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Introduction To Environmental Engineering 0132347474 9780132347471 Compress
Introduction To Environmental Engineering 0132347474 9780132347471 Compress
Environmental Engineering
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Introduction to
Environmental Engineering
Prentice Hall
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10 9 8 7 6 5 4 3 2 1
1.1 Welcome 1
1.2 What’s Your Definition of Environmental Engineering? 1
1.3 Environmental Engineers Make a Difference 2
1.3.1 Jobs in Demand 2
1.3.2 A Lousy Report Card 2
1.3.3 Basic Necessities—New Challenges 3
1.4 Duties and Important Characteristics of Environmental Engineers 3
1.4.1 Multidisciplinary Teams 4
1.4.2 Work Outdoors 4
1.4.3 Consulting Firms 4
1.4.4 Government 4
1.4.5 Regulatory Agencies 5
1.4.6 Industry 5
1.4.7 Academia 5
1.4.8 Does Environmental Engineering Match My Interests? 5
1.5 Environmental Calamities 5
1.5.1 Love Canal 5
1.5.2 Milwaukee Cryptosporidium Outbreak 6
1.5.3 Chernobyl Nuclear Disaster 7
1.6 Becoming an Environmental Engineer: A Lifelong Process 7
1.6.1 College Education 7
1.6.2 Professional Licensure 7
1.6.3 Engineering Ethics 8
1.6.4 Continuing Education 9
1.7 Problem Solving 10
1.8 Environmental Management 12
v
vi Contents
Summary 12
Key Words 13
Exercises 13
References 14
2.1 Introduction 15
2.2 Dimensions and Units 15
2.3 Essential Derived Units and Conversion Practice 18
2.3.1 Density 18
2.3.2 Concentration 20
2.3.3 Flow rate 26
2.3.4 Residence time 27
2.4 Precision, Bias, and Accuracy 28
2.5 Significant Figures 29
Summary 30
Key Words 30
References 30
Exercises 30
3.1 Introduction 32
3.2 Fundamentals 32
3.2.1 Atoms 32
3.2.2 Elements 32
3.3 Chemical Reactions 37
3.3.1 Stoichiometry 38
3.4 Solution Chemistry—Aqueous Phase 42
3.4.1 Acid-Base Chemistry 42
3.4.2 Strong Acids and Bases vs. Weak Acids and Bases 45
3.4.3 The Carbonate System and Alkalinity 47
3.5 Solid-Phase Equilibrium Reactions 48
3.6 Solution Chemistry—Gas Phase 51
3.6.1 Ideal Gas Law 51
3.6.2 General Gas Laws—Boyle’s, Charles’, Gay-Lussac, Combined Gas 51
3.6.3 Dalton’s Law of Partial Pressure 53
3.6.4 Raoult’s Law and Henry’s Law 54
Summary 56
Key Words 56
References 56
Bibliography 57
Exercises 57
4.1 Introduction 59
4.2 Biological Systems 59
Contents vii
5 • RISK ASSESSMENT 98
We would like to thank everyone who helped us with or has reviewed texts in this series.
Naeem Abdurrahman, University of Texas, Austin Donald Herling, Oregon State University
Stephen Allan, Utah State University Thomas Hill, SUNY at Buffalo
Anil Bajaj, Purdue University A. S. Hodel, Auburn University
Grant Baker, University of Alaska–Anchorage Kathryn Holliday-Darr, Penn State U Behrend
William Beckwith, Clemson University College, Erie
Haym Benaroya, Rutgers University Tom Horton, University of Virginia
John Biddle, California State Polytechnic University James N. Jensen, SUNY at Buffalo
Tom Bledsaw, ITT Technical Institute Mary Johnson, Texas A & M Commerce
Fred Boadu, Duke University Vern Johnson, University of Arizona
Gregory Boardman, Virginia Tech Jean C. Malzahn Kampe, Virginia Polytechnic
Tom Bryson, University of Missouri, Rolla Institute and State University
Ramzi Bualuan, University of Notre Dame Autar Kaw, University of South Florida
Dan Budny, Purdue University Kathleen Kitto, Western Washington University
Betty Burr, University of Houston Kenneth Klika, University of Akron
Fernando Cadena, New Mexico State University Harold Knickle, University of Rhode Island
Joel Cahoon, Montana State University Terry L. Kohutek, Texas A&M University
Dale Calkins, University of Washington Bill Leahy, Georgia Institute of Technology
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Arthur Clausing, University of Illinois Melvin J. Maron, University of Louisville
Barry Crittendon, Virginia Polytechnic and State James Mitchell, Drexel University
University Robert Montgomery, Purdue University
Donald Dabdub, University of CA Irvine Nikos Mourtos, San Jose State University
Kurt DeGoede, Elizabethtown College Mark Nagurka, Marquette University
John Demel, Ohio State University Romarathnam Narasimhan, University of Miami
James Devine, University of South Florida Shahnam Navee, Georgia Southern University
Heidi A. Diefes-Dux, Purdue University James D. Nelson, Louisiana Tech University
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John Glover, University of Houston Andrew Randall, University of Central Florida
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Otto Gygax, Oregon State University Larry Richards, University of Virginia
Malcom Heimer, Florida International University Marc H. Richman, Brown University
xii http://www.prenhall.com/esource/
ESource Reviewers xiii
topics. It presents case studies illustrating designs that are sustainable while mini-
mizing adverse affects on the environment. A review of nuclear physics is included,
since nuclear reactors will certainly be more widely used in the future to reduce
greenhouse-gas emissions. The major parameters used by environmental engineers
for assessing water quality are presented in Chapter 8.
Chapter 9 introduces the major unit operations and processes used for treat-
ing sources of potable drinking water. Chapter 10 follows up with an introduction to
the unit operations and processes used for treating municipal wastewater and the
sludge that is produced. Chapter 11 presents an overview of air pollution, global
warming theory, regulatory issues, and the major technologies used for treating par-
ticulate and gaseous air pollutants. Solid-waste generation, collection, and disposal
issues are discussed in Chapter 12.
Finally, Chapter 13 presents techniques used for remediating hazardous wastes,
along with background information on the Resource Conservation and Recovery Act
(RCRA) and Superfund, which encompasses the Comprehensive Environmental
Response, Compensation and Liability Act (CERCLA) and Superfund Amendments
and Reauthorization Act (SARA).
ACKNOWLEDGMENTS
We extend our sincere appreciation and gratitude to Dr. W. Jack Lackey (Professor
Emeritus, George W. Woodruff School of Mechanical Engineering, Georgia Institute
of Technology) for his thorough review of the manuscript and his ideas for improve-
ment. Laura’s Dad has far exceeded his role as a fabulous father by spending long
hours in reviewing our work and formulating invaluable suggestions.
We are also highly appreciative of the feedback from our students at Mercer
University, who used the manuscript in EVE 290, Introduction to Environmental
Engineering. And finally, Rich would be remiss if he did not acknowledge his major
professor, mentor, colleague, and friend, Dr. Joseph H. Sherrard (1942–2004), who
inspired and encouraged him through doctoral studies at Virginia Tech.
We are most grateful for the patience exhibited and support provided by our
families.
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CHAPTER
Environmental
Engineering as a
1
Profession
1.1 WELCOME
Objectives
As you begin your exploration of the environmental engineering profession,
In this chapter, you will you may be curious, excited—perhaps even a little fearful of what will be
learn about: expected of you. You are encountering the first challenge of your professional
The demand for journey. This book will give you tools to develop the skills you need for solving
environmental engineers, environmental engineering problems as a college student and later as a prac-
and the ways ticing engineer. This chapter will show you some of the exciting things you can
environmental do in environmental engineering.
engineering enhances the Your adventure with learning will not stop when you graduate. During
health and well-being of your career, you will continue to learn, as technology and regulations change
society and new environmental dilemmas evolve. Environmental engineering is a
Duties and important dynamically growing field, and you will be a part of its future.
characteristics of This book is an excellent source for students in the field of Civil Engi-
environmental engineers neering, and for students in biology, chemistry, and geology. It provides a
good background to the practical and valuable field of Environmental Engi-
Three major environmental
neering.
calamities that have
Welcome!
occurred since 1947
Professional licensure and
lifelong learning as an 1.2 WHAT’S YOUR DEFINITION OF ENVIRONMENTAL ENGINEERING?
environmental engineer
When we asked three people “on the street” what they thought an environ-
A five-step, structured
mental engineer would do, they replied:
approach for solving
engineering problems “Take care of garbage and stuff like that.”
“Keep the air and water clean so we can use it.”
“Take care of pollution.”
While these descriptions may be accurate to some degree, they only scratch
the surface of the responsibilities of an environmental engineer today.
2 Chapter 1 Environmental Engineering as a Profession
Wastewater D+ D D-
Solid waste C- C+ C+
Hazardous waste D- D+ D
Source: ASCE (2005), ASCE (2001), ASCE (1998).
Section 1.4 Duties and Important Characteristics of Environmental Engineers 3
America’s airports, bridges, dams, national power grid, public parks and recreation
areas, railroads, security, schools, transit systems, and waterways will encounter prob-
lems to be solved by a team of professionals including environmental engineers.
The Water Infrastructure Network (WIN, a broad-based coalition of elected
officials, water and wastewater providers, regulators, administrators, engineers, and
environmentalists dedicated to preserving and protecting America’s water and
wastewater infrastructure) also cited the enormity of the work ahead. They fore-
casted unprecedented financial problems over the next 20 years for America’s water
and wastewater infrastructure. WIN (2004) projects that an annual investment of
$23 billion over current allocations will be needed to meet the priorities as stated in
the Clear Water Act (passed by Congress in 1977). The purpose of the act was to
establish the “best available technology economically achievable” for wastewater
discharges containing toxic substances and to provide the “best conventional pollu-
tant control technology” for discharges containing conventional pollutants such as
biochemical oxygen demand (BOD) and suspended solids (SS).
1.4.4 Government
Some environmental engineers work for city or county governments and municipal-
ities. They oversee the operation of public works departments, engineering depart-
ments, water treatment plants, and wastewater reclamation facilities. Planning and
budgeting of major projects is their prime responsibility.
Section 1.5 Environmental Calamities 5
1.4.6 Industry
Industries such as pulp and paper manufacturing, textile processing, petroleum and
petrochemical, pharmaceutical, and meat processing employ environmental engi-
neers to ensure compliance with environmental regulations. Some environmental
engineers develop ways to reduce and minimize the quantity of water used and the
amount of pollutants produced at such facilities; while others are responsible for
operating on-site industrial wastewater treatment plants or pretreatment systems,
baghouses and electrostatic precipitators for air emissions, and disposal of residuals
and sludges in landfills.
1.4.7 Academia
Environmental engineers employed in academia teach and serve as mentors to the
next generation of engineers. They are rewarded and motivated by seeing their stu-
dents learn and become productive citizens in society. Professors also engage in
scholarly activities, such as research to explore innovative and cost-effective ways
to reduce the effects of pollution on the environment. They also develop new
teaching strategies and paradigms to enhance learning in the classroom. An impor-
tant aspect of being a professor is presenting ideas and research results on techni-
cal and education-related activities at conferences and in peer-reviewed journals.
and was later used as a chemical waste disposal site. The Hooker Chemical Company
(a subsidiary of Occidental Petroleum) acquired the site in 1947 and buried 21,800
tons of toxic waste in the area in a five-year period. In 1952, Hooker closed the site
and covered the canal with earth. The company later sold the site to the Niagara Falls
Board of Education, and a school and 100 homes were built on it.
During the intervening years, residents complained of strange odors and sub-
stances percolating to the surface in their yards. Numerous miscarriages and birth
defects were reported by the New York State Health Department. In 1978, after Lois
Gibbs and an associate held two Environmental Protection Agency (EPA) officials
hostage in her home, President Carter declared a federal emergency at Love Canal.
Finally on May 21, 1980, because of to the persistence of Lois Gibbs and other resi-
dents, President Carter and the Environmental Protection Agency agreed to relo-
cate all families living at Love Canal. Occidental Petroleum eventually spent more
than $200 million to clean up the site. This calamity led Congress to pass the Super-
fund Law, which holds companies responsible for the cleanup of hazardous waste
sites. Was it ethical for Hooker Chemical Company to sell the Love Canal to the Nia-
gara Falls Board of Education?
Calculus I Calculus II
Humanities I Humanities II
Statics Dynamics
Electrical I Electrical II
Biology Geology
Humanities IV Humanities V
EXAMPLE 1.1
Computing velocity of flow in a pipe
Calculate the average velocity of water flowing in a 6-inch-diameter pipe if the flow
rate is 3.0 cubic feet per second.
Solution
1. Find the average velocity of water in the pipe.
Q = volumetric flow rate = 3.0 ft3/s
pipe diameter = D = 6 inches
2. Draw a figure.
EXAMPLE 1.2
Calculating mass removal rates
Groundwater from a deep well is being pumped to a small water treatment plant at
5 m3/min. The water contains 0.05 mg/L of arsenic (As), and the primary drinking-
water standard is set at 0.01 mg/L of arsenic. Calculate the number of grams of
arsenic that must be removed from the water each day to meet the standard.
Solution
1. Find the mass of arsenic that must be removed daily.
Q = volumetric flow rate = 5 m3/min
C1 = concentration of arsenic in raw water = 0.05 mg/L
C2 = concentration of arsenic in treated water = 0.01 mg/L
2. Draw a figure.
Q 5 m3/min Q 5 m3/min
Water Treatment
Plant
C1 0.05 mg/L C2 0.01 mg/L
3. Assume that the volumetric flow rate is the same into and out of the water treatment
plant.
mass removed = mass in - mass out
mass of arsenic = Q * C
Q = volumetric flow rate, m3/min
C1 = concentration of arsenic in raw water = 0.05 mg/L
C2 = concentration of arsenic in treated water = 0.01 mg/L
4. Solve for the mass of arsenic entering and exiting the water treatment plant.
m3 mg 1000 L 60 min 24 h 1g
mass in = Q * C1 = 5 a0.05 b¢ 3
≤a ba ba b
min L 1m 1h 1d 1000 mg
mass in = Q * C1 = 360 g>d
m3 mg 1000 L 60 min 24 h 1g
mass out = Q * C2 = 5 a 0.01 b¢ 3
≤a ba ba b
min L 1m 1h 1d 1000 mg
12 Chapter 1 Environmental Engineering as a Profession
S U M M A RY
Environmental engineering is an engineering specialty that involves identifying,
designing, and implementing systems to protect human health and well-being and
the environment. Environmental engineers have a prominent role in maintaining a
high quality of life by providing potable water and clean air, remediating contami-
nated land, and minimizing the adverse effects of pollution on the environment.
Exercises 13
environmental engineer life long learning air, land, and water KEY WORDS
ecological balance professional engineer environments
pollution problem solving
EXERCISES
For Exercises 1 through 6, use the Internet to perform a Google search for help in
answering the questions. If necessary, seek out a professor or environmental engineer
to discuss the topics presented.Then prepare a written paragraph or two for each topic,
including the ideas discussed with the professor or engineer. Discuss the role each topic
plays in environmental engineering. Include comments on the types of problems that
the engineer may confront and how to solve these problems for each topic.
1.1 How are the principles from microbiology used in the design of wastewater
treatment processes and the remediation of contaminated soil?
1.2 List and discuss two equations from fluids and hydraulics that are used by
environmental engineers in the design of water distribution and wastewater
collection systems. [Hint: Continuity and Bernoulli’s equation.]
1.3 Environmental engineers and scientists have reported that global warming
may be a real problem. List and discuss the major causes and the air pollu-
tants that are associated with this phenomenon.
1.4 Environmental engineers are responsible for designing water treatment
plants that provide safe, potable drinking water to the public. What chemical
principles are used for removing pollutants from water? Give some examples
of unit processes used for treating water. [Hint: Oxidation/reduction, gas
transfer, precipitation.]
1.5 Many environmentalists promote the idea of recycling solid wastes. Collec-
tion, separation, and recycling systems are often designed by environmental
engineers. Discuss the advantages and disadvantages of recycling metals,
glass, and paper discarded in solid wastes. Some politicians advocate recycling
and reusing 50% of the materials discarded. Is this realistic or even possible?
Why or why not?
14 Chapter 1 Environmental Engineering as a Profession
REFERENCES
ASCE (2005). 2005 Report Card for America’s Infrastructure. Accessed May 21, 2008 from
http://www.asce.org/reportcard/2005/page.cfm?id=103&print=1m.
ASCE (2001). 2001 Report Card for America’s Infrastructure. Accessed May 21, 2008 from
http://www.asce.org/pressroom/news/pr030801_reportcard.cfm.
ASCE (1998). 1998 Report Card for America’s Infrastructure. Accessed May 21, 2008 from
http://www.asce.org/pdf/reportcard.pdf.
Bureau of Labor (2008). Occupational Outlook Handbook, 2006–07 Edition. Accessed May
21, 2008, 2007 from http://www.bls.gov/oco/ocos027.htm.
Corso, P.S., Kramer, M.H., Blair, K.A., Addiss, D.G., Davis, J.P, and Haddix, A.C. (2003). Cost
of illness in the 1993 waterborne Cryptosporidium outbreak, Milwaukee: Emerging Infec-
tious Diseases, Vol. 9, No. 4, 426–431.
Fisher, Anne (2005). Hot careers for the next 10 years, Fortune Magazine, March 21, 2005.
WIN (2004). Water Infrastructure Network Recommendations for Clean and Safe Water in the
21st Century. Accessed October 16, 2008 from http://www.win-water.org/reports/winow.pdf.
CHAPTER
Introduction to
Environmental Engineering
2
Calculations: Dimensions,
Units, and Conversions
2.1 INTRODUCTION
Objectives
A number without an associated dimension has no meaning in engineering; a
In this chapter, you will number with an improper unit has a misleading meaning. The importance of
learn about: proper units was highlighted by the loss of the 1999 NASA Mars Climate
Units and dimensions Observer, a 125-million-dollar spacecraft that was destroyed when it entered
Units of concentration for the Mars atmosphere traveling too fast. The error was blamed partially on the
liquid and gas phases failed translation of English units into metric units (Isbell et al., 1999). This
chapter introduces the units and dimensions commonly used by environmen-
Density
tal engineers and presents practice problems that require you to master the
Concept of flow rate and manipulation and conversion of these units.
residence time
Precision and accuracy
2.2 DIMENSIONS AND UNITS
Dimensions can be used to describe the measurable aspects of any object or
system, while units provide the increments necessary to quantify the dimen-
sions. All numerical engineering measurements should be dimensioned with
proper units. Common dimensions associated with environmental engineering
problems include length, mass, time, and temperature. Associated units that
scale the measured quantity for these dimensions include meters (m), kilograms
(kg), seconds (s), and degrees Fahrenheit (°F), respectively. Notice that dimen-
sions and units only qualitatively describe a measurement and that a numerical
value matched properly with units is required for a quantitative description
(e.g., 2.0 meters, 4 minutes). Four systems of units are commonly used: the
International System of Units, the Imperial Units (closely related to the
British engineering system), the U.S. Customary Units, and the Absolute or cgs
(centimeter-gram-second) system. The International System of Units is com-
monly referred to as the SI, metric, or MKS (meter-kilogram-second) system.
Because the SI hierarchy of units is founded on a decimal basis, such that the
addition of a prefix to a unit simply changes its value by a factor of 10, it has
been widely adopted internationally. Many seasoned engineers, as well as
American citizens in general, have continued to use the U.S. Customary Units,
so it is important to master both the U.S. Customary and the SI systems of units.
16 Chapter 2 Introduction to Environmental Engineering Calculations: Dimensions, Units, and Conversions
The list of fundamental dimensions includes length, mass, time, and often tempera-
ture. All other quantities are derived from these dimensions. Derived units commonly used
by environmental engineers include those of volume 1length32, density 1mass/length32,
and concentration 1mass/length32. Notice the similarity between density and concentra-
tion as this will become important in subsequent sections of this chapter. Some specific
units include the newton 1N = mass * length/time22, which quantifies the force on an
object, the joule 1N * length2, which quantifies the energy of a system, and the
pascal 1Pa = N * m-22, which describes a system pressure.Table 2.1 shows fundamental
dimensions, derived dimensions, and associated units for the four common systems of units.
Common prefixes used to describe units in the SI system are defined in Table 2.2, and some
frequently used conversions are listed in Table 2.3.
U.S. Customary Units (commonly referred foot pound mass second, °R, °F pound force BTU
to as English or Standard Units) 1lbm2 hour 1lbf2
Imperial Units (derived from English units; foot slug* second °R, °F pound force BTU ft # lb
often referred to as the British system) 1lbf2
newton 1N2 = kg # m
冫s2 joule 1J2 = N # m = kg # m2
冫s2
#
pound force 1lbf2 = 32.2 lbm ft冫s2 British thermal unit 1BTU2 = 252 cal = 1.054 J
giga G 109
mega M 106
kilo k 103
10
deka da
deci d 10-1
centi c 10-2
milli m 10-3
micro m 10-6
nano n 10-9
pico p 10-12
Section 2.2 Dimensions and Units 17
m 3.281 ft
m 1.094 yd
mile 5280 ft
in 2.54 cm
ft 12 in
mile 1.609 km
Å 10-10 m
Mass
lbm 453.6 g
kg 2.2 lbm
lbm 16 oz
Volume
gal 3.785 L
ft3 7.481 gal
m3 1000 L
3
ft 28.32 L
m3 35.31 ft3
m3 1.308 yd3
cm3 1 ml
Pressure
atm 760 mm Hg
Energy
kWh 1.341 hp # hr
1 cal 4.184 J
BTU 1055 J
Power
kW 1000 J/s
kW 1.34 hp
BTU/sec 1.055 kW
kW 737.56 ft # lbf/s
Temperature
°F = 1.81°C2 + 32
K = °C + 273.15
°R = °F + 459.67
m
r = (2.1)
V
where:
r = density, kg/m3,
m = mass, kg, and
V = volume, m3.
From this definition, we can conclude that the density of a substance is an intrinsic
property and therefore independent of sample size. Take note, however, that density
varies with temperature as well as with the concentration of any impurities dis-
solved in a solution. For example, the density of water at 0°C and 80°C is
0.9998 g/cm3 and 0.9718 g/cm3, respectively. If water at 0°C contains 1% sodium
chloride (table salt), the density of the aqueous solution is 1.0075 g/cm3, noticeably
higher than that of pure water. Possibly you have noticed that floating on your back
in ocean water seems easier than floating in a lake. This is because the salt content of
the ocean is higher than that of most lakes, causing the density of ocean water at the
Section 2.3 Essential Derived Units and Conversion Practice 19
Gasoline 0.72
Ethanol 0.802
Rubber 1.5
Glass 2.6
Aluminum 2.7
Uranium 18.7
sea surface to be approximately 1.1027 g/cm3. The two main factors that control
ocean water’s density are its temperature and its salinity. The density of some com-
mon items is shown in Table 2.4.
EXAMPLE 2.1
Density practice
Recall the story of Archimedes, a Greek mathematician who lived in the third
century BCE. Hiero II, the King of Syracuse on the Ionian Sea, charged
Archimedes to determine whether his newly acquired crown was made of pure
gold. While bathing in a public bath, the legend tells us, the famous mathemati-
cian discovered a method to test the purity of the crown and was so enamored
with his discovery he ran naked through the streets yelling “Eureka!” Archimedes’
principle can be simply stated as follows: When an object is submerged in a liquid,
the amount of liquid displaced is equal to the volume of the object. Use this idea to
solve the following problem.
A 2-liter graduated cylinder initially contains 500 ml of water. An irregularly
shaped object having a mass of 105 g is submerged into the water. The final volume
of the water in the cylinder is 1025 ml. Determine the density of the object.
Solution
Calculate the volume of the object by determining the difference in water-volume
readings within the graduated cylinder.
V = 1025 ml - 500 ml = 525 ml
Now, determine the density of the object by using the mass that was given and
substituting into Equation (2.1).
m 105 g
r = = = 0.20 g/ml
V 525 ml
20 Chapter 2 Introduction to Environmental Engineering Calculations: Dimensions, Units, and Conversions
EXAMPLE 2.2
Problem solving with density
During an environmental assessment of a natural wetland in the Everglades, it was
determined that 1.5 cubic meters of the dry native soil had a mass of 420 kg. Deter-
mine the mass of a cubic foot of that same soil.
Solution
Calculate the density of the wetland soil.
m 420 kg 1000 g 1m 3
r = = * * a b = 0.28 g/cm3
V 1.5 m3 1 kg 100 cm
Use the density found to calculate the mass associated with 1 ft3 of the Ever-
glades soil.
0.28 g 2.54 cm 3 12 in 3
m = rV = * a b * a b * 1 ft3 = 7929 g
cm3 1 in 1 ft
1 kg
m = 7929 g * = 7.9 kg
1000 g
2.3.2 Concentration
Concentrations of substances dissolved in a liquid phase are often described on a
mass-per-unit-volume basis such that
m
C = (2.2)
V
where:
C = concentration of dissolved substance, mg/L,
m = mass of solute or dissolved substance, mg, and
V = total volume, L.
Notice the similarity between Equations (2.1) and (2.2), which describe,
respectively, the density of a substance and the gravimetric-based definition for
concentration. The most commonly used mass-based concentration units include
milligrams per liter (mg/L) and micrograms per liter 1mg/L2. Although not as com-
mon, micrograms per cubic meter 1mg/m32 may also be used to express a mass-
based contaminant concentration.
In contrast, the concentration of dissolved substances in liquid phases may
alternatively be described on a mass-per-unit-mass basis (the mass of the solute dis-
solved per the mass of solution). The most common mass-based units are parts per
million (ppm) and parts per billion (ppb). For perspective, the maximum contami-
nant level goal (MCLG) of mercury in drinking water allowed by the Environmen-
tal Protection Agency (EPA) is 0.002 ppm (40 CFR, §141.51). This means that there
can be no more than 0.002 grams of mercury in every million grams of drinking
water purified and distributed by your local municipality. Assuming the density of
water is 1.0 g/ml, this is equivalent to allowing only 2 grams 10.0044 lbm2 of mercury
in approximately 264,000 gallons of drinking water.
Section 2.3 Essential Derived Units and Conversion Practice 21
EXAMPLE 2.3
Determine relationship between mg/L and ppm
In many environmental aqueous systems, it is appropriate to make the simplifying
assumption that 1 mg/L is equal to 1 ppm, provided that the fluid in question is pri-
marily water, so that the density of the solution essentially is 1 g/ml. (This assump-
tion is often made by environmental engineers.) Show that 1 mg/L = 1 ppm.
Solution
The solution requires that the concentration on a mass-per-unit-volume basis
(mg/L) be divided by the solution density, followed by simple unit conversions.
mg 1g 1 ml 1L 1
1 * * * = = 1 ppm
L 1000 mg 1g 1000 ml 106
The concentration unit molarity 1M = moles per liter2 is defined as one mole
per unit volume of substance. Avogadro’s number is used to define a mole (mol)
such that there are 6.02 * 1023 molecules of any material per mole. By definition,
the atomic mass of an element or substance is equal to the mass of one mole of that
substance. Example 2.4 applies this concept to a solution of water containing
sodium nitrate.
Concentrations may also be described on a molar, mass, or volume percentage
basis. For example the mass percent of species A in solution is defined as follows:
MA
mass A 1%2 = * 100 (2.3)
MA + MB
where:
MA = mass of compound A, lbm 1g2, and
MA + MB = total mass of the solution, lbm 1g2.
The volume percent concentration is defined similarly, with the volumes of sub-
stances A and B substituted into Equation (2.3) for mass. The molar concentration
or the mole fraction of species A is defined as
moles A in solution
xA =
total moles of solution
EXAMPLE 2.4
Determining solution concentration
A researcher has added 2.06 g of the salt sodium nitrate, NaNO3 , to a cylinder con-
taining water. The cylinder diameter is 2 inches and the depth of the water in the
cylinder is 4 inches (refer to Figure 2.1). Determine the concentration of salt in solu-
tion, showing your answer in the units specified.
a. mg/L
b. mass %
c. molarity
22 Chapter 2 Introduction to Environmental Engineering Calculations: Dimensions, Units, and Conversions
D 2 in.
h 4 in.
Figure 2.1
Schematic of cylinder
described in Example 2.4.
Solution
First, calculate the molecular weight of NaNO3 by summing the atomic weights of
the individual compound elements. The atomic weights of sodium, nitrogen, and
oxygen are 23, 14, and 16 g/mole, respectively.
MW NaNO3 = 23 + 14 + 31162 = 85 g/mole
Assume the density of water is 1 g/ml.
Part a. Calculate the volume of water stored in the cylinder.
pD2h
V =
4
2.54 cm 2
p B 12 in.2a bR
1 in. 2.54 cm
V = * 4 in. a b = 206 cm3
4 1 in.
1 ml 1L
V = 1206 cm32a 3
ba b = 0.206 L
1 cm 1000 ml
2.06 g 1000 mg
CNaNO3 1mg/L2 = a ba b = 10,000 mg/L
0.206 L 1g
Recognize that if the solution density is assumed to be 1 g/ml, then 10,000 mg/L
is equal to 10,000 ppm.
MA
Part b. Mass A 1%2 = * 100
MA + MB
Find the mass of solution (MA + MB) by multiplying the solution volume found
in Part a above with the density.
2.06 g
mass A 1%2 = * 100 = 1.0%
1g
206 ml *
ml
moles NaNO3
3NaNO34 =
L
1 mol
12.06 g NaNO32 ¢ ≤
85 g NaNO3
3NaNO34 = = 0.118 M
0.206 L
Molecular weight can be used to convert between mass- and molar-based con-
centrations. Using the information from Example 2.4, we can show that:
CNaNO3 = MWNaNO3 3NaNO34
g mol g
CNaNO3 = 85 * 0.118 = 10
mol L L
Gas-phase concentration units are usually presented on a mass-per-unit-vol-
ume-of-air basis 1mg/m32 at a known temperature and pressure or as parts per
million on a volume basis (ppmv). The ppmv is simply the volume or mole
fraction of the pollutant in the gas multiplied by 106.
volume of pollutant gas moles of pollutant gas
ppmv = 11062= 11062 (2.4)
volume of gas mixture total moles of gas mixture
Conversion between mass per unit volume and ppmv concentration requires
knowledge of the ideal gas law:
PV = nRT (2.5)
where:
P = absolute pressure, atm,
V = volume occupied by n moles of gas, L,
n = number of moles of gas,
#
R = universal gas constant, 0.08206 L atm冫gmol # K, and
T = absolute temperature, K.
R, the “universal gas constant,” has the same value for all gases. The values for R
with different pressure, volume, and temperature units are shown in Table 2.5.
Notice that a common set of units must be used to solve Equation (2.5).
3 # atm
82.06 cm 冫gmol # K
3 # atm
0.7302 ft 冫lbmol # °R
24 Chapter 2 Introduction to Environmental Engineering Calculations: Dimensions, Units, and Conversions
EXAMPLE 2.5
Practice with the ideal gas law
Use the ideal gas law to calculate the volume of one mole of gas at standard tem-
perature and pressure (STP), defined as 0°C and 1 atmosphere.
Solution
Convert 0°C into Kelvin:
T = 0°C + 273 = 273 K
and recognize that 1 gram mole = 1 gmol.
Solving for the volume of the gas sample by rearranging Equation (2.5), the ideal
gas law becomes
nRT
V =
P
Since we are interested in the volume of just one mole of gas, substitution provides
L # atm
gmol # K
11 gmol2a0.08206 b1273 K2
V = = 22.4 L
1 atm
So, for a gaseous system at STP, one mole of gas occupies 22.4 L.A similar calculation
shows that at 25°C and atmospheric pressure, one mole of gas occupies 24.5 L.
Consider committing both of these numbers to memory.
EXAMPLE 2.6
Unit-conversion practice
At standard conditions, the exhaust gas from a well-controlled coal-burning power
plant contains 5 ppmv sulfur dioxide 1SO22. At STP, determine the concentration of
SO2 emitted on a mg/m3 basis. MW SO2 32 2(16) 64 g/mol.
Solution
Simplifying the above solution, we obtain Equation (2.6), which can be used to con-
vert between mg/m3 and ppmv in gaseous environments.
mg ppmv * MW * 103
= 1at STP2 (2.6)
m3 22.4
Section 2.3 Essential Derived Units and Conversion Practice 25
In Equation (2.6), MW represents the molecular weight of the contaminant, and the
number 22.4 is the volume of one mole of an ideal gas at standard conditions. This
number is a variable in the conversion equation but can easily be calculated for any
environmental condition, as shown in Example 2.5 above. For example, if the system
temperature were 25°C at atmospheric conditions, Equation (2.6) would become:
mg ppmv * MW * 103
= 1T = 25°C; standard P = 1 atm2
m3 24.5
EXAMPLE 2.7
Conversion of gas-phase concentration units
The concentration of carbon dioxide exiting a car’s tailpipe is approximately 12%
on a volume basis. Assuming the exhaust-gas temperature is 500°C, determine the
concentration of CO2 in the gas stream in the units and temperature specified.
a. ppmv at 500°C and 25°C, respectively
b. mg/m3 at 500°C and 25°C, respectively
Solution
Part a. The tailpipe’s concentration is 12% at 500°C. This can easily be made
into a ratio.
12 X X parts
12% = = 6
=
100 10 million parts
12 * 10 6
ppmv = X = = 120,000 ppmv
100
To determine the exhaust-gas concentration in ppmv at a temperature of 25°C,
it is important to notice that the ratios of different gas volumes in a system
remain the same at any temperature, as long as condensation does not occur,
and that all gases retain an ideal character. So, the concentration of the tailpipe
exhaust at 25°C is 120,000 ppmv, equal to the value at 500°C.
Part b. Use Equations (2.5) and (2.6) to solve for the gravimetric concentra-
tions of CO2 . Calculate the volume of 1 mole of ideal gas at 500°C.
L # atm
gmol # K
11 gmol2a0.08206 b1273 + 5002 K
V = = 63.4 L
1 atm
Modify Equation (2.6), such that 63.4 L is the volume representing a mole of
gas at 500°C and solve for the mass-based concentration. The molecular weight
of CO 2 is 44 g/mol.
g
120,000 * 44 * 103
mg ppmv * MW * 10 3
mol
= =
m3 63.4 63.4
7 mgCO2 gCO2
= 8.33 * 10 = 83.3
m3 m3
26 Chapter 2 Introduction to Environmental Engineering Calculations: Dimensions, Units, and Conversions
nA PA
yA = = (2.7)
n P
Qm = r * Q
kg kg m3
= 3 * (2.8)
s m s
Earlier in the chapter we noted the similarity between Equations (2.1) and
(2.2), which define density and gravimetric concentration, respectively. This knowl-
edge lets us replace r in the above equation with C from Equation (2.2), allowing us
to calculate the mass flow of a substance in a stream or pipe if we know the associ-
ated volumetric flow rate and the compound concentration.
Section 2.3 Essential Derived Units and Conversion Practice 27
EXAMPLE 2.8
Illustration of flow-rate calculation
Drinking water delivered to homes from a municipality contains a residual free-
chlorine concentration of approximately 0.5 mg/L. If a sprinkler system delivers
6 gpm of water, calculate the mass flow rate of free chlorine released into the yard.
Solution
Assume that no residual chlorine evaporates (this is a convenient but probably not
a very good assumption). Modify Equation (2.8) by substituting C for to calculate
the mass flow rate of chlorine spread onto the lawn.
Qm = C * Q
mg g gal 60 min 24 h 3.785 L
= a0.5 * b * a6 * * * b
L 1000 mg min h d gal
g
= 16.3
d
Let’s work another example and pay particular attention to conversions. Assume
that a wastewater treatment system effluent flow is 20 million gallons per day
(MGD) and it contains 10 mg/L of solids. Calculate the mass flow rate of solids dis-
charged with units of lbm/day.
Qm = C * Q
mg MG kg 2.2 lbm 106 gal 3.785 L
= 10 * 20 ¢ 6 * * * b
L d 10 mg kg MG gal
lbm
= 1665
d
All unit conversions are done within the parentheses in the equation above. Cancel-
ing all units inside the parentheses and proceeding with the multiplication of the
conversion factors, we derive the following well-known conversion factor:
lbm * L
8.34
mg * MG
This conversion factor makes it simple to determine the mass flow rate in lbm/day
when concentration and volumetric flow data are given in mg/L and MGD, respec-
tively. We now solve the above example as
mg lbm * L lbm
Qm = 10 * 20 MGD * 8.34 = 1668
L mg * MG d
V
u = (2.9)
Q
EXAMPLE 2.9
Residence-time calculation
Consider a lagoon that can be modeled as a perfect hemisphere having a diameter
of 50 m (refer to Figure 2.2). If river water flows into (and out of) the reservoir at
7.5 m3/min, calculate the residence time of the lagoon.
Solution
4 3
sphere volume = pr
3
Use Equation (2.9) combined with unit-conversion skills to solve for the
lagoon retention time.
1 4
¢ p125 m23 ≤
V 2 3
u = = = 3.0 d
Q m3 60 min 24 h
¢ 7.5 ≤a ba b
min h d
D = 50 m
Q 7.5 m3/min
Figure 2.3
Illustrating the concepts of accuracy and precision: (a) accuracy, (b) precision, (c) accuracy with precision.
The concepts of bias, accuracy, and precision can be represented in terms of the
results obtained by marksmen of differing degrees of skill, as shown in Figure 2.3. If
the bull’s-eye represents the truth, the marksman firing the three shots shown in
Figure 2.3(a) was accurate but not very precise. Figure 2.3(b) shows the results from
a precise but inaccurate shooter: the shots are close together, but far from the bull’s-
eye. Notice that the bias was caused by a systematic (built-in) error. Consider target
practice with a rifle equipped with a scope. If the scope is not properly aligned with
the rifle barrel, the shots of even the most precise shooter will be directed to one side
of the bull’s-eye. The marksman producing the results shown in Figure 2.3(c) was
both accurate and precise.
When measured values are used in calculations, the precision of the result
obtained should not exceed the precision of the measured values. In general, the
following rules should be applied:
1. For addition and subtraction, the solution should contain the same number of
decimal places as the measurement that contained the least number of signifi-
cant figures. For example, 3.23 + 1.0 = 4.2. Notice that the solution is given to
only one decimal place and two significant digits—the same number of signif-
icant digits as in 1.0.
2. When a value is obtained by multiplying or dividing measured quantities, the
result should contain only as many significant figures as there were in the mea-
surement with the fewest significant digits. Applying this rule, the product of
3.07 * 3.1 should be reported with only two significant digits—that is, as 9.5.
S U M M A RY
Analytical problem solving is a skill all engineering students need to practice. This
chapter introduced some basic concepts that the competent problem solver must
master. The ideas associated with units and dimensions were introduced. Several
schemes used to classify units were presented, including the SI and U.S. Customary
systems. Four derived units (density, concentration, flow rate, and residence time)
were defined. The concept of unit conversion was explored and a variety of examples
were completed that exemplify this skill. The precision and accuracy of measure-
ments taken in the laboratory were discussed.
REFERENCES
Code of Federal Regulations, Title 40: Protection of Environment, Chapter 1: Environmen-
tal Protection Agency, Subchapter D: Water Programs, Part 141: National Primary Drink-
ing Water Regulations, §141.51: Maximum contaminant level goals for inorganic
contaminants.
Isbell, D., Hardin, M., and Underwood, J. (1999). Mars Climate Orbiter Team Finds Likely
Cause of Loss. Retrieved July 20, 2006 from http://mars.jpl.nasa.gov/msp98/orbiter/.
EXERCISES
2.1 Perform the following unit conversions by hand. You may use the unit-
conversion feature on your calculator to check your work.
(a) Convert 4000 grams into pounds.
(b) Convert 237.4 feet to meters.
(c) Convert 80 years to seconds.
(d) Convert 55 mph into a speed of nm per second.
(e) Convert 0.004 gallons into ml.
(f) Convert 10.8 mm to angstroms.
Exercises 31
Essential Chemical
3
Concepts
3.1 INTRODUCTION
Objectives
A solid foundation in chemical concepts is vital to both the environmental
In this chapter, you will learn engineering practitioner and the student. Chemistry is central to your under-
about: standing water and wastewater treatment processes and the design of treat-
Fundamental concepts in ment strategies for mitigating hazardous waste. You will need a knowledge of
atomic theory chemistry to understand issues associated with anthropogenic emissions caus-
Chemical reactions ing tropospheric ozone generation, acid rain, and the greenhouse effect. This
chapter gives an overview of essential chemistry concepts.
Acid-base chemistry
Carbonate system and
alkalinity 3.2 FUNDAMENTALS
Solid-phase reactions 3.2.1 Atoms
Gas laws The atom is the smallest part of an element that can exist and still retain all the
chemical properties associated with the element. The most current model of
the atom, provided by nuclear physicists and often referred to as the Standard
Model, includes components such as mesons, baryons, and quarks. The model
developed by Niels Bohr in 1913, however, is still useful. Bohr postulated that
the atom maintains a neutral charge and consists of a positively charged
nucleus and a negatively charged atomic shell that contains electrons. The
nucleus is composed of positively charged protons and of neutrons that have
no charge. For an atom to maintain a neutral charge, the number of protons
and electrons must be equal.
3.2.2 Elements
All matter is composed of 103 fundamental substances called elements, which
are distinguished by the number of protons within the atom.The number of pro-
tons in the nucleus, Z, is the element’s atomic number. The sum of protons and
neutrons in an atom’s nucleus is the element’s mass number, A. Atoms of the
same element contain the same number of protons, but the number of neutrons
may vary to form isotopes. Isotopes are atoms of the same element that contain
a different number of neutrons and thus have different weights.
Periodic Table of the Elements
1 18
1A 8A
1 2
11 Atomic number
1 H He
Hydrogen 2 Na Element symbol 13 14 15 16 17 Helium
1.01 2A Sodium Element name 3A 4A 5A 6A 7A 4.00
3 4 22.99 5 6 7 8 9 10
Average atomic mass*
2 Li Be B C N O F Ne
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
Sodium Magnesium 3 4 5 6 7 8 9 10 11 12 Aluminum Silicon Phosphorus Sulfur Chlorine Argon
22.99 24.31 3B 4B 5B 6B 7B 8B 1B 2B 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Cesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
132.91 137.33 138.91 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 (209) (210) (222)
87 88 89 104 105 106 107 108 109
7 Fr Ra Ac Rf Db Sg Bh Hs Mt
Francium Radium Actinium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium
(223) (226) (227) (261) (262) (266) (264) (269) (268)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
* If the average atomic mass number is in 140.12 140.91 144.24 (145) 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97
Section 3.2
parentheses it refers to the atomic mass 90 91 92 93 94 95 96 97 98 99 100 101 102 103
of the most stable isotope.
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
232.04 231.04 238.03 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)
Fundamentals 33
Figure 3.1
Periodic table.
34 Chapter 3 Essential Chemical Concepts
EXAMPLE 3.1
Determine atomic and molecular weights
Find the AW of each element and the MW of each compound in grams per mole
(g/mol) for each item in the list below. Use AW information from the periodic table.
Solution
After using the periodic table to determine the AW of each element, calculate the
molecular weight of calcium carbonate and sodium bicarbonate by summing the
atomic weights of the elements in each of these compounds. In most environmental
engineering problems, it is acceptable to round AWs and/or MWs to two (and often-
times fewer) decimal places.
MW
EW = (3.1)
z
In Equation (3.1), z represents the valence1 of the reactive unit. Although commonly
used to describe acid-base reactions, the reactive unit in any chemical reaction is often
1
Note that the concept introduced in Equation (3.1) has been simplified. Equivalent weight is commonly
defined using three methods. As discussed above, the first method relies on use of the valence the ele-
ment or radical assumes in a given compound. In acid-base reactions, the equivalent weight depends on
the number of protons or hydroxyl radicals that react. The equivalent weight for oxidation-reduction
reactions is based on the number of moles of electrons transferred. Further discussion of these topics is
beyond the scope of this book.
Section 3.2 Fundamentals 35
referred to as an equivalent. (A reactive species can have multiple EWs because of its
involvement in multiple types of reactions.) Typical units for EW include both grams
per equivalent (g/eq) and milligrams per milliequivalent (mg/meq).
