Hydrocarbons
Inorganic Nonmetal Species
2.5 Chemical and Physical Reactions in the Water Environment
2.6 Partitioning Behavior of Pollutants
Partitioning from a Diesel Oil Spil
2.7 Intermolecular Forces
Predicting Relative Attractive Forces
2.8 Predicting Bond Type from Electronegativities
Dipole Moments
2.9 Molecular Geometry, Molecular Polarity, and Intermolecular Forces
Examples of Nonpolar Molecules
Examples of Polar Molecules
The Nature of Intermolecular Attractions
Comparative Strengths of Intermolecular Attractions
2.10 Solubility and Intermolecular Attractions
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Chapter 3 Major Water Quality Parameters
3.1 Interactions Among Water Quality Parameters
3.2 pH
Background
Defining pH
Acid-Base Reactions
Importance of pH
Measuring pH
Criteria and Standards
3.3 Oxidation-Reduction (Redox) Potential
Background
3.4 Carbon Dioxide, Bicarbonate, and Carbonate
Background
Solubility of CO2 in Water
Soil CO2
3.5 Acidity and Alkalinity
Background
Acidity
Alkalinity
Importance of Alkalinity
Criteria and Standards for Alkalinity
Calculating Alkalinity
Calculating Changes in Alkalinity, Carbonate, and pH
3.6 Hardness
Background
Calculating Hardness
Importance of Hardness
3.7 Dissolved Oxygen (DO)
Background
3.8 Biological Oxygen Demand (BOD) and Chemical Oxygen Demand (COD)
Background
BOD5
BOD Calculation
COD Calculation
3.9 Nitrogen: Ammonia (NH3), Nitrite (NO2–), and Nitrate (NO3–)
Background
The Nitrogen Cycle
Ammonia/Ammonium Ion (NH3/NH4+)
Criteria and Standards for Ammonia
Nitrite (NO2–) and Nitrate (NO3–)
Criteria and Standards for Nitrate
Methods for Removing Nitrogen from Wastewater
3.10 Sulfide (S2–)
Background
3.11 Phosphorus (P)
Background
Important Uses for Phosphorus
The Phosphorus Cycle
Mobility in the Environment
Phosphorus Compounds
Removal of Dissolved Phosphate
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3.12 Metals in Water
Background
General Behavior of Dissolved Metals in Water
3.13 Solids (Total, Suspended, and Dissolved)
Background
TDS and Salinity
Specific Conductivity and TDS
TDS Test for Analytical Reliability
3.14 Temperature
Chapter 4 Soil, Groundwater, and Subsurface Contamination
4.1 The Nature of Soils
Soil Formation
4.2 Soil Profiles
Soil Horizons
Steps in the Typical Development of a Soil and Its Profile (Pedogenesis)
4.3 Organic Matter in Soil
Humic Substances
Some Properties of Humic Materials
4.4 Soil Zones
Air in Soil
4.5 Contaminants Become Distributed in Water, Soil, and Air
Volatilization
Sorption
4.6 Partition Coefficients
Air-Water Partition Coefficient
Soil-Water Partition Coefficient
Determining Kd Experimentally
The Role of Soil Organic Matter
The Octanol/Water Partition Coefficient, Kow
Estimating Kd Using Solubility or Kow
4.7 Mobility of Contaminants in the Subsurface
Retardation Factor
Effect of Biodegradation on Effective Retardation Factor
A Model for Sorption and Retardation
Soil Properties
4.8 Particulate Transport in Groundwater: Colloids
Colloid Particle Size and Surface Area
Particle Transport Properties
Electrical Charges on Colloids and Soil Surfaces
4.9 Biodegradation
Basic Requirements for Biodegradation
Natural Aerobic Biodegradation of NAPL Hydrocarbons
4.10 Biodegradation Processes
4.11 California Study
4.12 Determining the Extent of Bioremediation of LNAPL
Using Chemical Indicators of the Rate of Intrinsic Bioremediation
Hydrocarbon Contaminant Indicator
Electron Acceptor Indicators
Dissolved Oxygen (DO)
Nitrate + Nitrite Denitrification
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Iron (III) Reduction to Iron (II)
Sulfate Reduction
Methanogenesis (Methane Formation)
Redox Potential and Alkalinity as Biodegradation Indicators
References
Chapter 5 Petroleum Releases to the Subsurface
5.1 The Problem
5.2 General Characteristics of Petroleum
Types of Petroleum Products
Gasolines
Middle Distillates
Heavier Fuel Oils and Lubricating Oils
5.3 Behavior of Petroleum Hydrocarbons in the Subsurface
Soil Zones and Pore Space
