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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 stan

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LEWIS PUBLISHER S Boca Raton London New York Washington, D.C.

A Practical Guide for

Environmental Professionals

Applications of

Eugene R Weiner, Ph.D.

ENVIRONMENTAL CHEMISTRY

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This book contains information obtained from authentic and highly regarded sources Reprinted material is quoted with permission, and sources are indicated A wide variety of references are listed Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use.

Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage or retrieval system, without prior permission in writing from the publisher.

The consent of CRC Press LLC does not extend to copying for general distribution, for promotion, for creating new works, or for resale Specific permission must be obtained in writing from CRC Press LLC for such copying.

Direct all inquiries to CRC Press LLC, 2000 N.W Corporate Blvd., Boca Raton, Florida 33431.

Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation, without intent to infringe.

© 2000 by CRC Press LLC Lewis Publishers is an imprint of CRC Press LLC

No claim to original U.S Government works International Standard Book Number 1-56670-354-9 Library of Congress Card Number 99-087370 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0

Printed on acid-free paper

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

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“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

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