Normality, N, relates the mass of solute per volume of solution, as presented in
Equation (3.2). A 1 N solution contains 1 equivalent weight of a substance per liter
of solution.
N = z * M (3.3)
Table 3.1 Common Ions and Radicals Associated with Environmental Chemistry
Radical Chemical formula MW (g/mol) EW (g/eq)
Bicarbonate HCO3- 61 61
Carbonate CO2-
3 60 30
Ammonium NH4+ 18 18
-
Hydroxyl OH 17 17
Hypochlorite OCl- 51.5 51.5
Nitrate NO3- 62 62
Nitrite NO2- 46 46
Orthophosphate PO3-
4 95* 31.7*
Sulfate SO2-
4 96 48
Hydrogen sulfate HSO4- 97 97
-
Cyanide CN 26 26
Permanganate MnO4- 119 119
Chromate CrO2-
4 116 58
Dichromate Cr2O2-
7 216 108
*Example calculations for both molecular and equivalent weight of the free radical orthophosphate follows:
Molecular weight for phosphorus (P) is 31 and for oxygen (O) is 16. So, the MW of
PO3-
4 = 31 + 41162 = 95 g>mol. The equivalent weight for the radical is simply the MW divided by its
95 g>mol
valence of 3, giving EW of PO3-
4 = = 31.7 g>eq.
3 eq>mol
EXAMPLE 3.2
Calculation of equivalent weight
Determine the equivalent weight for the following species:
a. magnesium ion, Mg 2+
b. calcium carbonate, CaCO3
c. carbon dioxide, CO2
36 Chapter 3 Essential Chemical Concepts
Solution part a
From the periodic table (Figure 3.1), the AW of Mg 2+ is 24.3 g/mol, and the valence
is z = 2 in solution. Calculate the EW using Equation (3.1).
MW 24.3 g>mol g
EW for Mg 2+ = = = 12.15
z 2 eq>mol eq
Solution part b
AW for Ca = 40, for C = 12, and for O = 16 g/mol, so the MW of CaCO3 is 100 g/
mol. In solution, calcium carbonate dissociates into calcium and the free radical car-
bonate, as follows:
CaCO3 Δ Ca2+ + CO2-
3
MW 100 g>mol g
EW for CaCO3 = = = 50
z 2 eq>mol eq
Solution part c
The MW of CO2 is 44. In solution, carbon dioxide forms carbonic acid and has the
potential of giving up 2 H + ions.
CO2 + H2O Δ H2CO3 Δ H+ + HCO3- Δ 2H+ + CO2-
3
MW 44 g>mol g
EW for CO2 = = = 22
z 2 eq>mol eq
EXAMPLE 3.3
Calculate concentration in normality
Find the normality (N) of the following solutions:
a. 0.25 M solution of CaCO3 .
mg
b. 588 solution of K 2Cr2O7
L
Solution part a
Using Example 3.2, Part b, the equivalent weight of CaCO3 is 50 g/eq and z = 2.
Use Equation (3.3).
Solution part b
AW for K = 39, and for Cr2O2- 7 MW = 112 * 522 + 17 * 1622 = 216 g/mol. In
solution, potassium dichromate dissociates into potassium (K) and the free radical
dichromate 1Cr2O2- 7 2 as follows:
K 2Cr2O7 Δ 2 K+ + Cr2O2-
7
Section 3.3 Chemical Reactions 37
The following equations present two simple synthesis reactions involving lime or
calcium oxide (CaO). Equation (3.4) examines the reaction often referred to as slaking
that involves heating a mixture of water and lime to produce calcium hydroxide. Equa-
tion (3.5) presents the reaction where lime is added to sewage to remove phosphates
by precipitation.
-
3 CaO1s2 + 3 H 2O1l2 + 2 PO3-
4 1aq2 : Ca 31PO4221s2 + 6 OH 1aq2 (3.5)
Notice, in both reaction equations, that the reactants and products are sepa-
rated by an arrow, indicating that products to the right are yielded by or formed from
the specified reactants located to the left of the arrow. Although not required, the
state of the reactant and product is given in parentheses as a subscript. The subscripts
(s), (l), and (aq) refer to solid, liquid, and aqueous, respectively. Finally, the equations
must be balanced such that the mass of each element involved is conserved through-
out the reaction, so each side of the equation must contain the same number of moles
of each element. From Equation (3.4), notice that 1 mole of CaO and 1 mole of water
38 Chapter 3 Essential Chemical Concepts
are required (for a total of 2 moles of reactant) to produce 1 total mole of product,
Ca1OH22 . Similarly, Equation (3.5) requires 3 moles of CaO to form one mole of
product, Ca31PO422 . Although balancing an equation is often an arduous task for
students as they begin their chemistry endeavors, when it is done properly the ratio
of the number of moles produced to reactants involved is apparent.
Recognize that essentially all reactions are reversible and that both the for-
ward and reverse reactions are taking place simultaneously. Consider the reversible
reaction shown in Equation (3.6).
aA + bB Δ cC + dD (3.6)
3C4c 3D4d
K = (3.7)
3A4a 3B4b
where a, b, c, and d are the number of moles of constituents A, B, C, and D, respec-
tively. The brackets, [ ], denote concentration of a constituent in moles per liter.
3.3.1 Stoichiometry
Environmental engineers often use chemical equations for estimating the quantity
of chemicals that must be added to water or wastewater to achieve a specific result.
For example, the quantity of sludge that will be produced can be determined from a
balanced chemical equation. An equation is balanced when the law of the conservation
of mass is reflected: elements are not created or destroyed, just rearranged by the reac-
tion. Mass and charge are conserved in all chemical reactions, such that the quantity
of each type of element is equal on both sides of the equation and each compound
has a net charge of zero. When mass and charge are properly balanced, the chemical
equation should represent the stoichiometry observed in a reaction.
The concept of balancing reactions is fundamental to chemistry. Although equa-
tions can be balanced algebraically using linear systems, usually they are balanced by
inspection. To balance an equation by inspection, follow these simple rules:
1. Insure that all products and reactants are represented by the correct chemical
formula, appropriately written on the proper side of the equation, and are sep-
arated by plus signs.
2. Identify the most complicated compound in the equation. Assume that only
one unit or mole of this compound is in the reaction. Balance the elements in
this compound one at a time, placing coefficients appropriately in front of
products and reactants in the equation.
3. Focus your initial attention on those atoms present in the fewest compounds.
4. Continue the trial-and-error process for the remaining compounds. As a gen-
eral rule, balance the atoms that are most prevalent (i.e., hydrogen and oxygen)
near the end of the inspection.
5. Remove fractions and simplify such that the group of coefficients remaining
are the smallest whole numbers possible.
Use these rules of inspection to balance the equations in the example that follows.
Section 3.3 Chemical Reactions 39
EXAMPLE 3.4
Balancing chemical reactions
a. Because of the promulgation of the 1970 Clean Air Act, tetraethyl lead
was phased out of gasoline, and methyl tertiary-butyl ether (MTBE)
was added instead to serve as an octane booster. The aim was to make
the internal combustion engine “knock” less and burn “cleaner,”
emitting fewer unburned hydrocarbons into the atmosphere. Balance
the combustion reaction of MTBE 31CH 323COCH 34 in a pure oxygen
environment.
b. The formation of rust is a single-replacement reaction (it is also an
oxidation-reduction reaction) that commonly occurs in the environment.
Rust is formed when the iron (Fe) present in steel is oxidized to a
hydrated form, iron(III) oxide or ferric oxide, in the presence of oxygen
and water. Balance the reaction that describes the formation of rust.
[Hint: Hydrous ferric oxide 1Fe2O3 # 3 H 2O2 is the primary component in
red-brown rust.]
Solution part a
1. Recognize that carbon dioxide and water will be formed in the combustion of a
hydrocarbon and write appropriate products and reactants.
2. Assume only 1 mole of MTBE is reacting, and balance CO2 production by observ-
ing that 5 moles of C are reacting for each mole of MTBE.
3. Count the number of H atoms present on the left-hand side of the equation and
add the coefficient 6 to the H 2O on the right, forcing both sides of the equation
to have 12 moles of hydrogen.
15
4. Balance the O by adding the coefficient in front of the O2 on the left-hand
2
side of the equation. Now each side has 16 moles of oxygen.
15
1CH 323 COCH 3 + O : 5 CO2 + 6 H 2O
2 2
5. Remove the fractions by multiplying through by 2.
Solution part b
1. Write the reactant and products present in the reaction.
Fe + O2 + H 2O : Fe2O3 # 3 H 2O
40 Chapter 3 Essential Chemical Concepts
2. Recognize that 2 moles of Fe are needed to form the product. Add the coefficient
2 before the reactant Fe.
2 Fe + O2 + H 2O : Fe2O3 # 3 H 2O
2 Fe + O2 + 3 H 2O : Fe2O3 # 3 H 2O
O + 3 H 2O : Fe2O3 # 3 H 2O
3
2 Fe +
2 2
4 Fe + 3 O2 + 6 H 2O : 2 Fe2O3 # 3 H 2O
EXAMPLE 3.5
Reaction stoichiometry
Methane is a greenhouse gas that is about 23 times more effective on a molecular
basis than carbon dioxide in causing global warming. Methane is emitted by a vari-
ety of anthropogenic sources, including rice fields and cattle (IPCC, 2001). Accord-
ing to a recent study by Neue (1993), rice fields annually produce 20–100 teragrams
(1 Tg = 1 million metric tons) of methane through the anaerobic decomposition
(methanogenesis) of organic materials that are either applied to or native to the
fields. Estimating annual methane emissions of approximately 500 Tg (Cicerone and
Oremland, 1988), rice growing contributes 5% to 20% of annual anthropogenic
methane emissions. Using formic acid as an example of an organic that is anaerobi-
cally reduced,
a. Calculate the molar ratio of methane production to carbon dioxide pro-
duction when formic acid (CHOOH) is reduced. Reaction products will
include methane, carbon dioxide, and water.
b. Calculate the mass and volume of methane emitted from reducing 161 g of
formic acid.
Assume conditions of standard temperature and pressure (STP; T = 25°C and
P = 1 atm) and eventual emission of all products to the gas phase.
Solution part a
1. Write the reactants and products participating in the microbially mediated
reaction:
CHOOH : CH 4 + CO2 + H 2O
2. Balance the equation by confirming that all quantities of atoms are equal on
both sides of the equation.
4 CHOOH : CH 4 + 3 CO2 + 2 H 2O
Section 3.3 Chemical Reactions 41
Solution part b
1. Determine the mass of both methane and carbon dioxide produced from 161 g of
formic acid reacting. Begin by determining the number of moles of formic acid
available to react by dividing by the molecular weight of the compound.
1 mol CHOOH
161 g CHOOH * = 3.5 mol CHOOH
46 g
2. Determine the mass of methane and carbon dioxide produced. Remember that
the molecular weights of methane and carbon dioxide are 16 and 44, respectively.
1 mol CH4 produced 16 g CH 4
mass of CH4 1g2 = 3.5 mol CHOOH * *
4 mol CHOOH reacting 1 mol CH 4
= 14 g CH 4
To find the volume of methane and carbon dioxide gas produced at STP
(25°C and 1 atm), utilize the ideal gas law (Section 3.6.1), PV = nRT.
Rearrange and solve for the volume of methane:
L # atm
mol # K
a0.08206 b1273 + 252 K
nRT 14 g CH 4
V = = * = 21.4 L
p g 1 atm
16
mol CH 4
Similarly for CO2 , 64.2 L of gas are produced for every 161 g of formic
acid reduced. Notice that the volume of CO2 produced is three times that
for CH 4 , as expected from the stoichiometry observed in Part a.
EXAMPLE 3.6
Reaction stoichiometry
Calculate the moles of oxygen required to react with 1 mole of glucose 1C 6H 12O62
according to the following balanced chemical equation. Also determine the mass of
oxygen required to oxidize 1 gram of glucose.
1 C 6H 12O6 + 6 O2 : 6 CO2 + 6 H 2O
MW = 180 192
42 Chapter 3 Essential Chemical Concepts
Solution:
The stoichiometric or molar ratio of O2 to glucose 1C 6H 12O62 is 6:1. This means that 6
moles of oxygen are required for the oxidation of 1 mole of C 6H 12O6 to form carbon
dioxide and water. On a mass basis, 192 grams of oxygen are required to react with 180
grams of glucose to completely oxidize it to carbon dioxide and water.Therefore, 1.07 g
of oxygen are required to oxidize 1 g of glucose 1192/180 = 1.072.
EXAMPLE 3.7
Practice with reaction stoichiometry
Solution part a
160 grams of oxygen are required per mole of C 5H 7O2N, or 160 grams of oxygen
are required per 113 grams of C 5H 7O2N.
Solution part b
The concentration of oxygen required to oxidize 500 mg/L of C 5H 7O2N is given as:
500 mg C 5H 7O2N 160 g 708 mg O2
O2 concentration = a b =
L 113 g L
Recognize that this is also the theoretical chemical oxygen demand (COD) of a
500-mg/L solution of C 5H 7O2N.
greater than 14.0 are possible, however, and are frequently prepared in laboratory
settings, and also exist in nature. For example, acid mine waters characterized with a
pH = - 3.6 have been encountered underground in the Richmond Mine at Iron
Mountain, CA (Nordstrom et al., 2000). By definition, the pH is the negative of the
logarithm of the activity or the relative hydrogen-ion concentration. For dilute solu-
tions, pH is well defined mathematically as
pH = - log 3H +4 (3.8)
where 3H +4 represents the molar 1moles H +/L2 concentration of the hydrogen ions
in solution. Similarly, pOH can be defined as pOH = - log 3OH -4 such that
pH + pOH = 14.
The pH is useful when evaluating surface-water quality, regional and global
acid-rain effects, and industrial effluent and makeup waters. Surface-water pH is
influenced naturally by photosynthesis and respiration processes as well as by
regional geology, such as limestone or glacial deposits. Anthropogenic sources such
as acid-rain deposition and wastewater discharge also modify stream and lake pH.
Although some aquatic life species can thrive under extreme pH conditions, the
United States. Environmental Protection Agency (EPA) has identified that lakes
having a pH 6 5 are stressed and considered acidic. In particular, fish prefer a pH
between 6 and 9. Figure 3.2 shows pH ranges of common items.
As defined by J.N. Brønsted and T.M. Lowry in 1923, a Brønsted-Lowry acid is a
compound that donates a hydrogen ion or proton to another substance, while a base is
any substance that accepts a proton. A generic acid-base reaction is shown in Equa-
tion (3.9), where on the left-hand side, HA represents an acid and B- is the base.
HA B A HB
Acid Base Base Acid
(3.9)
Increasing Acidity
pH Scale 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Household
white vinegar
Wheaties
Black coffee
Figure 3.2
pH Estimates for common household items.
44 Chapter 3 Essential Chemical Concepts
In aqueous systems, the H + ion does not actually exist, because it readily com-
bines with water to form H 3O +, but throughout this text and many others, H + and
H 3O + are used interchangeably. Equation (3.11) describes the weak acid-base reac-
tion that occurs within a simple aqueous system.
H 2O Δ OH - + H + (3.11)
3OH -43H +4
K = (3.12)
3H 2O4
For dilute solutions, the molar concentration of water is 55.6 mol/L at 25°C, allowing
Equation (3.12) representing the ionization of water to simplify as follows:
EXAMPLE 3.8
Calculation of system pH and pOH
Determine the pH, pOH, and 3OH -4 of an aqueous system known to have a hydro-
gen-ion concentration of 10-3.5 M. Assume the system is at 25°C.
Solution
From Equation (3.8), we know that
pH = - log3H +4
Substitute 10-3.5 M for the concentration of hydrogen and solve for pH.
pH = - log110-3.52
pH = 3.5
Calculate pOH and then 3OH -4 by applying Equation (3.13).
pH + pOH = 14
pOH = 14 - 3.5 = 10.5
Section 3.4 Solution Chemistry—Aqueous Phase 45
3.4.2 Strong Acids and Bases vs. Weak Acids and Bases
Strong acids and bases will almost completely dissociate in water. The strength of an
acid or base is quantified by its dissociation constant. The dissociation constant
(often called equilibrium constant) for acids is Ka and for bases is Kb and can be
generalized by Equations (3.14) and (3.15), respectively. These equations provide
generic acid and base dissociation reactions, followed by their associated equation,
which determines the equilibrium constant. In the equations, HA is a generic acid
and BOH is a generic base.
HA Δ H + + A-
3H +43A-4
Ka = (3.14)
3HA4
BOH Δ B+ + OH -
3B+43OH -4
Kb = (3.15)
3BOH4
Similar to the log-based system used to describe water acidity (pH), acid and
base strength is described by the negative logarithm of the dissociation constant, as
shown below:
Table 3.2 Equilibrium Constants for Acids and Their Conjugate Base That Are
Commonly Found in the Environment (T ⴝ 25°C)
Acid pK a Base pKb
-
HCl Hydrochloric acid -3 Cl Chloride ion 17
H2CO…3 Carbon dioxide and carbonic acid 6.3 HCO3- Bicarbonate 7.7
-
H2S Hydrogen sulfide 7.1 HS Bisulfide 6.9
HPO2-
4 Monohydrogen phosphate 12.3 PO3-
4 Phosphate 1.7
Table 3.2 shows that both HCl and H 2SO4 are strong acids, and CO2- 3 and
-
OH are considered strong bases. Note that the stronger the acid, the weaker its
conjugate base, and the weaker the acid, the stronger its conjugate base.
EXAMPLE 3.9
pH calculation for a strong acid
Calculate the pH of a 0.01 M HNO3 solution at 25°C.
Solution
From Table 3.2, notice that nitric acid is a strong acid with pKa 6 1. Therefore, it is
reasonable to assume that the acid completely dissociates.
HNO3 : H + + NO3-
Stoichiometry provides that 0.01 M H + and 0.01 M NO3- are in solution, so
pH = - log3H +4
pH = - log10.012 = 2
Section 3.4 Solution Chemistry—Aqueous Phase 47
-8.34
CaCO31s2 Δ Ca2+ + CO2-
3 ; Ksp = 3Ca2+43CO2-
3 4 = 10 (3.19)
3CO21aq24 mol
= 10-1.5
L # atm
CO21g2 Δ CO21aq2 ; KH = (3.20)
CO21g2
Aqueous phase carbon dioxide reacts with water to form carbonic acid.
CO21aq2 + H 2O Δ H 2CO3
The term alkalinity quantifies the buffering capacity of a system, meaning how
well the system can resist changes in pH with the addition of an acid. Typically, alka-
linity is a function of the carbonate system and additional weak acids and bases such
as ammonia, silicates, and phosphates.
In natural systems, alkalinity depends strongly on regional bedrock composi-
tion. For instance, if a region’s bedrock contains dolomite 1CaMg1CO3222 or calcite,
i.e., limestone 1CaCO32, —high alkalinity carbonates—the buffering capacity of
surface waters is expected to be high. In contrast, surface waters in areas containing
primarily igneous bedrock typically exhibit low alkalinity and therefore have a min-
imal capacity to buffer the system. Wastewaters may contain additional compounds
such as hydroxide, ammonia, phosphates, organic acids, and silicates that contribute
to alkalinity.
The susceptibility of surface water to pH variations resulting from acid rain
and/or industrial effluents are classified by the EPA. Table 3.3 summarizes this clas-
sification. The table indicates that surface waters with an alkalinity concentration of
less than 20 mg/L as CaCO3 are deemed susceptible to acidity.
48 Chapter 3 Essential Chemical Concepts
Endangered 2–5
Sensitive 10–20
Not sensitive 7 20
Source: Godfrey et al.,1996; Van Loon and Duffy, 2005.
Equation (3.22) represents total alkalinity for most natural water systems and
holds true for all waters having proton activity from CaCO3 only. In the equation, the
carbonate concentration 3CO2- 3 4 is multiplied by 2 because it can consume 2 moles of
protons or acidity per mole of CO2- 3 .
eq
alk a b = 3HCO 3-4 + 23CO2- - +
3 4 + 3OH 4 - 3H 4 (3.22)
L
A aBb Δ aA + bB (3.23)
Table 3.4 Typical Solubility Product Constants, Ksp , for Solids Commonly Found in the
Environment (T ⴝ 25°C)
Compound *Solubility product (Ksp)
EXAMPLE 3.10
Solubility of solids
Calculate the solubility of the following ionic compounds. Assume a chunk of each
solid such that an excess exists, and assume T = 25°C.
Present results in g/L.
a. Ca1OH221s2
b. CaCO31s2
Solution part a
Referring to Table 3.4, the Ksp for Ca1OH22 is 5 * 10-9.
The dissolution reaction for Ca1OH22 is
-
Ca1OH221s2 Δ Ca 2+
1aq2 + 21OH 21aq2
Within the equilibrium expression, both 3Ca2+4 and 3OH -4 concentrations are
unknown. Mole ratios observed in the dissolution reaction show that for every 1 mole of
Ca2+ formed, 2 moles of OH - are formed. If x represents the concentration of Ca2+ ions,
then 2x moles of OH - will be produced at equilibrium. So the equilibrium expression is:
5 * 10-9 = 1x212x22
Use algebra to solve for x:
4x3 = 5 * 10-9
5 * 10-9
x = 3
B 4
x = 1.08 * 10-3 M
So, the solubility of Ca2+ and the Ca1OH22 solid is equal to 1.08 * 10-3 M.
Knowing the molecular weight of Ca1OH22 is 74 grams per mole, convert to a
mass-per-volume concentration:
1.08 * 10-3 mol Ca 1OH22 74 g Ca 1OH22 g Ca1OH22
* = 0.080
L 1 mol Ca 1OH22 L
Solution part b
The process for determining the solubility of CaCO3 is similar. From Table 3.4, the
solubility product is 5 * 10-9. Notice that the Ksp values for both Ca salts analyzed
in this example are the same. Write the equilibrium dissolution reaction and the sol-
ubility-product expression.
EXAMPLE 3.11
U s i n g s o l u b i l i t y k n o w l e d g e t o d e t e r m i n e Ksp
The solubility of AgCl is 1.34 * 10-5 M in pure water. Calculate the value of Ksp .
AgCl Δ Ag + + Cl-
x = solubility = 3Ag +4 = 3Cl-4 = 1.34 * 10-5 M
Ksp = 3Ag +4 3Cl-4 = 1x2 1x2 = x2 = 11.34 * 10-5 M22 = 1.8 * 10-10
Section 3.6 Solution Chemistry—Gas Phase 51
PV = nRT (3.25)
where:
P = absolute pressure, atm,
V = volume occupied by gas, L,
n = moles of gas,
R = universal gas law constant; 0.08206 atm # L>mol # K, and
T = temperature, K 1273.15 + °C2.
EXAMPLE 3.12
Practice with the ideal gas law
Calculate the volume that one mole of an ideal gas occupies at standard conditions
of 1 atm of pressure and 0°C.
atm # L
mol # K
11 mol2a0.08206 b13273 + 04K2
nRT
V = = = 22.4 L
P 11 atm2
different. Writing the law for each case with numerical subscripts to the vari-
ables produces:
This relationship is Boyle’s law and shows that for an isothermal system containing
a finite amount of gas, pressure and volume are inversely proportional such that as
pressure increases, the volume must decrease.
Similarly, Charles’ law is easily derived when the molar quantity of gas and
system pressure remain constant, and volume and temperature vary. Writing the
ideal gas law and assigning subscripts to the system variables produces:
PV1 = nRT1
PV2 = nRT2
V1 V2 nR
= = = constant (3.27)
T1 T2 P
Charles’ law implies that volume and temperature are directly proportional; when
temperature increases, volume increases.
V1 V2
= (3.28)
T1 T2
Similarly, the Gay-Lussac law relates pressure and temperature for ideal gases such
that when temperature increases, pressure increases.
P1 P2
= (3.29)
T1 T2
The combined gas law is easily derived when system pressure, temperature,
and volume are all allowed to vary while the quantity of gas stays constant:
P1V1 P2V2
= (3.30)
T1 T2
EXAMPLE 3.13
Illustrating Charles’ law
A stack gas leaving a paint-drying oven has a volumetric flow rate of 1000 standard
cubic feet per minute (scfm) and an operating temperature of 400ºF.
a. Find the actual volumetric flow rate exiting the stack at 400ºF.
b. Determine the actual volumetric flow rate if the process temperature is
altered such that the temperature of the stack gas as it exits is 600ºF.
Section 3.6 Solution Chemistry—Gas Phase 53
Solution part a
Charles’ law, Equation (3.28), relates the volume and temperature of a gas such that
V1 V2
=
T1 T2
Allow variable 1 to represent current operating conditions of 1000 scfm and 400ºF
and variable 2 to coincide with standard temperature and pressure (STP). As defined
by the U.S. Environmental Protection Agency, the temperature for standard condi-
tions is 68ºF (20ºC) and the pressure is 1 atm (101.325 kPa). Always use either the
Kelvin or Rankin absolute temperature scale when solving problems with the gas
laws. Recall that T1K2 = T1°C2 + 273 and that T1R2 = T1°F2 + 460. Begin by cal-
culating the absolute temperature for both conditions.
Apply Charles’ law to find the volumetric flow rate at operating conditions.
1000 scfm V2
=
528 R 860 R
1000 cfm
actual volumetric flow rate = V2 = * 860 R = 1629 cfm
528 R
Solution part b
Apply Charles’ law again to determine the volumetric flow rate for the gas phase, once
process conditions have changed such that the exit gas temperature is 600°F = 1060 R.
V1 V2
=
T1 T2
1629 cfm V2
=
860 R 1060 R
V2 = 2008 cfm
PT = P1 + P2 + P3 + Á + Pi (3.31)
Pi = yiPT (3.32)
ni Pi
where: yi = = ;
n PT
yi = mole fraction of component i in the gas phase,
ni = the number of moles of gaseous component i, and
n = the total number of moles of gas in the system.
Pi = P…i xi (3.33)
Pi = kiHxi (3.34)
EXAMPLE 3.14
U s e H e n r y ’s l a w t o d e t e r m i n e e q u i l i b r i u m l i q u i d - p h a s e
concentrations
The concentration of oxygen in the atmosphere is approximately 20.9% by volume.
Oxygen, however, is only slightly soluble in water, and its solubility is a function of
temperature. As temperature increases, oxygen solubility in water decreases. For
many aquatic systems that rely on the presence of oxygen, this poses a potential
problem during summer months, when both temperature and the rate of biological
activity are at their highest. Use Henry’s law to estimate the maximum oxygen con-
centration available to aquatic life during both summer and winter months in Norris
Lake located in Maynardville, Tennessee, assuming 1 atm of pressure. Assume that
L # atm
average winter and summer high temperatures in Maynardville are 43.5ºF and 87.2ºF,
respectively. The Henry’s law constant for oxygen in water is 527.3 at 43.5°F
L # atm mol
and 857.7 at 87.2°F.
mol
Solution
Use the following form for Henry’s law (from Table 3.5), PA = kCH 3A4, to deter-
mine the oxygen solubility in water at 43.5ºF (6.4ºC) and 87.2ºF (30.7ºC). First,
determine the partial pressure of oxygen in the environment.
20.9
PO 2 = 1 atm * = 0.209 atm
100
Now, solve for the aqueous-phase concentration at 43.5ºF
PO2 0.209 atm mol O2
3O2143.5°F24 = = # = 3.96 * 10-4
kC
H L atm L
527.3
mol
56 Chapter 3 Essential Chemical Concepts
mg O2
Similarly at 87.2ºF, the solubility of oxygen is O2187.2°F2 = 7.8 .
L
S U M M A RY
Fundamental chemistry concepts often used by environmental engineers were pro-
vided. The concepts of elements and molecules were introduced and units of concen-
tration and chemical reactions were reviewed. Reaction stoichiometry was defined
and practice in balancing reactions was provided. A working definition of pH was
introduced and its importance in acid-base chemistry discussions was illuminated.
The chemical compounds associated with the carbonate system were highlighted in a
summation on alkalinity that outlined its importance in both natural and engineered
environments. Concepts of gas-phase chemistry were introduced. The behavior of
ideal gases was characterized using the ideal gas, Boyle’s, Charles’, and Henry’s laws.
Practical exercises were provided to highlight key ideas.
REFERENCES
Cicerone, R.J., and Oremland, R.S. (1988). Biogeochemical Aspects of Atmospheric Methane.
Global Biochem Cycles 2/4: 299–327.
CRC Handbook of Chemistry and Physics, 87th ed., Ed. D.L. Lide, Taylor & Francis, Boca
Raton, FL, 2006.
Godfrey, P.J., M.D. Mattson, M.F. Walk, P.A. Kerr, O.T. Zajicek, and A. Ruby III (1996). The
Massachusetts Acid Rain Monitoring Project: Ten Years of Monitoring Massachusetts Lakes
and Streams with Volunteers. Publication No. 171. University of Massachusetts Water
Resources Research Center. Available online at: http://www.umass.edu/tei/wrrc/
WRRC2004/pdf/ARMfinalrpt.PDF.
IPCC (2001). Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the
Third Assessment Report of the Intergovernmental Panel on Climate Change, Ed. Houghton, J.T.,
Ding,Y., Griggs, D.J., Noguer, M., van der Linden, P.J., Dai, X., Maskell, K., and Johnson, C.A.,
Cambridge University Press, Cambridge, United Kingdom, and New York.
Exercises 57
Neue, H. (1993). Methane Emission from Rice Fields: Wetland Rice Fields May Make a
Major Contribution to Global Warming. BioScience 43:7, 466–73.
Nordstrom, D.K, C.N. Alpers, C.J. Ptacek, and D.W. Blowes (2000). Negative pH and Extremely
Acidic Mine Waters from Iron Mountain, California, Environ. Sci. Technol., 34 (2):254–258.
Sawyer, C. L., McCarty, P. L., and Parkin, G. F. (2003). Chemistry for Environmental Engineers,
McGraw-Hill, New York.
VanLoon, G.W., and S.J. Duffy (2005). Environmental Chemistry a Global Perspective, 2nd ed,
Oxford University Press, Great Britain.
BIBLIOGRAPHY
Benefield, L.D., Judkins, J.F., and Weand, B.L. (1982). Process Chemistry for Water and Waste-
water Treatment, Prentice-Hall, Englewood Cliffs, NJ.
Reynolds, T.D., and Richards, P.A. (1996). Unit Operations and Processes in Environmental
Engineering. PWS Publishing Company, 20 Park Plaza, Boston, MA.
Sander, R. (1999). Compilation of Henry’s Law Constants for Inorganic and Organic Species
of Potential Importance in Environmental Chemistry (Version 3). Available online at
http://www.henrys-law.org.
Sanks, R.M. (1982). Water Treatment Plant Design for the Practicing Engineer, Ann Arbor
Science, 230 Collingwood, Ann Arbor, Michigan.
Snoeyink, V.L., and Jenkins, D. (1980). Water Chemistry, John Wiley & Sons, New York.
Viessman,W., and Hammer, M.J. (2005). Water Supply and Pollution Control, Pearson/Prentice Hall,
Upper Saddle River, NJ.
EXERCISES
3.1 In the accompanying table, calculate the atomic or molecular weight in grams
per mole for each of the elements or compounds listed. Also provide the chemi-
cal symbol or formula for each element or compound.
3.2 In the accompanying table, calculate the equivalent weight in grams per
equivalent (g/eq) for each of the elements or compounds listed. Also provide
the chemical symbol or formula for each element, radical, or compound.
4.1 INTRODUCTION
Objectives
When evaluating natural and engineered systems that involve living organisms,
In this chapter, you will it is important to consider biological and ecological concepts, especially the role
learn about: that microorganisms play with regard to the flow of energy and nutrients in
The abiotic and biotic the biosphere.
components of planet We begin with a brief introduction to ecology, the branch of biology that
Earth deals with the way living organisms (biota) interrelate and interact with the
Cell structure and environment.
classification of organisms Ultimately, the radiant energy of the sun sustains all life on Earth; initiat-
ing the flow of energy through the biosphere. Through photosynthesis, green
The major groups of
plants and algae utilize the sun’s energy to transform inorganic compounds
organisms found in
and nutrients from the soil into organic compounds that are used in the syn-
biological and ecological
thesis of starches, sugars, amino acids, and proteins. Plants, algae, and phyto-
systems
plankton are primary producers that are ultimately consumed by animals and
Microbial growth and the humans (consumers). When plants and animals die, their remains are used by
equations used in decomposers, consisting primarily of bacteria and fungi, allowing nutrients and
modeling the growth rate organic matter to be recycled.
of microorganisms The consumption of plants by animals that are in turn eaten or consumed
The flow of energy in by higher animal forms is called a food chain. Each step in the food chain is
ecological systems and called a trophic level, with energy being transferred up through the levels. The
through the food chain transfer of energy through the food chain is very inefficient, and, unlike the
The cycling of carbon, nutrients, the energy is not recyclable. At each trophic level, much of the energy
nitrogen, phosphorus, and is dissipated and irrecoverably lost as heat.
sulfur in ecological
systems
Lake classification and 4.2 BIOLOGICAL SYSTEMS
stratification Planet Earth consists of abiotic and biotic components. The abiotic or non-
Streeter-Phelps Dissolved living component is represented by the atmosphere (air), lithosphere (soil),
Oxygen Sag Model for and hydrosphere (water). It includes, for example, organic and inorganic
streams compounds, nonliving elements, climate, and the hydrologic cycle. The biotic
component (biosphere) contains all the living organisms on Earth and
includes plants, animals, microorganisms, and humans.
60 Chapter 4 Biological and Ecological Concepts
Lipid
Cell membrane
Nuclear Nucleolus
membrane
Nucleus
Ribosomes
Vacuole
Cytoplasmic
membrane
Hexagonal
head
Nucleic
acid
core
Contractile
sheath
Base
plate
Tail
fiber
Figure 4.3
20 nm up to 400 nm in diameter Schematic of a virus.
is made up of five kingdoms: Monera, Protista, Fungi, Plantae, and Animalia. Each
kingdom is further classified in the following order: phylum, class, order, family, genus,
and species. In the 1970s, microbiologists developed a new system that relies on phy-
logeny. Phylogeny classifies organisms according to their genetic characteristics and is
based on their evolutionary history. Under the phylogenetic classification (Madigan et
al., 2000), three domains (kingdoms) comprise all organisms: Archaea, Bacteria, and
Eukarya. All prokaryotic organisms are found in the Archaea or Bacteria domain.
Microbiologists and environmental engineers need to identify and classify
microbes for many reasons. For example, the identification and enumeration of
pathogens or disease-causing microorganisms in drinking water is essential, so that
the proper disinfectant can be selected and added to the water to prevent disease.
Engineers are also interested in optimizing biological processes associated with
wastewater treatment and remediation of contaminated groundwater and soil;
therefore, it is imperative to identify and classify the microorganisms involved.
The basic taxonomic classification unit is species. Species are groups of indi-
vidual organisms or strains that have similar characteristics or attributes. Groups of
species that have major similarities are called genera. For example, the bacterium
that causes cholera is Vibrio cholera (Brock, 1979). The species name is cholera and
the genus (singular for genera) is called Vibrio.
Two genera of microorganisms typically encountered during the biological
treatment of wastewater using the activated sludge process are responsible for nitri-
fication. Nitrification is modeled as a two-step, sequential process, mediated by the
genera Nitrosomonas and Nitrobacter.
Anabaena
Chlorella
Figure 4.4
Schematics of Anabaena
and Chlorella algae. 0.5–1.0 mm up to 60 mm in diameter
cells are eukaryotes. Algae are autotrophic organisms that utilize inorganic carbon
as their carbon source. Algae are the primary producers in the aquatic food chain. A
major concern to environmental engineers is excessive algal growth or blooms in
water-supply lakes and reservoirs, where they can clog intake structures and cause
taste and odor problems in water. In wastewater treatment lagoons, algae play a sig-
nificant role by producing oxygen, which bacteria and other microbes use for the
oxidation and degradation of organics in the wastewater. Figure 4.4 shows two types
of algae: Anabaena and Chlorella.
Bacteria
Bacteria are essential in the recycling of nutrients through ecosystems. They are
used in treating contaminated water and wastewater, and some species cause plant
and animal diseases. Figure 4.5 shows three bacterial cellular forms and arrange-
ments: Micrococcus, Streptococcus, and Bacillus. They are classified as Monerans,
normally reproducing by binary fission (splitting into two identical cells). Individual
bacteria are shaped spherically, cylindrically, or spirally. Most bacteria range in size
from 0.5 to 14 mm (Sullia and Shantharam, 1998). All bacteria have a rigid cell wall
that maintains the shape of the cell. The genetic material of bacteria is not contained
in a true nucleus but just incorporated into their cytoplasm.
Daphnia
0.2 to 5 mm long
Figure 4.6
Diaptomus
Examples of a Diaptomus
0.5 to 5 mm long and Daphnia.
Fish
Fish are among the animals that have a spine or backbone (vertebrates). They are a
key unit in natural food webs and have a significant impact on plankton, macrophytes
(aquatic plants), and other aquatic organisms. Bioassays using fish and minnows are
used in toxicity testing of wastewater effluent. Change in the composition of a fish
may be attributed to pollution or to a change in its habitat.The diversity of fish species
is another indicator of environmental change. Figure 4.7 shows Dr. W. Jack Lackey
holding a rockfish.
Fungi
Fungi are nonphotosynthetic, eukaryotic protists. They are typically aerobic and
referred to as saprophytes, since they degrade and utilize decaying organic matter
from plant and animal remains. Fungi can tolerate low-pH or acidic conditions, low-
moisture, and low-nitrogen conditions better than most other microorganisms. They
are subdivided into molds, yeasts, and mushrooms. Molds are filamentous; yeasts are
nonfilamentous and are unicellular.
Mushrooms are a more highly differentiated form of fungi, forming basidia (the
structures we call mushrooms) above the ground. Molds and mushrooms reproduce
asexually (by budding or spores) and sexually (by spores). Yeasts reproduce asexu-
ally by binary fission or budding and sexually through the formation of ascospores;
they are facultative organisms that can grow either aerobically or anaerobically.
Yeasts are used in fermentation processes such as beer and wine production, in mak-
ing bread, and in producing antibiotics.
Fungi are important in the degradation of cellulose and in the composting of
sludge. Fungi cause athlete’s foot and ringworm. Two examples of fungi are shown in
Figure 4.8.
64 Chapter 4 Biological and Ecological Concepts
Figure 4.7
Photograph of Dr. W. Jack Lackey holding a rockfish (up to 200 cm long and 57 kg in weight).
Helminths
Worms collectively are described as helminths. They are macroinvertebrates—
that is, they lack a spine or backbone, and they are large enough to see with the
naked eye. Helminths are among the principal causative agents of disease in the
world and fall into three major phyla: Nematoda (roundworms), Platyhelminthes
(flatworms), and Annelida (segmented worms). Their primary significance is that
the species that cause most human diseases are infective as either adults or larvae,
while in other species it is the eggs that are infective. Helminth eggs have been
found to survive in oxidation pond sediments up to 10 years (Metcalf and Eddy,
2003). Chlorine disinfection and anaerobic digestion have been shown to be inef-
fective at inactivating helminth eggs. This raises questions regarding the applica-
tion of biosolids or sludge on land. Figure 4.9 shows an example of a leech and
flatworm.
Macrophytes
Macrophytes are large aquatic plants that may be attached to lake bottoms or
may be free floating; some are totally submersed, and others emergent. They pro-
vide habitat for microorganisms and other aquatic life. Examples of macrophytes
include duckweed, watercress, hydrilla, water lilies, water hyacinth, and water let-
tuce. Eutrophic lakes generally have an abundance of macrophytes; these can cause
Section 4.2 Biological Systems 65
nuisance conditions in lakes used for recreational purposes. When these aquatic
plants die, aerobic bacteria consume large quantities of oxygen in degrading and oxi-
dizing the carbon and nitrogen that becomes available.This may lead to low dissolved-
oxygen levels in the water column. Examples of macrophytes are presented in
Figure 4.10.
Figure 4.9
Examples of a leech
and flatworm.
Leech Planaria
3–6 cm 5–13 mm
Figure 4.10
Examples of macrophytes.
Protozoa
Protozoans are motile, eukaryotic protists that typically range in size from 10 to
300 mm. Most are aerobic, nonphotosynthetic, and reproduce by binary fission. Pro-
tozoa feed on bacteria and particulate matter, serving as polishers of the effluent
from biological wastewater treatment facilities. Well-known protozoans include
Entamoeba histolytica, which causes amebic dysentery; Giardia lamblia, which is
responsible for beaver’s disease or Giardiasis; and Cryptosporidium parvum, which
Amoeba causes cryptosporidiosis. Giardia and Cryptosporidium form cysts and oocysts that
30–600 mm are resistant to traditional chlorine disinfection (Metcalf and Eddy, 2003). Figure
4.11 shows an amoeba.
Figure 4.11
Example of a protozoan. Rotifers
Rotifers are microscopic eukaryotic animals. Figure 4.12 shows a rotifer. Rotifers
are aerobic heterotrophs that consume bacteria and particulate organic matter by
ingestion. The presence of rotifera and/or stalk ciliates indicates a highly efficient
aerobic system.
Viruses
Viruses are submicroscopic particles ranging in size from 10 to 250 nm (1nm
10-3 mm2 (Henry and Heninke, 1996). According to cell theory, viruses are not liv-
ing organisms and are considered as parasites, since they can reproduce only in a
living host.Viruses are composed of a nucleic core consisting of either deoxyribonucleic
acid (DNA) or ribonucleic acid (RNA), surrounded by a protein capsid. All viruses
are pathogenic.
Each type of virus can infect only a specific type of host cell. There are specific
viruses that infect bacteria, plants, animals, and humans. Viruses that infect bacteria
are called bacteriophages. Human enteric viruses that cause waterborne disease
include Norwalk viruses, rotaviruses, reoviruses, and adenoviruses (Metcalf and
Eddy, 2003). A diagram of the Herpes Simplex virus is presented in Figure 4.13.
0.4 mm
4.2.4 Microbial Growth
Figure 4.12
Example of a rotifer. Microorganisms play a critical role in recycling nutrients in the biosphere and in
the treatment of wastewater, contaminated groundwater, and hazardous wastes. We
need to understand their nutritional requirements for growth and their phases of
growth in order to develop technologies that can be implemented to treat wastes
biologically. Microorganisms known as decomposers are especially important in
breaking down dead plants and animals, and excreta, thus enabling the recycle of
organics and nutrients in the biosphere.
Bacteria are ubiquitous in nature and are found in water, air, and soil. Hoover
Herpes simplex
and Porges (1952) proposed the following formula as the composition of a bacterium:
180–200 nm C5H7O2N. Another well-known formula (McCarty, 1970) includes phosphorus:
C60H87O23N12P. Based on the latter composition, a bacterial cell has a total formula
Figure 4.13 weight of 1374 and consists of approximately 52.4% carbon, 12.2% nitrogen, and
Diagram of a virus.
2.3% phosphorus by dry weight. It is easy to recognize that bacteria and other
microbes require carbon, nitrogen, and phosphorus so that their growth will not be
limited. Other trace nutrients such as sodium, iron, and potassium are also required.
In order to flourish, all microorganisms require acceptable environmental
conditions, including proper moisture, a pH in the range of 6 to 8.5, and a tempera-
ture ranging from 15° to 30°C. Various species of organisms can withstand extreme
pH and temperature conditions, and even a lack of moisture; however, this is not
routinely the case.
Section 4.2 Biological Systems 67
1 2 3 4 5
ial
Declining growth
s
nt
Stationary
ne
po
Ex
Lag
Figure 4.14
Time Bacterial growth curve.
dX
a b = mX (4.1)
dt G
mmax S
m = (4.2)
KS + S
Combining Equations (4.1) and (4.2) yields Equation (4.3), which represents
microbial growth rate under batch operating conditions.
dX mmax XS
a b = (4.3)
dt G KS + S
dX
a b = - kdX (4.4)
dt ED
dX
where: a b = endogenous decay rate, mass/(volume·time), and
dt ED
kd = endogenous decay-rate constant, time-1.