Partitioning of Light Nonaqueous Phase Liquids (LNAPLs) in the Subsurface
Oil Mobility Through Soils
Processes of Subsurface Migration
Behavior of LNAPL in Soils and Groundwater
Summary of LNAPL Behavior
“Weathering” of Subsurface Contaminants
5.4 Petroleum Mobility and Solubility
5.5 Formation of Petroleum Contamination Plumes
Dissolved Contaminant Plume
Vapor Contaminant Plume
5.6 Estimating the Amount of Free Product in the Subsurface
Effect of LNAPL Subsurface Layer Thickness on Well Thickness
Effect of Soil Texture
Effect of Water Table Fluctuations on LNAPL in Subsurface and Wells
Effect of Water Table Fluctuations on Well Measurements
5.7 Estimating the Amount of Residual LNAPL Immobilized in the Subsurface
Subsurface Partitioning Loci of LNAPL Fuels
5.8 DNAPL Free Product Plume
Testing for the Presence of DNAPL
5.9 Chemical Fingerprinting
First Steps in Chemical Fingerprinting of Fuel Hydrocarbons
Identifying Fuel Types
Age-Dating Diesel Oils
Simulated Distillation Curves and Carbon Number Distribution Curves
References
Chapter 6 Selected Topics in Environmental Chemistry
6.1 Acid Mine Drainage
Summary of Acid Formation in Mine Drainage
Noniron Metal Sulfides Do Not Generate Acidity
Acid-Base Potential of Soil
6.2 Agricultural Water Quality
6.3 Breakpoint Chlorination for Removing Ammonia
6.4 De-icing and Sanding of Roads: Controlling Environmental Effects
Methods for Maintaining Winter Highway Safety
Antiskid Materials
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Chemical De-icers
De-icer Components and Their Potential Environmental Effects
6.5 Drinking Water Treatment
Water Sources
Water Treatment
Basic Drinking Water Treatment
Disinfection Byproducts and Disinfection Residuals
Strategies for Controlling Disinfection Byproducts
Chlorine Disinfection Treatment
Drawbacks to Use of Chlorine: Disinfection Byproducts (DBPs)
Chloramines
Chlorine Dioxide Disinfection Treatment
Ozone Disinfection Treatment
Potassium Permanganate
Peroxone (Ozone + Hydrogen Peroxide)
Ultraviolet (UV) Disinfection Treatment
Membrane Filtration Water Treatment
6.6 Ion Exchange
Why Do Solids in Nature Carry a Surface Charge?
Cation and Anion Exchange Capacity (CEC and AEC)
Exchangeable Bases: Percent Base Saturation
CEC in Clays and Organic Matter
Rates of Cation Exchange
6.7 Indicators of Fecal Contamination: Coliform and Streptococci Bacteria
Background
Total Coliforms
Fecal Coliforms
E. coli
Fecal Streptococci
Enterococci
6.8 Municipal Wastewater Reuse: The Movement and Fate of Microbial Pathogens
Pathogens in Treated Wastewater
Transport and Inactivation of Viruses in Soils and Groundwater
6.9 Odors of Biological Origin in Water
Environmental Chemistry of Hydrogen Sulfide
Chemical Control of Odors
6.10 Quality Assurance and Quality Control (QA/QC) in Environmental Sampling
QA/QC Has Different Field and Laboratory Components
Essential Components of Field QA/QC
Understanding Laboratory Reported Results
6.11 Sodium Adsorption Ratio (SAR)
What SAR Values Are Acceptable?
6.12 Oil and Grease (O&G)
Oil and Grease Analysis
References
Chapter 7 A Dictionary of Inorganic Water Quality Parameters and Pollutants
7.1 Introduction
Water Quality Constituents: Classified by Abundance
7.2 Alphabetical Listing of Inorganic Water Quality Parameters and Pollutants
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Aluminum (Al)
Ammonia/Ammonium Ion (NH3/NH4+
Antimony (Sb)
Arsenic (As)
Asbestos
Barium (Ba)
Beryllium (Be)
Boron (B)
Cadmium (Cd)
Calcium (Ca)
Chloride (Cl–)
Chromium (Cr)
Copper (Cu)
Cyanide (CN–)
Fluoride (F–)
Iron (Fe)
Lead (Pb)
Magnesium (Mg)
Manganese (Mn)
Mercury (Hg)
Molybdenum (Mo)
Nickel (Ni)
Nitrate (NO3–)
Nitrite (NO2–)
Selenium (Se)
Silver (Ag)
Sulfate (SO42–)
Hydrogen Sulfide (H2S)
Thallium (Tl)
Vanadium (V)
Zinc (Zn)
Appendix A Drinking Water Standards
Appendix B National Recommended Water Quality Criteria
Appendix C Sampling Containers, Minimum Sample Size, Preservation Procedures,
and Storage Times
Copyright © 2000 CRC Press, LLC