The net growth rate of microorganisms in a biological reactor can then be
expressed as Equation (4.5).
dX dX dX
a b = a b + a b (4.5)
dt NG dt G dt ED
Substituting Equations (4.3) and (4.4) into the above expression yields:
dX mmax XS
a b = - kdX (4.6)
dt NG KS + S
Section 4.3 Ecological Systems 69
1dX>dt2G
Y = (4.7)
1dS>dt2U
dS
a b = UX (4.8)
dt U
1dX>dt2G m
Y = = (4.9)
1dS>dt2U U
Umax S
U = (4.10)
Ks + S
Equation (4.11) is another way of expressing net microbial growth rate by sub-
stituting Equations (4.4) and (4.7) into Equation (4.5).
dX dS
a b = Ya b - kdX (4.11)
dt NG dt U
environment, such as a pond, field, forest, or desert, and their dependence upon
each other and the abiotic environment for their survival. As an example, in a
lake ecosystem, the biotic components could consist of phytoplankton, Daphnia,
fish, submergent plants, and emergent plants. The abiotic components would include
temperature, inorganic and organic compounds, and nutrients in the water column
in addition to those found in the lake sediments. In an ecosystem, a population
denotes a group of organisms belonging to one species. A community is defined as a
number of populations living together.
Sunlight provides the energy for driving the reaction, and carbon dioxide pro-
vides the carbon source for the synthesis of glucose 1C6H12O62. The standard free
energy for the synthesis of glucose is 2800 kJ per mole. The glucose is then used
for synthesizing other organic compounds and plant biomass with the uptake of
nitrogen, phosphorus, sulfur, and other trace nutrients as needed by the plant. An
Sunlight Phototroph
Humans
Eagle
Herring gull
Cormorant Snapping
Salmon/lake trout Turtle
Forage Fish
Sculpin
Smelt
Chub Alewife
Mineral nutrients
Note:
Bacteria and fungi Vegetation This is a simplified representation of the
food web showing the main pathways.
Food (energy) moves in the direction of
the arrows. The driving force is sunlight.
Depictions of the various organisms are
Dead animals and plants not to scale.
Figure 4.17
Example of a food web.
Source: http://www.epa.gov/glnpo/atlas/images/big05.gif
Section 4.3 Ecological Systems 73
EXAMPLE 4.1
Energy balance and efficiency
A cow has consumed 100 kJ of energy in the form of grass, with 63% of it being
wasted in the form of excrement, urine, and gas.
a. If 5 kJ of energy is stored in the form of body tissues, how much energy was
used in respiration?
b. What is the energy efficiency of conversion for this trophic level?
Solution part a
energyin = energyout + energyrespiration + energyexcreta
energyexcreta = 0.63 1100 kJ2 = 63 kJ
100 kJ = 5 kJ + energyrespiration + 63 kJ
energyrespiration = 100 - 5 - 63 = 32 kJ
Solution part b
The energy efficiency of conversion is calculated using the following equation.
EXAMPLE 4.2
Energy use through food chain
Using the rule of thumb that 10% of the energy consumed is used in the production of
biomass, calculate the amount of energy passing up through the food chain depicted in
Figure 4.16, assuming that the grass contains 1000 joules of energy.
Solution
First, determine the energy passing through each trophic level by using the 10% rule.
For trophic level 1 (Grass), 100 J 11000 J * 0.10 = 100 J2 are passed to trophic level 2
(Grasshopper). From trophic levels 2 to 3 and 3 to 4, 10 J 1100 J * 0.10 = 10 J2 and
1 J 110 J * 0.10 = 1 J2, respectively, are passed up through the food chain.
1000 J 100 J 10 J 1J
Grass ¡ Grasshopper ¡ Mouse ¡ Hawk
At trophic level 4 (Hawk), only 1 J of energy from the grass goes into produc-
tion of biomass or body tissue in the hawk. The overall energy efficiency through
this food chain is calculated as follows:
Zooplankton 0.123
Source: http://www.epa.gov/glnpo/atlas/glat-ch4.html#3
Section 4.4 Nutrient Cycles 75
Fossil fuel
CO2 aqueous combustion, Plants Animals
Volcanic activity,
Forest firess Decomposition,
Aquatic Plants and Organisms Accumulation,
Compaction of
Water Peat, Dead Plants
Coal, Oil,
Natural Gas Land
Carbonate Rocks
Section 4.4 Nutrient Cycles 77
Wastewater Precipitation
Effluent Dustfall Runoff Atmosphere
Fixation NH3
NH3/NH4 NO3 Volatilization
Organic N Synthesis
Water NO33-
NO
Column
+
/NH44
NH33/NH
NH
Sediment
Layer Ammonification
Synthesis
Figure 4.19
The nitrogen cycle in surface water.
Source: EPA Nitrogen Control Manual (1993), p. 7.
from agricultural and urban areas, must be properly managed if cultural eutrophica-
tion is to be curtailed. The discharge of ammonia to receiving waters promotes the
consumption of large quantities of oxygen by the nitrification process, leading to
anaerobic conditions and the death of fish and other aquatic life. Free undissociated
ammonia is toxic to fish at a concentration of approximately 0.02 mg/L as nitrogen
(Benefield and Randall, 1980).
Nitrification
Nitrification is an aerobic transformation process that uses autotrophic microorgan-
isms to oxidize ammonium 1NH4+2 into nitrate 1NO3-2. Biological nitrification is
modeled as a two-step sequential reaction mediated by bacteria consisting of the
genera Nitrosomonas and Nitrobacter (EPA, 1993). Equations (4.13) and (4.14) show
the oxidation of ammonium and nitrite, respectively. Equation (4.15) is the overall
nitrification reaction excluding the synthesis of biomass.
NH4+ + 1.5 O2
Nitrosomonas " NO- + 2 H+ + H O (4.13)
2 2
NO2- + 0.5 O2
Nitrobacter " NO- (4.14)
3
NH4+ + 2 O2
Nitrifiers " NO- + 2 H+ + H O (4.15)
3 2
78 Chapter 4 Biological and Ecological Concepts
EXAMPLE 4.3
Nitrification stoichiometric coefficients
Calculate the stoichiometric coefficients for oxygen consumption and alkalinity con-
sumption during nitrification using Equation (4.15).
Solution
For oxygen consumption:
Denitrification
Denitrification is a biologically mediated, anoxic process that involves the reduction
of nitrate 1NO3-2 into nitrogen gas 1N22. It is widely used in advanced wastewater
treatment for the removal of nitrogen. A carbon source is required, since the denitri-
fiers are heterotrophic organisms. Biological dissimilatory denitrification is typically
modeled as a two-step sequential reaction, as follows, when synthesis of biomass is
excluded and methanol 1CH3OH2 is used as the carbon source.
6 NO 3- + 5 CH 3OH
Denitrifiers " 3 N + 5 CO + 7 H O + 6 OH - (4.18)
2 2 2
Section 4.4 Nutrient Cycles 79
EXAMPLE 4.4
Denitrification stoichiometric coefficients
Calculate the stoichiometric coefficient for alkalinity production during denitrifica-
tion using Equation (4.18).
Solution
Deamination
Deamination or ammonification is the conversion of organic nitrogen to ammo-
nium/ammonia nitrogen 1NH4+/NH32. When plants and animals die, proteins are
first hydrolyzed by hydrolytic enzymes produced by bacteria. Specific types of bac-
teria are capable of removing the amino group 1NH22 from amino acids under
either aerobic or anaerobic conditions, releasing ammonia nitrogen and making it
available for recycling in the biosphere.
Water Column
Zooplankton Fish
Insoluble inorganic
Organic phosphorus
phosphates
Sediments
Figure 4.20
The phosphorus cycle.
Reduction: Desulfovibrio
H2S SO3
Sulfide Sulfates
S2 SO32
Oxidation: Thiobacillus
Organic S
Figure 4.21
Degradation/Mineralization R-SH Assimilation Schematic of simplified
sulfur cycle.
H2S + 2 O2
Sulfur Bacteria " H SO (4.22)
2 4
DO Concentration, mg/L
0 1 2 3 4 5 6 7 8
0
20
40
Depth, ft
60
80
100
120
Figure 4.22
DO profile for Norris Lake, September 5, 2007.
Source: http://tnfish.org/WaterQualitySampling_TWRA/.
(plant species such as algae) and zooplankton (animal species such as crustacean,
rotifers, and protozoa). Macrophytes are large aquatic plants that may be free
floating or attached to the bottom (emergent). Water-quality data for various
lakes are accessible by the internet. Typical data collected include: conductivity,
dissolved-oxygen (DO) concentration, pH, and temperature as a function of
depth. Figures 4.22 and 4.23 show the DO and temperature profile of Norris Lake
near Knoxville, Tennessee. Other water-quality data for Norris Lake and other
lakes in Tennessee may be accessed at the following website: http://tnfish.org/
WaterQualitySampling_TWRA/.
4.5.1 Stratification
Twice annually in temperate latitudes, normally during summer and winter, lakes
undergo stratification—i.e., formation of layers of water at different temperature
and density. Three distinct zones develop in a lake from the surface to the bottom:
the epilimnion, metalimnion, and hypolimnion, as shown in Figure 4.24. This phe-
nomenon is attributed to the affect of temperature on the density of water. Water
has a unique characteristic, in that the solid form (ice) has a lower density than the
liquid at 0°C. The maximum density occurs at a temperature of approximately 4°C.
At freezing, or 0°C, the ice that forms has a lower density than water at 4°C, so the
ice floats. Therefore, lakes freeze from the top down, making it possible for fish and
other aquatic life to live when ice covers the surface.
During the spring, energy from the sun heats the upper layer of water in the
lake (epilimnion), warming it from 0°C toward 4°C. The denser water sinks to the
bottom, creating currents that bring colder water to the surface. During this spring
Section 4.5 Limnological Concepts and Eutrophication 83
Temperature, F
0 10 20 30 40 50 60 70 80 90
0
20
40
Depth, ft
60
80
100
120
Figure 4.23
Temperature profile for Norris Lake, September 5, 2007.
Source: http://tnfish.org/WaterQualitySampling_TWRA/.
turnover, because of the mixing action, sediments along with nutrients re-enter the
water column. During both the spring and the fall turnover, the contents of the lake
are well mixed, resulting in uniform levels of temperature, dissolved oxygen, and
nutrients throughout the water column.
As spring turns into summer, the top layer or epilimnion continues to be heated,
so that a warm layer of water overlies the cooler, denser layers. The epilimnion is well
mixed, well oxygenated, and essentially has the same temperature throughout. Below
the epilimnion is a layer of more dense water known as the metalimnion. During sum-
mer stratification, a significant change in the temperature occurs with depth ( Ú 1°C
per meter of depth) in the metalimnion, and this temperature gradient is known as the
thermocline. Below the metalimnion is the bottom layer of water, the densest and
coolest one, known as the hypolimnion. The temperature in the hypolimnion is essen-
tially the same throughout. Figure 4.24 also shows the temperature and DO profile
during summer and winter stratification in a typical lake. Note that these profiles are
similar in shape to those presented in Figures 4.22 and 4.23. Figure 4.25 shows the mix-
ing patterns during spring and fall turnover, and the temperature profile during winter
and summer stratification of a typical lake.
During the fall, the temperature in the epilimnion decreases, resulting in denser
water overriding warmer water beneath it. Eventually it cools and sinks to the bot-
tom, causing the warmer water to be forced to the surface. This is known as the fall
turnover. It causes complete mixing of the lake, allowing sediments, organics, and
nutrients to re-enter the water column. As temperatures drop during the winter
months, the lake continues to cool, and ice forms at the surface that is less dense than
the cooler water below it. The temperature profile increases from 0°C at the surface
to 4°C, causing winter stratification of the lake.
84 Chapter 4 Biological and Ecological Concepts
Epilimnion Epilimnion
Metalimnion
Metalimnion
Hypolimnion
Hypolimnion
4C 0 mg/L DO
Epilimnion
Metalimnion
Hypolimnion
44˚C
C 0 mg/L DO
Figure 4.24
Lake stratification during summer and winter.
Ice Cover
0C 4C
2C 4C
4C 4C
4C
4C
25C
4C 4C
22C
20C
8C 8C
8C
7C
8C
6C 6C
Figure 4.25
Temperature and mixing profiles during turnover and stratification.
1.0 14.22
2.0 13.83
3.0 13.46
4.0 13.11
5.0 12.77
6.0 12.45
7.0 12.14
8.0 11.84
9.0 11.56
10.0 11.29
11.0 11.03
12.0 10.78
13.0 10.54
14.0 10.31
15.0 10.08
16.0 9.87
17.0 9.67
18.0 9.47
19.0 9.28
20.0 9.09
21.0 8.92
22.0 8.74
23.0 8.58
24.0 8.42
25.0 8.26
(DO) concentration will decrease with time and distance downstream from the
point of discharge. This process is known as deoxygenation; typically it is modeled
by a first-order reaction using the parameter, ultimate biochemical oxygen
demand (L):
where:
RDEOXYGENATION = rate of deoxygenation, equal to the rate at which oxygen
is being removed from a stream, mg/L # d,
kD = deoxygenation rate coefficient (base e), equal to the BOD rate con-
stant (k), d-1, and
L = ultimate biochemical oxygen demand (BOD), mg/L.
The ultimate BOD represents the total quantity of oxygen consumed by bacteria at
20°C for the oxidation of organic compounds to carbon dioxide and water.
As dissolved oxygen is being removed from the stream due to deoxygenation,
another process called reaeration is occurring simultaneously. Reaeration is the
process in which oxygen is transferred by diffusion across the water surface exposed
to the atmosphere. Water traveling over rocks and through rapids entrains more oxy-
gen than does a slower-moving river. The equilibrium or saturation concentration of
dissolved oxygen is estimated using Henry’s law and is a function of temperature.
Table 4.3 lists the DO concentrations in fresh water as a function of temperature. A
listing of reaeration-rate coefficients for various types of water bodies is presented in
Table 4.4. The reaeration process is modeled as a first-order reaction:
RREAERATION = - k2D (4.27)
where:
RREAERATION = rate of reaeration which is equal to the rate at which oxy-
gen is transferred into the stream or water body, mg/L # d,
k2 = reaeration rate coefficient (base e), d-1, and
D = dissolved-oxygen deficit, mg/L.
The DO deficit is the difference between the DO saturation concentration and
the actual or measured dissolved-oxygen concentration in the water:
D = DOsat - DO (4.28)
where:
D = DO deficit, mg/L,
DOsat = DO saturation concentration at a specified temperature and pres-
sure, mg/L, and
DO = actual or measured DO concentration in the water, mg/L.
Figure 4.26 shows a plot of DO versus time of travel in a river.The concepts of deoxy-
genation and reaeration are illustrated in this figure.
DO Saturation Concentration
Critical
Deficit
Reaeration Rate
Exceeds Deoxygenation Rate
Deoxygenation Rate
Exceeds Reaeration Rate
Figure 4.26
DO versus time. Time of Travel
dD
= kDL - k2D (4.29)
dt
where:
L = Lo e-kD t (4.30)
where:
Lo = ultimate BOD concentration after the stream and wastewater discharge
have mixed, mg/L,
t = time of travel of wastewater discharge downstream, days, and
e = base “e”, 2.71828.
Section 4.5 Limnological Concepts and Eutrophication 89
dD
= kDLoe-kD t - k2D (4.32)
dt
Equation (4.32) may be integrated using the boundary conditions at t 0,
D D0, and L = Lo , and at t = t, D = Dt , and L = Lt , resulting in the general
form of the Streeter-Phelps Equation (4.33) used for estimating the DO deficit
at downstream locations from the point of discharge:
kDLo
Dt = C e1-kDt2 - e1-k2t2 D + Doe1-k2t2 (4.33)
k2 - kD
where:
Dt = DO deficit at any time t, downstream of the discharge point, mg/L,
t = time of travel of wastewater discharge downstream, days, and
Do = DO deficit at the point of discharge, mg/L.
To calculate the DO deficit at the point of discharge, the DO concentration at
the point of discharge must be calculated using Equation (4.34).
Qstream 1DOstream2 + Qww 1DOww2
DOo = (4.34)
Qstream + Qww
where:
DOstream = DO concentration of stream prior to wastewater discharge,
mg/L, and
DOww = DO concentration of wastewater, mg/L.
The DO deficit 1Do2 at the point of discharge can then be calculated using Equa-
tion (4.35).
Do = DOsat - DOo (4.35)
Both the reaeration 1k22 and deoxygenation 1kD2 rate coefficients must be
corrected for temperature variations other than 20°C. Metcalf and Eddy (1991)
recommend the following temperature-correction coefficients 1u2 for adjusting
these rate coefficients for temperature variations. A theta 1u2 value of 1.024 should
be used for correcting k2 . The deoxygenation 1kD2 rate coefficient should be cor-
rected with a 1u2 value of 1.145 when the temperature is … 20°C and 1.056 when
the temperature is between 20 and 30°C.
The maximum dissolved-oxygen deficit will occur where the reaeration rate
equals the deoxygenation rate. This point is known as the critical point, and the time
required to reach it can be determined by differentiating Equation (4.33) and set-
ting the derivative equal to zero. Solving for time gives:
1 k2 Do 1k2 - kD2
tc = ln B ¢1 - ≤R (4.37)
k2 - kD kD kDLo
where tc = time of travel to the critical deficit point in the stream, days.
The distance traveled (x) for a river flowing at a constant velocity (u) can be deter-
mined by multiplying the stream velocity by the travel time (t). Example 4.5 illustrates
how to use the Streeter-Phelps equations for locating the critical deficit point in a stream.
EXAMPLE 4.5
Calculating critical deficit point in a stream
A municipal WWTP discharges 22.5 million gallons per day of secondary effluent
containing 30 mg/L of ultimate BOD at 26.7°C with 1.5 mg/L of dissolved oxygen.
The stream flow is 161 cubic feet per second (cfs) at a velocity of 1.5 feet per second
(fps) and an average depth of 5 ft. The temperature of the stream before the waste-
water enters is 21°C. The stream is 85% saturated with oxygen and has an ultimate
BOD of 2.0 mg/L. The reaeration 1k22 and deoxygenation 1kD2 rate coefficients are
0.35 d-1 and 0.20 d-1, respectively at 20°C. Determine the following:
a. the wastewater flow rate in cfs;
b. the temperature of the combined wastewater and stream;
c. the dissolved-oxygen concentration of the mixture of wastewater and
stream;
d. the DO deficit of the mixture of wastewater and stream;
e. the ultimate BOD concentration of the mixture of wastewater and stream;
f. the distance downstream 1xc2 to the point of minimum DO concentra-
tion, and
g. the minimum DO concentration in stream. Also:
h. Plot the DO deficit versus time starting at 0 and going to 3.0 days in incre-
ments of 0.1 day.
Solution part a
The wastewater flow rate is converted from million gallons per day to cubic feet per
second to be consistent with the flow units for the stream. Alternatively, the stream-
flow units of cfs could be converted to million gallons per day.
Solution part b
The temperature of the mixture of the stream and wastewater is determined as follows:
Qstream 1Tstream2 + Qww 1Tww2 161 cfs121°C2 + 34.8 cfs126.7°C2
To = = = 22°C
Qstream + Qww 161 cfs + 34.8 cfs
Solution part c
Determine the DO concentration of the combined water and wastewater at the point of
discharge. The DO concentration in the stream above the discharge is estimated as fol-
lows.The DO saturation in water at 21°C is 8.92 mg/L; however, the stream is only 85%
saturated, therefore the saturated concentration must be multiplied by 0.85, as follows:
DOstream = 0.8518.92 mg>L2 = 7.6 mg>L
Qstream 1DOstream2 + Qww 1DOww2
DOo =
Qstream + Qww
161 cfs17.6 mg>L2 + 34.8 cfs11.5 mg>L2
= = 6.5 mg>L
161 cfs + 34.8 cfs
Solution part d
Calculate the initial oxygen deficit 1Do2 at the point of discharge. First, look up in
Table 4.3 the DO saturation concentration of water at 22°C (the temperature of the
mixture of water and wastewater), which is 8.74 mg/L.
Do = DOsat - DOo = 8.74 mg>L - 6.5 mg>L = 2.2 mg>L
Solution part e
Determine the ultimate BOD concentration 1Lo2 of the mixture of water and
wastewater at the point of discharge.
Qstream 1Lstream2 + Qww 1Lww2 161 cfs12.0 mg>L2 + 34.8 cfs130 mg>L2
Lo = =
Qstream + Qww 161 cfs + 34.8 cfs
= 7.0 mg>L
Solution part f
Next, correct the reaeration and deoxygenation rate coefficients for the tempera-
ture of 22°C. Use theta values 1u2 of 1.024 and 1.056 for correcting k2 and kD ,
respectively.
Determine the time of travel 1tc2 to reach the point of minimum DO in the stream.
1 k2 Do1k2 - kD2
tc = ln B ¢ 1 - ≤R
k2 - kD kD kDLo
mg
-1 2.2 10.37 - 0.22 d-12
1 0.37 d L
tc = -1 -1
ln C £1 - ≥ S = 1.9 days
0.37 d - 0.22 d 0.22 d-1 0.22 d-117.0 mg>L2
92 Chapter 4 Biological and Ecological Concepts
Solution part g
The value of the minimum deficit is found by substituting the critical time 1tc2 into
Eq. (4.33).
kDLo
Dc = C e1-kDtc2 - e1-k2tc2 D + Doe1-k2tc2
k2 - kD
Solution part h
A plot of the dissolved oxygen deficit versus time from 0 to 3.0 days in increments of
0.1 days is presented in the following figure. Notice the deficit at the critical time of
1.9 days is 2.8 mg/L.
3.00
Dc 2.8
2.50
Dissolved oxygen deficit, mg/L
2.00
1.50
1.00
0.50
0.00
0.0 0.5 1.0 1.5 tc 1.9 2.0 2.5 3.0 3.5
Time of travel, days
References 93
S U M M A RY
This chapter introduced the basic concepts of biology and ecology that are important
to environmental engineers. Ecology was defined as the branch of biology dealing
with the interrelationships between living organisms and the interactions between
these organisms and their environment. Biological concepts were presented in
which the cell was described as the basic functional and structural unit of all living
organisms. The taxonomic classification of organisms based on genus and species
was discussed. This was followed by a description of the major groups of organisms
encountered in environmental problems: algae, bacteria, crustaceans, fish, fungi,
helminths, macrophytes, protozoa, rotifers, and viruses. Microbial growth rate and
the equations used for modeling microbial growth were presented. The importance
of photosynthesis and the flow of energy from the sun through ecosystems was
explained. Food chains consisting of primary producers (plants and algae) that are
consumed by primary and secondary consumers (herbivores and carnivores) allow
energy to be transferred through the biosphere. Bioconcentration of a toxic com-
pound involves the uptake of the compound into an organism from the aqueous
phase whereas bioaccumulation is the magnification in concentration of a com-
pound as it passes up through food chains. The use and recycling of nutrients in
ecosystems was discussed by presenting the carbon, nitrogen, phosphorus, and sulfur
cycles. The chapter concluded with an introduction to limnology, the study of the
physical, chemical, and biological characteristics of fresh water lakes and rivers. The
Streeter-Phelps Dissolved Oxygen Sag Model was presented along with an example
problem to illustrate how the discharge of municipal wastewater effluent can lead to
low dissolved oxygen levels in receiving streams.
REFERENCES
American Public Health Association, American Water Works Association, Water Environment
Federation (1998). Standard Methods for the Examination of Water and Wastewater, 20th ed.,
American Public Health Association, Washington, DC.
Benefield, L.D., and Randall, C.W. (1980), Biological Process Design for Wastewater Treatment,
Prentice Hall, Englewood Cliffs, NJ.
Brock, T.D. (1979). Biology of Microorganisms, Prentice Hall, Englewood Cliffs, NJ.
Crites, R., and Tchobanoglous, G. (1998). Small and Decentralized Wastewater Management
Systems, WCB/McGraw-Hill, New York, NY.
Davis, M.L., and Masten, S.J. (2004). Principles of Environmental Engineering and Science,
McGraw Hill, New York, NY.
Environmental Protection Agency (1985). Design Manual Odor Control and Corrosion Control
in Sanitary Sewerage Systems and Treatment Plants, EPA/625/1-85/0187, Office of Research
and Development, Washington, DC.
Environmental Protection Agency (1993). Manual Nitrogen Control, EPA/625/R-93/010,
Office of Research and Development, Washington, DC.
94 Chapter 4 Biological and Ecological Concepts
EXERCISES
4.1 The following chemical formula is often used for representation of a bacterial
cell, C60H87O23N12P1 .
(a) Determine the mass (mg) of each element in 3000 mg of bacterial cells.
(b) Suppose 25 mg/L of ammonia nitrogen and 5 mg/L of orthophosphate as
phosphorus are available for growing bacteria. If other nutrients are in
abundance, which is the limiting nutrient—nitrogen or phosphorus?
(c) What mass of bacterial cells could be produced in terms of milligrams of
bacterial cells per liter of water based on the limiting nutrient in Part b?
(d) Suppose the nitrogen source was cut to 15 mg/L of ammonia nitrogen.
How much bacterial cell mass (mg/L) could be produced?
(e) Suppose the phosphorus source was cut to 4 mg/L of orthophosphate as
phosphorus. How much bacterial cell mass (mg/L) could be produced?
4.2 The term C10H19O3N1 is often used to represent the biodegradable organic
material in wastewater. In the past, most biological denitrification processes
occurred after aerobic treatment of the wastewater, necessitating the addition
of a carbon source such as methanol 1CH3OH2. If the denitrification process
precedes aerobic treatment, the organic matter in the influent wastewater can
serve as the carbon source for denitrification. The following stoichiometric
Exercises 95
(a) Calculate the quantity (grams) of alkalinity as CaCO3 consumed per gram
of ammonium nitrogen 1NH4+ - N2 oxidized.
(b) How does this compare with the alkalinity consumption from
Equation (4.15)?
(c) Calculate the quantity (grams) of oxygen required per gram of NH4+ - N
oxidized.
(d) How does this compare with the oxygen consumption from Equation (4.15)?
4.4 A continuous-flow, completely mixed reactor was operated at various flow
rates to collect specific growth-rate data. The specific microorganism growth
rate and soluble substrate concentration data are presented below.
S (mg/L) M(h-1)
20.0 0.66
10.0 0.50
6.6 0.40
5.0 0.33
4.0 0.28
(a) Determine the maximum specific microorganism growth rate 1mm2 and
the half-velocity rate constant (Ks) by making a double-reciprocal plot
(Lineweaver-Burke Plot) of Equation (4.2). Plot 1 versus S1. See
linearized form of Equation (4.2) below:
1 KS 1 1
= +
m mmax S mmax
Alternatively, the above coefficients may be found by using the Solver
function in Excel.
(b) Give the magnitude and units for each of the coefficients determined.
96 Chapter 4 Biological and Ecological Concepts
4.5 A pure culture of bacteria was grown at 25°C under batch conditions. The fol-
lowing experimental data were collected.
1 Q3Si - Se4
= Y¢ ≤ - kd
SRT XV
A plot of 1/SRT versus Q1Si - Se)/1XV2 yields a slope equal to Y, the yield
coefficient, and the endogenous decay coefficient 1kd2 as the Y-intercept.
Determine the magnitude and units for Y and kd , given the following data
collected on a continuous-flow activated sludge bench-scale unit.
4.7 Draw a simplified food chain with at least four trophic levels of organisms in
a fresh-water pond feeding on plankton.
4.8 Draw a sketch of a lake in the Northern Hemisphere, and label and describe
the epilimnion, hypolimnion, and thermocline. Explain what happens during
spring turnover and summer stratification.
4.9 Draw a simplified diagram showing the major carbon forms comprising the
carbon cycle.
4.10 An industrial WWTP discharges into a large river 0.5 m3/s of industrial waste-
water containing an ultimate BOD concentration of 220 mg/L at a temperature
Exercises 97
of 26°C and a DO concentration of 2.0 mg/L. The velocity of the river is 0.85
m/s. Upstream of the point of discharge, the river has a temperature of 12°C, an
ultimate BOD of 15 mg/L, and flow rate of 2.5 m3/s. The deoxygenation- and
reaeration-rate coefficients are 0.2 d-1 and 0.4 d-1 at 20°C.
(a) Calculate the dissolved-oxygen concentration (mg/L) at the point of
discharge.
(b) Calculate the dissolved-oxygen deficit 1Do2 in mg/L at the point of
discharge.
(c) Calculate the ultimate biochemical oxygen demand 1Lo2 in mg/L at the
point of discharge.
(d) Calculate the dissolved-oxygen deficit (mg/L) 50 km downstream, assuming
that the temperature in the river remains the same as at the point of
discharge.
(e) Calculate the dissolved-oxygen concentration (mg/L) 50 km downstream,
assuming that the temperature in the river remains the same as at the point
of discharge.
CHAPTER
5
Risk Assessment
Table 5.1 Fifteen Leading Causes of Death in the United States, 2004
Cause Annual deaths Risk (%)
1. Heart disease 654,092 27.3
2. Malignant neoplasms (cancer) 550,270 22.9
3. Cerebrovascular (strokes) 150,147 6.3
4. Chronic low respiratory disease 123,884 5.2
5. Accidents (unintentional injury) 108,694 4.5
6. Diabetes mellitus 72,815 3.0
7. Alzheimer’s disease 65,829 2.7
8. Influenza and pneumonia 61,472 2.6
9. Nephritis 42,762 1.8
10. Septicemia 33,464 1.4
11. Suicide 31,647 1.3
12. Chronic liver and cirrhosis 26,549 1.1
13. Essential hypertension and hypertensive renal disease 22,953 1.0
14. Parkinson’s disease 18,018 0.8
15. Pneumonitis due to solids and liquids 16,959 0.7
All other causes 418,810 17.5
Table 5.1 lists the fifteen leading causes of death in the United States during
2004. Cardiovascular or heart disease was the leading cause of death and cancer was
the second leading cause. Neglecting age, gender, and ethnicity, an American’s risk of
dying from heart disease is estimated at 27.3% (or, expressed first as a fraction,
654,092/2,398,365 = 0.273). According to Wilson and Crouch (2001), there are about
40,000 fatalities per year from automobile accidents. The annual risk of dying in a
motor vehicle accident is approximately 40,000/2,398,365 = 0.017 or 1.7%.
EXAMPLE 5.1
Calculating risk
Using the data in Table 5.1, estimate the risk or probability of an American dying from
influenza (flu) or pneumonia in 2004. Express the risk as a fraction and as a percentage.
Solution
First, identify the number of individuals who died from influenza and pneumonia in
2004 from Table 5.1. There were 61,472 deaths attributed to this category, which
ranked eighth.
Second, from Table 5.1, identify the total number of deaths recorded in the
United States during 2004, which was 2,398,365.
100 Chapter 5 Risk Assessment
Next, calculate the risk or probability of dying from the flu or pneumonia by
dividing the number of deaths attributed to flu or pneumonia by the total number of
deaths recorded for 2004:
61,472
risk = = 0.026 or 2.60 %
2,398,365
EXAMPLE 5.2
Additional risk calculation
Bath County, Virginia, is located in the northwest portion of the state. The county
population is approximately 5000. Using the data from Table 5.1, estimate the num-
ber of persons in Bath County who died from cancer in 2004. Assume that 100 per-
sons passed away in Bath County in 2004.
Solution
First, in Table 5.1, look up the risk or percentage of Americans dying from can-
cer in the United States. In 2004, approximately 22.9% 1risk = 550,270/
2,398,365 * 100 = 22.9%2 of the deaths in the United States were attributed to
some form of cancer.
Next, estimate the number of persons dying from cancer in Bath County by
multiplying the number of deaths in Bath County for 2004 (100) by the risk or frac-
tion of deaths attributed to cancer in the entire United States 122.9/100 = 0.2292.
100 * 0.229 = 22.9 ⬵ 23
The number of persons dying from cancer in Bath County is estimated to be approx-
imately 23.
Activities that increase mortality risk by one in a million 110-62 are presented
in Table 5.2. Each of these activities produces essentially the same amount of risk.
Living 2 summer months in Denver on vacation from New York Cancer by cosmic radiation
Section 5.2 Risk Assessment 101
Risk of accident by living within 8 km (5 mi) of a nuclear reactor for 50 years Cancer caused by radiation
Source: Wilson, 1979.
Smoking 1.4 cigarettes has the same probability or risk of causing death as driving
484 km (300 miles) in a car. A person has a one-in-a-million chance of dying from
drinking 0.5 liters of wine or from living for 50 years within an 8-km (5-mile) radius
of a nuclear reactor.
In this chapter, we will focus on the risk to human health due to the release of
chemicals and pollutants into the environment.
Exposure Toxicity
Assessment Assessment
Risk
Characterization
Risk
Management
102 Chapter 5 Risk Assessment
Hazard Identification
Hazard identification is the process of determining whether exposure to a chemical,
biological, or physical agent (toxicant) is linked to a particular health effect such as
cancer or birth defect. This stage of the process relies on toxicity studies performed
on animals, such as mice and rats, or animal tissue. Since living organisms are used,
such tests are called bioassays.
Once in the body, the toxicant is absorbed by the blood and transported
throughout the body, where it may accumulate in tissues and organs, be transformed
into less innocuous compounds or more harmful metabolites, and/or excreted in
urine and feces. For example, both the liver and kidneys are susceptible to chlori-
nated organic compounds and heavy metals.
Some toxicants promote acute toxicity, whereas others accumulate over time,
causing chronic toxicity. Chronic toxicity may result in mutagenesis—mutation of the
genetic material, deoxyribonucleic acid (DNA). This may lead to cancer, tumors, birth
defects, or miscarriages and other reproductive failure. Toxicants capable of causing
cancer are called carcinogens and those causing birth defects are called teratogens.
Dose-Response Assessment
Dose-response assessment is the process of evaluating the relationship between the
level of exposure to the toxicant and the incidence and extent of adverse effect on
the exposed individual (animal, human, cell, tissue). The response to the agent may
be carcinogenic or noncarcinogenic and the tests conducted may be short-term
acute tests or long-term chronic tests.
Section 5.2 Risk Assessment 103
100
Cumulative
Mortality
Percent
50
0 Figure 5.2
1 10 LD50 100 1000 10000 Typical dose-response
Dose (mg/kg) mortality curve and LD50.
The dose of a toxicant is a major factor determining the level of harm caused.
Dose is defined as the mass of chemical received by the exposed individual or ani-
mal, with units expressed in milligrams per kilogram (mg/kg) of body weight. It is not
unusual to express the dose with units of time if the individual or animal receives the
compound over time. Typical units would be expressed as milligrams per kilogram
per day 1mg/kg # d2. (Although they share similar units, the concentration of a com-
pound or toxicant is not the same as the dose. Concentration is related to the mass of
the compound per unit volume in the ambient air, soil, or water.)
One way to predict the toxicity of a chemical is to perform acute-toxicity tests
on rats or mice. The quantity of a specific chemical that is required to kill the organ-
ism is determined. The relationship between dose and response of a population of
living organisms normally follows a logistic or S-shape curve, as shown in Figure 5.2.
This curve is developed by exposing the test organisms to increasing doses of a spe-
cific toxic compound. As the dose is increased, the number of deaths also rises. Dose
expressed in mg of toxicant per kilogram of body weight (mg/kg) is plotted on the
abscissa scale versus the cumulative mortality (number of deaths). The dose at
which 50% of the organisms die is called the median lethal dose (LD50).
Carcinogenic Effects Instead of mortality, the response could be reported as the
probability or risk of causing cancer. Figure 5.3 shows dose-response curves for
Figure 5.3
Typical carcinogenic
dose-response curves.
Carcinogen
Linear
Cumulative
Response
or
Risk
Carcinogen
Non-linear
Dose
104 Chapter 5 Risk Assessment
Non-Carcinogen
Non-Linear
Cumulative
Response
or
Risk
Figure 5.4
Typical noncarcinogenic
dose-response curve. Dose
carcinogenic agents. This type of response curve is typically used for evaluating the
risks associated with carcinogens. For carcinogens, it is assumed that a threshold
level does not exist, since there is a cancer risk associated with all doses. Dose-
response curves can be developed for both acute and chronic toxicity; however, we
are generally more interested in the long-term, chronic studies, as they are generally
linked to cancer. There is no absolute scale for toxicity; therefore it is only possible
to state that one compound is more or less toxic than another, due to its effects on
animals and humans.
Noncarcinogenic Effects Figure 5.4 shows a dose-response curve for a noncarcino-
genic agent. The dose-response curves for noncarcinogens indicate there is some expo-
sure threshold to the toxicant that results in an adverse effect on the animal or human.
Below this threshold level, no adverse effect will result. Toxicity tests are performed
to identify and determine the magnitude of these thresholds. The lowest dose
administered during testing that elicits an adverse response is called the lowest-
observed-adverse-effect level (LOAEL), while the highest dose administered that
does not create an adverse effect is termed no-observable-adverse-effect level
(NOAEL).
Figure 5.5 illustrates a dose-response curve for a noncarcinogenic toxicant
along with the NOAEL, LOAEL, and reference dose (RfD). The reference dose is
estimated by dividing the NOAEL by an uncertainty factor, which typically is 10,
Figure 5.5
Non-Carcinogen
Reference dose, NOAEL,
LOAEL for noncarcinogenic
compound.
Cumulative
Response
or
Risk NOAEL
Actual
RfD Threshold
LOAEL
Dose (mg/kg·day)
Section 5.2 Risk Assessment 105
Arsenic 0.0003
Benzene 0.004
Chlorine 0.100
Chloroform 0.010
Nitrate 1.60
Phenol 0.300
Strontium 0.600
Xylenes 0.200
100, or 1000. These numbers reflect the uncertainty associated with the variability of
response to the toxicant by humans and animals, extrapolation from high compound
doses in animals to a low dose in humans, and lacking or incomplete data sets. An
uncertainty factor of 10 is used if there is minimal uncertainty, and the value
increases to 1000 with less certainty. Table 5.3 lists the oral reference doses for
chronic, noncarcinogenic effects of several chemicals.
where:
P1d2 = lifetime risk or probability of cancer, dimensionless,
d = dose of toxicant or chemical, and
q0 and q1 = parameters that are picked to fit the data set.
106 Chapter 5 Risk Assessment
The background rate for the incidence of cancer, P(0), may be estimated by
substituting a value of zero for d into Equation (5.1):
x2 x3 x4 xn
ex = 1 + x + + + + Á (5.3)
2! 3! 4! n!
For small values of x, this expansion can be expressed as:
ex ⬵ 1 + x (5.4)
Substituting this result into Equation (5.2), the background rate for cancer
incidence, P(0), can be expressed as:
At low doses, then, the additional risk of cancer above the background level
can be expressed as follows:
where the qi are positive constants selected to yield the best fit to the response-dose
data. It is easy to see that Equation (5.1) for the one-hit model is a special case of the
multistage model.
When we perform toxicological tests on carcinogenic compounds in animals,
two major problems arise. First, how do we extrapolate the data collected at high
doses down to low doses? Second, will the response exhibited by the animal popula-
tion be the same, lower, or higher than in humans?
The Environmental Protection Agency uses a modified multistage model
called the linearized multistage model, replacing the linear term in the polynomial
function with its 95% confidence limit to achieve a more stable estimate. This model
assumes a linear relationship between risk and dose at low doses. The slope of the
dose-response curve is called the slope factor (SF) or potency factor (PF). Slope fac-
tors for several chemical compounds are presented in Table 5.4.
The EPA maintains a database with background information on the toxicolog-
ical properties of selected compounds called the Integrated Risk Information Sys-
tem (IRIS). The slope factors for oral and inhalation exposure routes for these
compounds may be found there.
Section 5.2 Risk Assessment 107
Table 5.4 Slope Factors for Selected Chemicals for Oral Route
Chemical Slope factor (kg.day/mg)
Arsenic 1.5
Benzene 1.5 * 10-2 to 5.5 * 10-2
Heptachlor 4.5
2,4,6-trinitrotoluene 3 * 10-2
A generic equation for estimating chronic daily intake (CDI) is given as Equa-
tion (5.11). Table 5.5 lists some of the equations used for calculating CDI for various
exposure routes. Definitions and units for each parameter in Table 5.5 are listed after
Equation (5.11).
C * IR * EF * ED
CDI = (5.11)
BW * AT
where:
AT = averaging time, the period over which exposure is averaged, d,
BW = body weight, the average body weight over the exposure period, kg,
C = chemical concentration, the average concentration contacted over the
exposure period (e.g., mg/L for water),
CDI = chronic daily intake, mg/kg # d,
ED = exposure duration, yr,
Section 5.2 Risk Assessment 109
EXAMPLE 5.3
Calculating chronic daily intake
Estimate the chronic daily intake (CDI) of arsenic from exposure to a city water
supply that contains an arsenic concentration of 0.010 mg/L, the maximum contam-
inant level (MCL) established by the Environmental Protection Agency. Suppose
that a 70-kg person consumes 2 L of water each day for 70 years. Determine the
chronic daily intake (CDI) of arsenic in mg/kg # d.
110 Chapter 5 Risk Assessment
Solution
Substitute the above values into Equation (5.11) to calculate the CDI.
mg L 365 d
a0.010 b * a2.0 b * a b * 170 yr2
C * IR * EF * ED L d yr
CDI = =
BW * AT 365 d
170 kg2 * 170 yr2a b
yr
mg
= 2.86 * 10-4
1kg # d2
At high doses of carcinogenic compounds (with risk above 0.01), risk is calcu-
lated using a modified form of Equation (5.2):.
If several carcinogenic compounds are involved, the risks are added together
to calculate the overall risk to the individual.
EXAMPLE 5.4
Risk calculations using CDI and slope factors
Using the chronic daily intake (CDI) value of 2.86 * 10-4 mg # kg-1 # d-1 determined
in Example 5.3 along with the other data provided, determine:
a. The upper-bound cancer risk per person.
b. The number of extra cancers that would be expected per year in a city of
100,000 people if they consumed the same water containing arsenic.
Solution part a
Determine the upper-bound cancer risk for this person by substituting into Equa-
tion (5.12). First, obtain from Table 5.4 the slope factor for arsenic by the oral route,
which is 1.5 kg # d # mg-1.
Section 5.2 Risk Assessment 111
Solution part b
Finally, the number of extra cancers that would be expected per year in a city of
100,000 is calculated by multiplying the incremental lifetime cancer risk by the pop-
ulation of the city and dividing by the 70-year period.
cancers city population
= incremental lifetime cancer risk *
year exposure duration
100,000 people
= 4.29 * 10-4 a b = 0.61
70 yr
The extra number of cancers expected per year in the city described is 0.61.
EXAMPLE 5.5
Calculating hazard index
Suppose a 70-kg adult drinks 2.0 liters per day of water for a 20-year period. Assume
that the water contains 0.05 mg/L of chloroform and 0.6 mg/L of nitrates.
a. Determine the hazard index and state whether this is acceptable or
unacceptable.
b. Chloroform is a potential carcinogen. Determine the carcinogen risk associ-
ated with drinking water containing 0.05 mg/L of chloroform. Would it meet
the goal of 1 * 10-6 that is usually recommended by EPA?
Solution part a
First, the CDI for chloroform is estimated. From Table 5.5, use the following equa-
tion for ingestion of drinking water.
112 Chapter 5 Risk Assessment
CW * IR * EF * ED
CDI =
BW * AT
10.05 mg>L2 * 12.0 L>d2 * 1365 d>yr2 * 120 yr2
CDI = = 1.43 * 10-3 mg>kg # d
170 kg2 * 1365 d>yr2 * 120 yr2
Second, locate in Table 5.3 the reference dose (RfD) for chloroform, which is
0.010 mg/kg # day. Third, calculate the HI for chloroform using Equation (5.14).
Solution part b
First, recall that incremental lifetime cancer risk is estimated using Equation (5.12).
Second, the slope factor for chloroform for the oral exposure route is deter-
mined from Table 5.4 as 6.1 * 10-3 kg # d # mg-1.
Third, calculate the incremental cancer risk of drinking this water over a lifetime
using Equation (5.12). Use the CDI value of 1.43 * 10-3 mg # kg-1 # d-1 calculated in
Part a for chloroform
incremental lifetime cancer risk = CDI * slope factor
incremental lifetime cancer risk = 11.43 * 10-3 mg # kg-1 # d-12
* (6.1 * 10-3 kg # d # mg-12
incremental lifetime cancer risk = 8.72 * 10-6
From a cancer-risk perspective, this drinking water would not meet the accept-
able risk goal of 1 * 10-6 normally used by EPA, since 8.72 * 10-6 7 1 * 10-6.
risk, the potential to create more risk (e.g., where dredging sediments may result in
the release of contaminants into the water column), statutory requirements, and
public opinion. Ultimately, risk analysis is the basis for decisions on implementing
and enforcing drinking-water and wastewater effluent standards; defining accept-
able exposure doses; locating industries, landfills, and wastewater treatment facili-
ties; and establishing the desired level of cleanup at a hazardous waste site.
where:
EI = environment impact (dimensionless),
IFi = importance factor for ith environmental concern (ranges from 0 to 5),
MFi = magnitude factor for ith environmental concern (ranges from 0 to 5),
Ei = effect term for the area of environmental concern, +1 for beneficial or
positive effect, and -1 for detrimental or negative effect, and
n = number of areas of environmental concern.
Example 5.6 illustrates the assessment procedure for an overly simplified envi-
ronmental impact analysis using Equation (5.15) and the procedure just discussed.
Evaluation
The final step in writing the environmental impact statement is to analyze the
results obtained from performing the assessment. Final conclusions are developed
and presented in this step. These conclusions will be used by the public, politicians,
and regulatory agencies in making the final decision to proceed, or not, with the pro-
posed project. Often, common sense does not win out.
EXAMPLE 5.6
Simplified environmental assessment problem
A city is considering two alternatives for handling sludge that will be produced at its
new wastewater treatment facility (WWTF). The first alternative involves incinera-
tion of the stabilized sludge, with disposal of the ash to a landfill. The second alter-
native is to truck the stabilized sludge offsite and apply it to agricultural land near
the new proposed WWTF.
Solution
The best way to solve this problem is to use a spreadsheet. First, set up two tables,
listing environmental concerns in Column 1. Second, select Importance Factors
(IF) and Magnitude Factors (MF) ranging from 0 to 5 for each concern. Third, place
the effect term (E) in Column 4. Recall that E has a value of +1 for a beneficial
effect and -1 for a detrimental effect. Fifth, calculate the environmental impact
(EI) for each area of concern by using Equation (5.15), as presented in Column 5.
Finally, calculate the overall EI for each alternative by summing the values in
Column 5. This procedure is repeated for the second alternative, truck sludge off-
site and apply to land.
The overall environmental impact (EI) value for Alternative 1 is - 40, versus
-68 for Alternative 2. Based on this simplified assessment procedure, Alternative 1,
incineration of the stabilized sludge with the remaining ash disposed of in a landfill,
would be selected to minimize adverse effects on the environment. Keep in mind that
these types of analyses are subjective and the results will vary significantly, depend-
ing on the individual performing the assessment. A cost-benefit analysis will eventu-
ally be performed for the two alternatives, and it is highly likely that the cost of
implementing Alternative 2 will be significantly less than that for Alternative 1. Ulti-
mately, capital costs along with operating and maintenance (O & M) costs, rather
than environmental impact assessments, often end up driving political decisions.
a) Cover Sheet
b) Summary
c) Table of Contents
d) Purpose of and Need for Action
e) Alternatives Including Proposed Actions
f) Affected Environment
g) Environmental Consequences
h) List of Preparers
i) List of Agencies, Organizations, and Persons to Whom Copies of EIS Sent
j) Index
k) Appendices
116 Chapter 5 Risk Assessment
Environmental Consequences The scientific and analytical basis for the pro-
posed project and alternatives is presented in this section. Major items to be cov-
ered include: the environmental impact of the proposed project and alternatives;
adverse effects that cannot be avoided if the proposed project is implemented; the
relationship between short-term uses of the environment and the sustainability of
long-term productivity; and any irreversible or irretrievable commitments of
resources that would be involved if the proposed project were implemented.
Alternatives Including the Proposed Action This section is the heart of the envi-
ronmental impact statement. The environmental impacts of the proposed project
and alternatives are compared, so that decision makers and the public have a clear
choice among the options. Specific areas that must be addressed are listed below:
S U M M A RY
Risk relates to the probability that an adverse effect or outcome will occur. Risk has
no units; it is expressed as a fraction or a percentage. The Environmental Protection
Agency normally sets contaminant concentration levels in air, water, and soil so that
the risk of developing cancer is one additional cancer per million 110-62 or one hun-
dred additional cancers per million people 110-42. In most scenarios, a risk of one-
in-a-million is normally used.
Risk assessment is the scientific methodology used by engineers, scientists, and
regulators to quantify risk of a contaminant’s adverse effect on human health and the
environment. Four major steps involved in risk assessment include: data collection
and evaluation, toxicity assessment, exposure assessment, and risk characterization.
Two types of chemicals or toxicants evaluated by EPA are carcinogenic and
noncarcinogenic compounds. Dose-response curves are developed from acute- and
chronic-toxicity studies. For noncarcinogens, a threshold level exists such that no
adverse effect is produced at concentrations below this value. Threshold values for
carcinogenic compounds do not exist, since exposure to even small doses might
induce a cancer response.
The EPA uses a linearization of the multistage model for modeling the effect
of a toxicant from animal studies to human populations. A toxicant can enter the
body by three pathways: inhalation (air), ingestion (food and liquids), and absorp-
tion (dermal through skin or eyes). Exposure media include surface water, ground-
water, sediment, soil and dust, air, and food. Various equations were presented for
calculating the chronic daily intake (CDI) value through the various exposure
routes. These values are used in conjunction with a reference dose to calculate the
Exercises 117
REFERENCES
Centers for Disease Control (2007). Death and Death Rates for 2004 and Age-Adjusted Death
Rates and Percent Changes in Age-Adjusted Rates from 2003 to 2004 for the 15 Leading
Causes of Death: United States, Final 2003 and Preliminary 2004. http://webappa.cdc.gov,
accessed June 20, 2007.
Crump, K.S. (1984). An Improved Procedure for Low-Dose Carcinogenic Risk Assessment
from Animal Data, Journal of Environmental Pathology, Toxicology, and Oncology, 5-4(5):
339–348.
Environmental Protection Agency (2007). http://www/epa/gov/IRIS, accessed June 24, 2007.
Environmental Protection Agency (1991). Risk Assessment Guidance for Superfund.Volume 1.
Human Health Evaluation Manual, Supplemental Guidance “Standard Default Exposure
Factors” Interim Final. Office of Emergency and Remedial Response, Toxics Integration
Branch, U.S. Environmental Protection Agency, Washington, DC.
Environmental Protection Agency (1989). Risk Assessment Guidance for Superfund.Volume 1.
Human Health Evaluation Manual (Part A), EPA/540/1-89/002.
Vesilind, P.A., and Morgan, S.M. (2004). Introduction to Environmental Engineering, 2nd ed.,
Brooks/Cole, Belmont, CA.
Wilson, R. (1979). Analyzing the Daily Risks of Life, Technology Review, 81(4): 41–46.
Wilson, R., and Crouch, E.A.C. (2001). Risk Benefit Analysis, Harvard University Press, Digital
Design Group, Newton, MA.
EXERCISES
5.1 Estimate the number of persons who would die annually from smoking a
pack of cigarettes daily in a city of 200,000 people. Assume the risk of smok-
ing a pack of cigarettes each day is 3.6 * 10-3. Calculate the risk of dying per
year from cigarette smoking if a person lives 70 years.
5.2 Consider the lifetime health risk of drinking water containing 0.02 mg/L of
DDT for a 70-kg adult. The slope factor for DDT as estimated by EPA is
3.4 * 10-1 1kg # day/mg2. Estimate the annual number of additional cancers
per year one might expect in a population of 150,000 people.
5.3 A new wastewater treatment plant (WWTP) is to be constructed to service a
part of the Knoxville, Tennessee, metropolitan area. The anticipated design
capacity of the facility is 113,550 m3/day (30 million gallons per day). Two
alternatives have been proposed for disposing of the effluent from the facility.
118 Chapter 5 Risk Assessment
Alternative 2: Silvaculture
Area of concern IF MF E EI
Air pollution 4 3 -1
Groundwater pollution 4 5 -1
Noise 1 2 -1
Odor 2 3 -1
Surface water pollution 4 3 -1
Tree farming 5 4 +1
Wildlife 4 4 +1
5.4 Calculate the chronic daily intake (CDI) for the various exposure routes for a
young adult male who is exposed to drinking water containing toluene at a
concentration equal to the drinking-water standard (MCL) of 1 mg/L. Assume
that he weighs 70 kg, consumes 2 liters of water each day, showers for a total
of 12 minutes each day, and swims for 60 minutes, 5 days a week, for 20 years
while training for the Olympics. During showering, assume that the average
toluene concentration in the air is 2 mg/m3, that the dermal uptake rate from
water (PC) is 10 * 10-6 m/h, and that dermal absorption during showering is
only 10% of the available dose. Assume the surface area of an adult male to
be 1.94 m2, use an inhalation rate of 20 m3/day, and assume that 50 ml of
water are ingested per hour during swimming.
5.5 The U.S. drinking-water standards for the following carcinogens are given
below. For each carcinogen, determine the lifetime individual cancer risk and
the incremental cancer risk per year in a population of 300 million people.
Calculate risk based on residential exposure factors recommended by EPA.
(a) Arsenic, MCL = 0.01 mg/L, and SF = 1.5 kg # day/mg
(b) Benzene, MCL = 0.005 mg/L, and SF = 5.5 * 10-2 kg # day/mg
(c) Carbon tetrachloride, MCL = 0.005 mg/L, and SF = 1.3 * 10-1 kg # day/mg
(d) Polychlorinated biphenyls (PCBs), MCL = 0.0005 mg/L, and SF = 2.0
kg # day/mg, upper-bound, high-risk.
(e) Trichloroethylene, (TCE) MCL = 0.005 mg/L, and SF = 1.1 * 10-2
kg # day/mg
(f) Vinyl chloride, MCL = 0.002 mg/L, and SF = 1.5 kg # day/mg
Exercises 119
5.6 Determine the number of additional deaths per year occurring in a popula-
tion of 300 million people from motor-vehicle accidents. Assume the annual
risk of dying in a motor vehicle accident is 2.4 * 10-4. Calculate the number
of deaths over an average lifetime of 70 years.
5.7 Suppose drinking water contains 5.0 mg/L of phenol, 0.5 mg/L of xylene, and 0.35
mg/L of acetone. If a 70-kg adult drinks 2.0 liters per day of this water for 20 years,
calculate the hazard index and discuss whether this is a safe level of exposure.
5.8 Suppose your campus water supply was contaminated with trichloroethylene
(TCE) at a concentration of 10 mg/L. Determine the total intake over a four-
year academic program. Assume students live on campus and attend classes 9
months each year, and therefore, use 275 days per academic year and a 70-kg
adult male in your calculations.
5.9 Estimate the lifetime incremental cancer risk for a 50-kg woman exposed to an
airborne carcinogen in the work place. Exposure is based on inhaling 1 m3/h of
air containing 0.1 mg/m3 of carcinogen, 8 hours per day, 5 days per week, 50
weeks per year, for 20 years.Assume the carcinogen has an absorption factor of
85% and the inhalation potency or slope factor is 2 * 10-3 1mg/kg # day2-1.
Also estimate the lifetime incremental cancer risk for a 70-kg adult male
exposed to the same contaminant under similar circumstances.
5.10 Georgia Power is considering building a new 1000-megawatt power plant to
provide additional electricity to its customers in the southeast. Two alterna-
tives are being considered for providing the energy necessary to drive the
steam turbines: coal-fired versus nuclear. Use the tables below to perform an
environmental impact assessment (determine the EI value of each alterna-
tive) and select the best alternative to implement. Discuss political factors
that might influence the decision.
Alternative 1: Coal-Fired Alternative
Area of concern IF MF E EI
Air pollution 5 5 -1
Groundwater pollution 3 2 -1
Noise 2 1 -1
Odor 3 3 -1
Residuals disposal 2 3 -1
Radiation 1 1 -1
Surface-water pollution 4 5 -1
6.1 INTRODUCTION
Objectives
The design and modeling of environmental systems requires a thorough under-
In this chapter, you will standing of material, energy, and flow balances. Material balances are performed
learn about: on “black boxes” or control volumes that serve as the boundaries of the system
Rates and order of being studied. Usually, the control volume represents a unit process in which a
reactions chemical or biochemical reaction is taking place. It is important to know the
Performing material and order of reaction and whether materials are conserved, produced, or removed
flow balances on control during the process. Batch, completely mixed, and plug flow reactors, each with
volumes or processes and without reactions, are used extensively in environmental and chemical engi-
neering.These reactors are utilized to treat water, wastewater, and contaminated
Completely mixed, plug,
air and soil. Thermodynamic principles that involve changes in free energy (G),
and dispersed plug flow
enthalpy (H), and entropy (S) are used by scientists and engineers to determine
regimes
whether chemical and biochemical reactions will proceed as written. More
The design and modeling importantly, engineers and chemists are concerned about how fast a reaction
of batch, completely takes place. Kinetics is the study of the rate of a process or reaction.
mixed, and plug flow
reactors with and without
reactions occurring within 6.2 CHEMICAL AND BIOCHEMICAL REACTIONS
Performing energy Environmental engineers manipulate chemical and biological reactions. Some
balances around simple of these reactions, like radioactive decay, occur naturally or spontaneously.
environmental engineering Others will not proceed unless energy is added to the system. We will focus on
systems
chemical and biological (biochemical) reactions.
Environmental engineers design water and wastewater treatment processes,
air pollution abatement technologies, and groundwater treatment systems. These
processes, technologies, and systems utilize biochemical and chemical reactions to
oxidize, reduce, precipitate, and/or transform pollutants into harmless forms. In
some applications no reactions are taking place. For example, water flowing into
and out of a water storage tank and water flowing through a pipe exhibit no chem-
ical or biological reaction. In these examples, the water or substance that flows
through the system is conserved or considered as a “nonreactive” substance. In
other systems, a reaction such as oxidation or reduction may occur, involving the
Section 6.2 Chemical and Biochemical Reactions 121
transformation of some of the chemical species. The rate of reaction, or time required
for a reaction to run to completion, is a significant parameter used in the design of reac-
tors and environmental treatment systems.
1A + 1B:1C (6.1)
The rate (r) of the above chemical reaction can be expressed as differentials as
follows:
dA dB dC
r = - = - = (6.2)
dt dt dt
where:
dA mass
volume # time
= change in species A concentration with time, ,
dt
dB mass
volume # time
= change in species B concentration with time, ,
dt
dC mass
volume # time
= change in species C concentration with time, , and
dt
mass
volume # time
r = rate of reaction, .
A negative sign is placed before the differentials for A and B, since they are being
dA dB
removed during the reaction. In other words, and are negative. A positive sign
dt dt
dC
is inferred before differential , since C is being produced during the reaction.
dt
When the stoichiometric coefficients are not all unity, the rate of change in the
concentration of a given species with respect to time must be modified. This is done
by multiplying by the reciprocal of the stoichiometric coefficient. Equation (6.3) is a
chemical reaction where the stoichiometric coefficients have a value other than one.
2A + 4B:3C (6.3)
The rate for this chemical reaction can be expressed in a generalized form as:
1 dA 1 dB 1 dC
r = - = - = (6.4)
2 dt 4 dt 3 dt
show that the rate of the reaction is linear with respect to the concentrations of A
and B. Knowing this, we could write the rate law for Equation (6.1) as follows:
dC
r = = kA B (6.5)
dt
where:
k = reaction rate constant, volume/time # mass,
A = concentration of A, mass/volume, and
B = concentration of B, mass/volume.
A general form of Equation (6.5) is:
dC
r = = kAaBb (6.6)
dt
The superscripts a and b are used to define the reaction order. Since in our example
a and b are both equal to 1, the reaction is said to be first order with respect to A
and first order with respect to B. The sum of all the exponents 1a + b2 is called the
total reaction order. In this case, the total reaction order is 2. Fractional reaction
orders are possible for biological systems, but often an integer value for reaction
order is determined or assumed in order to solve kinetic problems.
Table 6.1 presents the general form of the equation for zero-, first-, and second-
order removal and production reactions. These equations are applicable only to uni-
molecular reactions that can be described as A : P. The reaction-rate constant is
denoted as k and the reaction time is t. The concentration of a given constituent is
denoted as C. A “removal” reaction denotes the removal or reduction in concentra-
tion of a given species during the reaction or process. Similarly, the increase in con-
centration of a given species would signify a “production” reaction.
A:P (6.7)
dC
r = - = kC 0 = k (6.8)
dt
First Ct = C0 e-kt Ct = C0 ek t
1 1 1 1
Second = + kt = - kt
Ct C0 Ct C0
Section 6.2 Chemical and Biochemical Reactions 123
where:
dC mass
volume # time
= rate of change in the concentration of A with time, , and
dt
k = reaction-rate constant, volume/(mass # time).
Equation (6.8) is a differential equation. Using calculus, Equation (6.8) can be
rearranged by integrating over the limits, where C0 = initial concentration of A at time
equal to 0 and Ct = concentration of A at any time, t, as shown in Equation (6.9). The
integrated form of Equation (6.9) is Equation (6.10).
Ct t
dC = - k dt (6.9)
LC0 L0
Ct - C0 = - kt (6.10)
Figure 6.1
Plot of zero-order removal
Y-intercept C0 reaction.
Ct
Slope k
Time (t)
Figure 6.2
Plot of zero-order production
reaction.
Slope k
Ct
Y-intercept C0
Time (t)
124 Chapter 6 Design and Modeling of Environmental Systems
changes with time, an arithmetic plot of product concentration for a first-order produc-
tion reaction will be curvilinear, as shown in Figure 6.3.
Consider the irreversible conversion of a single reactant (A) to a single prod-
uct (P), as shown by Equation (6.11).
A:P (6.11)
Writing the rate law equation for a removal reaction, assuming a first-order
reaction, results in:
dC
r = - = kC 1 (6.12)
dt
Rearranging differential Equation (6.12) and establishing the following integration lim-
its, where C0 = initial concentration of A at time equal to zero and Ct = concentration
of A at any time t, results in:
Ct 1 t
dC = - k dt (6.13)
LC0 C L0
Taking the antilog of both sides of Equation (6.14) results in the familiar form of a first-
order or exponential equation, Equation (6.15).
Ct = C0 e -kt (6.15)
Figure 6.3
Arithmetic plot of first-order
production reaction.
Ct
Time (t)
Section 6.2 Chemical and Biochemical Reactions 125
Y-intercept ln[C0]
ln[Ct]
Slope k
Figure 6.4
Semilog plot of first-order
Time (t) removal reaction.
A:P (6.18)
dC
r = - = kC 2 (6.19)
dt
1 1
= + kt (6.21)
Ct C0
A second-order removal reaction will plot as a straight line with slope of k, as shown
in Figure 6.5.
126 Chapter 6 Design and Modeling of Environmental Systems
Slope k
Ct
Y-intercept C0
Figure 6.5
Plot of second-order
removal reaction. Time (t)
EXAMPLE 6.1
Reaction order and k determination
Consider the irreversible conversion of a single reactant (A) to a single product (P)
for the following reaction: A : P. Evaluate the following data to determine
whether the reaction is zero order, first order, or second order. Also determine the
magnitude of the rate constant k and list the appropriate units.
Solution
First, make an arithmetic plot of the concentration of A (g/L) on the ordinate
scale versus time (minutes) on the abscissa scale. If the plot produces a straight
line, the reaction is zero order and the slope of the line is equal to the value of the
rate constant k.
1.20
1.00
Concentration of A, g/L
0.80
0.60
0.40
0.20
0.00
0 20 40 60 80 100 120
Time, minutes
Section 6.2 Chemical and Biochemical Reactions 127
Since a plot of the concentration of A versus time produces a curve, the reac-
tion is probably not best modeled as zero order. Therefore, make a semilog plot of
the natural log (ln) of the concentration of A on the ordinate scale versus time (min-
utes) on the abscissa scale. If the plot produces a straight line, the reaction is first
order. The natural log of the concentration of A must be determined before plotting,
as shown below. The use of Excel or similar spreadsheet software is recommended
for completing such repetitive calculations.
0.00
0 20 40 60 80 100 120
0.50
1.00
ln(Concentration of A)
1.50
2.00
2.50
3.00
3.50
Time, minutes
A plot of the reciprocal of A versus time yields a straight line, so the reaction
is second order. The slope of the line is equal to the magnitude of the reaction-rate
constant k, which in this case is 0.1865. The units for k are L/1g # min2.
25.0
y 0.1865x 0.5357
R2 0.9963
20.0
(Concentration of A)1
15.0
10.0
5.0
0.0
0 20 40 60 80 100 120
Time, minutes
If none of the above plots produces a straight line, the reaction order may be
fractional or variable. Other texts, such as Levenspiel (1972) or Metcalf and Eddy
(2003), should be consulted.
k = Ae -1Ea/RT2 (6.22)
where:
k = reaction rate constant,
A = a constant that is independent of temperature for a specific reaction,
Ea = activation energy, cal/mol,
R = ideal gas constant, 1.98 cal/(mol # K), and
T = reaction temperature, K.
At a given temperature, if the reaction-rate constant is known, the Arrhenius
relationship can be used to predict the rate constant at another temperature. For
example, consider the Arrhenius equation for temperatures identified as T1 and T2 .
For temperature T1 :
k1 = Ae -1Ea/RT12 (6.23)
For temperature T2 :
k2 = Ae -1Ea/RT22 (6.24)
Section 6.2 Chemical and Biochemical Reactions 129
k2 Ae -1Ea/RT22
= (6.25)
k1 Ae -1Ea/RT12
By taking the natural log of both sides of Equation (6.25) and rearranging yields:
k2 -Ea Ea
ln ¢ ≤ = + (6.26)
k1 RT2 RT1
k2 Ea 1T2 - T12
ln ¢ ≤ = (6.27)
k1 R T2 T1
Ea
For most situations in environmental engineering, the term may be consid-
RT2T1
ered a constant (C) and Equation (6.27) can be rearranged as follows:
k2
ln ¢ ≤ = C1T2 - T12 (6.28)
k1
k2
= eC1T2 - T12 (6.29)
k1
Replacing eC with the temperature correction factor 1u2 results in the following
equation, which is commonly used for correcting biochemical and chemical reac-
tions for temperature variations:
k2
= u1T2 - T12 (6.30)
k1
where:
k2 = reaction-rate constant at temperature T2 , and
k1 = reaction-rate constant at temperature T1 .
Absolute temperature values must be used in other forms of the Arrhenius
equation, but the use of Celsius is acceptable in Equation (6.30), since only a differ-
ence in temperature is involved.
EXAMPLE 6.2
Te m p e r a t u r e e f f e c t s o n r a t e c o n s t a n t s
A u of 1.047 is typically used for making temperature corrections to the biochemical
oxygen demand (BOD) rate constant k. If the BOD rate constant at 25ºC is 0.20 d-1,
determine the value of the BOD rate constant k for a temperature of 20ºC.
130 Chapter 6 Design and Modeling of Environmental Systems
Solution
First, solve Equation (6.30) for k2 . Make appropriate substitutions and solve as follows.
k2 = k1u1T2 - T12
0.20 d-1 = k111.0472125°C - 20°C2
k1 = 0.20 d-1/11.04725°C = 0.16 d-1
EXAMPLE 6.3
Mass balance on flows and solids
A manhole receives inflows from two sewer laterals and has one outflow as seen in
the diagram below.The flow rates and suspended solids (SS) concentrations in each of
the flow streams are given on the diagram. Perform a materials balance on flows and
suspended solids concentrations around the manhole to determine the unknown flow
and suspended solids concentration.
Q2 ? L/h Control
volume
SS2 150 mg/L
Q3 56 L/h
Q1 40 L/h
Manhole
Solution
First, perform a flow balance around the manhole by substituting into Equation (6.31).
The steady-state assumption will be used; therefore, the accumulation term will be
zero. Since there are no reactions occurring in the manhole, the last term on the
right side of Equation (6.31) is also zero.
0 = Q1 + Q2 - Q3 + 0
Q1 + Q2 = Q3
L L
40 + Q2 = 56
h h
L L L
Q2 = 56 - 40 = 16
h h h
Next, perform a materials balance on suspended solids (SS) concentration
around the manhole as follows. The mass of solids is calculated by multiplying the
flow by the SS concentration:
EXAMPLE 6.4
Mass balance on air flow and particulates
Estimate the concentration of particulate matter, a form of air pollution, in the ambi-
ent air above the city of Atlanta, Georgia, assuming the following data. The average
annual wind velocity is 20 miles per hour and the assumed mixing height above the
city is approximately 4000 feet. Also assume that the city of Atlanta is 10 miles long
and 10 miles wide. The annual quantity of particles discharged into the air is approx-
imately one million tons.
Solution
The solution of this problem requires the use of the continuity equation, where
Q = AV. It will also be necessary to perform a materials balance on air flow and
particulate matter entering and exiting the volume of air above the city. The control
volume in this example is assumed to be a rectangular box 4000 feet in height and
10 mi * 10 mi in surface area. The diagrams below help to envision the problem.
10 mi
10 mi Airout
Qout
Cout
4000 ft
Pollutantsin
Airin
Qin
Cin
Section 6.3 Material Balances 133
Airin Airout
Qin Qout
Cin Cout
Pollutantsin
First, estimate the air flow rate entering the side of the control volume using
the continuity equation: Q = AV.
ft mi ft ft3
Q = a4000 ft * 10 mi * 5280 b a20 b a5280 b = 2.230 * 1013
mi h mi h
The air flow rate into and out of the control volume (rectangular box) over the
city is equal to 2.230 * 1013 ft3/h.
Next, estimate the quantity of pollutants or particles that are discharged into
the atmosphere in micrograms per hour as follows:
6.4.2 Reactors
Environmental engineers design reactor systems for treating water, wastewater, air,
and solid and hazardous wastes. Three types of reactors encountered in environ-
mental engineering include: batch, completely mixed, and plug flow. Batch reactors
do not have a continuous input and output of materials. Both completely mixed and
plug flow reactors generally have continuous inputs and outputs, with chemical
and/or biochemical reactions occurring within. Kinetically, batch and plug flow reac-
tors are evaluated similarly. Completely mixed reactors are less efficient than either
batch or plug flow reactors.
In reality, it is difficult to achieve ideal completely mixed flow or ideal plug
flow. Dispersed plug flow reactors can be designed which result in a flow regime in-
between plug flow and completely mixed. Environmental engineers often use a
series of completely mixed reactors which approximate the efficiency of plug flow
reactors while providing the benefit of resisting shock loadings. Exercise 1 at the end
of this chapter involves using a series of completely mixed reactors to simulate plug
flow. Detailed design of reactor systems is beyond the scope of this text. The reader
should consult the following texts to learn more about reactor design: Levenspiel,
1972; Reynolds and Richards, 1996; and Metcalf and Eddy, 2003. A brief explanation
for each type of reactor will be presented along with derivations of zero-, first-, and
second-order reactions.
contents are completely mixed. First, the reactor is filled with the process stream
containing the constituents to be processed. Next, the flow to the reactor is stopped,
and air or chemicals are added to the reactor so that treatment may begin. The reac-
tor is operated in this mode until the desired degree of treatment or conversion has
been accomplished. Processing time may be several hours to several months,
depending on the application. Once processing or treatment of the flow has been
accomplished, the contents of the reactor are removed and a new batch of influent is
added to the reactor for processing.
The advantage of using a batch reactor is that it allows flexibility of operation,
since the reaction time can be varied. The main disadvantage is that multiple reac-
tors may be required, and they are generally limited to small flows. A simple
schematic diagram of a batch reactor is presented in Figure 6.6.
dC dC
r = - = kC0 or = -k
dt dt
To derive the detention time equation for a batch reactor, we begin with the materi-
als balance equation, Equation (6.31). A materials balance will be performed on
constituent “C”:
A materials balance involves calculating the mass of a constituent per unit of time as
it enters, exits, accumulates, increases, or decreases within the reactor. Equation (6.31)
Figure 6.6
Schematic of a batch reactor.
Q Q
C0 Ct
V Ct
136 Chapter 6 Design and Modeling of Environmental Systems
dC dC
a b V = QC0 - QCt + a bV (6.32)
dt accum dt
Since batch reactors do not have continuous flows into and out of them, the input
and output terms are zero. Because we are assuming that a zero-order removal reac-
tion occurs in the reactor, the reaction term is replaced with Equation (6.8). Substi-
tuting Equation (6.8) into Equation (6.32) yields:
dC
a b V = 0 - 0 + 1- k2V (6.33)
dt accum
dC
a b = -k (6.34)
dt accum
Ct t
dC = - k dt (6.35)
LCo L0
Integrating Equation (6.35) between the limits for t from zero to t, and for the con-
centration C which varies from C0 , the concentration of C at time zero, to Ct , the
concentration C at any time t, yields:
Ct - C0 = - kt (6.36)
Rearranging Equation (6.36) and solving for t results in Equation (6.37), the deten-
tion time equation for an ideal batch reactor with a zero-order removal reaction
taking place within.
C0 - Ct
t = (6.37)
k
where:
t = hydraulic detention time, time, and
k = zero-order removal rate constant, mass/volume # time.
Knowing the rate constant, along with the influent and effluent characteristics,
the design engineer can determine the detention time or reaction time necessary for
the desired degree of treatment. Table 6.2 lists the equations for detention times for
zero-, first-, and second-order reactions in a completely mixed batch reactor. The
Greek letter theta (u) is used rather than t to denote detention time in most chemi-
cal and environmental engineering texts.
Section 6.4 Flow Regimes and Reactors 137
Table 6.2 Detention Times for Zero-, First-, and Second-Order Removal and Production
Reactions in a Completely Mixed Batch Reactor
Removal Production
Zero C0 - Ct Ct - C0
u = u =
k k
First ln1C02 - ln1Ct2 ln1Ct2 - ln1C02
u = u =
k k
Second 11>Ct - 1>C02 11>C0 - 1>Ct2
u = u =
k k
EXAMPLE 6.5
Completely mixed batch-reactor design
A CMBR is to be designed to treat pharmaceutical wastewater that contains 600 mg/L
of chemical oxygen demand (COD). A treatability study on the pharmaceutical waste-
water determined the kinetics for COD removal to be zero order with a rate constant
of 55 mg/(L # h).
Determine:
a. Detention time necessary to reduce the COD of the wastewater to 50 mg/L
so it can be discharged into the municipal sewerage system.
b. The volume of the reactor to treat 3000 m3 of wastewater daily.
Solution part a
First, use Equation (6.37) to calculate the required detention time, since the batch
reactor uses a zero-order removal reaction. The required detention time is 10 hours.
Solution part b
Next, assume that two batches of wastewater will be processed each day with 1500 m3
of wastewater per batch.This will allow the reactor to be filled in 1 hour and drained in
1 hour, resulting in a total time of 12 hours for each batch of processed wastewater. Use
a reactor volume that is approximately 10% more than the required volume to allow
additional depth for freeboard—in this case, 1650 m3 11.10 * 1500 m32. Freeboard is
extra height added to the depth of the reactor so that the reactor contents do not
overflow.
dC dC
r = - = kC1 or = - kC
dt dt
To derive the detention-time equation for the CMFR, we must first use Equation
(6.31) to perform a materials balance on constituent C.
Equation (6.31) is written in differential form to show mass flow through the
reactor.
dC dC
a b V = QC0 - QCt + a bV (6.38)
dt accum dt
Figure 6.7
Schematic of a continuous
flow, completely mixed
reactor.
Q Q
C0 Ct
V Ct
Section 6.4 Flow Regimes and Reactors 139
The detention time 1u2 is defined as the volume divided by the volumetric flow rate.
When substituted into the equation above, we get:
Table 6.3 lists the detention equations for continuous-flow, completely mixed reac-
tors for zero-, first-, and second-order removal and production reactions.
Table 6.3 Detention Times for Zero-, First-, and Second-Order Removal and
Production Reactions in a Continuous Flow, Completely Mixed Reactor
Removal Production
C0 - Ct Ct - C0
Zero u = u =
k k
First 1C0>Ct - 12 11 - C0>Ct2
u = u =
k k
1 C0 1 C0
Second u = ¢ - 1≤ u = ¢1 - ≤
k Ct Ct kCt Ct
EXAMPLE 6.6
Completely mixed reactor design
A completely mixed flow reactor is to be designed to treat an influent stream con-
taining 150 mg/L of chemical oxygen demand (COD) at a flow rate of 100 gallons
per minute (gpm). COD represents the total quantity of oxygen required to oxidize
organic matter to carbon dioxide and water. Assume COD removal follows a first-
order removal reaction with a rate constant k of 0.40 h-1.
Determine:
a. The detention time in hours.
b. The volume of the reactor in ft3 if the effluent is to contain 20 mg/L of COD.
Solution part a
First, determine the required detention time by substituting the appropriate values
into Equation (6.41). The detention time is equal to 16.25 hours.
Solution part b
Next, calculate the volume of the reactor by rearranging the equation for detention
time 1u2. Recall that the definition of detention time is volume divided by volumetric
flow rate.
Q ¢C
a b = ;r (6.42)
A ¢X
Figure 6.8
Q Q
Schematic of a continuous V Volume
plug flow reactor showing C0 Ct
concentration decreasing
along length of reactor.
C0
CONC.
Ct
Distance X
Section 6.4 Flow Regimes and Reactors 141
L Q
Ct
Q
C
X Figure 6.9
CX
X
C0 Schematic of a continuous
plug flow reactor.
Recall from Equation (6.19) that a second-order removal reaction takes the
following form:
dC
r = = - kC 2
dt
Substituting for r into Equation (6.42) and replacing ¢C/¢X in Equation (6.42) with
dC/dX results in:
Q dC
a b = - kC 2 (6.43)
A dX
Rearranging Equation (6.43) and establishing integration limits yields:
A L 1 Ct 1
- dX = dC (6.44)
Q L0 k LC0 C 2
Integrating Equation (6.44) for X between the limits of 0 and L and for C between
C0 , the concentration of C at time zero, and Ct , the concentration of C at time t,
produces:
AL V 1 1 1
- = - = -u = B - ¢ ≤ - ¢ - ≤ R (6.45)
Q Q k Ct C0
1 1 1
u = B¢ ≤ - ¢ ≤R (6.46)
k Ct C0
Table 6.4 lists the detention time equations for continuous plug flow reactors for zero-,
first-, and second-order removal and production reactions. Notice the detention-time
Table 6.4 Detention Times for Zero-, First-, and Second-Order Removal and
Production Reactions in a Continuous Plug Flow Reactor
Removal Production
C0 - Ct Ct - C0
Zero u = u =
k k
equations shown in Table 6.4 for PFRs are identical to those shown in Table 6.2 for
batch reactors.
EXAMPLE 6.7
Plug flow reactor design
A continuous PFR is to be designed to treat an influent stream containing 200 mg/L
of acetic acid at a flow rate of 400 liters per minute (lpm). A second-order removal
reaction is occurring, where the rate constant k is 0.0085 L/1mg # h2.
Determine:
a. The detention time in hours.
b. The volume of the reactor in m3 to achieve 90% removal of acetic acid.
Solution part a
First, it is necessary to calculate the concentration of acetic acid in the effluent. This
may be accomplished using the definition of percent removal (%):
1Cin - Cout2100
percent removal 1%2 = (6.47)
Cin
Cout = 20 mg/L
Next, the detention time required to achieve 90% removal of acetic acid for a
second-order removal reaction can be determined using Equation (6.46).
1 1 1 1 1 1
u = B¢ ≤ - ¢ ≤R = # B¢ ≤ - ¢ ≤R
k Ct C0 0.0085 L>(mg h) 20 mg>L 200 mg>L
= 5.29 h
Solution part b
Finally, determine the volume of the plug flow reactor by rearranging the equation
for detention time 1u2. Recall that detention time is equal to volume divided by the
volumetric flow rate. Therefore, the volume of the reactor is equal to u * Q.
400 L 60 min 1 m3
V = u * Q = 5.29 ha b a b¢ ≤ = 127 m3
min h 1000 L
Section 6.5 Energy Balances 143
E = U + KE + PE (6.48)
Regardless of the process, energy conversion is not 100% efficient, and a loss of useful
energy occurs, normally through waste heat. The second law of thermodynamics states
that there will always be some waste heat released during energy conversions.
Heat is a form of internal energy expressed as the thermodynamic property
enthalpy (H), which is a function of temperature, pressure, and volume. The enthalpy
of a substance is defined by:
H = U + PV (6.51)
where:
U = the internal energy of the substance,
P = pressure of the system, and
V = volume of the system.
When a process occurs without a change in volume, the change in internal
energy can be calculated as follows:
Δ U = mcv ΔT (6.52)
where:
m = mass of substance,
cv = specific heat or heat capacity of the substance at constant volume, and
ΔT = temperature change.
For constant-pressure systems, thermal or heat energy changes can be estimated
using the equation:
Δ H = mcp Δ T (6.53)
where:
ΔH = change in enthalpy or thermal (heat) energy,
m = mass of substance, and
cp = specific heat or heat capacity of the substance at constant pressure.
For incompressible substances, such as solids under normal environmental condi-
tions and most liquids, cv and cp are nearly the same and are replaced with c.Therefore,
ΔU = ΔH, and Equation (6.52) is rewritten as follows, where c replaces cv:
Δ U = mc Δ T (6.54)
where:
c = specific heat or heat capacity of the substance.
For most environmental applications, we are concerned with the rate of energy
change across boundaries of systems. Therefore, Equation (6.54) is modified to
#
account for the mass flow rate 1m2:
#
3rate of change in stored energy4 = mc ΔT (6.55)
Section 6.5 Energy Balances 145
EXAMPLE 6.8
Thermal discharges to river
An Industrial WWTP in Covington, Virginia, discharges approximately 2.0 million
gallons per day (MGD) of treated effluent to the Jackson River at an average tem-
perature of 80°F. If the temperature and flow rate of the Jackson River upstream of
the discharge are 50°F and 100 ft3/s, respectively, determine the temperature in the
river downstream of the industrial discharge.
WWTP Discharge
Q 2 MGD
T 80ºF
Jackson river
Q 64.6 MGD
T 50ºF
Q 66.6 MGD
T ? ºF
Solution
First, we must convert the river flow rate from cubic feet per second to MGD.
Next, we calculate the heat energy in the wastewater and then in the river
upstream prior to the discharge, using a modified form of Equation (6.53):
3heat energy4 = mcT
Performing an energy balance on the two flows using Equation (6.49) results
in the following equation. Steady-state conditions are assumed, so the accumulation
term goes to zero.
T = 50.9°F
We can also determine the same answer by calculating the flow weighted aver-
age of the two streams with the following equation:
T1Q1 + T2Q2
T3 =
Q1 + Q2
where T1 , T2 , and T3 represent the temperature of the wastewater, river, and com-
bined streams, respectively.
Q1 and Q2 are the flow rates for the wastewater discharge and the river upstream.
The flow in the river downstream of the discharge is the sum of the two streams:
EXAMPLE 6.9
Coal-Fired power plant mass and energy balances
A 2000-megawatt (MW) coal-fired power plant is only 33.5% efficient at convert-
ing the coal’s energy into electrical energy. Assume that the coal has an energy
content of 25 kJ/g and contains 60% carbon, 2% sulfur, and 9% ash. Perform a
materials and energy balance around the coal-fired power plant. Assume that 65%
of the ash is released as fly ash and 35% of the ash settles outside of the firing
chamber and is collected as bottom ash. Approximately 15% of the waste heat is
assumed to exit in the stack gases, and the cooling water dissipates the remaining
heat. Air emission standards restrict sulfur and particulate quantities to 260 g SO2
per 106 kJ of heat input and 13 g particulates per 106 kJ of heat input into the coal-
fired power plant.
Section 6.5 Energy Balances 147
Solution part a
Perform the energy balance around the coal-fired power plant using Equation
(6.49). Power is the correct term when expressing energy per unit of time in the
balances. Energy is expressed in units of BTU (joules), whereas power has units of
BTU/h (watts).
At steady state, the energy accumulated is zero and the equation reduces to
the following form.
We estimate the energy in the coal 1MWt2 or thermal power by dividing the
useful energy produced as electrical power 1MWe2 by the efficiency of the coal-fired
power plant as follows:
output power 2000 MWe
input power = = = 5970 MWt
efficiency 0.335
Estimate the stack losses, assuming 15% of the total energy lost is through stack-gas
emissions:
stack losses = 0.15 13970 MWt2 = 595.5 MWt
energy out
5970 MWt = 595.5 MWt + B R + 2000 MWe
cooling water
energy out
B R = 3374.5 MWt
cooling water
148 Chapter 6 Design and Modeling of Environmental Systems
Solution part b
Calculate the mass flow of water required to cool the process using Equation (6.55)
and a specific heat (c) equal to 4.18 kJ/kg # °C.
#
3rate of change in stored energy4 = mc ¢T
# kJ 1 MW 1000 J
3374.5 MWt = m a4.18 # b110°C2 ¢ 6 ≤a b
kg °C 10 J>s kJ
#
m = 8.07 * 104 kg>s
1 m3
Q = 8.07 * 104 kg>s ¢ ≤ = 80.7 m3>s
1000 kg
Solution part c
Determine the quantity of sulfur dioxide and particulates that can be emitted per
unit of heat input into the coal-fired power plant. First calculate the heat input into
the plant.
260 g kJ 1 kg
6
a5.16 * 1011 ba b = 1.34 * 105 kg SO2>d
10 kJ d 1000 g
Next, calculate the quantity of particulates (fly ash) that is permitted to be dis-
charged daily.
13 g kJ 1 kg kg
6
a5.16 * 1011 ba b = 6708
10 kJ d 1000 g d
kg coal kg S 64 kg SO2 kg
SO2 produced = 2.06 * 107 a0.02 ba b = 8.24 * 105
d kg coal 32 kg S d
Section 6.5 Energy Balances 149
The removal efficiency for the air pollution control equipment can be calcu-
lated using the following equation:
Estimate the removal efficiency for sulfur dioxide to meet air standards.
Solution part d
Next, knowing that the coal is 9% ash, calculate the quantity of particulates or fly
ash released:
kg coal kg ash kg
fly ash produced = 2.06 * 107 a 0.09 b10.652 = 1.21 * 106
d kg coal d
A schematic summarizing the mass and energy flow through the plant is given
in Figure 6.10.
Figure 6.10
595.5 MW Mass and energy (power)
Energy loss
flows in a typical coal-fired
Particulates power plant.
6708 kg/d
SO2
2000 MW 1.34 105 kg/d
Electrical
output
Stack
5970 MW
Energy input Fly ash
5.16 1011 kJ/d 33.5 % 1.21 106 kg/d Air
Efficient pollution
power control
2.06 107 kg Coal/d SO2
plant 8.24 105 kg/d system
S U M M A RY
A brief introduction to chemical and biochemical reactions with specific emphasis on
the rates of reactions and order of reactions was presented. Zero-, first-, and second-
order removal and production reactions were derived for batch, plug, and completely
mixed reactor systems. Material balances were performed around these three reactor
systems with and without reactions occurring within. Examples illustrating how to
perform material and flow balances were presented. The design of batch, plug flow,
and completely mixed reactors was presented. The concepts and definitions neces-
sary to perform simple energy balances were introduced. Designing and modeling
environmental engineering systems requires that the engineer have a good under-
standing of kinetics of reactions in addition to being able to perform material and
energy balances around these systems.
REFERENCES
Levenspiel, O. (1972). Chemical Reaction Engineering, John Wiley & Sons, New York.
Metcalf and Eddy (2003). Wastewater Engineering: Treatment and Reuse, McGraw-Hill,
New York.
Reynolds, T.D., and Richards, P.A. (1996). Unit Operations and Processes in Environmental
Engineering, PWS Publishing, Boston, MA.
EXERCISES
6.1 Several reactor configurations are to be considered for reducing the influent sub-
strate concentration from 100 mg/L to 20 mg/L at a design flow rate of 1.0 million
gallons per day. Assume that substrate removal follows first-order kinetics, and
the first-order rate constant is 0.8 days-1. The following equation may be used
for estimating the removal efficiency for completely mixed reactors operating in
series, assuming first-order removal reactions.
n
Sn 1
= a b
S0 1 + ku
where:
Determine and compare the volume required for the following reactor con-
figurations.
(a) One continuous flow, ideal completely mixed reactor
(b) One continuous flow, ideal plug flow reactor
(c) Two continuous flow, ideal completely mixed reactors in series
(d) Four continuous flow, ideal completely mixed reactors in series
6.2 During a chemical reaction, the concentration of Species A was measured as a
function of time. The observed concentration at various time intervals is pre-
sented below. Determine the reaction order and rate constant, k. Is Species A
being removed or produced?
intervals is presented below. Determine the reaction order and rate constant,
k. Is Species B being removed or produced?
6.8 A sanitary landfill receives 600 ft3 of municipal solid waste 5 days per week at
a density of 500 lb/yd3. If the solid waste is compacted to 1000 lb/yd3 and the
average depth of each cell is 10 feet, estimate the expected life of the landfill in
years if 25 acres of space are still available 11 acre = 43,560 ft22. Draw a mate-
rials-balance diagram to solve the problem.
6.9 Perform a materials balance on substrate (S) around a chemostat (completely
mixed reactor without recycle) assuming a first-order removal 1dS/dt = - kS2
for substrate with a rate-constant k value of 0.5 h-1. The influent substrate
concentration is 150 mg/L, and 90% removal is desired. Determine the deten-
tion time in hours for the chemostat, assuming steady-state conditions.
6.10 Calculate the volume of an ideal plug flow reactor for the following scenario.
The volumetric flow rate is 6500 m3/day and Species A is being removed or
converted according to a first-order reaction as follows: dCA/dt = - kCA ,
where CA is the concentration of Species A and k = 9000 d-1. A 95%
removal or conversion of Species A is required.
6.11 A 1000 MW coal-burning power plant is burning West Virginia bituminous
coal with 8% ash content. The power plant is 33% efficient, with 35% of the
ash settling out in the firing chamber as bottom ash. A simplified schematic
diagram is shown below. Assume 3.5 kWh per pound of coal.
(a) Draw an energy diagram for the facility and calculate the rate of heat
emitted to the environment in kJ/s;
(b) Determine the rate of coal input to the furnace in kg/day; and
(c) Assuming that the electrostatic precipitator (ESP) is 99% efficient,
calculate the rate of fly ash emitted to the atmosphere in kg/day.
Exercises 153
Gases and
fly ash
Coal Stack
Furnace ESP
Bottom Fly
ash ash
6.12 A pristine stream flowing at 100 cubic feet per second (cfs) in the Rocky
Mountains contains 5 mg/L of suspended solids (SS). During the spring, ice
melt conveys an additional 250 mg/L of SS at a rate of 20 cfs into the stream.
Determine the concentration of SS in the stream during the spring.
6.13 Calculate the minimum rate at which 15°C make-up water from a river must
be pumped to evaporative cooling towers for a 1000-MW nuclear power
plant. The efficiency of the plant is 32%, and all of the waste heat is assumed
to be dissipated through evaporative cooling with no direct heat lost to the
atmosphere.
CHAPTER
7.1 INTRODUCTION
Objectives
Environmental consciousness and safety have surfaced as primary initiatives
In this chapter, you will learn during the last half of the 20th century and into the 21st. The negative effects
about: of modern society on the earth’s natural environment are the result of numer-
The importance of ous anthropogenic environmental calamities and the misuse of earth’s nat-
sustainable development ural resources. Industry as well as individuals have exploited and wasted
Green engineering natural resources for convenience and economics at the expense of future
generations.
Case histories on
Sustainable development and green engineering are two relatively new,
sustainable development
interrelated topics that are being integrated into engineering courses to help
and green engineering
increase awareness and to promote the design of engineering systems that
have minimum impact on the environment. In addition, sustainable develop-
ment is focused on technology, processes, and resources that can be used for
long time spans while conserving earth’s natural resources. The American
Society of Civil Engineers (ASCE, 2004) has recently added sustainability to
the first fundamental canon of its Code of Ethics:
For example, natural processes and systems should be selected where appropriate
when treating wastewater or other types of contamination. The use of algae, aquatic
plants, and bacteria in a symbiotic relationship to treat industrial or municipal
wastewater in a stabilization pond is an example of sustainable development. The
algae and aquatic plants produce oxygen using sunlight through photosynthesis. In
turn, heterotrophic bacteria use the oxygen produced by the algae and plants to oxi-
dize the organic compounds in the wastewater to carbon dioxide and water. Period-
ically, some of the algae and aquatic plants are harvested and used for animal feed
or digested to produce “biogas.”
Sustainable designs are those that do not deplete the earth of all its current
natural resources; leaving them available for future generations. Many of our nat-
ural resources, such as fish and forests, are renewable. Other renewable resources
include solar, tidal, wave, hydro, and wind power. Natural resources that have finite
quantities (depletable resources) include coal, natural gas, and oil. Sustainability
also ensures that systems, processes, or developments have minimal impact on the
environment and ecological systems. Not only is it important that engineered sys-
tems have a positive impact on people and their well-being, but they also must pre-
serve wildlife, plants, and animals for our descendants. The biosphere must be
maintained and sustained because, ethically, it is the right choice.
4. Ensure that all material and energy inputs and outputs are as inherently safe
and benign as possible.
5. Minimize depletion of natural resources.
6. Strive to prevent waste.
7. Develop and apply engineering solutions, while being cognizant of local geog-
raphy, aspirations, and cultures.
8. Create engineering solutions, beyond current or dominant technologies; improve,
innovate, and invent (technologies) to achieve sustainability.
9. Actively engage communities and stakeholders in development of engineering
solutions.
The key to green engineering is to apply these principles when it will be most effec-
tive and economical to do so—in the early design and developmental phases of a
process or product. Diwekar (2003) recommends introducing green engineering
principles as early as possible into the engineering decision-making process.
Each year, billions of tons of waste are created worldwide that potentially could
adversely affect human health and well-being and the environment. Many of these
wastes are associated with industry and the production of chemical compounds. Pro-
duction costs along with treatment and disposal costs continue to escalate.
The continual rise in production costs occurs as economical sources of raw
materials in the earth’s crust become depleted and more difficult sources must be
used. Treatment and disposal costs rise as larger quantities of wastes are removed at
treatment facilities, due to more stringent regulations requiring higher removal effi-
ciencies. Engineers must use alternative chemicals and processes to minimize the
toxicity of specific chemicals and to reduce the quantity of pollutants discharged to
the ecosystem.
Risk assessment is being applied to pollution prevention to help ameliorate
the effects of harmful chemicals. Risk can be expressed mathematically as a function
of hazard and exposure. Anything that produces an adverse effect on human health
and the environment or ecosystem is defined as a hazard. Exposure as defined by
the EPA is the qualitative or quantitative assessment of contact to the skin or ori-
fices of the body by a chemical. Risk-assessment software tools are available to both
academia and industry that can be used to prioritize, design, and select “green” engi-
neering processes and products.
Figure 7.1 is a schematic diagram showing the relationship between sustain-
able development, green engineering, and sustainability. According to Vallero and
Vesilind (2007), sustainability is achieved by applying green engineering principles
to ideal sustainable development.
Figure 7.1
Relationship between sustainable development, green engineering, and sustainability.
Section 7.2 Sustainable Development and Green Engineering 157
severity of the impact on the environment has been recognized for many years, but
doing this accurately is very complex, and a generally accepted methodology has not
been devised. Nevertheless, progress is being made, and a good introductory review of
the topic is available (Ashby, 2005).
First, consider one of the simpler approaches for including the impact on the
environment when performing materials selection. This method compares the energy
expended in making the item of interest from various possible materials. The material
requiring the least energy would be selected, since, presumably, less environmental
impact would result.
It is assumed, not always accurately, that the pollution caused by particulate
and undesired gases emitted during production of the material is proportional to
the energy consumption. Consider, for example, a component made from plain
carbon steel. Mining the ore and converting it to steel requires an expenditure of
energy. It has been estimated that the energy required per kilogram of steel pro-
duced is about 25 MJ/kg. Forming the steel into the desired shape also requires
energy, but the amount is typically insignificant compared to the above value.
Table 7.1 gives the total energy required to produce and manufacture several com-
mon materials (Ashby, 2005). Notice that aluminum requires much more energy
(200 MJ/kg) than steel, primarily because the electrolysis process used to reduce
alumina ore 1Al 2O32 to aluminum metal (Al) requires an extremely large amount
Table 7.1 Approximate Energy Requirements and CO2 Created During Production
of Common Materials
Material Energy (MJ/kg) CO2 (kg/kg)
Metals
Silicon 60 3.1
Titanium 900 59
Ceramics
Concrete 1.1 0.16
Glass 14 0.8
Polymers
Polyethylene 85 2.1
facilities. Two significant disadvantages of using nuclear energy are high capital costs
to build nuclear reactors and their auxiliary systems, and concerns over the disposal
of high-level radioactive wastes.
An atom of a specific element contains neutrons, electrons, and protons. The
atomic number of an element represents the number of protons, which are posi-
tively charged particles in the nucleus. Neutrons are uncharged particles in the
nucleus. The total number of both protons and neutrons represents the mass num-
ber. Elements with the same atomic number but different mass number are called
isotopes. One way of identifying isotopes is to write the chemical symbol with the
mass number written as a superscript to the upper left and the atomic number as a
subscript to the lower left. Three of the numerous isotopes of uranium (U) are ura-
nium-235 (U-235), uranium-238 (U-238) and uranium-239 (U-239). They each con-
tain 92 protons, and their chemical symbols, mass numbers, and atomic numbers are
written as follows:
235 238 239
92U uranium-235 92U uranium-238 92U uranium-239
EXAMPLE 7.1
Identifying radioactive elements
What are the elements 147X and 226
88X (where X represents the element)?
Solution
A periodic table can be used to solve this problem. Recall that the upper left number
represents the mass number and the lower left number the atomic number. The first
element is nitrogen (N), which has an atomic number of 7 and a mass number of 14.
It is the most abundant isotope of nitrogen and is stable—that is, it does not undergo
radioactive decay.
The second element is radium (Ra), which has an atomic number of 88 and a
mass number of 226. As discussed below, it does undergo radioactive decay to
radon.
7.3.1 Radioactivity
We live in a radioactive world with naturally occurring radioactive atoms or radionuclides.
Some atoms are unstable, and those elements that have more than 83 protons are consid-
ered naturally radioactive. Radionuclides emit various forms of radiation as they decay to
more stabilized forms. The three major forms of radiation are alpha particles, beta parti-
cles, and gamma rays.
An alpha particle is essentially a helium nucleus, consisting of two protons and
two neutrons. Alpha particles are relatively massive, slow moving, and easily
stopped. Because of their short penetration range in tissue, the alpha emitter tends
to be harmful only if ingested. When alpha particles are emitted by an unstable
atom, the atomic number decreases by two units and the mass number decreases by
four units. The transformation or decay of plutonium-239 illustrates what happens
when alpha radiation is released.
239
94Pu : 235
92U + 2a + g
4
(7.1)
160 Chapter 7 Sustainability and Green Development
where:
a = alpha particle or alpha radiation, and
g = gamma radiation or gamma ray.
A beta particle 1b2 is a free electron emitted from an unstable nucleus during the spon-
taneous transformation of a neutron into a proton and an electron. During this transfor-
mation, the atomic number of the element increases by one and the mass number
remains the same.A gamma ray 1g2 may or may not accompany the transformation.An
example of b radiation being emitted from an element is the transformation or decay of
strontium-90 into yttrium-90.
90
38Sr : 90
39Y + b (7.2)
Beta particles are negatively charged, and they travel further and penetrate
deeper than alpha particles. Concrete, steel, lead, or water must be used to protect
individuals from being exposed to beta radiation.
Gamma (G) radiation or gamma rays are electromagnetic waves or photons that
do not have mass or charge and travel at the speed of light. This is a damaging type of
radiation because it is highly penetrating. Several centimeters to several feet of lead,
concrete, or lead-glass must be used to shield individuals from gamma radiation.
The energy associated with the release of radiation from radionuclides can be
estimated from Einstein’s energy-mass-equivalence equation:
E = mc2 (7.3)
where:
E = energy expressed in units of grams # cm/s 1ergs2;
m = mass of particle, grams; and
c = speed of light 12.998 * 1010 cm/sec2.
When radioactive decay occurs, there is a decrease in the mass of the system. The
energy produced, which may be calculated using Equation (7.3), is present as kinetic
energy of any alpha or beta particles emitted plus the energy of the gamma rays.These
particles are slowed and the gamma rays are absorbed as the radiation travels through
matter and the energy is converted into thermal energy—that is, the matter is heated.
EXAMPLE 7.2
Determining mass number and atomic number
Determine the values of a and b, where a is the mass number and b the atomic number
of elements X and Y.
88X : a + bY
226 a
a.
55X : b +
a 132
b. bY
Solution part a
Recall that when an alpha particle is emitted from an unstable nucleus, the atomic
number decreases by two units and the mass number by four. For the reaction in Part a,
the new element “Y” that is formed has an atomic number of 86 188 - 2 = 862 and
the mass number is 222 1226 - 4 = 2222. Therefore, the element Y is radon-222 with
a = 222 and b = 86. X is radium-226.
Section 7.3 Nuclear Physics 161
Radon gas is a naturally occurring radioactive gas that is invisible and odor-
less. It forms from the radioactive decay of small amounts of uranium and thorium
naturally present in rocks and soils. Certain rock types, such as black shale and
selected igneous rocks, can have uranium and thorium in amounts higher than is
typical for the earth’s crust.
Solution part b
Recall that when a beta particle is emitted from an unstable nucleus, the atomic number
of the element increases by one and the mass number remains the same. For the reaction
in Part b, the element “Y” that is formed has an atomic number of 56 155 + 1 = 562 and
a mass number of 132; therefore, a = 132 and b = 56. “X” is cesium-132 and “Y” is
barium-132.
Sources of Radioactivity
Naturally occurring radioactive atoms are found in the earth, air, vegetation, and
our bodies. According to Johansen (2007), naturally occurring radionuclides in the
earth bombard us with approximately 15,000 photons each second. There are two
main classes of natural radioactive elements: primordial and cosmogenic.
Primordial radionuclides have been present since the formation of the earth.
Uranium (U) and thorium (Th) are the best known and have no stable isotope. They
eventually decay to stable lead (Pb) isotopes. Potassium-40 is another example of a
primordial radionuclide; its stable form is nonradioactive potassium.
Cosmogenic radionuclides are those produced by cosmic-ray bombardment of
earth’s atmosphere. There are 22 different cosmogenic radionuclides that eventually
are incorporated into plants and animals. The best known are carbon-14 (C-14),
hydrogen-3 (H-3), and beryllium-7 (Be-7).
Units of Radioactivity
The basic unit of radioactivity is the curie (Ci). One curie corresponds to approximately
3.7 * 1010 disintegrations per second, the decay rate of one gram of radium (Ra). The
curie is used for defining the quantity of radioactive material. One curie of an alpha
emitter is the quantity that releases 3.7 * 1010 alpha particles per second, whereas one
curie of a gamma emitter is the quantity of material that releases 3.7 * 1010 photons
per second.
As mentioned earlier, there are several sources of natural radioactivity. Radioac-
tive materials enter our bodies through the food we eat and the air we breathe.The unit
in which concentration of radioactivity in naturally occurring radioactive material
(NORM) is expressed is the picoCurie (pCi). A picoCurie is one-trillionth of a curie
and is equal to 2.22 disintegrations per minute. The standard 70-kilogram adult con-
tains the following amounts of NORM: 30 pCi of uranium, 3 pCi of thorium, 30 pCi of
radium, 110,000 pCi of K-40, and 400,000 pCi of C-14 (ICRP, 1985; NCRP, 1994).
The energy released by radionuclides can be measured. The amount of energy
deposited in the human body from radioactive decay is called the “dose.” The
internal dose is the amount of radioactivity deposited within our bodies from the
radionuclides we ingest from breathing and eating. The external dose comes primar-
ily from gamma rays emitted by terrestrial sources, such as the ground and buildings,
along with cosmic rays.
The unit of gamma or X-ray radiation intensity—the roentgen (R)—is used in
the study of the biological effects induced by radiation within cells. The roentgen is
defined as the quantity of gamma or X-ray radiation that will produce one electrostatic
162 Chapter 7 Sustainability and Green Development
unit (esu) of electricity in one cubic centimeter of dry air at 0ºC and 760 mm of pres-
sure. This unit represents an exposure dose in air and must be translated into an
absorbed dose. The term radiation absorbed dose (rad) corresponds to the absorption
of 100 ergs of energy per gram of any substance and can be used for any type of radia-
tion—a, b, g, or X-ray. In the International System of Units (SI), the unit for absorbed
dose is the gray (Gy). One gray is equivalent to the absorption of 1 joule of energy per
kilogram (kg) of substance. One gray is equal to 100 rads and can be used to quantify
any type of ionizing radiation. The effect that different types of radiation have on
human beings is measured in roentgen equivalent man (rem).The SI unit, sievert (Sv),
is a unit of biological dose equal to the radiation dose having the same biological effect
as one gray of gamma radiation. One sievert is equal to 100 rem.
In the United States, the standard absorbed dose unit is the rem, and the average
annual dose is 300 millirem (mrem), (Johansen, 2007).A millirem is one-thousandth of a
rem. Therefore, 300 mrem is equal to 0.003 Sv or 0.3 mSv. All persons who work at
nuclear plants are directed to keep their radiation exposure as low as reasonably achiev-
able (ALARA). Adult workers are restricted to 5 rem per year; minors to 0.5 rem per
year. Women who are pregnant are restricted during the term of the pregnancy to
0.5 rem (Nuclear Tourist, 2007).
where:
Ct = concentration or quantity of element at time equal to t, mg/L, g;
C0 = concentration or quantity of element at time equal to 0, mg/L, g;
k = first-order removal or decay rate constant with units of inverse time,
min-1, hr -1; and
t = decay time, min, hr.
The half-life equation (Equation 7.5) is obtained by substituting 0.5 C0 for Ct
and t1/2 for t into Equation (7.4) and rearranging as follows.
Carbon-14 5730 b
Strontium-90 28.1 b
Cesium-137 30 b
Plutonium-239 24,000 a
Uranium-238 4.51 * 10 9 a
-kt1/2 = ln10.52
- ln10.52 0.693
t1/2 = = (7.5)
k k
EXAMPLE 7.3
Radioactive decay calculations
24
A waste contains 100 mg/L of Na. The half-life for sodium-24 is approximately
15.0 hours.
Calculate the following:
a. The decay constant k.
b. The time required to reduce the concentration to 10 mg/L.
Solution part a
First, substitute into Equation (7.5) and rearrange to solve for the decay constant (k).
0.693
t1/2 = = 15 h
k
0.693
k = = 0.0462 h-1
15 h
Solution part b
Next, substitute C0 = 100 mg/L, Ct = 10 mg/L, and k = 0.0462 h-1 into Equation
(7.4) and solve for time (t).
Ct = C0e -k t
mg mg -0.0462 h-11t2
10 = 100 e
L L
10 mg>L -1
= e -0.0462 h 1t2
100 mg>L
Taking the natural log (ln) of both sides of the above equation and then solv-
ing for time (t) yields:
10
ln a b = - 0.0462 h-11t2
100
- 2.3026 = - 0.0462 h-11t2
t = 50 h
products, and decay products) (Ma, 1983). The proposed procedure for disposing of
the radioactive waste is to immobilize it by incorporating it in a specially formulated
glass that has a high resistance to leaching if inadvertently exposed to water. The raw
materials for making the glass and the waste are mixed and melted, and the molten
glass is poured into stainless steel canisters.The canisters are cooled to allow the glass
to solidify and then welded shut. Each canister is 24 inches in diameter and almost 10 feet
long and holds over 3000 pounds of glass. This process has been performed on a large
scale since 1996 at the Department of Energy’s Savannah River facility in South
Carolina. Over 7 million pounds of glass have been processed.
The plan, which remains to be approved, is to transport the immobilized waste to
a geologic repository for long-term storage. Storage times on the order of a thousand
years are required to permit the waste to decay to an acceptable level of radioactivity—
a level similar to that of the original uranium ore. Initially, deep salt mines were chosen
as storage sites, since the presence of salt indicates the absence of water. The aim was
that any future leakage of radioactive material would be retained in the salt deposit
rather than contaminating groundwater. Most recently, Yucca Mountain in Nevada has
been extensively evaluated for future use as a geologic repository.The proposed reposi-
tory would cover 1159 acres, and the waste canisters would be located in tunnels 1000
feet below the surface and 1000 feet above the water table.
health and the environment. The AIWPS uses a series of ponds to treat either
domestic or industrial wastewater to produce a high-quality effluent. The major
components of a type 2 AIWPS system are described briefly below. Additional
information on AIWPS may be found in the following references: Downing et al.,
2002; Green et al., 2003; Green et al., 1995; and Green et al., 1995. Another advan-
tage of these pond systems is the ability to harvest algal cells that may be used for
animal feed or the production of biogas (Oswald, 1994; Oswald, 1991).
Type 2 AIWPS
A schematic of a type 2 Advanced Integrated Wastewater Pond System is presented
in Figure 7.2. The system consists of four ponds in series including a facultative
pond, a high rate pond (HRP), a settling pond, and a maturation pond. Domestic or
industrial wastewater must be pretreated before entering the system. Typically it
passes through bar racks and coarse screens to remove large objects such as tree
limbs, tires, debris, paper, and plastic.
Facultative Pond The upper layer of the facultative pond is aerobic, the lower
layer anaerobic. Typically, four deep anaerobic pits are constructed in the bottom
of the facultative pond. All incoming wastewater must pass through these pits.
where anaerobic digestion of the incoming solids occurs. Under anaerobic condi-
tions, complex solids are hydrolyzed by extracellular enzymes produced by the
microorganisms indigenous to the process. The soluble organic matter produced
during hydrolysis, as well as with the soluble organics in the influent wastewater,
are metabolized by the facultative and anaerobic microorganisms into volatile
fatty acids (VFAs) and alcohols. Methanogenic (strict anaerobes) bacteria con-
vert the VFAs and alcohols to carbon dioxide gas and methane, which are
released to the atmosphere. In the upper aerobic layer of the facultative pond,
aerobic bacteria oxidize organics to carbon dioxide, and hydrogen sulfide gas is
oxidized to sulfate.
High-Rate Pond In the high-rate pond algae and bacteria grow in a symbiotic
relationship. Algae utilize the sunlight in this shallow pond for producing carbohy-
drates and oxygen. Bacteria use the soluble and particulate organic material
remaining in the wastewater exiting from the facultative pond for synthesizing new
biomass (growing new bacteria) and for oxidizing some organic material to provide
for their energy needs. Aerobic bacteria use the oxygen produced by the algae,
because it serves as an electron acceptor during the oxidation of the organic matter.
The dissolved oxygen (DO) level may be supersaturated during the day and may
become anaerobic during the early morning hours as the oxygen produced by alga
respiration is depleted.
Settling Pond Agglomeration of the algae and bacterial flocs occurs in the set-
tling pond. The settling pond provides additional time for disinfection of the waste-
water to occur by ultraviolet radiation from the sun.
Maturation Pond The major function of the maturation pond is to allow addi-
tional time for bacteria to die as a result of exposure to ultraviolet light. Protozoa
and rotifers will be present for polishing off the final effluent in efficient systems.
Process Performance
St. Helena, California The St. Helena AIWPS is a four-pond system. It consists of
facultative ponds with deep fermentation pits, high-rate ponds without paddlewheel
mixers, settling ponds, and maturation ponds.
Based on the annual average values, the percent removal for biochemical oxy-
gen demand (BOD), total nitrogen (TN), and total phosphorus (TP) are 97%, 90%,
and 64%, respectively. Most of the organics and nitrogen are removed in the facul-
tative ponds.
Hollister, California The AIWPS at Hollister, California, is a four-pond system
that treats wastewater from a paper reclamation facility. It has facultative ponds,
high rate ponds, settling ponds, and maturation ponds. The HRP does not have a
paddlewheel mixer. Based on the annual average values, the percent removals for
BOD and total volatile solids (TVS) are 96% and 42%, respectively. A five-log
(99.999%) removal of Escherichia coli occurs through the pond system.
S U M M A RY
Sustainable development was introduced as meeting the needs of the present with-
out compromising the ability of future generations to meet their own needs. Green
engineering involves designs of processes, systems, and technologies that minimize
the generation of pollutants at the source while reducing risk to human health and
the environment. Applying green engineering principles leads to sustainability. A
brief introduction to nuclear physics was presented, because the production of elec-
trical energy by nuclear reactors is anticipated to increase significantly, since it does
not produce greenhouse gases. Radioactive atoms or radionuclides were defined as
unstable atoms that release alpha, beta, or gamma radiation so they can assume sta-
ble forms. An example of nuclear fission indicated that the bombardment of ura-
nium-235 with a neutron produces two fission fragments and energy, which may be
used for steam production and the generation of electricity. Five case histories were
discussed to show some of the challenges and dilemmas that citizens, politicians, and
environmental engineers face in the 21st century as we strive to provide sustainable
development using green engineering principles.
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Exercises 171
EXERCISES
7.1 Gabbard (2007) presented a startling account of the detrimental impact that
electrical utilities have on the environment. Disturbing findings presented in
his paper include the following:
Americans living near coal-fired power plants are exposed to higher radiation
doses than those living near nuclear power plants that meet government regula-
tions.
The population effective dose equivalent from coal plants is 100 times that from
nuclear plants.
The energy content of nuclear fuel released in coal combustion is greater than
that of the coal consumed.
How can one validate or repudiate the claims made by Gabbard? Should the
Environmental Protection Agency ban coal-fired electrical generating power
facilities?
7.2 The half-life of iodine-131 is approximately 8 days. Determine the decay con-
stant k for iodine-131. Calculate the amount of iodine-131 that will remain
after a year if the initial quantity of iodine-131 is 64 grams.
7.3 If “X” represents an element, determine the elements for 168X and 20782X.
7.4 What “Y” is formed from the following disintegration reactions where a is the
mass number and b is the atomic number?
90Th : a + bY
a
(a) 230
(b) 19K : b + bY
40 a
7.5 Several fast-food restaurants use paper containers for their food products
while others use Styrofoam (polystyrene). Perform a Google search on the
internet to find articles that present the advantages and disadvantages of using
each.
7.6 As a concerned citizen who believes in sustainable development, list some
things that can be done in our lives to reduce waste, recycle, conserve, etc. to
help minimize adverse affects on the environment and our natural resources.
For example, take shorter showers to decrease the volume of gray water gener-
ated and save energy costs associated with heating the water. Recycle glass,
aluminum, paper, plastics, newspapers, etc. to decrease the quantity of materi-
als that are disposed of in landfills and to allow recovery and reuse of these
materials, thereby saving our natural resources.
CHAPTER
8
Water Quality and Pollution
Annual evaporation1
From world oceans 85 350 0.025
Annual precipitation
On world oceans 78 320 0.024
thermoelectric power. Figure 8.1 is a pie chart showing the percent by category of
water used in the United States during 2000. Each of these categories will be dis-
cussed briefly, and the quantities of water used will be summarized.
Figure 8.1
Percent by category of
water used in the United
States for 2000.
164,000 megaliters per day (ML/d), or 43,300 million gallons per day (MGD) of
water withdrawals went to public supply.
8.2.2 Domestic
Water used both for indoor and outdoor household purposes is called domestic.
Within the home, water is used for bathing, cooking, drinking, flushing toilets, and
washing clothes. Outdoor water use primarily involves watering gardens and lawns.
Water withdrawals in 2000 for domestic usage in the United States were 13,600
ML/d (3,590 MGD).
8.2.3 Irrigation
Irrigation water use includes providing water for all agricultural and horticultural
activities, for golf courses, cemeteries, and turf farms, and for preplant irrigation,
frost protection, and dust suppression. This is the second highest category of water
withdrawal. In 2000, approximately 519,000 ML/d (137,000 MGD) were withdrawn
for irrigation use in the United States.
8.2.4 Livestock
Livestock water use is associated with dairy operations, feedlots, livestock watering
operations, and other on-farm usages. In 2000, approximately 6,660 ML/d (1,760
MGD) of water went for these purposes.
8.2.5 Aquaculture
Water used for raising finfish and shellfish for food, conservation, restoration, or sport
is classified as aquaculture use. In the United States, about 14,000 ML/d (3,700 MGD)
of water were used in 2000 for aquaculture activities.
8.2.6 Industrial
Industrial water use includes water used to cool, dilute, fabricate, transport, and
wash. Examples of industries that consume large quantities of water include: chem-
ical, food, paper, petroleum, and primary metal processing. In 2000, 74,900 ML/d
(19,800 MGD) of water were used by industry.
Section 8.4 Water Pollution 175
Atmosphere
Condensation
Precipitation Evaporation
Evapotranspiration
Surface runo
ff
Soil mantle
Ocean
Aquifers Figure 8.2
Groundwater
flow Hydrologic cycle.
8.2.7 Mining
Mining water is used to extract minerals such as coal, iron, sand, and gravel, crude
petroleum, and natural gas. During 2000, an estimated 13,200 ML/d (3,500 MGD) of
water were used for mining activities.
River
Point sources
Domestic wastewater discharge Industrial wastewater discharge
-Suspended solids -Suspended solids
-Organics -Organics
Figure 8.3 -Phosphorus -Phosphorus
-Oil & Grease -Nitrogen
Four major types of water -Pathogens -Metals
pollution.
Point sources of pollution are those that emanate from a single point. Exam-
ples include domestic and industrial wastewater treatment facilities that discharge
treated wastewater into surface waters. Nonpoint or diffuse sources of pollution are
land areas such as fields, parking lots, and roads that generate surface runoff con-
taining various types of contaminants.
In the past, control of water pollution focused mainly on point sources of
pollution from publicly owned treatment works (POTWs). These are domestic
wastewater treatment facilities that treat sewage that may contain some indus-
trial wastewater. More recently, regulatory agencies are targeting nonpoint
sources of pollution, both agricultural and urban runoff, since the pollutional
strength of these types of wastewaters may be two to three times that of domestic
wastewater.
Management of both water and wastewater flows in entire watersheds is now
being practiced to encourage a holistic approach to pollution control. This allows
regulatory agencies to better manage these resources and to develop total maxi-
mum daily loads (TMDLs) for receiving streams, thus being able to maintain high
water quality. Understanding the importance and interrelationship between drink-
ing water and wastewater treatment is an integral part of managing a particular
watershed. Figure 8.4 shows a schematic of this relationship.
A city uses a river and wells to provide water to its citizens. Water with-
drawn from these sources must be transported to a water treatment plant (WTP),
where various chemicals are added and several types of treatment processes are
used to produce safe and palatable water. The water is pumped from the treat-
ment plant throughout the city’s water distribution system. Consumers, busi-
nesses, and industries use the water and return it to the city’s wastewater
collection system or sewerage system in the form of gray water and wastewater.
Raw sewage or domestic wastewater is then conveyed through gravity sewers
and pressurized force mains to the wastewater treatment plant (WWTP). At the
WWTP, physical, chemical, and biological processes transform the sewage into
reclaimed water that can be used for irrigation, drinking, or aquifer recharge, or
discharged back into a river. Upstream and downstream of a city, other munici-
palities and stakeholders use the water in the stream the same way, and some use
it for other purposes.
Section 8.5 Water Quality Parameters 177
Wastewater
collection
system
Raw
sewage
Wastewater
Deep treatment
well plant
injection
Wastewater
effluent
Cesium Heptachlor
Chloride Lindane
Cobalt Toluene
Copper Trichloroethylene
Fluoride Toxaphene
Lead Xylenes
Magnesium 2,4-D
Manganese
Mercury
Nickel
Nitrate
Nitrite
Phosphorus
Potassium
Strontium
Zinc
use to assess water quality and the effectiveness of treatment at water and waste-
water treatment plants.
Turbidity
Turbidity is a measure of water clarity.Turbidimeters measure the intensity of light that
is scattered by suspended matter, primarily colloidal and fine dispersions. Clay, silt,
finely divided organic and inorganic matter, plankton, and microorganisms are exam-
ples of matter causing turbidity. Turbidity is expressed in nephelometric turbidity units
(NTUs). The procedure for measuring turbidity is found in Section 2130 of Standard
Methods (1998). As of January 14, 2005, drinking water systems cannot exceed 1 NTU
and must not exceed 0.3 NTU in 95% of the daily samples in any given month.
Section 8.5 Water Quality Parameters 179
Solids
Total solids (TS) in a water or wastewater sample consist of suspended and dissolved
solids. The procedures for measuring the various types of solids are found in Section
2540 of Standard Methods (1998). To determine total solids, a known volume of sam-
ple is placed in a preweighed crucible or aluminum tare and then evaporated and
dried to a constant weight in an oven at 103–105°C. The crucible or aluminum tare is
cooled in a desiccator and reweighed.The difference in the weight divided by the vol-
ume of sample yields the total solids concentration, expressed mathematically as:
mg WTS WDS - WTare
TSa b = = (8.1)
L V V
where:
TS = total solids concentration, mg/L,
WTS = mass of total solids, mg,
WDS = mass of dried solids and tare, mg,
WTare = mass of tare, mg, and
V = volume of sample, L.
Total suspended solids (TSS) are the portion of total solids that can physically
be removed by passing through a filter with a specific pore size opening. Settleable
solids relate to the fraction of suspended solids that will settle out of solution by the
force of gravity. Suspended solids are determined by passing a specified volume of
sample through a preweighed 0.45-mm fiberglass filter pad and then drying the pad at
103–105°C. The concentration of suspended solids is then determined by dividing the
weight of the dry solids accumulated on the filter pad by the volume of the sample:
mg WTSS WDSFP - WFP
TSS a b = = (8.2)
L V V
where:
TSS = concentration of total suspended solids, mg/L,
WTSS = mass of total suspended solids, mg,
WDSFP = mass of dried solids, filter pad, and tare, mg,
WFP = mass of filter pad and tare, mg, and
V = volume of sample, L.
The total dissolved solids (TDS) concentration, which relates more to the
chemical quality of water, is determined as:
TDS = TS - TSS (8.3)
where:
TDS = concentration of total dissolved solids, mg/L,
TS = concentration of total solids, mg/l, and
TSS = concentration of total suspended solids, mg/L.
Each of the above solids species has a volatile fraction (related to organic content)
and a fixed fraction (related to mineral content). The volatile fraction is determined
by igniting the dry solids in a muffle furnace at 550°C. The total volatile solids (TVS)
concentration can be calculated from:
where:
TVS = concentration of total volatile solids, mg/L,
WTVS = mass of total volatile solids, mg,
WDS = mass of dried solids and tare, mg,
WFS = mass of fixed solids and tare after ignition at 550°C, mg, and
V = volume of sample, L.
Equation (8.5) is used to calculate the total volatile suspended solids (TVSS)
concentration.
where:
TVSS =
concentration of total volatile suspended solids, mg/L,
WTVSS =
mass of total volatile suspended solids, mg,
WDSFP =
mass of dried solids, filter pad, and tare, mg,
WFSFP =
mass of fixed solids, filter pad, and tare after ignition at 550°C, mg,
and
V = volume of sample, L.
Equation (8.6) is used to calculate the total fixed solids (TFS) concentration (mg/L):
Example 8.1 illustrates the determination of total solids, total volatile solids, total
fixed solids, total suspended solids, and total dissolved solids.
EXAMPLE 8.1
Solids analyses
The following test results were obtained for a sample of river water. All solids analy-
ses were performed using a sample volume of 100 ml.
Determine:
a. The total solids concentration.
b. The total suspended solids concentration.
c. The total dissolved solids concentration.
d. The total volatile solids concentration.
e. The total fixed solids concentration.
Section 8.5 Water Quality Parameters 181
Solution part a
First, calculate the total solids concentration using Equation (8.1).
Solution part b
Next, calculate the total suspended solids concentration using Equation (8.2).
Solution part c
Now, using Equation (8.3), calculate the total dissolved solids (TDS) concentration.
mg
TDS = TS - TSS = 250 - 75 = 175
L
Solution part d
Next, calculate the total volatile solids (TVS) concentration using Equation (8.4).
Solution part e
Finally, using Equation (8.6), calculate the total fixed solids (TFS) concentration.
mg
TFS = TS - TVS = 250 - 170 = 80
L
Color
True color is due to colloidal and dissolved substances. The decomposition of leaves,
conifer needles, and wood produces tannins, humic acid, fulvic acid, and humates,
which are the organic compounds causing color in water. Inorganic compounds that
cause color include iron and manganese. The procedure for measuring the color
concentration is found in Section 2120 of Standard Methods (1998).
Apparent color is due to suspended materials in the water, such as suspended
solids. When color is measured on unfiltered samples, it is called “apparent color,”
whereas color measured on filtered water samples 10.45-mm filter2 is termed “true
color.”
182 Chapter 8 Water Quality and Pollution
EXAMPLE 8.2
Calculating threshold odor number
A 100-ml sample of water is diluted with 200 ml of dilution water so that there is no
detection of the odor. Calculate the threshold odor number (TON).
Solution
Substitute the appropriate values into Equation (8.8) to solve for TON.
100 ml + 200 ml
TON = = 3
100 ml
Section 8.5 Water Quality Parameters 183
Temperature
Temperature is an important physical parameter that affects the density, viscosity,
vapor pressure, and surface tension of water. Biological and chemical reactions
increase with an increase in temperature. A 10ºC increase often doubles the rate of
biological and chemical reactions. Gas solubility is affected by temperature, and oxy-
gen’s solubility increases with a decrease in temperature. The solubility of certain
chemical compounds, such as sodium chloride, increases with an increase in water
temperature. Temperature is normally measured with a thermometer. The procedure
for measuring temperature is found in Section 2550 of Standard Methods (1998).
Nitrogen (N)
Nitrogen is a nutrient required by all living organisms. In excess amounts in surface
waters it contributes to excessive algal growth, which results in eutrophication.
Nitrogen enters the water supply in agricultural and urban runoff as fertilizers, and
in industrial and domestic wastewater treatment discharges.
The most common and important forms of nitrogen are listed in Table 8.3.
Oxidized nitrogen 1NOx2 is the sum of NO2- + NO3- , whereas total Kjeldahl nitro-
gen (TKN) is the sum of the ammonia and organic nitrogen. Organic nitrogen is
nitrogen found in protein, amino acids, and urea 1NH 2CONH 22. The primary drink-
ing water standard for nitrate is 10 mg/L as N, because it is linked to infant methe-
moglobinemia (blue baby syndrome).
Most organisms use ammonium nitrogen as their nitrogen source, but algae
normally assimilate nitrate. Some bacteria are capable of fixing nitrogen gas from
the atmosphere to form ammonium nitrogen. Nitrogen found in most organic com-
pounds exists with a negative-3 valence 1N 3-2.
The total nitrogen concentration in a sample consists of the total Kjeldahl
nitrogen and oxidized nitrogen:
The ammonium ion exists in equilibrium with ammonia according to the following
equilibrium equation. At pH values normally encountered in environmental engi-
neering, the ammonium ion is the predominant species, whereas ammonia occurs at
pH values greater than 10.
Ammonium NH4+ -3
Nitrogen gas N2 0
Nitrite NO2- +3
Nitrate NO3- +5
184 Chapter 8 Water Quality and Pollution
Phosphorus (P)
Phosphorus is an essential nutrient required by all living organisms. It, like nitro-
gen, is linked to eutrophication of surface waters if present in excessive amounts.
Phosphorus enters the water supply from phosphorus-based detergents, corrosion
inhibitors added to drinking water systems, and domestic and industrial wastewater
discharges:
Organic-P is found in proteins and amino acids and is normally only a minor considera-
tion. Inorganic-P species include orthophosphates, polyphosphates, and metaphos-
phates. Polyphosphates and metaphosphates are also known as condensed phosphates.
Condensed phosphates and organic phosphorus must be converted to orthophosphate
before they can be measured.
The procedures for performing the various types of phosphorus analyses are found
in Section 4500-P of Standard Methods (1998).
EXAMPLE 8.3
Calculating theoretical oxygen demand
Calculate the theoretical oxygen demand of a water sample containing 1000 mg/L of
C 5H 7O2N.
186 Chapter 8 Water Quality and Pollution
Solution
Start by writing the stoichiometric equation showing the oxidation of the chemical
compound to carbon dioxide, water, and ammonia. Make sure that the equation is
properly balanced.
C 5H 7O2N + 5 O2 : 5 CO2 + 2 H 2O + 1 NH 3
Next, calculate the gram-molecular and atomic weights of C 5H 7O2N and O2,
respectively.
mg C 5H 7O2 N 160 g O2 mg O2
1000 ¢ ≤ = 1416
L 113 g C 5H 7O2N L
Figure 8.5 Lu
Oxygen consumed and
Oxygen consumed (Y ) or
Lt
Time
Section 8.5 Water Quality Parameters 187
1
dL = - k dt (8.18)
L
Integration limits for Equation (8.18) are shown as follows, where L goes from
the ultimate BOD 1Lu2 to the BOD at any time t, and t goes from zero to t:
Lt 1 t
dL = - k dt (8.19)
LLU L L0
Integrating Equation (8.19) results in:
Rearranging Equation (8.20) and taking the antilog of both sides of the equa-
tion yields:
Lt = Lue -k t (8.21)
From Figure 8.5, the ultimate BOD 1Lu2 is equal to Y plus the BOD at any
time t, Lt , or:
Lu = Y + Lt (8.22)
Lt = Lu - Y (8.23)
Rearranging Equation (8.24) and solving for Y (BOD exerted) results in:
Y = Lu A 1 - e -kt B (8.25)
where:
Y = BODt = amount of oxygen consumed or BOD exerted at some time,
t, mg/L, and
Lu = BODu = ultimate BOD of the sample, mg/L.
EXAMPLE 8.4
C a l c u l a t i n g B O D g i v e n BODu a n d r a t e c o n s t a n t
Calculate the 5-day and 17-day BOD of a domestic wastewater, given the BOD rate
constant of 0.22 d-1 and an ultimate BOD of 300 mg/L.
188 Chapter 8 Water Quality and Pollution
Solution
First, substitute a time of 5 days and an ultimate BOD of 300 mg/L into Eq. (8.26),
which yields a 5-day BOD of 200 mg/L:
mg -1 mg
BOD5 = 300 A 1 - e -0.22 d 15 d2 B = 200
L L
Next, substitute a time of 17 days and an ultimate BOD of 300 mg/L into Eq. (8.26)
which yields a 17-day BOD of 293 mg/L:
mg -1 mg
BOD17 = 300 A 1 - e -0.22 d 117 d2 B = 293
L L
BOD Laboratory Procedure The procedure for performing the biochemical oxy-
gen demand analysis is found in Section 5210 of Standard Methods (1998). The
BOD test involves mixing a milliliters of sample (water or wastewater) with b mil-
liliters of dilution water, which is distilled water to which nutrients and oxygen
have been added. If the sample contains bacteria, then it is unnecessary to add
“seed” or inoculum to the dilution water. The mixture is placed in a minimum of
four 300-ml BOD bottles. Figures 8.6 and 8.7 are schematics illustrating the proce-
dure for performing a “seeded” BOD analysis. The dissolved-oxygen (DO) concen-
tration of the mixture in two of the bottles is determined using a DO meter and
oxygen probe or by titration using the azide modification of the Winkler method.
Two of the bottles are incubated in the dark at 20°C for five days, or some other
desired time period, and then the DO is measured. For the results of the BOD test
to be valid, at least 1 mg/L of DO should remain after incubation and at least 2 mg/L
Figure 8.6
BOD laboratory apparatus.
“a” ml
Water or “b”ml
wastewater Dilution water
sample
Nutrients
Dilution
Bacteria water
or seed Air
Section 8.5 Water Quality Parameters 189
BOD BOD
bottle bottle
B1 D1
Measure DO on day 1
of DO should be used during the incubation period. The BOD for a “seeded” test is
calculated according to Equation (8.27). Average values are used for D1 , D2 , B1 ,
and B2 .
where:
BODt = biochemical oxygen demand exerted for an incubation period of
t days, mg/L,
t = incubation period at 20°C, days,
D1 and D2 = initial and final DO concentrations in the diluted sample, mg/L,
B1 and B2 = initial and final DO concentrations in the blanks, mg/L,
Blanks are BOD bottles containing dilution water and seed,
P = decimal fraction of sample used, and
f = ratio of the seed in sample to seed in blank or control.
ml of sample
P = (8.28)
volume of BOD bottle
% seed in D1
f = (8.29)
% seed in B1
When the sample already contains bacteria, Equation (8.27) is modified as fol-
lows for calculating the BOD for an “unseeded” test:
mg 1D1 - D22
BODt a b = (8.30)
L P
190 Chapter 8 Water Quality and Pollution
EXAMPLE 8.5
Calculating BOD for a “seeded” sample
A 5-day BOD test is performed on a sample of chlorinated wastewater effluent. Sixty
milliliters of wastewater sample and 2 ml of “seed” are added to 300-ml BOD bottles
and mixed with enough dilution water to fill the bottles. “Seed” must be added, since
wastewater effluent is chlorinated, which kills pathogens and bacteria. For the blanks
or controls, 2 ml of “seed” are added to 300-ml BOD bottles and mixed with enough
dilution water to fill the bottles. The average dissolved-oxygen concentrations of the
diluted wastewater samples and blanks on day 1 of the test were 6.8 and 7.4 mg/L,
respectively. After incubation at 20°C for 5 days, the average DO concentrations of
the diluted wastewater samples and blanks were 2.5 and 7.1 mg/L, respectively. Using
Equation (8.27), calculate the 5-day BOD of the chlorinated effluent.
Solution
First, calculate the decimal fraction (P) of sample used according to Equation (8.28).
Next, calculate the ratio of seed in the sample to seed in the blanks according to
Equation (8.29). The “seed” inoculates the dilution water, resulting in 240 ml being
seeded for D1 and 300 ml for B1 .
EXAMPLE 8.6
Calculating BOD for an “unseeded” sample
A 5-day BOD test is performed on a sample of raw wastewater. Six milliliters of
wastewater sample are added to 300-ml BOD bottles and mixed with dilution
water. The average dissolved-oxygen concentration of the diluted wastewater sam-
ples on day 1 of the test was 7.6 mg/L and after incubation at 20°C for 5 days was
2.6 mg/L. Calculate the 5-day BOD of the raw wastewater. Since raw wastewater
already contains bacteria, it is not necessary to add “seed” to the sample or to the
dilution water. Therefore, Equation (8.30) must be used for determining the 5-day
BOD concentration.
Section 8.5 Water Quality Parameters 191
Solution
First, determine the decimal fraction of sample (P) used according to Equation (8.28).
ml of sample 6 ml wastewater sample
P = = = 0.02
volume of BOD bottle 300 ml
mg as O2 1A - B2 * M * 8000
COD ¢ ≤ = (8.32)
L ml sample
where:
COD = chemical oxygen demand, mg O2/L,
8000 = conversion factor,
A = ml FAS used for blank,
B = ml FAS used for sample, and
M = molarity of FAS.
The COD of a sample of water or wastewater will always be less than the theo-
retical oxygen demand, since certain compounds may be refractory or difficult to
treat. On the other hand, the BOD value will always be less than the COD value, since
BOD measures only the biodegradable organic content. For domestic wastewater,
environmental engineers often assume that the ultimate BOD 1Lu2 is equivalent to
the actual COD of the wastewater and that the 5-day BOD value is approximately
two-thirds of the COD value. The procedure for performing the chemical oxygen
demand analysis is found in Section 5220 of Standard Methods (1998).
worms. Bacteria are single-cell microorganisms, and certain strains are pathogenic.
They may be spheroid, rod, or spiral in shape and consist of prokaryotic cells with a
single strand of DNA. Escherichia coli is an example of a bacterium. Protozoa are
motile, microscopic eukaryotes that are usually single cell. Two examples of protozoa
are Cryptosporidium parvum and Giardia lamblia. Viruses are obligate intracellular
parasites that can replicate only in a living host cell. Examples of viruses encountered
in water and wastewater are the Hepatitis A virus and the Enteroviruses (polio, echo,
coxsackie). Helminths or worms are parasites that are usually found in wastewater
and contaminated water. Examples are tapeworm, stomach worm, and whip worm.
Isolating and identifying pathogens in water samples is difficult and expensive.
Large volumes must be processed in order to find certain pathogens, and special
analytical equipment is needed to grow and identify them. Working with pathogenic
organisms is dangerous, so indicator organisms that are nonpathogenic are used to
determine the presence of potential pathogens in water and wastewater.
Indicator organisms such as total coliform bacteria and fecal coliform bacteria
are used to indicate the presence of pathogenic or harmful microorganisms. Coliform
bacteria are found in the digestive tract of warm-blooded animals, and most are non-
pathogenic. They are numerous in water and wastewater and easily detected. Their
survival times are similar to those of pathogenic organisms.
Enumeration and identification of these indicator organisms is accomplished
by direct microscopic counts, pour and spread plates, the membrane-filter technique,
and the multiple-tube fermentation method. The latter two are the traditional pro-
cedures used by engineers to enumerate indicator organisms.
Membrane-Filter Technique The membrane-filter technique involves filtering samples
of water or wastewater through sterilized filter pads (0.45-mm openings) for collecting
indicator organisms.The filter pads are then placed in specified media (M-Endo) in petri
dishes. These are incubated (35°C) for approximately 24 hours, the number of colonies
formed are counted, and the results are reported in colony-forming units (CFUs) per
100 ml of sample. Typical coliform bacteria colonies appear pink to dark red in color
with a green metallic sheen. Absence of bacteria growth is considered a negative test.
Figure 8.8 shows a photograph of a membrane-filtration apparatus and associated filter
Figure 8.8
Photograph of membrane
filtration apparatus and
filter pad.
Section 8.5 Water Quality Parameters 193
10 ml Sample 1 ml Sample
0.1 ml Sample
Positive results
4-3-2
Figure 8.9
Multiple-tube fermentation
test.
pad. The procedure for performing the membrane-filter technique for members of the
coliform group is found in Section 9222 of Standard Methods (1998).
Multiple-Tube Fermentation Technique Another method for detecting coliform
bacteria is the multiple-tube fermentation technique. This procedure involves inoc-
ulating a series of test tubes filled with lactose broth with varying amounts of sam-
ple. Figure 8.9 shows a typical multiple-tube fermentation setup. Normally, 15 test
tubes are used, with sample volumes of 10 ml, 1.0 ml, and 0.1 ml being added. Col-
iform bacteria ferment lactose broth under anaerobic conditions, resulting in gas
production 1CO22 and bacterial growth, as indicated by a cloudy broth. Equation (8.33)
or statistical tables in Standard Methods (1998) can be used for calculating the most
probable number (MPN) per 100 ml of sample. The MPN is a statistical estimate of
the number of coliforms that are potentially present, since a number of other micro-
bial species can also ferment lactose. The procedure for performing the multiple-
tube fermentation filter technique for members of the coliform group is found in
Section 9221 of Standard Methods (1998).
EXAMPLE 8.7
Calculating the most probable number
Calculate the MPN in a set of 15 test tubes with the following number of positive
tubes: 4, 3, and 2 for sample sizes of 10.0, 1.0, and 0.1 ml, respectively.
Solution
First, determine the volume of sample used in all the test tubes.
Next, determine the volume of sample used in the test tubes that were negative.
ml of sample in neg. tubes = 1110.02 + 211.02 + 310.12 = 12.3
194 Chapter 8 Water Quality and Pollution
Finally, estimate the most probable number (MPN) per 100 ml of sample by
substituting into Equation (8.33).
MPN 19 * 1002
= = 34.4
100 ml 3112.3 ml2 * 155.5 ml240.5
The Total Coliform Rule in the Safe Drinking Water Act specifies a maximum
contaminant level goal (MCLG) of zero for total coliforms, fecal coliforms, and
Escherichia coli.
pH
The pH of water is a function of the hydrogen ion 1H +2 concentration. Mathemati-
cally, pH is defined as the negative logarithm of the hydrogen ion concentration:
pH = - Log3H +4. The pH scale goes from 0 to 14 with 7 being neutral. A pH value
above 7 indicates alkaline or basic conditions, and a value below 7 indicates acidic
conditions. Both water and wastewater are treated to produce a pH between 6 and
8.5. Besides determining the solubility of various chemical species, pH affects bio-
logical and chemical reactions. A calibrated pH meter with a glass electrode is rou-
tinely used for measuring pH.
Giardia lamblia TT1 Gastrointestinal illness (e.g., Human and fecal animal waste
diarrhea, vomiting, cramps)
Alachlor 0.002 Eye, liver, kidney, or spleen Runoff from herbicide used on
problems; anemia; increased row crops
risk of cancer
Color 15 c.u.
Corrosivity Noncorrosive
pH 6.5 to 8.5
Zinc 5 mg/L
Table 8.6 Typical NPDES Permit Limits for Secondary Wastewater Treatment
Annual average Monthly average Weekly average
BOD (mg/L) 20 30 45
TSS (mg/L) 20 30 45
Table 8.7 Water Classification Based on Best Beneficial Use for the State of Florida
Class or
category Description
Class I Potable water supplies
S U M M A RY
This chapter introduced the importance and beneficial uses of water. Ninety-seven
percent of the earth’s waters are saline and are found in the oceans; the remaining
3% comprises fresh water. Only 0.62% of the earth’s water is both fresh and acces-
sible, since 2% is in the form of snow, ice, or glaciers. The eight major beneficial
uses of water in the United States are public supply, domestic, irrigation, livestock,
198 Chapter 8 Water Quality and Pollution
aquaculture, industrial, mining, and thermoelectric power. During the year 2000,
the thermoelectric category withdrew the most water in the United States, followed
by irrigation.
As water passes through the hydrologic cycle, it becomes contaminated. Four
major sources of water pollution include domestic wastewater discharges, indus-
trial wastewater discharges, agricultural stormwater runoff, and urban stormwater
runoff. Water quality parameters are divided into four major categories: physical,
chemical, microbiological, and radiological. The procedures for conducting analyses
on water, wastewater, and sludge are found in Standard Methods for the Examination
of Water and Wastewater (1998). Parameters that traditionally have been used for
assessing water quality include: turbidity, solids, color, taste and odor, temperature,
nitrogen, phosphorus, biochemical oxygen demand (BOD), chemical oxygen demand
(COD), and indicator-organisms testing, using either the membrane-filter technique
or multiple-tube fermentation technique.
A brief introduction to primary drinking water standards (health related) and sec-
ondary drinking water standards (aesthetics) was presented along with typical maxi-
mum contaminant levels (MCLs).Wastewater effluent standards were briefly addressed
by describing the National Pollution Discharge Elimination System (NPDES) permit in
addition to typical wastewater effluent standards for a secondary wastewater treatment
facility. Surface water quality standards or stream standards were discussed and a water
classification system based on the best beneficial use for the State of Florida was pre-
sented. In conclusion, a brief case history of the kepone contamination of the James
River in Virginia was presented.
REFERENCES
APHA, AWWA, WEF (1998). Standard Methods for the Examination of Water and Waste-
water, American Public Health Association, 1015 Fifteenth Street, NW, Washington, DC.
American Water Works Association (2005). http://www.awwa.org/Advocacy/learn/info/
HistoryofDrinkingWater.cfm.
Environmental Protection Agency (2005). EPA 841—B-05-005, Handbook for Developing
Watershed Plans to Restore and Protect Our Waters, October 2005.
Huggett, R. J. (1989). Kepone and the James River, Contaminated Marine Sediments: Assessment
and Remediation, The National Academy of Sciences.
Huggett, R.J., and Bender, M.E. (1980). Kepone in the James River, Environmental Science &
Technology, 14 (8), 918–920.
Huggett, R. J., Nichols, M., and Bender, M.E. (1980). Kepone Contamination of the James
River, American Chemical Society, Division of Environmental Chemistry, 19:1, 341–342.
Nichols, M.M. (2003) Sedimentologic Fate and Cycling of Kepone in an Estuarine System: Exam-
ple from the James River Estuary, The Science of the Total Environment, 97–98, 407–440.
Exercises 199
Sawyer, Clair N., McCarty, Perry L, and Parkin, Gene F. (1994). Chemistry for Environmental
Engineers, McGraw-Hill, New York.
Swanson, P. (2001). Water: The Drop of Life, Minnetonka, Minnesota, Northword Press.
U.S. Geological Survey (2006). Estimated Water Use in the United States, 2000, http://water.
usgs.gov/watuse/, accessed October 11, 2006.
Van Der Leeden, F., Troise, F.L., and Todd, D.K. (1990). The Water Encyclopedia, 2nd ed.,
Lewis Publishers, Chelsea, Michigan.
EXERCISES
8.1 There are eight categories of beneficial uses of water. List four of them and
briefly describe the types of water uses in each.
8.2 As water passes through the hydrologic cycle, it becomes contaminated with
natural and anthropogenic contaminants. List the four major types of water
pollution. Give a brief qualitative description of the water quality of each.
Explain the difference between a point source and nonpoint source of pollu-
tion and give an example of each type of source.
8.3 Water quality is classified by physical, chemical, biological or microbiological,
and radiological parameters. Go to the United States Environmental Protec-
tion Agency’s website at www.epa.gov under the Office of Drinking Water.
List three water quality parameters in each of the four categories (physical,
chemical, microbiological, and radiological) along with the current maximum
contaminant level (MCL) concentration or the required treatment technique
(TT). Select from both primary and secondary standards.
8.4 Solids analysis is one of the most widely used parameters for assessing water
quality. Use the following data for calculating total solids (TS), volatile solids
(VS), dissolved solids (DS), total suspended solids (TSS), and total volatile
suspended solids (TVSS). A sample volume of 150 ml was used in performing
all solids analyses.
9
Water Treatment
9.1 INTRODUCTION
Objectives
The removal of substances from water is accomplished by using biological,
In this chapter, you will chemical, and physical methods. For treatment of potable water sources,
learn about: chemical and physical techniques are more widely used than biological ones.
The selection of A water treatment plant uses a combination of several methods, normally
appropriate unit operated in series. If the treatment method involves physical forces, it is called
operations and unit a unit operation. Treatment technologies that are biological or chemical are
processes that are used called unit processes.
for treating drinking water Each sequence of unit operations and/or unit processes represents a
Primary and secondary “liquid” treatment train. Multiple “liquid” treatment trains are normally
drinking water standards operated in parallel so that high-quality water can be produced in the event a
unit operation or process fails. Parallel treatment trains are also necessary so
Typical water treatment
that equipment maintenance and basin drainage can be accomplished without
flow diagrams for treating
shutting down the entire plant. The residuals, or sludge, produced during water
surface and groundwater
treatment must be collected, thickened, dewatered, and ultimately disposed.
How to design mixing The unit operations and processes involved with sludge handling are called the
systems, flocculation “sludge” trains. Reliability and redundancy issues for sludge handling, treat-
basins, settling basins, ment, and disposal are not quite as critical as those for the liquid treatment
and granular media filters train. It is not uncommon, however, to provide dual units and pumps so that
Water softening and the the sludge can be processed with the largest unit out of service.
lime-soda ash method for Typical unit operations commonly encountered in water treatment include
removing hardness from screening, mixing, aeration, sedimentation, filtration, and ultraviolet-light dis-
water infection. Chemical unit processes in which chemicals are added for removing
The importance of contaminants include coagulation, chemical oxidation, chemical disinfection,
disinfection and selection and chemical precipitation. Biological unit processes in water treatment are less
of the appropriate prevalent than those encountered in wastewater treatment. Biological nitrifica-
disinfectant tion (conversion of ammonia to nitrate under aerobic conditions) and biological
denitrification (reduction of oxidized nitrogen under anoxic conditions) are the
two primary biological processes practiced in water treatment.
202 Chapter 9 Water Treatment
9.2.3 Microconstituents
A number of microconstituents are likely to be regulated by the EPA in the future.
The list includes the following: perchlorate, N-nitrosodimethylamine (NDMA),
endocrine disrupters, pharmaceuticals, personal care products, methyl tertiary butyl
ether (MTBE), and nanoparticles. Additional information on these contaminants
can be found on the EPA and American Water Works Association (AWWA) home
websites (www.epa.gov and www.awwa.org). Endocrine disruptors, pharmaceuti-
cals, and personal care products found in sewage and eventually in our water sup-
plies are of major concern. Those that may cause serious health effects include
antibiotics, hormones, blood lipid regulants, and antidepressants. The effects of these
substances, even at low concentrations, are still unknown, but they are believed to
cause problems with human reproduction systems, the thyroid, and the hypothala-
mus and pituitary systems (MWH, 2005). Nanoparticles may also pose significant
health threats, since these particles range in size from 1nm 110-9 m2 to 100 nm and
are capable of crossing the blood-brain barrier.
An oxidant and/or disinfectant will be added to the filtered effluent to oxidize any
remaining substances and ensure that any remaining pathogens are killed. The
water is then sent to a clear well (storage tank) to allow the oxidant and/or disin-
fectant sufficient detention time to react with the constituents in the water. From
the clear well, the water will be pumped throughout the distribution system by
high-service pumps (high capacity, high head). Supplemental disinfectant, normally
in the form of chloramines, is added to the water pumped into the distribution sys-
tem to ensure a chlorine residual of 0.1–0.2 mg/L is provided at the furthest water
tap in the system.
A similar process train known as direct filtration consists of the same unit
operations and processes presented in Figure 9.1, except that sedimentation is not
used. Another variation of the conventional process train is known as in-line or con-
tact filtration, where both the flocculation and sedimentation processes are omitted.
Both direct and in-line filtration processes are used for higher-quality surface
waters having low turbidity 1615 NTU2, moderate to low color 1620 c.u.2, and low
TOC 164 mg/L2.
Screens
Flow measurement
pH adjustment
Oxidant/disinfectant
Coagulant
Mixing
Flocculation
Sedimentation Sludge
Oxidant/disinfectant
Clear well
High-service pumps
Oxidant/disinfectant
To distribution system
Section 9.4 Overview of Groundwater Treatment Systems 205
Raw water
Bar racks
Screens
Flow measurement
pH adjustment
Oxidant/disinfectant
Catridge filters or
microscreens
Membrane filtration
Washwater recovery or disposal
modules
pH adjustment
Oxidant/disinfectant/fluoride
Clear well
CO2
Recarbonation &
Sludge
sedimentation
Oxidant/disinfectant
Clear well
High-service pumps
Oxidant/disinfectant
To distribution system
Section 9.5 Surface Water Treatment Processes 207
Wells
Flow measurement
pH adjustment
Oxidant/disinfectant
Antiscalant
Catridge filters or
microscreens
Reverse osmosis
Concentrate to disposal
modules
Aeration
Clear well
removing color and natural organic matter (NOM), which are precursors for disin-
fection and disinfection by-products (DDBPs). Figure 9.4 presents a flow diagram
of a typical reverse-osmosis (RO) WTP equipped for hardness removal. One major
drawback to using any type of membrane process is the disposal of concentrate gen-
erated during treatment. Regulatory agencies are sometimes unwilling to permit
deep-well injection of these waste streams.
Rapid Flocculation
mixing Agglomeration Settling Filtration
Figure 9.5 Destabilization
Schematic of coagulation
process. Sludge
Colloidal Particles
A large portion of the solids in surface water and groundwater cannot be removed by
sedimentation because they are colloidal particles. Colloidal particles are extremely
small and have negligible mass and large surface area per unit volume. Colloidal parti-
cles are defined by their size, generally ranging from 1 nm 110-9 m2 to 1 mm 110-6 m2.
Because of their large surface area, colloidal particles tend to acquire a negative sur-
face charge.
Turbidity in water is caused primarily by colloidal and suspended matter such
as clay, silt, nonliving organic particles, plankton, and microbes. Clays are a major
portion of natural turbidity. Kaolinite, montmorillonite, and other clay suspensions
can be removed by adding alum.
Color in water is usually attributed to colloidal forms of iron and manganese
or to organic compounds (humic and fulvic acids) resulting from the decay of veg-
etation. Coagulation is effective in removing color and many organic macromole-
cules and particles from water. Iron (III) and aluminum (III) salts are effective at
removing humic acids, but not as effective with fulvic acids.
Coagulation and filtration readily remove algae and amoebic cysts and can
achieve bacterial removals of 99%. Toxic organic compounds such as polychlori-
nated biphenyls (PCB) and dichloro-diphenyl-trichloro-ethane (DDT) and many
inorganic toxic materials are adsorbed, and thus removed, on naturally occurring
inorganic and organic particulates. Removal of the particulates removes the toxic
substances.
Colloidal Destabilization
Stability of the colloidal particles depends both on the repulsive forces associ-
ated with the electrical charge of the double layer and on the attractive forces
associated with van der Waals forces. If the electrostatic charge on the particles
Section 9.5 Surface Water Treatment Processes 209
Fixed or stern
layer __ Diffuse layer
__
- __
- -
- -
- - -
__ __
__
Colloid
Plane of shear
Electrical
potential
Zeta potential
Figure 9.6
Schematic of the electrical
Distance from surface double layer.
can be reduced or neutralized, the attractive van der Waals forces cause the desta-
bilized colloids to agglomerate or coalesce when particles get close enough
together.
Chemicals called coagulants or flocculants are added to water for destabilizing
colloidal particles. Destabilization can be accomplished by one of four methods:
Coagulants
Aluminum and iron salts are the major types of coagulants used in water treatment,
primarily aluminum sulfate, ferrous sulfate, ferric chloride, ferric sulfate, and sodium
aluminate. Alkalinity is consumed with the addition of inorganic metallic coagulants.
Stoichiometric equations showing the formation of hydroxide precipitates and the
consumption of alkalinity for the various coagulants may be found elsewhere (MWH,
2005; Viessman and Hammer, 2005). Only aluminum sulfate will be discussed in this
section, since its low cost makes it the coagulant of choice in the United States
(MWH, 2005).
Aluminum sulfate or filter alum 3Al2 1SO423 # 14 H2O4 is the major coagulant
used for coagulating turbidity in surface waters. Alum readily dissolves in water, with
sulfate ions (SO 2
4 ) being dispersed throughout the liquid. Aluminum ions exist in
water as hydrated ions. There are no free aluminum ions in the form of Al3+. The sim-
plest hydrated form of aluminum is Al(H 2O)3 6 . Other forms of aluminum include:
Al1OH22+, Al 21OH24+ 4 5 1
2 , Al7(OH)17 , Al13(OH) 34 , and Al(OH) 4 . Al(OH)
2
and
-
Al1OH24 are called monomers, since they have only one Al atom. Al1OH231S2 is a
solid, amorphous, gelatinous precipitate that forms. Each mg/L of alum decreases
210 Chapter 9 Water Treatment
water alkalinity by 0.50 mg/L as CaCO3 and produces 0.44 mg/L of CO2 (Viessman
and Hammer, 2005).
Alum causes coagulation in two ways: adsorption and charge neutralization
or “sweep coagulation.” Adsorption and charge neutralization results when posi-
tively charged aluminum monomers and polymers are adsorbed onto negatively
charged colloids, neutralizing the charge. The alum dose required is less than the
solubility limit of the metal hydroxide. For “sweep coagulation,” a sufficient alum
dose is added such that the solubility limit of the metal hydroxide is exceeded,
allowing the precipitation of Al1OH23 . Colloidal matter and suspended matter
become covered with a gelatinous, sticky sheath, causing them to settle out of
solution.
Coagulant Aids
Coagulant aids include acids and bases that may be added to the water to maintain a
specific pH. Alkalinity is often added in the form of lime (CaO), soda ash 1Na2CO32,
or sodium hydroxide (NaOH) to increase the buffering capacity of the water. Recall
that alkalinity is consumed when inorganic metallic coagulants are used. Therefore,
during water treatment, engineers must design chemical feed and storage facilities
to provide for alkalinity addition during treatment. Other coagulant aids include
anionic, cationic, or nonionic polymers, powdered activated carbon (PAC), and clays.
PAC is added for removing color and the sorption of specific organic compounds.
Clays may be added to provide turbidity or targets for coagulants. Clays should be
added before alum addition. Polymers are normally added after alum or coagulant,
if they are used together.
Polymers are long chains of small subunits or monomers. Polymers may be
cationic or positively charged 1+2, anionic or negatively charged 1-2, or non-ionic
(neutral). The charge is related to functional groups and pH. Major functional groups
associated with polymers include carboxyl (COOH); amines 1NH3+2, and hydroxyl
1OH-2. Polymers must be adsorbed onto the turbidity particles. Charge neutraliza-
tion normally occurs with low-molecular-weight polymers. High-molecular-weight
polymers are used to “bridge” between particles that would otherwise repel each
other. Polymer dosages are normally 61 mg/L. Polymers are ineffective at very low
turbidities; therefore, alum or clay is often added to the water to provide targets or
nuclei for precipitation reactions to occur. If used, the targets should be added prior
to adding the polymer.
The quantity of coagulant that must be added to a particular type of water
must be determined through experimentation. This may be accomplished by per-
forming jar tests in the laboratory using a 6-gang stirring mechanism. Optimum dose
is dependent on pH, temperature, turbidity, and alkalinity. Figure 9.7 is a photo of a
typical jar test apparatus.
9.5.2 Mixing
Mixing is the process whereby chemicals are added and instantaneously dispersed
into the water. Mixing of coagulants has primarily been accomplished by mechani-
cal units. Mechanical mixing is often called rapid or “flash” mixing, since the deten-
tion times used are generally less than 2 minutes and more frequently on the order
of 20 to 30 seconds. Actual chemical reaction times are usually less than 1 second.
Rapid-mix tanks are either square or circular. Stator blades and/or baffles along the
sides of the walls should be used to prevent vortexes from forming. The design of
rapid-mix units is based on detention time and the velocity gradient, G. Detention
Section 9.5 Surface Water Treatment Processes 211
Figure 9.7
Photograph of jar test
apparatus.
time (U) is mathematically defined as the volume of the basin divided by the volu-
metric flow rate:
V
u = (9.1)
Q
where:
u = detention time, min,
V = volume of the mix tank, ft3 1m32, and
Q = volumetric flow rate into mix tank, ft3/min 1m3/min2.
The velocity gradient, G, is a measure of the relative velocity between two fluid
particles divided by the distance between them. For example, if two fluid particles are
traveling at 3 feet per second relative to each other and the distance between the two
is 1.5 feet; the velocity gradient would be calculated as follows:
3 fps 2 fps
G = = = 2 s-1
1.5 ft ft
In the design of rapid-mix and flocculation basins, the velocity gradient is defined by
Equation (9.2).
W 0.5 P 0.5
G = a b = a b (9.2)
m mV
where:
G = velocity gradient, s-1 or fps/ft (mps/m),
W = power input per unit volume, ft # lb/s # ft3 1N # m/s # m32,
V = volume, ft3 1m32,
m = viscosity of water, lb # s/ft2 1Pa # s or N # s/m22, and
P = power input, ft # lb/s 1W or N # m/s2.
212 Chapter 9 Water Treatment
Chemical Chemical
feed feed
a) Back-mix impeller b) Flat-blade mixer
Chemical
feed
Figure 9.8
Schematic for three methods
of injecting coagulant. c) In-line blender
EXAMPLE 9.1
Design of a rapid-mix basin
A water treatment plant processes 30,000 cubic meters of water each day. A square
rapid-mix tank with vertical baffles and flat impeller blades will be used. The design
detention time and velocity gradient are 30 seconds and 900 s-1, respectively.
Determine:
a. The dimensions of the rapid-mix tank.
b. Power input, if the temperature of the water is 20°C.
Solution part a
Solve for the volume of the basin by rearranging Equation (9.1).
m3 min h d
V = u * Q = 30 s * 30000 * * * = 10.4 m3
d 60 s 60 min 24 h
Assuming the depth of the rapid-mix basin is 6 meters, determine the length
and width of the unit. Solve for the area by dividing the volume by the depth.
V 10.4 m3
A = = = 1.74 m2
D 6m
For a square rapid-mix basin, length (L) is equal to width (W), so A = W2.
Solution part b
The power input to the rapid-mix basin is determined by rearranging Equation (9.2).
The absolute viscosity of water at 20°C is 1.002 * 10-3 N # s/m2 11.002 * 10-3 kg/m # s2.
The volume of the rapid-mix basin is: 11.32 m2 * 11.32 m2 * 16 m2 = 10.45 m3.
N#s N#m
P = G2 mV = 1900 s-122 ¢ 1.002 * 10-3 b110.45 m3
2 = 8481
m2 s
N#m 1W
1 N # m/s
P = 8481 a b = 8481 W = 8.5 kW
s
CDArvr 3
P = (9.3)
2
where:
P = power dissipated in the water, ft # lb/sec 1N # m/sec2,
CD = coefficient of drag, equal to 1.8 for flat blades, dimensionless,
A = area of paddles, ft 2 (m2),
r = mass density of water, lb # s2/ft4 1kg/m32, and
vr = velocity of the paddles relative to water, fps (mps).
Normally vr is 0.50 to 0.75 of the paddle velocity 1vp2. The velocity of the pad-
dle blade is calculated from the following equation:
vp = 2prN (9.4)
where:
vp = velocity of the paddle blade, fps (mps),
r = distance from the center of the shaft to the center of the blade, ft (m),
N = rotational speed, revolutions/second.
214 Chapter 9 Water Treatment
EXAMPLE 9.2
Design of a flocculation basin
A four-arm paddlewheel with the following configuration will be used in a floccula-
tion basin. Each arm has two paddles 3.0 meters long by 0.1 meter wide.The distance from
the shaft to the center of the blade is 1.0 meter for the inner paddle and 1.5 meters for the outer
paddle.The minimum anticipated temperature of the water is 20°C with an absolute viscosity,
m = 1.002 * 10-3 N # s/m2 and density, r = 998.2 kg/m3. The angular or rotational
speed is 4 revolutions per minute (rpm). The flocculation basin treats 6.0 * 106 liters
per day. Assume: vr = 0.75vp and CD = 1.8.
a. Determine how much power (P) is dissipated into the water.
b. Determine the Gt value for the flocculation basin if the dimensions of the
flocculation basin are 4 meters long by 4 meters wide by 4 meters deep.
R2 1.5 m
R1 1 m
Solution part a
Solution part b
Calculate the velocity gradient G using Equation (9.2) so that the Gt value can be
estimated.
V = 4 m * 4 m * 4 m = 64 m3
N#m 0.5
0.5 0.5 1
W P 146 W s
N#s
G = a b = a b = § * § ¥¥
m mV 1W
1.002 * 10-3 2 * 164 m32
m
G = 47.7 s-1
V 64 m3 1000 L 24 h 60 min 60 s
u = = * ¢ ≤¢ ≤¢ ≤¢ ≤ = 922 s
Q 6 * 10 lpd
6
1m 3 1d 1h 1 min
Gt = 47.7 s-1 * 922 s = 4.4 * 104 OK because between 104 and 105
Chemical Precipitation
Chemical precipitation through the addition of lime (CaO) and soda ash 1Na2CO32
is the primary means of removing hardness from water. The extent of chemical pre-
cipitation of hardness is based on the solubilities of calcium carbonate 1CaCO32 and
magnesium hydroxide 1Mg1OH222. The solubility products of CaCO3 and Mg1OH22
are presented in Equations (9.5) and (9.6) below (Sawyer et al., 1994).
CO2
Lime
CO2
CaCO3
Mg(OH)2
Soda Flocculator/
ash clarifier Recarb
Figure 9.9
Schematic of two-stage
lime-soda ash softening CaCO3
WTP.
Mg(OH)2 precipitation, the pH must be greater than 11.0. Typically, 1.25 meq/L of
lime are added above the stoichiometric quantity to raise the pH above 11. Adding
lime increases the Ca2+ concentration in the water, thus forcing the concentration of
CO2-3 to be lowered according to Equation (9.5), which is accomplished by the pre-
cipitation of CaCO3 . Also, lime addition raises the pH of the water, causing a shift in
the solubility of Mg1OH22 according to Equation (9.6), resulting in the precipitation
of Mg1OH22 . The addition of soda ash also raises the pH causing the precipitation of
Mg1OH22 as well. When excess lime treatment is used, the residual total hardness is
about 40 mg/L as CaCO3 . Approximately, 30 mg/L as CaCO3 is associated with
CaCO3 solubility, and 10 mg/L as CaCO3 is associated with Mg1OH22 solubility.
Figure 9.9 is a schematic of a two-stage softening process using chemical pre-
cipitation. Solids contact units are shown in lieu of the conventional coagulation,
flocculation, sedimentation process that uses rapid mixers and flocculation followed
by settling basins. Solids contact units provide all three functions in one compact unit.
Before any hardness removal can occur, any lime that is added will first neutralize
any carbonic acid present according to Equation (9.9). The carbonic acid is precipi-
tated as CaCO3 .
Lime is added for the precipitation of calcium and magnesium carbonate hard-
ness. Equations (9.10) through (9.12) show reactions associated with the removal of
Section 9.5 Surface Water Treatment Processes 217
Excess lime treatment is often practiced, wherein 1.25 milliequivalents per liter
(meq/L) of lime are added above the amount predicted by the stoichiometric
equations to ensure that the pH of the water is raised above 11. Recarbonation is
the process of adding carbon dioxide to lower the pH and stabilize the water.
Equation (9.17) shows that excess lime, Ca1OH22 , is converted to CaCO3 by
adding carbon dioxide. This reaction lowers the pH from around 11 to about 10.2
(Viessman and Hammer, 2005):
EXAMPLE 9.3
Excess-lime soda-ash softening problem
Calculate the lime and soda-ash requirements to achieve the practical limits of hard-
ness removal given the following water analysis. Develop a bar graph showing the
original theoretical species in the water.
CO2 = 8.8 mg/L alkalinity 1HCO3-2 = 135 mg/L as CaCO3 Mg2+ = 14.7 mg/L
Solution
Figure 9.10 is a bar graph showing the theoretical combination of species in the
raw water. If CO2 is present, it is placed on the left side of the bar graph. Cations
are always placed at the top of the bar graph; calcium, magnesium, and sodium
are shown in this order. Anions are shown at the bottom of the bar graph and
should be sequenced as follows: hydroxide, carbonate, bicarbonate, sulfate, and
chloride. The water should be electrically neutral, so the concentration of cations
must balance the anions. If not, the water analysis is suspect. Viessman and Hammer
(2005) present the details of developing bar graphs.
The accompanying table presents the theoretical species, along with the
dosages of lime as calcium oxide (CaO) and soda ash as sodium carbonate
1Na2CO32 that must be added to achieve a residual hardness of approximately
40 mg/L as CaCO3 . Excess-lime treatment is assumed, which involves adding
1.25 meq/L of lime as CaO (equivalent to 35 mg/L as CaO) beyond the stoichio-
metric dosage. Equations (9.11) and (9.12) must both be used to determine the
quantity of lime required for precipitating magnesium bicarbonate. For each
mole of Mg1HCO322 , 2 moles of lime are required. Similarly, Equations (9.13
and 9.15) must be used to determine the quantity of lime and soda ash required
for removing magnesium sulfate.
Component (1) Equation (2) Concentration (3) (meq/L) CaO (4) (meq/L) Na2CO3 (5) (meq/L)
The total lime dosage as CaO, assuming 100% purity, is the sum of all species in
Column 4:
If the purities of CaO and Na2CO3 are both 90%, the total dosages for each are
as follows:
9.5.5 Sedimentation
Sedimentation is a unit operation involving solids-liquid separation by gravita-
tional settling to remove suspended solids. In water treatment, two types of settling
are encountered: Type I—free or discrete settling, and Type II—flocculent settling.
Each will be discussed, and examples will be presented illustrating the procedure
for designing settling basins.
Type I—Free or Discrete Settling
Free or discrete settling is the settling of discrete, nonflocculent particles whose size,
shape, and density do not change with time as they settle. Particles settle as individ-
ual entities, and there is no interaction between particles. Examples of discrete set-
tling include grit and sand particles in grit-removal systems and plain sedimentation
(no coagulation) of surface waters.
The settling velocity of a spherical particle (Newton’s law) is calculated as follows:
4 g rp - rw 0.5
Vs = B ¢ ≤dR (9.19)
3 CD rw
where:
Vs = settling velocity, fps (m/s),
g = acceleration of gravity, ft/s2 1m/s22,
CD = coefficient of drag (dimensionless),
m = mass of particle, lb (kg),
rp = density of particle, lb # s2/ft4 1kg/m32,
rw = density of liquid, lb # s2/ft4 1kg/m32, and
d = diameter of particle, ft (m).
The coefficient of drag 1CD2 is a function of the flow regime, which is estimated by
calculating the Reynolds number 1NR2.
rwVsd Vsd
NR = = (9.20)
m v
where:
m = absolute or dynamic viscosity of water, lb # s/ft2 1kg/m # s2, and
v = kinematic viscosity of water, ft2/s 1m2/s2.
When the Reynolds number is 61, laminar flow conditions exist, and CD is
calculated using Equation (9.21).
24
CD = (9.21)
NR
Section 9.5 Surface Water Treatment Processes 221
24 3
CD = + + 0.34 (9.22)
NR 1NR20.5
The coefficient of drag is assumed to be equal to 0.4 for turbulent flow when
NR 7 104.
For laminar flow conditions, Newton’s law simplifies to Stokes’ law by substi-
tution of 24/NR for the coefficient of drag, resulting in Equations (9.23) and (9.24).
g1rp - rw2d2
Vs = (9.23)
18m
g1SGp - 12d2
Vs = (9.24)
18v
Figure 9.11 shows a settling column with sampling ports. The curves in the plot
represent isoremoval lines (SS removal %). Equation (9.26) is used for calculating
the overall percent removal of solids that may be achieved at a given detention time.
where:
RT = total fraction of suspended solids removed at a given detention time, %,
R0 = isopercent removal line intersecting the time axis at specified settling
column depth, %,
¢R = difference between adjacent isopercent removal lines, %,
Zi = distance from top of settling column or water level in column to the
midpoint between two adjacent isopercent removal lines, ft (m), and
Z0 = total depth of settling column, ft (m).
0.0
0 10 20 30 40 50 60
0.5
Depth, m
70%
1.0
1.5
60%
2.0
20% 30% 40% 50%
2.5
0.0 10 20 30 40 50
Time, min
Figure 9.11
Settling column and plot.
Q Q
Vh Effluent
Influent
H
Vs
Figure 9.12
Ideal settling basin. L
to determine the size of settling basins. Water treatment plant operators regulate the
overflow rate of settling basins to ensure optimal removal of suspended solids. The
overflow rate 1Vo2 is just another way of expressing the settling velocity 1Vs2 associ-
ated with a particle having a specific diameter. Recall that the settling velocity of a
particle is primarily a function of the particle diameter, as expressed in Equations
(9.23) and (9.24). Engineers select an overflow rate (which actually relates to a parti-
cle having specific size or diameter) and assume that particles equal or larger in diam-
eter will theoretically be 100% removed. The derivation of the overflow rate follows.
Recall that distance traveled is equal to the rate or velocity times time
1D = R * t2. The time that a particle remains in a settling basin is expressed by
Equations (9.27) and (9.28).
t = H>Vs (9.27)
t = L>Vh (9.28)
Section 9.5 Surface Water Treatment Processes 223
The continuity equation states that the volumetric flow rate (Q) is equal to the
cross-sectional area multiplied by the velocity of flow:
Q = AV (9.29)
Q Q
Vh = = (9.30)
A WH
where:
t = settling time, min, hours,
H = depth of settling basin, ft (m),
L = length of settling basin, ft (m),
W = width of settling basin, ft (m),
Q = flow rate through basin, ft3/s 1m3/s2,
V = average flow velocity, fps (mps),
Vh = horizontal flow-through basin velocity, fps (mps),
Vs = settling velocity, fps (mps), and
A = cross-sectional area = W * H, ft2 1m22.
To derive the overflow rate equation, Vo is substituted into Equation (9.27) for
Vs as follows:
H H
t = = (9.31)
Vs Vo
L L
t = = (9.32)
Vh Q>1WH2
H L
t = = (9.33)
Vo Q>1WH2
HQ Q Q
Vo = = = (9.34)
LWH LW As
Q
Vo = (9.35)
As
The detention time is defined as the time that the water remains in the settling
basin. Normally the Greek letter theta 1u2, rather than t, is used for denoting deten-
tion time. Substituting Vh from Equation (9.30) into Equation (9.28) results in the
detention-time equation as presented below:
L LHW V
u = t = = = (9.36)
Vh Q Q
Q
weir loading rate = (9.37)
weir length
Figure 9.13
Q Q
Schematic of settling basin Settling zone
with inlet, settling, outlet, Influent Effluent
and sludge zones. Vh
Outlet zone
Inlet zone
Vs
Sludge zone
L
Section 9.5 Surface Water Treatment Processes 225
Overflow rate 1Vo2, gpd/ft2 500 to 800 700 to 1000 700 to 1500
Detention time, h 4 to 6 4 to 6 4 to 8
Weir loading rate, m3/1d # m2 150 to 220 200 to 270 270 to 320
Weir loading rate, gpd/ft 12,000 to 18,000 16,000 to 22,000 22,000 to 26,000
Next, the detention time is chosen and the depth determined by dividing the vol-
ume by the surface area. The weir loading rate is calculated after the planning of
the weir configuration.
Table 9.1 lists typical design criteria for settling basins. Rectangular basins nor-
mally have a length-to-width (L:W) ratio of 2:1 to 4:1 and a length-to-depth (L:D)
ratio of 10:1 to 20:1. Bottom slopes are 1/100. Settling-basin depths range from 8 to 10
feet (2.5 to 3 m) for discrete particles and from 10 to 13 feet (3 to 4 m) for flocculent
particles. Square tanks have dimensions ranging from 35 to 200 feet (11 to 91 m) and
depths ranging from 6 to 19 feet (2 to 6 m). Where circular tanks are used, tank
diameters of 15 to 300 feet (4.5 to 91 m) may be used. Normally, however,
diameters … 200 feet 1… 61 m2 are used, and depths are usually 6 to 16 feet (2 to 5 m).
All depths reported are in terms of side water depth (SWD), which is the depth of
water at the side of the tank from the top of the effluent weir to the bottom of the
tank. An additional 1 to 2.5 feet (0.3 to 0.8 m) must be added to the SWD to account
for flow variations, which are relatively insignificant in water treatment plant design
but are appreciable in wastewater applications. Figure 9.14 is a photo of a long rectan-
gular settling basin.
Figure 9.14
Photo of long rectangular
settling basin.
226 Chapter 9 Water Treatment
EXAMPLE 9.4
Rectangular settling basin example
Two rectangular settling basins, each 90 ft long, 16 ft wide, and 12 ft deep, are operated
in parallel to settle 1.5 MGD of water (0.75 MGD to each basin). The effluent weir
length in each basin is equal to 3 tank widths.
Determine:
a. Detention time.
b. Horizontal flow velocity.
c. Surface overflow rate.
d. Weir length.
e. Weir loading rate.
Solution part a
The detention time is determined using Equation (9.1).
V 90 ft * 16 ft * 12 ft 7.48 gal 24 h
u = = ¢ ≤a b = 4.14 h
Q 0.75 * 106 gal>d ft3 d
Solution part b
The horizontal flow-through velocity is calculated using Equation (9.30).
Solution part c
The overflow rate 1Vo2 is determined from Equation (9.34).
Solution part d
Next, the weir length is estimated so that the weir loading rate may be determined:
Solution part e
Finally, the weir loading rate is calculated.
9.5.6 Filtration
Filtration is a unit operation that involves the separation of nonsettleable solids
from water or wastewater by passing the water through a porous medium. In
conventional filtration, water must be coagulated, flocculated, and settled
Section 9.5 Surface Water Treatment Processes 227
before passing through the filter. Direct filtration of water is sometimes prac-
ticed in which coagulated water is applied directly to filters without having
undergone sedimentation. Flocculation may or may not be included in the treat-
ment train.
Filters are generally classified according to the types of media used. Single, or
monomedia filters, have only one type of media, which is usually sand or crushed
anthracite coal. Dual-media filters typically consist of a layer of coarse anthracite
coal above a layer of sand. Multimedia filters, such as trimedia filters, typically con-
sist of a layer of coarse anthracite coal above a layer of sand and a layer of garnet
below the sand.
Sand
24-30 in
V-2
Gravel V-3
To 15-20 in
washwater
recovery FC
ponds V-4
Underdrains
Clear well
228 Chapter 9 Water Treatment
accomplished by partially opening the flow-control valve (FCV) and, as the filter
run progresses, opening the valve wider to allow the same amount of flow as the
head loss increases.
Although not shown, water from the clear well is pumped throughout the water
distribution system using high-service pumps. Other valves shown in Figure 9.15 are
either open or closed during the filtration and backwashing cycles. The underdrain
system is approximately 1 foot (0.3 m) in depth. The static water head on the sand
media generally varies from 3 to 4 feet (0.9 to 1.2 m).
L 11 - e2 V2a X
œ ij
hL = ©f (9.38)
w e3 g di j
1 - e
fœ = 150 ¢ ≤ + 1.75 (9.39)
NR
where:
hL = frictional head loss, ft (m),
L = depth of filter bed, ft (m),
e = porosity of bed, dimensionless,
w = dimensionless shape factor for different types of media,
Va = filtration velocity or velocity of approach, total flow applied to the
filter divided by the filter area, fps (mps),
g = gravitational acceleration, ft/s2 1m/s22,
di j = particle size = geometric mean of adjacent sieve sizes, ft (m),
Xi j = weight fraction of media retained on adjacent sieve sizes,
NR = dimensionless Reynolds number, and
fœ = Carman-Kozeny dimensionless friction factor.
Shape factors for several types of media are as follows: pulverized coal = 0.73,
angular sand = 0.73, rounded sand = 0.82, and Ottawa sand = 0.95.
EXAMPLE 9.5
Head loss across a filter of nonuniform particles
Determine the head loss for a clean filter bed using the Carman-Kozeny equation
for a stratified bed with uniform porosity of 0.45. The rapid sand filter is made up
of a 24-inch-deep bed of sand, specific gravity 2.65, shape factor () 0.82, tem-
perature of 50°F, and filtration rate of 2.5 gpm/ft2. A sieve analysis is presented
below.
Section 9.5 Surface Water Treatment Processes 229
% Sand retained di j f¿ X
f¿
ij ij
Sieve (2) (3) NR ij di j
(1) 1Xi j2 1ft * 10-32 (4) (5) (6)
14–20 0.87 3.2883 1.07E +00 7.92E +01 210
20–28 8.63 2.333 7.56E -02 1.11E +02 4103
28–32 26.30 1.779 5.76E -01 1.45E +02 21422
32–35 30.10 1.500 4.86E -01 1.72E +02 34420
35–42 20.64 1.258 4.08E -01 2.04E +02 33501
42–48 7.09 1.058 3.43E -01 2.42E +02 16248
48–60 3.19 0.888 2.88E -01 2.89E +02 10365
60–65 2.16 0.746 2.42E -01 3.43E +02 9935
65–100 1.02 0.583 1.89E -01 4.39E +02 7673
100 © = 137,876
Solution
At a temperature of 50°F, v = 1.410 * 10-5 ft2/sec. First, calculate the approach
velocity as follows:
gpm 1 ft3 1 min
Va = 2.5 2
¢ ≤¢ ≤ = 5.57 * 10-3 fps
ft 7.48 gal 60 s
For sieves 14–20, the Reynold’s number is calculated as follows, using Equation (9.20).
The shape factor 1w2 must be included in Equation (9.20) to account for particles that
are not completely spherical.
fVd 0.8215.57 * 10-3 fps213.2883 * 10-3 ft2
NR = = = 1.065
v 1.410*10-5 ft2>s
The new friction factor, fœ, is calculated using Equation (9.39) as follows:
1 - e 1 - 0.45
fœ = 150 ¢ ≤ + 1.75 = 150a b + 1.75 = 79.2
NR 1.065
Calculate the following quantity:
fiœ jXi j fiœ jXi j 79.210.87>1002
a = = = 210
di j di j 3.2883*10-3 ft
The values in the table were calculated using a spreadsheet; hand calculations may
differ slightly, because of round-off error.
Next calculate the head loss in the clean filter using Equation (9.38) as follows.
L11 - e2V2a fiœ jXi j
hL = a
fe3 g di j
2 ft11 - 0.45215.57 * 10-3 fps22
hL = 1137,8762 = 1.96 ft
10.822 0.453 132.2 ft>s22
The head loss of a clean filter typically ranges from 0.5 to 1.5 feet (0.15 to 0.46 m),
depending on filtration rate and depth of media.
230 Chapter 9 Water Treatment
Backwashing of Filters
Granular media filters must be backwashed to remove particulates and turbidity that
build up during filter operation.Typically, operators backwash a filter when: a) the head
loss through the filter reaches 8 to 10 feet (2.4 to 3 m), or b) the turbidity in the effluent
reaches a specific level, such as 0.25 NTU, or c) the filter has been in operation for a
specified amount of time (such as 24 to 48 hours). The water used for the backwashing
process is filtered, disinfected, and stored in a tank that is either elevated, at ground
level, or underground. Figure 9.16 is a cross-sectional view of a rapid sand filter during
the backwashing process. High-pressure backwash pumps are necessary if an elevated
backwash storage tank is not used. Backwash water at a rate of around 15 to 20 gpm/ft2
(611 to 815 lpm/m2) for 15 to 20 minutes is required to properly expand and clean a
dirty filter. Approximately 1% to 5% of the filtered water is used during the back-
washing process. The dirty washwater is collected in the backwash water troughs and
transported to the washwater recovery pond, where the solids are settled out of solu-
tion and the supernatant is returned to the head of the water treatment plant.
Filter Media
Filter media is characterized by its effective size and uniformity coefficient. The
effective size 1de2 is defined as the 10-percentile diameter, or the sieve size in mm that
will pass 10% (by weight) of the filter media. The uniformity coefficient is the ratio of
the 60-percentile to 10-percentile diameters. Table 9.2 lists the effective size, unifor-
mity coefficient, depth of media (D), and media or bed depth to effective size 1D/de2
ratios for various types of filter media. The specific gravities of sand, anthracite, and
garnet are 2.65, 1.4 to 1.6, and 4 to 4.1, respectively. Silica sand and anthracite coal are
the most widely used media types. The D/de ratio is used to estimate the depth of each
layer of media, once the effective size has been selected. Figure 9.17 is a schematic
showing the media configurations of sand, dual-media, and mixed-media filters.
Number of Filters
For water treatment plants processing 62.0 MGD 188 L/s2, a minimum of two filters
should be used. If the capacity of the WTP exceeds 2.0 MGD, the minimum should be
four filters. Equation (9.40) is used for estimating the number of filters (N) required
as a function of flow.
V-2
V-3
Washwater
FC
to recovery
pond V-4
Clear well
Section 9.5 Surface Water Treatment Processes 231
Coal
Coal
24-36 in
30-40 in
28-48 in
Sand Sand
Finer
Sand
Garnet
Coarse Fine Finest
N = 1.2Q0.5 (9.40)
where:
N = total number of filters, and
Q = maximum daily flow rate, MGD.
For large WTPs processing over 20 MGD 175,700 m3/day2, filters have 2 cells
each with a gullet running down the center. Figure 9.18 shows a layout of a single fil-
ter for a large WTP.
Size of Filters
According to Kawamura (1991), conventional gravity filters use length-to-width
(L:W) ratios of 2:1 to 4:1. Surface areas of gravity filters typically range from 250 to
1000 ft2 (25 to 100 m2), and filter depths range from 12 to 20 feet (3.2 to 6 m).
232 Chapter 9 Water Treatment
Cells 1 and 2
comprise Settled
Gullet
one filter water
Filtration Rates
Filtration rates depend on the type of media used in design. Kawamura (1991)
recommends the following filtration rates:
• Medium sand filters: 2 to 3 gpm/ft2 (5 to 7.5 m/h)
• Coarse sand filters: 4 to 12 gpm/ft2 (10 to 30 m/h)
• Dual and multimedia filters: 4 to 10 gpm/ft2 (10 to 25 m/h)
• Granular activated-carbon (GAC) filters: 3 to 6 gpm/ft2 (7.5 to 15 m/h)
EXAMPLE 9.6
Filter dimensions and backwash quantity
A water treatment plant has four rapid sand filters. Each filter is designed for a
capacity of 1 MGD. Backwashing is accomplished for 9 minutes at a rate of
15 gpm/ft2 once every 24 hours. The terminal head loss prior to backwashing aver-
ages 4 to 10 feet.
Determine:
a. The filter dimensions if an application or filtration rate of 3.5 gpm/ft2 is
used.
b. The quantity of water required for backwashing and percentage of filtered
water used in backwashing.
Solution part a
Determine the surface area 1As2 of the filters by dividing the design flow rate by the
filtration rate 13.5 gpm/ft22 and making appropriate conversions.
1 * 106 gal/d
As = = 198 ft2
13.5 gal/min # ft2211440 min/d2
Solution part b
The backwash flow rate 1Qb2 is estimated by multiplying the backwash velocity or
rate by the filter surface area 1As2 times the backwash duration (9 min/day).
15 gal>min 9 min
Qb = ¢ 2
≤ 114 ft * 14 ft2a b = 2.65 * 104 gpd
ft d
The amount of water used for backwashing varies from 2% to 4% of the filtered
water.
9.5.7 Disinfection
Disinfection is a unit process in which a chemical is added to the treated water to
oxidize residual organics and pathogens. The objective of disinfection is to kill path-
ogenic (disease-causing) microorganisms, whereas the objective of sterilization is to
destroy all microorganisms. Conventional water treatment, which includes coagula-
tion, flocculation, sedimentation, and filtration, removes over 90% of the pathogens
found in water. Pathogens are also killed at high pH levels, therefore, the excess
lime-soda ash process is effective. The conventional water treatment scheme
described above along with disinfection as the last process will produce safe, potable
water that will meet regulatory requirements.
Selection of the appropriate disinfectant is essential, because some types are
more effective at killing viruses versus bacteria or vice versa. The type of disinfec-
tant used also affects the production of potential or suspected carcinogens, such as
trihalomethanes (THMs) and haloacetic acids. The disinfectant selected should act
as a powerful oxidizing agent in addition to providing a residual in the water distri-
bution system to eliminate regrowth of pathogens.
There are four major categories of human enteric pathogens: bacteria, viruses,
protozoa, and helminths. Some of the diseases and associated organisms for each
group are presented below.
1. Bacteria: typhoid fever is caused by Salmonella typhi; paratyphoid by
Salmonella paratyphi; and cholera by Vibrio cholerae.
2. Protozoan parasites: amoebic dysentery is caused by Entamoeba histolytica;
diarrhea and gastrointestinal problems by Cryptosporidium parvum and
Giardia lamblia.
3. Helminth parasites: hookworm is caused by Necator americanus; roundworm
by Ascaris lumbricoides; and whipworm by Trichurus trichiura.
4. Viruses: poliomyelitis is caused by the Poliovirus species; and hepatitis or
inflammation of the liver by the Hepatitis A or Hepatitis E strain.
Additional information on these pathogens may be found in MWH, 2005;
Masters, 1997; and Viessman and Hammer, 2005.
234 Chapter 9 Water Treatment
Regulatory Requirements
The Surface Water Treatment Rule (SWTR) and Disinfection and Disinfection By-
Products Rule (D-DBP) are two important regulations promulgated by the EPA
that have a significant impact on the disinfection process. These regulations specify
certain removal levels for Giardia lamblia and viruses and therefore must be con-
sidered when selecting the appropriate disinfectant.
Surface Water Treatment Rule Primary drinking water regulations have
been established for surface waters and ground waters under the direct influence of
surface water. Under these regulations, filtration and disinfection are required for
all surface water sources and those groundwaters that are directly influenced by sur-
face water. A 3-log reduction or 99.9% removal in Giardia lamblia and a 4-log
reduction or 99.99% in viruses must be achieved.
Disinfectants and Disinfection By-Products Rule: D-DBP Under the Disinfection
and Disinfection By-Products Rule there are limits required for haloacetic acids and
trihalomethanes. The five haloacetic acids regulated (HAA5) include: mono-
chloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and
dibromoacetic acid. The maximum contaminant level (MCL) for HAA5 is 0.06 mg/L.
Total trihalomethanes (TTHMs) consist of chloroform, dibromochloromethane, and
bromoform. The MCL for TTHMs is 0.08 mg/L.
Chick’s Law
An effective disinfectant should act quickly (fast rate of kill) and provide a residual.
The rate of kill is modeled as a first-order removal equation known as Chick’s law:
Nt = N0e-kt (9.41)
where:
Nt = number of microorganisms at time t,
N0 = number of microorganisms at time zero,
k = rate constant, time-1, and
t = contact time, time.
The rate constant (k) and contact time (t) necessary to achieve a specified
kill are a function of the type of pathogen and the type of disinfectant used. The
Ct parameter is useful for selecting the proper disinfectant and for designing
tanks and reactors to accomplish a specified level of kill. Ct values are calcu-
lated by multiplying the concentration of disinfectant (mg/L) by the contact
time (minutes). Research results on various types of disinfectants at different
contact times have been published for a variety of pathogens (Reynolds and
Richards, 1996).
Figure 9.19 shows a plot of chlorine concentration as hypochlorous acid
(HOCl) versus contact time (minutes) for various types of pathogens (three viruses
and one bacterium). These types of figures allow environmental engineers several
options when designing disinfection systems. For instance, to achieve a 99% kill of
Escherichia coli, the design engineer could use a chlorine dosage of 0.3 mg/L at a
contact time of 1 minute or use a chlorine dosage of 0.02 mg/L at a contact time of
10 minutes. Engineers must provide a flexible design, since a tank or reactor’s size is
fixed upon construction. The only variable that can change is the disinfectant
dosage. Therefore, the disinfectant feed system must be capable of achieving a wide
range of dosages.
Section 9.5 Surface Water Treatment Processes 235
10.0
N
l
H2
Cl
0.1 H
O
Cl
Figure 9.19
Chlorine concentration ver-
0.01 sus contact time for 99% kill
1 10 100 1000 of E. coli by various forms
Contact time, minutes of chlorine.
Mechanisms of Disinfectants
The effectiveness of the disinfection process, as previously discussed, is determined
by both the concentration and contact time. Other parameters that influence
pathogen kill include: pH, temperature, type of disinfectant, type of microorganism,
and turbidity.
Several mechanisms are proposed for killing pathogenic microorganisms. They
include:
1. Destroying the cell walls
2. Altering cell permeability
3. Penetrating the cell, causing reactions with enzymes and protoplasm
4. Damaging the cell’s DNA and RNA
Details on these mechanisms can be found in Crites and Tchobanoglous, 1998;
Peavy, Rowe, and Tchobanoglous, 1985; and MWH, 2005.
Chemistry of Chlorination
At most water and wastewater treatment plants, chlorine gas is injected into water
under pressure to ensure dissolution of the gas and the formation of hypochlorous
acid (HOCl). The hypochlorous acid dissociates into the hydrogen ion and the
hypochlorite ion 1OCl-2. Both hypochlorous acid and the hypochlorite ion are
strong disinfectants, producing free chlorine residual. However, they do not provide
a long chlorine residual. The following two reactions illustrate the formation of
HOCl and OCl-. HOCl is a more powerful oxidant than OCl-. The proportion of
HOCl and OCl- is a function of pH. At 20ºC and a pH of 7.5, both HOCl and OCl-
represent 50% of the chlorine concentration.
Chloramines
Frequently, ammonia is added to finished drinking water so that a long-lasting chlo-
rine residual can be maintained through the formation of chloramines. Chloramines
are not as strong of a disinfectant as hypochlorous acid and hypochlorite ion, but
they maintain much longer residuals in the water distribution network. Analytical
measurement of ammonia nitrogen measures both the ammonium nitrogen 1NH4+2
and ammonia gas 1NH32 dissolved in the sample. Ammonium dissociates according
to the following reaction.
NH 4+ Δ H + + NH 3 (9.46)
Breakpoint Chlorination
Some facilities practice breakpoint chlorination, which involves adding high
dosages of chlorine to achieve a free chlorine residual, rather than a combined
chlorine residual, as associated with chloramines production. Figure 9.20 shows
the chlorine residual curve as a function of the chlorine dose applied. In Figure
9.20, moving from point A to B indicates that the chlorine added to the water
reacts with reducing compounds such as nitrite 1NO2-2, ferrous iron 1Fe2+2, and
hydrogen sulfide 1H2S2, resulting in a negligible chlorine residual. From point B
to C, addition of more chlorine results in chloramine production and formation
of combined residual. From point C to D, further chlorine addition results in
the oxidation of chloramines, thereby reducing chlorine residual. Point D is
known as the breakpoint, and addition of more chlorine results in free chlorine
residual.
Section 9.5 Surface Water Treatment Processes 237
Applied Chlorine
Chlorine residual
Combined Cl2
C residual
Free Cl2
D
residual
Figure 9.20
B
Breakpoint chlorination
A Chlorine dosage curve.
2. OCl- 2. OCl-
3. Chloramines 3. HOCl
238 Chapter 9 Water Treatment
Chlorine Dioxide Chlorine dioxide 1ClO22 is a powerful oxidizing agent that does
not form chloroform or chloramines. It provides a stable chlorine residual, and typi-
cal dosages are 0.10 to 3.0 mg/L for terminal disinfection and up to 10 mg/L for con-
trolling taste and odor problems. It is easily removed from water by aeration and
readily decomposes by being exposed to UV radiation. A potential disadvantage is
that it may reduce to chlorate, a potential carcinogen.
UV Radiation UV radiation with wavelengths in the range 245 to 285 nm can be
produced by mercury-vapor arc lamps. UV mercury-vapor lamps are placed in
quartz sleeves, which are then placed into the water. UV radiation is effective
against bacteria and viruses, but turbidity and suspended solids inhibit it and should
be removed prior to UV exposure. A typical dosage is 24,400 mwatts # sec/cm2. Two
disadvantages are that (1) there is no residual, so chlorine or alternative disinfec-
tants must be added; (2) the quartz sleeves must be cleaned periodically.
High-pH Treatment Lime addition to raise the pH of water to a range of 11.2 to
11.3 with a contact time of 1.56 to 2.4 hours has proven effective in killing pathogens.
Flocculation
Recycle
Clear well
High-service pumps
Drying P&F
Lagoons Centrifuges
beds presses
To distribution system
Dewatered sludge
of sludge handling, dewatering, and disposal of water treatment residuals. The types
of chemicals used during water treatment have a significant impact on the treatment
and ultimate disposal of water treatment sludges. Water-softening residuals may
have beneficial impacts on soil and crop yields, whereas there are concerns about
the application of aluminum and iron sludges to crops (MWH, 2005). An excellent
resource on water-residuals management is Water Treatment Principles and Design,
Chapter 20 (MWH, 2005). Dewatered sludge has primarily been disposed of in san-
itary landfills. Some municipalities such as the Macon Water Authority blend it with
stabilized wastewater biosolids, compost it, and then sell it for soil amendment for
application on agricultural lands.
S U M M A RY
Providing safe, potable water to the public is one of the major responsibilities of
environmental engineers. If primary and secondary drinking water standards are to
be achieved, the selection of appropriate unit operations and unit processes for
treating water is critical. This chapter presented and discussed typical water treat-
ment flow diagrams that have been successfully used for treating surface water and
groundwater. Examples were given of how to design rapid-mix basins, flocculation
basins, settling basins, and filters. Although not a health concern, hardness removal
using the lime-soda ash softening process was discussed, and an example was pre-
sented of how to calculate the quantity of lime and soda ash required to achieve a
residual hardness of 40 mg/L as CaCO3 . Also discussed were the importance and
selection of the appropriate disinfectant, as well as the technologies used for han-
dling and treating water treatment plant residuals.
REFERENCES
Carman, P.C. (1937) Fluid Flow Through Granular Beds. Transactions of Institute of Chemical
Engineers (London) Vol. 15, p. 150.
Crites, R. and Tchobanoglous, G. (1998) Small and Decentralized Wastewater Management
Systems, WCB/McGraw-Hill, Boston, MA.
Great Lakes – Upper Mississippi Board of State Public Health and Environmental Managers.
(1992) Recommended Standards for Water Works. Ten State Standards. Albany, NY.
Kozeny, G. (1927) Sitzber. Akad. Wiss. Wein. Math. – Naturw. Kl,. Abt. Ila 136.
Kawamura, S. (1991) Integrated Design of Water Treatment Facilities, John Wiley & Sons, Inc.,
New York, NY.
Masters, G.M. (1997) Introduction to Environmental Engineering and Science, Prentice-Hall,
Upper Saddle River, NJ.
MWH (2005) Water Treatment Principles and Design, John Wiley & Sons, Inc., Hoboken, NJ.
Peavy, H.S., Rowe, D. R., and Tchobanoglous, G. (1985) Environmental Engineering, McGraw-
Hill, New York, NY.
240 Chapter 9 Water Treatment
EXERCISES
9.1 Draw a schematic diagram of a water treatment plant that uses a river as the
source. Briefly discuss the purpose of each unit operation or unit process
shown on the schematic.
9.2 Draw a schematic diagram of a water treatment plant that uses a ground-
water as the source. Briefly discuss the purpose of each unit operation or
unit process shown on the schematic.
9.3 A circular rapid-mix basin with stator blades is to be designed to treat 2.0 mil-
lion gallons of water per day. The detention time should be 60 seconds with a
velocity gradient of 900 s-1. The minimum temperature anticipated is 60°F
and the absolute viscosity 1m2 is 2.359 * 10-5 lb # s/ft2. Determine the diame-
ter (ft) if two rapid-mix basins are operating in parallel with a depth of 10
feet. Also calculate the power input to the basin (HP). 1 HP = 550 ft # lb/sec.
9.4 A flocculation basin is to be designed with a 30-minute detention time and a mean
velocity gradient of 40 s-1. Determine the power (W) required if the average
design flow to the flocculation basin is 30,000 m3/d. m = 1.002 * 10-3 N # s/m2..
9.5 A flocculation basin 60 feet long, 45 feet wide, and 14 feet deep treats a coag-
ulated water flow of 10 million gallons per day (MGD) at a temperature of
50°F (absolute viscosity, m = 2.735 * 10-5 lb # s/ft2). The power (P) input to
the paddlewheel is 930 ft # lb/sec, resulting in a paddle blade-tip velocity of 1.4
and 1.0 feet per second (fps) for the outer and inner blades, respectively.
Determine the following:
(a) The detention time in hours.
(b) The horizontal flow-through velocity (Vh) in feet per minute.
(c) The mean velocity gradient (G) in s1.
(d) The Gt value (dimensionless).
9.6 A groundwater was analyzed and found to have the following constituents:
CO2 = 17 mg/L Bicarbonate = 180 mg/L as CaCO3
Ca2+ = 80 mg/L Na+ = 25.3 mg/L
Mg2+ = 29 mg/L Cl- = 138.5 mg/L
(a) Draw a bar graph in milliequivalents per liter (meq/L) for determining
lime and soda-ash requirements to soften the water to the practical limits
of hardness removal (40 mg/L as CaCO3 and 10 mg/L magnesium
hardness as CaCO3).
(b) Calculate the quantity of lime in kilograms per day as calcium oxide
(CaO) with a 95% purity to treat 18,000 m3/day of flow using excess-lime
treatment (1.25 meq/L).
(c) Calculate the quantity of soda ash 1Na2CO32 needed in kilograms per
day with a 90% purity to treat 18,000 m3/day of flow.
Exercises 241
(a) Draw a bar graph in milliequivalents per liter (meq/L) for determining
lime and soda-ash requirements to soften the water to the practical
limits of hardness removal (40 mg/L as CaCO3 and 10 mg/L magnesium
hardness as CaCO3).
(b) Calculate the quantity of lime in pounds per day as calcium oxide (CaO)
with a 98% purity needed to treat 5.0 MGD of flow using excess-lime
treatment (1.25 meq/L).
(c) Calculate the quantity of soda ash 1Na2CO32 in pounds per day with a
95% purity needed to treat 5.0 MGD of flow.
9.8 Use Stokes’ law [Equation (9.23) or (9.24)] to calculate the settling velocity
(meters per second) of a spherical particle with a diameter of 1.0 mm and a
specific gravity (S.G.) of 3.0 in water at a temperature of 30°C. The absolute
and kinematic viscosities of water at 30°C are 0.798 * 10-3 N # s/m2 and
0.8 * 10-6 m2/s, respectively. The water density 1r2 is 995.7 kg/m3.
9.9 A spherical particle with a diameter of 0.02 mm and a specific gravity (S.G.)
of 2.8 settles in water having a temperature of 20°C. Use Stokes’ law [Equa-
tion (9.23) or (9.24)] for calculating the settling velocity in meters per second.
The absolute and kinematic viscosities of water at 20°C are 1.002 *
10 -3 N # s/m2 and 1.003 * 10-6 m2/s, respectively. The water density 1r2 at
20°C is 998.2 kg/m3. Convert the settling velocity from meters per second to
gallons per day per square foot 1gpd/ft22, which represent the units com-
monly used for expressing the overflow rate.
9.10 Two long rectangular settling basins operate in parallel to treat 5 MGD of
coagulated water. A length-to-width (L:W) ratio of 4:1 and length-to-depth
(L:D) ratio of 10:1 will be used in design. Overflow rate = 1000 gpd/ft2
(a) Determine the dimensions of the settling basin in feet, assuming a depth
of 10 feet.
(b) Calculate the detention time of each basin in hours.
(c) Determine the length of the effluent weir in each basin if the weir loading
rate is not to exceed 12,000 gpd/ft.
9.11 Two circular settling basins operating in parallel are to be designed for treat-
ing 40,000 m3/d of coagulated water. Each basin is 2.3 meters deep and has a
single peripheral weir attached to its outside wall. Vo = 0.6 m/h
(a) Determine the diameter of each basin in meters.
(b) Calculate the detention time of each basin in hours.
(c) Calculate the weir loading rate 1m3/d # m2.
9.12 A rapid sand filter has a sand-bed depth of 762 mm. Other pertinent data include:
sand specific gravity 2.65, porosity () 0.41, filtration rate 1.53 lps/m2
shape factor () 0.80, and temperature 15ºC. A sieve analysis is presented
below. Determine the head loss for a clean filter using the Carman-Kozeny
equation [Equation (9.38)] for a stratified bed. m = 1.139 * 10-3 kg/m # s;
r = 999.1 kg/m3.
242 Chapter 9 Water Treatment
9.13 A new water treatment plant is to be constructed for treating 30 MGD. Esti-
mate the number of filters required and calculate the area of each filter 1ft22,
assuming that a length-to-width ratio (L:W) of 4:1 is employed in construct-
ing the rapid sand filters and using a filtration rate of 6 gpm/ft2.
9.14 Chlorine gas, 70% granular calcium hypochlorite 3Ca1OCl224, and 12%
sodium hypochlorite solution are being considered as the primary disinfec-
tants for a 6000-m3/d water treatment plant. The anticipated chlorine dose is
2.5 mg/L. Calculate the quantity of each disinfectant required in kilograms
per month (30 days) to supply the dosage of 2.5 mg/L. Which disinfectant is
the most cost effective if chlorine gas, Ca1OCl22 , and NaOCl cost $0.50/kg,
$1.50/kg, and $0.95/kg, respectively?
CHAPTER
Domestic Wastewater
10
Treatment
10.1 INTRODUCTION
Objectives
Wastewater is water that has been contaminated to the degree that it is no
In this chapter, you will longer beneficial, and therefore must be treated before it can be used or
learn about: released back into the environment. The four major types of wastewater are
The objectives of domestic domestic or municipal, industrial, urban runoff, and agricultural runoff. Domes-
wastewater treatment and tic and industrial wastewaters are considered point sources of pollution, since
the major ways of they emanate from a single point of discharge. Urban and agriculture runoff
classifying wastewater are associated with stormwater that does not percolate into the ground. They
treatment plants are nonpoint sources of pollution, since they emanate from an area. Domestic
How to design major unit or municipal wastewater consists of sewage generated from residential, com-
operations and processes mercial, and public facilities.
for treating wastewater Table 10.1 presents typical characteristics of domestic wastewater. Indus-
trial wastewaters are those generated from companies such as pulp and paper
Microbial growth in
mills, steel mills, pharmaceutical facilities, and food-processing plants. In some
heterogeneous cultures
cities, domestic wastewater may contain a significant proportion of industrial
Sludge volume and weight wastes. Stormwater runoff in urban areas is a major source of pollution that
relationships generates wastewater containing nitrogen, phosphorus, heavy metals, organics,
How to design sludge and pathogens. Stormwater runoff from agricultural areas contains high concen-
thickening systems trations of suspended solids, nitrogen, phosphorus, sediment, and pathogens.
How to design anaerobic This chapter deals only with the treatment of domestic wastewater.
and aerobic sludge- Treatment and disposal of human excrement has been handled in numer-
digestion systems ous ways throughout history. In rural areas, on-site wastewater treatment sys-
tems have varied from low-tech facilities such as “outhouses” to cesspools and
septic tanks. Outhouses, privies, or Johnny houses consist of a wooden structure
built over a pit. A wooden seat with a hole is used by the patron. Sometimes
lime is dumped into the pit to reduce odors. A cesspool system is similar to a
septic system, but instead of a concrete or fiberglass septic tank for holding
sewage generated in a home, a pit is dug and logs or pieces of lumber are placed
over it. Human wastes are then flushed down the toilet and drained into the
cesspool.
244 Chapter 10 Domestic Wastewater Treatment
Sulfate mg/L 20 30 50
In the septic tank, anaerobic processes occur to reduce the solids and oxidize the
organics. The effluent (the liquid that exits the septic tank) receives further treatment
in the drain field, where aerobic facultative microorganisms decompose remaining
organics as the water percolates through the soil.
Septic tanks and cesspools do not perform well where the groundwater table is
high or the soil permeability is very low. Septic tanks and cesspools must be pumped
periodically to remove inert solids.Typically, rather than being maintained by removal
of excrement, outhouses are abandoned and new ones constructed to replace them.
Today, cesspools are no longer permitted. Instead, septic-tank systems should be used.
Section 10.2 Wastewater Treatment Categorization 245
BOD 20 30 45
TSS 20 30 45
NH 4+ + 2 O2
Nitrifiers " NO - + 2 H + + H O (10.1)
3 2
6 NO 3- + 5 CH 3OH
Denitrifiers " 3 N c + 6 OH - + 5 CO + 7 H O (10.2)
2 2 2
Bar racks
and
screens
Figure 10.1
Secondary WWTP schematic.
for removing paper, plastics, and debris that may inhibit subsequent processes. The
next unit operation, grit removal, removes inorganic particles such as sand, silt, grit,
coffee grinds, and eggshells that can accumulate in clarifiers and digesters if not
removed from the wastewater. It is necessary to measure the flow rate of the waste-
water so that proper dosing of chemicals can be accomplished. Then the wastewater
enters the aeration basin, a biological process, where air is injected into the wastewater
to provide microorganisms with the correct amount of oxygen necessary for oxidizing
the organic matter as measured by BOD or chemical oxygen demand (COD) and
to keep the microorganisms in suspension. The TSS in the influent, along with the
microorganisms that are grown in the aeration basin, are separated from the liquid
portion of the wastewater in the secondary clarifier. The treated liquid wastewater
flows over the effluent weir of the secondary clarifier.Thickened suspended solids and
microorganisms (biomass) that accumulate at the bottom of the clarifier are returned
to the aeration basin (return activated sludge). Chlorine is added to the secondary clar-
ifier effluent, and the chlorine contact basin provides sufficient time for the chlorine to
kill potential pathogens in the wastewater. Although not shown in the diagram, the
waste activated sludge must be thickened and stabilized before ultimate disposal.
The design capacity of most WWTPs is based on either the annual average daily
flow (AADF) or maximum monthly flow (MMF).This means that all unit processes are
designed for either the AADF or MMF.All unit operations, especially pumps, pipes, and
conveyance structures, are typically designed to handle the peak hourly flow (PHF).
The annual average daily flow can be estimated by multiplying 120 gallons of
wastewater generated per person per day by the design population (Viessman and
Hammer, 2005). This value includes nominal infiltration into the sewerage system.
Maximum monthly, peak hourly, and minimum design flows can then be determined
by assuming appropriate peaking factors. Detailed information regarding design
flows is provided by Reynolds and Richards, 1996; Viessman and Hammer, 2005;
and Metcalf and Eddy, 2003.
10.4.1 Screening
Mechanically cleaned bar racks are used first, followed by bar screens with smaller
openings. Bar racks have clear openings ranging from 1.5 to 6 inches (38 to 150 mm).
Bar racks are used for removing large objects such as logs or other debris. Mechanically
cleaned coarse screens with openings from 1 to 2 inches (30 to 50 mm) are used for
removing rags, paper, and other debris that may clog pipes, pumps, and valves. Bar racks
and bar screens are made up of parallel bars or rods, while fine screens consist of wires,
grating, wire mesh, or perforated plates. Figure 10.2 is a photo of a coarse bar screen.
Figure 10.2
Photograph of a bar screen.
Section 10.5 Primary Treatment 249
Figure 10.3
PISTA® Grit Removal System
(manufactured by Smith &
Loveless, Inc.).
Figure 10.4
High-performance SLUR-
RYCUP™ grit washing and
classification unit mounted on
a GRIT SNAIL™ Quiescent
Dewatering Escalator
(manufactured by EUTEK®
Systems™, Inc.).
makes the PISTA® system and EUTEK® makes the Teacup. Figures 10.3 and 10.4
show typical vortex removal systems.
Once grit has been separated from the wastewater, it must be washed to
remove organic matter that may be attached to the grit particles. For this purpose,
both inclined-rake and inclined-screw conveyor washer systems are used. In some
cases, hydrocyclones are used prior to the grit washer to enhance separation of the
grit and organics. Detailed design information for these systems can be found in
Metcalf and Eddy (2003), WEF MOP #8 (1998), and Reynolds and Richards (1996).
Primary treatment does not remove soluble or colloidal organic materials. Light-
weight organics that float to the surface are skimmed off and pumped to the digesters
for treatment. The sludge that accumulates at the bottom of a primary clarifier is
normally stabilized by anaerobic digestion before disposal. Primary sludge is called
“raw” sludge and is objectionable, since it contains pathogens and organics and
produces odors, especially if it becomes anaerobic. Typical removal efficiencies
observed during primary treatment for BOD and TSS range from 30% to 40% and
50% to 70%, respectively (Metcalf and Eddy, 2003).
Primary clarifiers are normally circular by design. Where land space is limited,
however, long, rectangular basins are often used. Typical dimensions and design criteria
for primary clarifiers are presented by Metcalf and Eddy, 2003. Depths of primaries range
from 10–16 ft (3–4.9 m). Rectangular primary clarifiers have lengths ranging from 50–300
ft (15–90 m) and widths varying from 10–80 ft (3–24 m). The diameters of circular clari-
fiers range from 10–200 ft (3–60 m). Detention times in primaries range from 1.5–2.5
hours.Average overflow rates vary from 800–1200 gpd/ft2 [30–50 m3/(d # m224. Weir load-
ing rates vary from 10,000–40,000 gpd/ft2 [125–500 m3/(d # m224.
The design of primary clarifiers is based on the overflow rate, detention time,
and weir loading rate. The overflow rate 1Vo2 is defined as the flow rate divided by
the surface area of the clarifier:
Q
Vo = (10.3)
AS
where:
Vo = overflow rate gpd/ft2 1m3/d # m22,
Q = design flow rate, MGD 1m3/d2, and
A S = surface area of the clarifier, ft2 1m22.
The surface area of the clarifier is determined by dividing the design flow rate by the
overflow rate. This area calculated is then converted into either a circular or a rectan-
gular area. Once the detention time is selected and the total volume of the clarifier is
calculated, clarifier depth may be determined. It is calculated by dividing the clarifier
volume by the surface area of the clarifier. Detention time 1u2 is the average unit of
time that the wastewater remains in the clarifier and is determined as follows:
V
u = (10.4)
Q
where:
V = volume of the primary clarifier in ft3 1m32, and
Q = design flow rate, MGD 1m3/h2.
Weir loading rate (q) is the third parameter that must be determined when design-
ing primary clarifiers. Mathematically, q is defined as the design flow rate divided by
the length of the weir:
Q
q = (10.5)
weir length
where:
q = weir loading rate, gpd/ft 1m3/d # m2,
Q = design flow rate, gpd 1m3/d2, and
weir length = length of primary clarifier effluent weir, ft (m).
Section 10.5 Primary Treatment 251
The weir loading rate is the last parameter to be checked. For circular clarifiers, a
peripheral weir which extends around the entire circumference of the clarifier is
used. For rectangular clarifiers, the design engineer uses inboard box weirs to provide
the necessary weir length to meet the weir loading rate. Example 10.1 illustrates the
procedure for designing primary clarifiers.
EXAMPLE 10.1
Primary clarifier design
A municipal WWTP receives 20,000 m3/day of flow. Two primary clarifiers operating
in parallel will handle the flow. The state’s regulatory agency’s criteria are as follows:
average overflow rate = 20 m3/(d # m2 ), and the average detention time = 3.0 hours.
Determine:
a. Clarifier diameter.
b. Side water depth.
c. Weir loading rate if an inboard peripheral weir is used that is 0.25 m from
the edge of the clarifier.
Solution part a
10,000 m3/day
10,000 m3/day
Q 10,000 m3>d
AS = = = 500 m2
Vo 20 m3>d # m2
pD2
AS = = 500 m2
4
D = 32000>p40.5 = 25.2 m
Solution part b
Next, calculate the volume of the clarifier so the side water depth may be determined
by dividing the volume by the surface area:
d m3
V = u Q = 3.0 h ¢ ≤ ¢ 10,000 ≤ = 1250 m3
24 h d
252 Chapter 10 Domestic Wastewater Treatment
Since we have selected a diameter of 25 rather than 25.2 meters, calculate a new
surface area:
p125 m22
AS = = 491 m2
4
V 1250 m3
depth = = = 2.55 m
AS 491 m2
Solution part c
Peripheral weirs are usually placed around the circumference of the clarifier. In this
case, the weir is placed 0.25 m from the edge of the clarifier. Therefore, the diameter
of the peripheral weir is 24.5 meters.
Peripheral weir diameter is equal to 25 meters - 210.25 m2 = 24.5 meters.
10,000 m3>d
= 130 m3/(d # m)
Q
q = =
weir length p124.5 m2
Peak weir loading rates generally should not exceed 248 m3/(d # m) (Reynolds
and Richards, 1996).
organics + O2 + N + P
Microorganisms " C H O N P (10.7)
60 87 23 12
The overall growth rate in continuous flow systems with a heterogeneous culture of
microorganisms is expressed as follows (Heukelekian et al., 1951):
dX dS
a b = Ya b - kdX (10.8)
dt NG dt U
where:
Q S0 Aeration Effluent
Secondary
Xi basin X, V, Se
(Q Qr) clarifier
Si (Q Qw)
X, Se Xe, Se
RAS/WAS WAS
Return activated Qr, Xr, Se Pumping
sludge, RAS station Qw, Xr
254 Chapter 10 Domestic Wastewater Treatment
The quantity of biomass wasted from the system determines the mean cell res-
idence time (MCRT), which sets the concentration of MLSS that can be maintained
in the aeration basin. To maintain steady-state operating conditions, the quantity of
biomass grown within the system is equal to the quantity of biomass that must be
wasted from the system. The sludge wasted 1Qw2 from the system is called waste acti-
vated sludge (WAS). Sludge wasting is normally accomplished by pumping the thick-
ened sludge from the RAS/WAS pumping station to the sludge thickening or sludge
stabilization processes.
The concentration of suspended solids in the thickened sludge generally ranges
from 0.5% to 1.5% solids, where, 1% = 10,000 mg/L, assuming that the specific
gravity of the sludge is approximately 1. The sludge settling rate depends on the
MLSS concentration entering the clarifier, the characteristics of the wastewater,
MCRT, and the sludge return rate.
where:
X = biomass or microorganism concentration in aeration basin expressed
as TSS or VSS, mg/L,
Xe = secondary effluent TSS or VSS concentration, mg/L,
Xr = TSS or VSS concentration in return activated sludge, mg/L,
V = volume of the aeration basin, MG 1m32,
Q = influent wastewater flow rate, MGD 1m3/d2,
Qr = return activated sludge flow rate, MGD 1m3/d2,
Qw = sludge wastage flow rate, MGD 1m3/day2, and
Qe = 1Q - Qw2 = effluent wastewater flow rate, MGD 1m3/d2.
MCRT typically varies from 5 to 30 days and determines the overall removal
efficiency of the process. Generally, the longer the MCRT, the lower the effluent
substrate concentration as measured by BOD or COD. MCRT is much longer than
the hydraulic detention time 1u2. Typically, uc is 10 to 40 times u. Recall that deten-
tion time is defined as the volume of the reactor or basin divided by the volumetric
flow rate with units of time. Equations (10.10) and (10.11) present the equations
used for calculating detention time (Lawrence and McCarty, 1970).
V
u = (10.10)
Q
V
uœ = (10.11)
1Q + Qr2
where:
u = detention time based on influent wastewater flow rate, d or h, and
uœ = actual detention time for recycle systems, d or h.
Section 10.6 Secondary Treatment 255
QS0
F:M = (10.12)
XV
where:
F:M = food-to-microorganism or food-to-mass ratio, mg/1mg # d2, and
S0 = influent substrate concentration to aeration basin expressed as
BOD, COD, or TOC, mg/L.
dS kXSe
a b = (10.14)
dt U KS + Se
where k = maximum specific substrate utilization rate, d-1.
Substituting Equation (10.14) into Equation (10.13) results in Equation (10.15),
which is used for calculating the effluent soluble substrate concentration 1Se2 from
the activated sludge process.
Ks11 + kd uc2
Se = (10.15)
uc1Yk - kd2 - 1
Y1S0 - Se2 uc
X = (10.16)
1 + kd uc u
YQ1S0 - Se2 uc
V = (10.17)
1 + kd uc X
YQ1S0 - Se2
Px = (10.18)
1 + kd uc
Oxygen Requirements
Oxygen serves as an electron acceptor in the activated sludge process, so suffi-
cient quantities of oxygen must be provided to ensure that microbial growth is not
negatively affected. Under most operating conditions, a dissolved oxygen concen-
tration of 2.0 mg/L should be maintained in the aeration basin to meet process
requirements for both the carbonaceous oxygen demand and nitrogenous demand
(total oxygen demand). Equation (10.19) is used for estimating the quantity of oxy-
gen required to meet the total oxygen demand. The nitrogenous demand (NOD)
is the amount of oxygen required for the nitrifying bacteria, Nitrosomonas and
Nitrobacter.
where O2 = total oxygen required to meet the carbonaceous and nitrogenous oxy-
gen demand, pounds per day, ppd (kg/d).
EXAMPLE 10.2
Activated sludge design
A completely mixed activated sludge process is designed to treat 20,000 m3/day of
domestic wastewater having a BOD5 concentration of 250 mg/L following primary
treatment. The NPDES permit requires that the effluent BOD5 and TSS concentra-
tions not exceed 20 mg/L on an annual basis. The following biokinetic coefficients
are to be used in the design of the process: Y = 0.6 mg VSS/mg BOD5 , k = 5 d-1,
KS = 60 mg/L BOD5 , and kd = 0.06 d-1. Assume that the MLVSS concentration in
the aeration basin will be maintained at 3000 mg/L and the ratio of VSS:TSS is 0.75.
Determine the following:
Solution part a
First, it is necessary to estimate the BOD5 of the effluent suspended solids (particu-
late BOD5-PBOD5) so that the soluble effluent BOD5 concentration may be deter-
mined. The particulate BOD5 can be estimated using the following equation:
2 2 mg mg VSS
particulate BOD5 = a b11.42 VSS2eff = a b a1.42 * 20 * 0.75 b
3 3 L mg TSS
mg
= 14.2
L
Solution part b
Calculate the mean cell residence time using Equations (10.13) and (10.14).
dS kXSe
a b =
dt U KS + Se
uc = 4.89 days
Typically, MCRTs for completely mixed activated sludge processes range from
3 to 15 days.
Solution part c
Next, the volume of the aeration basin may be determined using Equation (10.17).
0.6 mg VSS
120,000 m3>d21250 - 5.8 mg>L214.89 d2
YQ1So - Se2 uc mg BOD5
V = =
1 + kd uc X 11 + 0.06 d-1 * 4.89 d2 13000 mg VSS>L2
= 3690 m3
258 Chapter 10 Domestic Wastewater Treatment
Solution part d
The quantity of waste sludge produced at a MCRT of 4.89 days is determined using
Equation (10.18). First, change the units on the growth yield coefficient as follows:
0.6 mg VSS 1 mg TSS 0.8 mg TSS
Y = ¢ ≤¢ ≤ =
mg BOD5 0.75 mg VSS mg BOD5
YQ1So - Se2
Px =
1 + kd uc
mg TSS m3 mg
0.8 120,000 21250 - 5.8 2
mg BOD5 d L 1 kg 1000 L
Px = -1
¢ ≤¢ ≤
11 + 0.06 d * 4.89 d2 6
10 mg m3
kg
Px = 3020
d
The largest quantity of sludge produced occurs at short MCRTs. At long MCRTs,
less sludge is produced.
Figure 10.6
Mechanical aerator in
operation.
Section 10.6 Secondary Treatment 259
Figure 10.7
Diffused aeration system in
operation.
sizes. In general, diffused aeration systems are more efficient in transferring oxygen
into the wastewater and are more widely used than mechanical aeration systems.
Figure 10.7 is a photo showing a diffused aeration system in operation.
Aeration manufacturers test aeration equipment using standard conditions,
which include using clean tap water at 20°C containing zero mg/L of dissolved oxy-
gen (initially) and at 1 atmosphere of pressure. Aeration equipment must transfer
the desired quantity of oxygen to the microorganisms in the wastewater. Alpha 1a2
and beta 1b2 coefficients are used to translate the oxygen transfer rate under stan-
dard conditions to those under process conditions (i.e., in the wastewater). Each
coefficient is defined by the following equations:
1KLa2ww
a = (10.21)
1KLa2tap water
1DOsat2ww
b = (10.22)
1DOsat2tap water
where:
1KLa2ww = overall oxygen transfer coefficient under process conditions in
wastewater, time1,
(KLa)tap water overall oxygen transfer coefficient under standard conditions
in water, time-1,
1DOsat2ww = dissolved oxygen (DO) saturation concentration at specified
temperature and pressure in wastewater, mass/volume,
1DOsat2tap water = DO saturation concentration at standard conditions in
water, mass/volume, and
T = actual temperature of wastewater under process conditions,°C.
260 Chapter 10 Domestic Wastewater Treatment
The actual oxygen transfer rate equation under process conditions (transferring
oxygen into wastewater) is:
Figure 10.9
Photo of conventional
trickling filter with rock
media.
Figure 10.10
Trickling filter with plastic
media and biological
growth.
Q
AC = (10.24)
Vo
where:
A C = the area of clarifier based on clarification, ft2 1m22,
Q = design flow rate, excluding sludge return flow applied to the secondary
clarifier, MGD 1m3/d2, and
Vo = overflow rate or surface loading rate, gpd/ft2 3m3/1d # m224
When considering thickening of the solids, the area of the secondary clarifier is esti-
mated by dividing the total suspended solids loading to the secondary clarifier by the
design solids loading rate (SLR). Routinely, a solids loading rate is assumed and the
area of the clarifier based on thickening considerations is estimated. Equation (10.25)
is used for determining the secondary clarifier area based on thickening considerations.
1Q + QR2MLSS
AT = (10.25)
SLR
where:
A T = secondary clarifier surface area based on thickening considera-
tions, ft2 1m22,
Q = wastewater design flow rate applied to the secondary clarifier, excluding
the return activated sludge flow rate, MGD 1m3/d2,
QR = return activated sludge flow rate, MGD 1m3/d2,
MLSS = suspended solids concentration in the aeration basin, and
SLR = solids loading rate design criteria, typically 25 ppd/ft2 3122 kg/1d # m224
at average daily flow.
Figure 10.11
Photo of circular secondary
clarifier.
Section 10.7 Secondary Clarification 263
Typical design criteria for secondary clarifiers (EPA, 1975) are presented as fol-
lows: average overflow rates ranging from 400–800 gpd/ft2 [16.3–32.6 m3/(d # m2)],
solids loading rates of 20–30 ppd/ft2 [98–147 kg/(d # m224, and depths of 12–15 ft
(3.7–4.6 m). Secondary settling basins are normally rectangular or circular in plan
view. Standard sizes come in 5 ft (1.6 m) intervals. The design of a secondary clarifier
is presented in Example 10.3.
EXAMPLE 10.3
Secondary clarifier design
Design a secondary clarifier system for an activated sludge WWTP that treats 10.0
MGD of wastewater. The MLSS concentration is 3000 mg/L, return activated sludge
(RAS) flow = 4.0 MGD, overflow rate is 600 gpd/ft2, and a solids loading rate of
30 ppd/ft2 will be used. Assume a minimum of two circular units. Determine the
diameter of the clarifiers.
Solution
First, determine the surface area of the secondary clarifiers based on clarification
considerations using Equation (10.24):
Q 10 * 106 gpd
AC = = = 16,700 ft2
Vo 600 gpd>ft2
Next, determine the surface area of the secondary clarifiers based on thicken-
ing considerations using Equation (10.25).
8.34 lb>MG
110 + 4 MGD213000 mg>L2a b
1Q + QR2MLSS mg>L
AT = =
SLR 30 ppd>ft2
= 11,700 ft2
The surface area of the secondary clarifiers must equal to 16,700 ft2, since it is
the larger of the two areas calculated. Since there are two circular clarifiers, the sur-
face area must be divided by 2. The radius and diameter of the clarifiers can then be
determined.
A 16,700 ft2
= = pr2
clarifier 2
(CCB). Length-to-width (L:W) ratios of 10:1 to 40:1 are used in design to prevent
short circuiting (Metcalf and Eddy, 1991). The design of a CCB is based on deten-
tion time, which is calculated by dividing the volume of the basin by the design
flow rate.
EXAMPLE 10.4
Chlorine contact basin design
A chlorine contact basin is to be designed for maintaining a detention time of 15 min-
utes at peak hourly flow (PHF) and/or 30 minutes at the average daily flow (ADF).
The activated sludge wastewater treatment plant treats an average daily flow of
60,000 m3/d, and the ratio of the estimated peak hour flow to average daily flow is
3:1. Design a three-pass, serpentine chlorine contact basin using a length-to-width
ratio of 10:1.
Solution
Calculate the volumes for the chlorine contact basin for the two flow scenarios.
First, rearrange the detention time equation so that the volume may be calculated.
Volume of CCB at ADF:
1h 1d 60,000 m3
V = uQ = 30 min ¢ ≤¢ ≤¢ ≤ = 1250 m3
60 min 24 h d
Once the peak hourly flow is estimated, the volume of CCB at PHF can be
determined.
The PHF is calculated as:
m3 m3
PHF = 3 ¢ 60,000 ≤ = 180,000
d d
1h 1d 180,000 m3
V = uQ = 15 min ¢ ≤¢ ≤¢ ≤ = 1875 m3
60 min 24 h d
The volume of the CCB is controlled by the PHF and should be 1875 m3.
Assume that we have two chlorine contact basins of equal size, 3 m deep. The
volume per basin and the surface area are calculated below.
volume 1875 m3
= = 938 m3 ⬵ 940 m3
basin 2
area 940 m3
= = 313 m2
basin 3m
Assuming three passes per basin and a L:W ratio of 10:1 1L = 10W2, the area
of the basin per pass is calculated as:
Use a width of 5.6 m and length of 313/5.6 = 56 m. Each CCB basin will have
a plan view as shown below.
Q
5.6 m
5.6 m
Q
5.6 m
56 m
WW + WS
S = (10.26)
1WW>1.02 + 1WS>SS2
where:
S = specific gravity of wet sludge,
WW = weight of water, lb (kg),
Section 10.9 Sludge Treatment and Disposal 267
WS
V = (10.27)
1s>1002g S
where:
s = solids content, %, and
g = specific weight of water, 62.4 lb/ft3 (1000 kg/m32.
EXAMPLE 10.5
Gravity belt thickener design
Design a gravity belt thickener (GBT) to be used for thickening waste activated
sludge (WAS) from 1% solids to 5% solids. Ten thousand pounds of WAS are pro-
duced daily. The WAS is pumped from the RAS/WAS pumping station to a sludge
holding tank. Positive displacement pumps are used to pump the WAS from the hold-
ing tank to the GBT. The GBT will operate 8 hours a day, 5 days a week. The TSS
concentration in the filtrate is 1000 mg/L. Use the following design criteria in design-
ing the GBT: hydraulic loading rate = 140 to 450 gpm/m, solids loading rate = 370
to 1200 lb/(m # hr), and washwater rate = 25 gpm/meter of belt width.
Solution
First, calculate the daily solids loading rate to the GBT.
7 d 1 wk 1 d lb lb
10,000 ppda ba ba b = 1750 or 14,000
wk 5d 8h hr d
Next, determine the sludge volume entering the GBT using Equation (10.27)
and assuming the specific gravity of the wet sludge (S) is equal to 1.0.
WS 14,000 ppd
V = = = 168,000 gpd or 350 gpm
1s>1002g S 11%>100218.34 lb>gal211.02
Next, draw a schematic diagram so that a flow and materials balance can be
performed.
Washwater
0% solids
Sludge
Sludge
cake
feed
GBT
1% Solids 5% Solids
14,000 ppd
1,000 mg/L
Filtrate
Determine the belt width of the GBT. Belt widths range from 0.5 to 3 meters in
increments of 0.5 meter. Typical GBTs in service use 2.0-meter belts. Pick a hydraulic
loading rate of 175 gpm/m from the design criteria given:
350 gpm
belt width = = 2.00 m
175 gpm>m
Check the actual solids loading rate (SLR) to see if it meets the design criteria:
= 875 lb>1m # h2
1750 pph of solids
solids loading rate =
2m
This is acceptable, since the SLR design criteria specify 370 to 1200 lb/1m # h2.
Next, determine the sludge cake and filtrate flows by performing a flow and
materials balance around the GBT. Cake and filtrate flows are denoted as QC and
QF , respectively.
Qsludge + Qwashwater = QF + QC
400 gpm = QF + QC
gal 60 min 8 h 1 MG
400 a ba b¢ 6 ≤ = 0.192 MGD
min h d 10 gal
0.192 MGD = QF + QC
QC = 0.192 MGD - QF
lb lb
MG mg MG mg
14,000 ppd = QC a8.34 b15 * 10,000 2 + QF a8.34 b 11000 2
mg L mg L
L L
Section 10.9 Sludge Treatment and Disposal 269
lb>MG
10.162 MGD2a8.34 b11000 mg>L2 = 1351 ppd
mg>L
The percent capture through the GBT can be calculated using the following
equation:
0% Solids
Washwater 50 gpm
Sludge Sludge
feed cake
GBT
1% Solids 5% Solids
14,000 ppd 12,649 ppd
350 gpm 63 gpm
1,000 mg/L
1351 ppd
337 gpm
Filtrate
10.9.3 Stabilization
The objectives of sludge stabilization are to reduce the liquid volume and quantity of
sludge solids, prevent nuisance odors, and reduce the pathogen content. Two primary
means of stabilizing wastewater sludge or biosolids include anaerobic and aerobic
digestion. Presented next is a brief description of anaerobic digestion, followed by a
discussion of aerobic digestion.
Anaerobic Digestion
Anaerobic digestion is a biological process that takes place in an enclosed reactor
with no oxygen present. It is modeled as a three-step process: hydrolysis, acidogene-
sis, and methanogenesis. During hydrolysis complex organic solids are hydrolyzed
270 Chapter 10 Domestic Wastewater Treatment
Actively digesting
sludge
Sludge
heater
Digested
sludge
Equation (10.29) is used for determining the volume of a high-rate anaerobic digester.
VI = Q1 * T (10.29)
where:
VI = digester capacity required for first-stage or high-rate digestion, ft3 1m32, and
T = period required for digestion, d.
The volume of a second-stage, low-rate anaerobic digester is determined as:
Q1 + Q2
VII = * T1 + Q2 T2 (10.30)
2
where:
VII = digester capacity required for second stage, ft3 1m32,
Q1 = volume of digested sludge feed = volume of average daily raw sludge
feed cfd 1m3/d2,
Q2 = volume of daily digested sludge accumulation in tank, cfd 1m3/d2,
T1 = period required for thickening, days, and
T2 = period required for digested sludge storage, days.
Example 10.6 shows how to design a single-stage conventional anaerobic digester.
EXAMPLE 10.6
Conventional anaerobic digester design
Calculate the anaerobic digester capacity 1m32 required for conventional single-stage
anaerobic digestion, given the following data: raw sludge production = 630 kg/d; VS
in raw sludge = 70%; moisture content of raw sludge = 95%; percent solids content
of raw sludge = 5% solids; digestion period = 30 days; VS reduction = 50%; mois-
ture content of digested sludge = 93%; storage time required = 90 days; and per-
cent solids in thickened digested sludge = 7%.
Solution
First, calculate the volume of raw sludge fed to the digester using Equation (10.27)
assuming S is 1.0.
Ws 630 kg/d
V = = = 12.6 m3>d
1s>1002g S 15%>100211000 kg>m3211.02
Perform a materials balance on the mass of solids or sludge entering and exiting
the digester. First, determine the volatile and fixed solids in the raw sludge fed to the
digester. By definition, total solids (TS) ⴝ volatile solids (VS) ⴙ fixed solids (FS).
Next, calculate the volatile and total solids quantities remaining after digestion.
Digestion of the solids causes a 50% reduction in the volatile solids, and the fixed
solids are assumed to remain unchanged.
Mass of volatile solids remaining after digestion = 0.50 * 441 kg/d = 220.5 kg/d
Now, calculate the volume of digested sludge that accumulates daily in the
tank, assuming that the sludge thickens to 7% solids, using Equation (10.27) and
taking the specific gravity of the digested sludge to be 1.0.
WS 409.5 kg/d
V = = = 5.85 m3>d
1s>1002g S 17%>100211000 kg>m3211.02
Aerobic Digestion
Aerobic digestion is similar to the activated sludge process and is actually a continu-
ation of the process operating in the endogenous phase. Organic sludge is aerated
for extended periods so that the organic material is oxidized biologically and the
microorganisms oxidize their own protoplasm, once the exogenous (external) carbon
has been exhausted. Equation (10.31) is a qualitative biochemical reaction, showing
what happens during aerobic digestion:
organic matter + O2
aerobic microbes " new cells + energy + CO + H O (10.31)
2 2
+ end products
Equation (10.32) indicates that the pH will drop due to the production of hydrogen
ions 1H +2 and that digestion requires approximately 1.98 lb of oxygen per lb of cells
17 * 32/1132 or 1.98 kg of oxygen per kg of cells.
The process may utilize continuous flow or batch operation. Aerobic digestion
works best on waste activated sludge, since exogenous carbon has been depleted, and
therefore synthesis of new biomass does not occur. Aerobic digestion is called a
process for significant reduction of pathogens (PSRP). Equation (10.33) is used for
calculating the required detention time for completely mixed aerobic digesters:
Section 10.9 Sludge Treatment and Disposal 273
V 31X02 - 1Xe24
u = td = = (10.33)
Q Kd 31Xe2 - 1Xn24
where:
u = td = detention time or digestion time, d,
Kd = degradation constant or aerobic digestion rate constant, d-1,
X0 = total VSS concentration in influent sludge to digester, mg/L,
Xe = total VSS concentration in effluent digested sludge, mg/L, and
Xn = nondegradable VSS in effluent digested sludge, mg/L.
The detention time 20°C in an aerobic digester ranges from 12 to 22 days (Reynolds
and Richards, 1996).
The detention time may be corrected for temperatures other than 20°C as follows:
Sufficient oxygen must be supplied to the aerobic digester so that oxygen does
not limit the biological reactions that are occurring. For design purposes, 2.0 lb of
oxygen per lb of solids destroyed (2.0 kg/kg) must be supplied to meet process oxy-
gen requirements. This value is used for both waste activated sludge and trickling fil-
ter humus. Approximately 1.9 lb of oxygen per lb of BOD (1.9 kg/kg) is used for
computing the oxygen required for stabilizing primary sludge (Reynolds and
Richards, 1996). Also, air or mechanical energy must be input to the digester to keep
the microorganisms in suspension. Mechanical mixers need 0.5 to 1.25 HP/1000 ft3
(13 to 40 kW/1000 m3) to meet the mixing requirement. Diffused aeration systems
must supply 20 to 35 cfm/1000 ft3 [25 to 35 m3/(min # 1000 m3)] for digesters treating
WAS and 60 cfm/1000 ft3 360 m3/(min # 1000 m324 for aerobic digesters treating a
combination of primary sludge and WAS. The design of aerobic digesters is usually based
on hydraulic detention time or solids loading rate.The hydraulic detention time at 20°C varies
from 12–22 days depending on the type of sludge being treated (Reynolds and Richards,
1996). Reynolds and Richards (1996) indicate that the volatile-solids loading rate
will vary from 0.04–0.20 lb VS/1d # ft 32 30.64–3.20 kg VS/1d # m324. The operating
temperature should be greater than 15°C.
The design of an aerobic digestion system is presented in Example 10.7.
EXAMPLE 10.7
Aerobic digester design
An aerobic digester is to be designed to stabilize 3266 lb of combined primary and waste-
activated sludge. The volume of the combined sludge that will be fed to the digester is
1036 cfd. The volatile solids concentration of the combined sludge is 70%, and the mini-
mum design operating temperature is 16°C.The primary sludge contains 940 lb of BOD
with an oxygen demand of 1.9 lb of oxygen per lb of BOD, whereas the WAS consists of
865 lb of VSS with an oxygen demand of 2.0 lb of oxygen per lb of VSS destroyed.
Determine the following:
a. Design hydraulic detention time or digestion time in days.
b. The aerobic digester volume.
c. The volatile solids loading rate to the aerobic digester.
d. The quantity of oxygen required to stabilize the primary sludge.
e. The quantity of oxygen required to stabilize the secondary sludge (WAS).
274 Chapter 10 Domestic Wastewater Treatment
Solution part a
Use a hydraulic detention time of 20 days and correct it for the minimum design
operating temperature of 16°C, using Equation (10.34).
tT°C = t20°C 11.0652120 - T°C2 = 20 d11.0652120 - 16°2 = 25.7 days
Solution part b
The aerobic digester volume is calculated by multiplying the hydraulic detention
time by the volume of sludge fed to the digester:
ft3
V = tQsludge = 25.7 days ¢ 1036 ≤ = 26,600 ft3
d
Solution part c
Next, calculate the volatile solids loading to the digester.
VS loading = 3266 ppd10.702 = 2286 ppd
The volatile solids loading rate to the digester is determined as:
2286 ppd VS lb VS
VS loading to digester = = 0.086
26,600 ft3 ft3 # d
Solution part d
Oxygen required to stabilize the BOD in the primary sludge is estimated as:
lb BOD lb O2 lb O2
O2 to stabilize primary BOD = a940 b ¢ 1.9 ≤ = 1786
d lb BOD d
Solution part e
Oxygen required to stabilize the VS in the secondary sludge (WAS) is estimated as:
lb VS lb O2 lb O2
O2 to stabilize VS in WAS = a2286 b ¢ 2.0 ≤ = 4572
d lb BOD d
Solution part f
The total oxygen required to stabilize the combined primary and secondary sludge
is determined below:
lb O2
total O2 required = 1786 + 4572 = 6358
d
Solution part g
Finally, the total air required (cfm) to stabilize the combined sludge is estimated
as follows, assuming that air contains 0.0175 lb O2/ft3 and the diffuser transfer
efficiency is 5%:
6358 lb O2>d 1d 1h
air required = a ba b = 5050 cfm
310.0175 lb O2>ft 210.0524 24 h 60 min
3
Summary 275
10.9.4 Dewatering
Dewatering operations consist of reducing the sludge volume and increasing the
solids content, primarily using mechanical means. Typical dewatering operations and
their anticipated solids concentration include: centrifuges (5% to 40% solids), belt
filter presses (12% to 50% solids), vacuum filtration (20% to 30% solids), plate and
frame presses (34% to 60% solids), and sand drying beds (up to 50% solids). In most
instances the sludge must be conditioned by adding a polymer or coagulant aid such
as lime or ferric chloride to increase the effectiveness of the dewatering operations.
Material balances on flow and solids must be performed when designing any type of
solids-handling equipment and process.
S U M M A RY
This chapter presented the objectives of treating wastewater along with a classification
system for identifying the types of wastewater treatment plants (WWTPs).Various unit
operations and unit processes used for treating wastewater were discussed, and exam-
ples were presented showing how to design primary clarifiers, activated sludge systems,
secondary clarifiers, and chlorine contact chambers.You learned that unit operations involve
physical treatment of the wastewater,whereas unit processes involve a biological or chemical
276 Chapter 10 Domestic Wastewater Treatment
reaction. Biokinetic equations were presented that are used for designing activated
sludge processes.
Unit operations and unit processes used in handling, treating, and disposing
of wastewater sludge or biosolids were introduced. Design of these systems requires
that material balances on flow and solids be performed around the specific
system. Example problems were presented to illustrate the design of thickening,
and destabilzation systems.
REFERENCES
Ardern, E., and Lockett, W.T. (1914). Experiments on the Oxidation of Sewage Without the
Aid of Filters, Journal Society Chemical Industry, 22, 523–539, 1122–1124.
Benefield, Larry D., and Randall, C.W. (1980). Biological Process Design for Wastewater
Treatment, Prentice Hall, Englewood Cliffs, NJ.
Eckenfelder, W.W. (1989). Industrial Water Pollution Control, McGraw Hill, New York.
EPA (1994). A Plain English Guide to the EPA, Part 503 Biosolids Rule, EPA/832/R-93/003.
EPA (1993). Manual Nitrogen Control, EPA/625/R-93/010, Office of Research and Develop-
ment, Office of Water, Washington, DC.
EPA (1975). Suspended Solids Removal, Process Design Manual, Office of Research and
Development, Office of Water, Washington, DC.
Heukelekian, H., Oxford, H.E., and Manganelli, R. (1951). Factors Affecting the Quantity of
Sludge Production in the Activated Sludge Process, Sewage and Industrial Wastes, 23, 945.
Lawrence, A.W., and McCarty, P.L. (1970). Unified Basis for Biological Treatment and Design
and Operation, Journal of Sanitary Engineering Division, ASCE, 96, 757–778.
Metcalf and Eddy, Inc. (2003). Wastewater Engineering: Treatment and Reuse, McGraw Hill,
New York.
Metcalf and Eddy, Inc. (1991). Wastewater Engineering: Treatment, Disposal, and Reuse,
McGraw Hill, New York
Reynolds, T.D., and Richards, P.A. (1996). Unit Operations and Unit Processes in Environmental
Engineering, PWS Publishing Company, Boston.
Sherrard, J.H., and Schroeder, E.W. (1973). Cell Yield and Growth Rate in Activated Sludge,
Journal Water Pollution Control Federation, 5, 1189.
Thabaraj, G.J. (1993). AWT Processes in Florida, Florida Department of Environmental Regu-
lation, Tampa, FL, 1–19.
Viessman, Warren, and Hammer, Mark J. (2005). Water Supply and Pollution Control, Pearson/
Prentice Hall, Upper Saddle River, NJ.
Water Environment Federation (1998). Biological and Chemical Systems for Nutrient Removal,
601 Wythe Street, Alexandria, VA.
Water Environment Federation (1998). MOP #8, Design of Wastewater Treatment Facilities, 601
Wythe Street, Alexandria, VA.
Exercises 277
EXERCISES
10.1 Two circular primary clarifiers are to be designed to treat domestic waste-
water following preliminary treatment. State regulatory requirements stipu-
late that the overflow rate must be 600 gpd/ft2 at the average daily flow and
1000 gpd/ft2 at the peak hourly flow. The detention time should be between
1 and 2 hours for all flows. The minimum weir loading rate at peak hourly
flow cannot exceed 30,000 gpd/ft. The average daily flow to the primary
clarifiers is 9 MGD. The peaking factor for the PHF:ADF is 2.5:1. Deter-
mine the minimum-diameter clarifier to the nearest 5-ft interval for two
clarifiers operating in parallel to meet the criteria. Determine the side water
depth (SWD) to meet the detention time requirements. Calculate the weir
length necessary to meet the weir loading condition established by the reg-
ulatory agency.
10.2 Two rectangular primary settling basins operating in parallel are to be designed
to treat domestic wastewater following preliminary treatment. The average
daily flow coming into the treatment plant is 10,000 m3/d and the PHF:ADF
ratio is 3:1. Each basin is expected to treat 75% of the peak hourly flow
with one unit out of service. State regulatory requirements stipulate that
the maximum overflow rate must not exceed 100 m3/1d # m22. The detention
time should be between 1 and 2 hours at the average daily flow. The maxi-
mum weir loading rate at peak flow cannot exceed 350 m3/1d # m2. Determine
the dimensions (L, W, D) of the settling basins using a L:W ratio of 4:1 to
meet the design criteria. Determine the side water depth (SWD) to meet the
detention time requirements. Calculate the weir length necessary to meet the
weir loading condition established by the regulatory agency.
10.3 Design a completely-mixed activated sludge process using three different
design approaches (i.e., calculate the volume of the aeration basin). Base
your design for the first approach on detention time, for the second one on
BOD loading, and for the third one on kinetics. The influent design flow rate
to the activated sludge process is 10,000 m3/day with a BOD5 concentra-
tion of 200 mg/L. Completely-mixed activated sludge processes typically
have a detention time ranging from 3 to 6 hours and BOD5 loadings rang-
ing from 50 to 120 lb BOD5/1d # 1000 ft32. Typical biokinetic coefficients
(Reynolds and Richards, 1996) used in design are: Y = 0.6 mg VSS/mg
BOD5 , k = 3 d-1, KS = 60 mg/L, and kd = 0.06 d-1. Use a MCRT = 10 days
and X = 2500 mg/L VSS.
10.4 A completely-mixed activated sludge process is to be designed to treat 10
MGD of domestic wastewater containing 200 mg/L of COD. Use the follow-
ing design parameters in the design process: X = 2500 mg/L MLVSS, influent
TKN = 20 mg/L. The following biokinetic coefficients should be used: Y =
0.40 mg VSS/mg COD, k = 7 d-1, KS = 75 mg/L, and kd = 0.06 d-1 . Deter-
mine the volume and the oxygen required at a MCRT = 15 days.
10.5 A circular secondary is to be designed for a pure oxygen activated sludge
process. The state’s regulatory agency design criteria are as follows: peak
overflow rate = 50 m3/1d # m22, average overflow rate = 20 m3/1d # m22, peak
solids loading rate = 245 kg/1d # m22, peak weir loading rate = 375 m3/1d # m2,
and depth = 3.5 to 4.5 meters. The average daily flow to the aeration basin
prior to the junction with the recycle flow is 6800 m3/day. The maximum recy-
cled sludge flow is 100% of the average daily flow. The design mixed liquor
suspended solids concentration is 5000 mg/L, and the ratio of the peak hourly
278 Chapter 10 Domestic Wastewater Treatment
to the average daily flow is 2.8. Determine the diameter, detention time at
peak hourly flow, and peak weir loading, assuming a peripheral weir is used.
10.6 A rectangular settling basin is to be designed for a conventional, plug flow acti-
vated sludge process. The flow is 10 MGD, the overflow rate 1Vo2 is 700 gpd/ft2,
the detention time 1u2 is 5 hours, and the weir loading rate is 22,000 gpd/ft. The
settling basin sludge rake mechanism that will be used is for square basins;
therefore, two will be used in tandem to provide a length-to-width ratio of 2:1.
Determine the dimensions of the settling basin (L, W, and D) and the total
length of the effluent weir.
10.7 Compute the volume 1m32 of 1000 kg of waste activated sludge if the moisture
content is 96%. What volume will it occupy if the solids content is increased to
8% by gravity thickening?
10.8 A gravity belt thickener (GBT) is proposed for thickening 7000 kg/day of waste
activated sludge containing 1% solids. The hydraulic loading rate to the GBT
will be 200 gpm/meter and the solids loading rate will be between 200 to
600 kg/1m # h2. The anticipated concentration of solids in the thickened sludge is
6%. Assume that 5 kg of dry polymer are required per Mg (1 Mg = 106 g) of dry
solids fed to the GBT. Determine the effective width of the belt, assuming that
25 gpm of wash water is required per meter of belt and determine the suspended
solids concentration in the centrate. Assume that the solids capture rate is 95%.
10.9 Design a conventional, single-stage anaerobic digester based on the following
parameters: daily raw sludge production = 650 kg; volatile solids in undigested
sludge = 70%; solids content in raw sludge = 5%; digestion period = 30 days;
storage volume for digested sludge = 90 days; volatile solids destruction during
digestion = 50%; and solids content of thickened, digested sludge = 7%.
10.10 An aerobic digester is to be designed to treat the waste activated sludge (WAS)
from a completely-mixed activated sludge process that does not have primary
clarifiers. Approximately 1300 kg of dry solids (WAS) are produced daily con-
taining 0.6% solids and 70% volatile solids and having a wet specific gravity of
1.10. The minimum design temperature is 60°F and a temperature correction
factor of 1.065 will be used in design. The detention time in the digester should
be between 18 and 22 days at a temperature of 20°C. Determine the following:
(a) design detention time (days) at 60°F,
(b) volume of the aerobic digester 1m32 if the sludge is thickened to 2.5%
solids prior to digestion,
(c) the quantity of oxygen (kg) required daily if 2.0 kg of O2 are required per
kg of volatile solids destroyed (assume that 60% of the volatile solids are
destroyed during aerobic digestion),
(d) the air flow rate 1m3/min2 if air contains 0.281 kg of oxygen per m3 and the
efficiency of the diffused aeration system is 5%,
(e) the volatile solids loading rate on the digester 31.6–3.2 kg/1d # m324, and
(f) the volume of air required for mixing 3m3/1min # 1000 m324.
10.11 A belt filter press (BFP) with an effective belt width of 2.0 meters is used for
dewatering 100 gpm of anaerobically digested sludge with a solids content of
7.0%. The polymer dosage is 6.5 gpm, containing 0.20% powdered polymer
by weight. The wash water consumption is 30 gpm per meter of effective belt
width. The cake solids content is 30%, and the suspended solids concentration
in the filtrate is 1800 mg/L. Calculate the hydraulic loading rate, solids loading
rate, and polymer dosage, and estimate the solids recovery.
CHAPTER
11
Air Pollution
11.1 INTRODUCTION
Objectives
Air pollution can be categorized into segments including personal, occupa-
In this chapter, you will tional, indoor, and ambient pollution. Personal air pollution is usually asso-
learn about: ciated with the contamination of respired air from cigarette, pipe, or cigar
Sources and effects of air smoking. Other activities that result in personal air pollution include glue
pollutants sniffing and other volatile-substance abuse practices. Occupational air pol-
Air pollution regulations lution from the contamination of ambient breathing air in industrial settings
where gases, vapors, and respirable particles are generated can result in poten-
Global environmental
tially high levels of exposure to workers. The Occupational Safety and Health
issues
Administration (OSHA) is tasked to ensure that the work environment is safe
Applications and design such that workers are protected from exposure to air toxics and irritants. Dur-
of air pollution control ing the late 1980s, the United States Congress empowered the Environmental
equipment Protection Agency (EPA) to assess the extent of the indoor radon problem
and to educate the public on hazards associated with radon exposure. Regula-
tions associated with indoor air pollution and secondary, or passive, cigarette
smoke were promulgated in the 1990s. This chapter focuses on ambient or
community air pollution, which can be defined as the introduction of pollu-
tants into the ambient air for durations which adversely affect human health,
the public welfare, and the ecological balance. It introduces ambient-air pol-
lution sources, associated environmental and health effects, and current regu-
latory practices. End-of-pipe unit operations and processes for treating air
streams laden with gases and particulates are explored.
Humans are totally dependent upon air for survival. Each day the aver-
age male ingests approximately 1.4 lb (0.64 kg) of food on a dry-weight basis
(NASA, 1991), drinks 4.4 lb (2.0 kg) of water (U.S. EPA, 2000), and inhales
40 lb (18.1 kg) of air (U.S. EPA, 1997). Principal factors causing air pollution to
increase include: (1) overdependence on the burning of fossil fuels for trans-
portation and energy needs, (2) population growth—according to U.S. Census
Bureau (2004 data), the world’s population will exceed 9 billion by the year
2050, (3) technological changes that result in new products, (4) a rising stan-
dard of living, and (5) societal changes such as urbanization, which is charac-
terized by the population shift from rural areas to the urban environment.
280 Chapter 11 Air Pollution
O2 20.9% 21% O2
CO2 0.033%
The major constituents of air are nitrogen, oxygen, argon, and carbon dioxide.
Table 11.1 provides the volumetric percent concentration of each gas. For most engi-
neering calculations, nitrogen and oxygen concentrations are assumed to be 79%
and 21% by volume, respectively.
11.2 HISTORY
Air pollution is not a new phenomenon. Historical evidence indicates that ambient
air pollution from copper smelting occurred in Turkey as early as the sixth millen-
nium B.C.E. Similarly, pollution from iron smelting is believed to have occurred dur-
ing the late third millennium B.C.E., and pollution from lead smelting during the rule
of the Roman Empire has been traced all over Europe. One could argue that air
pollution has been an issue since human species have controlled fire. Although
somewhat controversial, evidence found in Kenya indicates that the Homo erectus
species was intentionally using fire up to 1.5 million years ago. Tending of continu-
ous fire has been dated back 460,000 years in China. In 61 C.E. the Roman Philosopher
Seneca wrote: “As soon as I had gotten out of the heavy air of Rome, and from the
stink of the smoky chimneys thereof, which, being stirred, poured forth whatever
pestilential vapours and soot they had enclosed in them, I felt an alteration of my
disposition.”
Modern-era air pollution issues date to the early 13th century, when England’s
King Edward I recognized that nuisance fumes were produced from the burning of
sea coal. This awareness prompted the introduction of a law prohibiting the burning
of sea coal while Parliament was in session, a violation punishable by the torturing
and hanging of those who sold or burned the coal.
The air pollution generated as a result of the Industrial Revolution, the inven-
tion of Watt’s steam engine, and the burning of fossil fuels for power generation
motivated many smoke-control ordinances enacted in England and the United
States during the late 1800s and early 1900s. An era of air pollution episodes also
began in the early 1900s.
An air pollution episode is defined as a major air pollution disaster ensuing
from high levels of pollution that results in a large number of people dying. The first
reported modern-day air pollution episode was recorded in the Meuse Valley,
Belgium, where stable atmospheric conditions caused by a temperature inversion
and a high-pressure system caused a buildup of sulfur-containing compounds, metal-
lic oxides, and inorganic acids in the air of the densely populated, highly industri-
alized town. Reportedly, 63 people died, as well as a number of cattle. Many
people became ill, with symptoms including sore throats, shortness of breath,
cough, phlegm, nausea, and vomiting. Other notorious air pollution episodes
occurred in Donora, Pennsylvania (1948), London, England (1952), Bhopal, India
(1984), and New York City (September 11, 2001). Each incident deserves to be
recognized and remembered. Most of the disasters occurred in densely populated
Section 11.3 Regulatory Overview 281
Title I Focused on attaining national air quality standards for criteria pollutants
Title II Establish more stringent fuel standards for and control of tailpipe emissions from vehicles
Title III Aspires to reduce emissions of hazardous air pollutants from major sources
Title VI Focused on global climate issues, such as protecting the stratospheric ozone layer by regulating the production
of substances with an ozone-depleting potential (CFCs, HCFCs) and monitoring greenhouse gases
Table 11.3 Summary of Primary National Ambient Air Quality Standards for Criteria Pollutants
Primary standard
Criteria
pollutant Time average Concentration
CO 8-hr (not to be exceeded more than once/year) 9 ppmv
PM10 24-hr average (not to be exceeded more than once/yr on average over 3 years) 150 mg>m3
O3 Maximum daily 1-hr average (to be exceeded no more than once/yr averaged over 0.12 ppmv
3 consecutive years)
3-year average of the annual fourth highest daily 8-hr average 0.08 ppmv
Source: Table adapted from www.epa.gov/air/criteria.html.
the EPA considers there is still health or environmental risk associated with contami-
nants emitted, more stringent emissions standards may be imposed.
11.4.1 Particulates
Particulate matter (PM) is classified as any dispersed airborne solid or liquid particle
that is larger than a single molecule and has an aerodynamic size of 2 * 10-10 m up to
5 * 10-4 m. (Refer to Section 11.5 for a definition of aerodynamic size.) Particu-
lates are generated by both anthropogenic and natural processes. Anthropogenic
particulate generation can occur from burning wood, gasoline, and diesel fuel. Many
Section 11.4 Sources and Effects 283
industrial sites produce particles through crushing and grinding operations. A variety
of agricultural practices, including plowing and burning off fields, produce particu-
lates. Both biotic and abiotic sources contribute to natural PM production. For exam-
ple, the decomposition of plants, radiological decomposition, dust storms, sea spray,
forest fires, and volcanic eruptions produce significant quantities of respirable PM.
Routinely, particles having an aerodynamic size less than 2.5 mm 11 mm = 10-6 m2
are classified as the fines fraction, while those with diameters greater than 2.5 mm and less
than 10 mm are considered coarse.The term PM 2.5 refers to particles that are … 2.5 mm in
diameter. PM 10 particles are defined as having a diameter … 10 mm. Fumes are particles
formed by either a chemical reaction or condensation having an aerodynamic diameter
between 0.001 μm and 1 mm. Mists, large compared to fumes, have an aerodynamic size
between 0.1 μm and 10 mm and are formed through condensation. The term aerosol
embodies a variety of particulates, including fumes, mist, smoke, and fog.
Reduced visibility is a common effect of PM. Particulate emissions also have
an effect on materials, vegetation, and animals. For example, particulates cause soil-
ing of painted surfaces, clothing, and curtains. Acidic aerosols are corrosive to
metal and cement surfaces and are potentially harmful to buildings, monuments,
and statues. Particulates containing fluorides, which are emitted naturally from
rock weathering and volcanoes as well as generated anthropogenically through
mining processes and coal combustion, can cause damage to plants. Animals that
graze on these plants may exhibit dental fluorosis. Particulates from mining, smelt-
ing, and coal-fired power plants may also contain arsenic, which has been shown to
cause arsenic poisoning in cattle and sheep.
Human health concerns associated with particulates are focused primarily on
particles of respirable size. It has been shown that particles ranging in size from 2.5
to 10 mm are most likely to be inhaled and trapped within the respiratory system.
Serendipitously, these particles are inherently difficult to remove with end-of-pipe
air pollution-control technology.
In humans, atmospheric particulates can interfere with the mechanisms which
normally clear the respiratory tract. Particles may also be intrinsically toxic because
of their chemical or physical properties, or they may serve as carriers of sorbed toxic
substances. Factors that determine the degree of damage include the exposure time,
concentration of particulates, synergistic effects, and particle size. Common medical
problems resulting from exposure to particles include respiratory infections, cardiac
diseases, bronchitis, asthma, pneumonia, lung cancer, cough, and pulmonary emphy-
sema. Additional effects include a decreased respiratory efficiency, diminished pul-
monary circulation, and the enlargement of the heart and blood vessels. Allergic skin
and eye irritation may also occur. Health and environmental concerns associated
with particulate emissions and other criteria pollutants are summarized in Table 11.4.
Table 11.4 Health and Environmental Effects from Exposure to Criteria Pollutants
Criteria Environmental/property
pollutant Affected body system Health effects effects
Carbon Circulatory—pollutant interferes • CO poisoning • None
monoxide with oxygen transfer to the body • Angina pectoris
• Brain damage
• Asphyxiation
Ozone Respiratory • Lung and throat irritant • Damages plants and trees
• Eye irritant • Reduce visibility
• Reduced resistance to • Damages rubber
infection
dominant SOx species formed are sulfur dioxide 1SO22 and sulfur trioxide 1SO32,
such that the ratio of SO2 :SO3 typically observed during the combustion of fossil
fuels ranges from 40:1 to 80:1 (Wark, et al. 1998). Acidic aerosols, such as sulfuric
acid 1H 2SO42, are formed when SO2 reacts with water. The reaction series can be
generalized as follows:
1
SO21g2 + O : SO31g2
2 21g2
11.4.5 Lead
Historically, the burning of leaded gasoline was the primary source for lead emission
into the atmosphere.As a result of the 1970 CAA, lead was phased out of gas, and now
stationary sources associated with lead storage battery manufacturing, iron and steel
production, lead smelting, and the painting of cars and houses are the primary emit-
ters of lead. Lead compounds tend both to persist and to bioaccumulate in the envi-
ronment. In humans, low-level lead poisoning results in kidney and neurological cell
damage. Lead may also contribute to hypertension and resulting heart disease.
Children are particularly sensitive to the effects of lead exposure, and in animal stud-
ies, lead has been shown to reduce fertility and cause birth defects.
Space
SUN
Incoming short wave
solar radiation
⬃343W/m2 Outgoing
longwave
radiation
Atmosphere
(Location of greenhouse gases
that absorb IR energy)
Back-scatter
by air Absorption by
clouds, water
Reflected by clouds vapor and gases
and earth’s surface
Energy emissions by
clouds, water vapor
and gases
Absorbed by water vapor,
clouds, dust, ozone
Longwave
radiation Surface gains more heat
(and IR is emitted again)
from IR reemitted by
⬃49% absorbed by Earth’s greenhouse gases
land and water (⬃168 W/m2)
Earth
Figure 11.1
Summary of the greenhouse gas effect and potential for global warming.
snow, sand, and water). This reflective property, known as the albedo, can change as
earth’s surface becomes more or less reflective. Plausible destinations for the 69%
that does not get reflected include absorption by the stratospheric ozone layer
1 ' 19%2, tropospheric clouds 1 ' 4%2, or the earth’s surface 1 ' 47%2.
The average energy that reaches a specified area of the earth’s surface per
unit time is defined as insolation. Because the majority of the sun’s UV energy
is absorbed by the stratospheric ozone layer, the majority of the insolation that
reaches the earth is in the visible region. For equilibrium to occur, the incoming
solar radiation must be balanced by the outgoing radiation (terrestrial radiation)
from the earth. The average temperature of the earth is about 300 K, and thus it pri-
marily emits infrared radiation having an average wavelength of 10 mm. The tem-
perature of the earth’s surface predicted from this steady-state radiative equilibrium
is considerably lower than the actual average temperature on earth by about 30ºC
(Kellogg, 1996; Peixoto and Oort, 1992; Henderson-Seller and Robinson, 1986). This
difference is caused by the presence of IR energy-absorbing compounds in our
atmosphere. Trace atmospheric compounds (as compared to N2 and O2), such as
water vapor, nitrous oxide, methane, and carbon dioxide, are almost transparent to
solar UV energy but effectively absorb IR radiation and then reradiate in many
wavelengths in all directions. Some of this energy is redirected downward, allowing
288 Chapter 11 Air Pollution
heating of the earth’s atmosphere and surface. This is the greenhouse effect. The
upward shift in earth’s temperature caused by the greenhouse effect is analogous
to covering one’s body with a blanket on a cold winter night. The blanketing
greenhouse gases do not completely prevent heat emission into space, but they
make it more difficult, causing the covered layer’s surface equilibrium tempera-
ture to rise.
To understand the potential problem of global warming, consider both natural
and anthropogenic sources as well as sinks for CO2 and other greenhouse gases.
CO2 is released into the environment by a variety of natural events, including
(1) volcanic eruptions, (2) forest fires, (3) decomposition of vegetative matter, and
(4) mammalian respiration. Removal of atmospheric CO2 also occurs naturally
through the photosynthesis process and by absorption of CO2 by water bodies. Such
natural processes help keep atmospheric CO2 concentrations reasonably balanced.
Some scientists argue that, since the invention of Watt’s steam engine and the
resulting Industrial Revolution that began in the late 1700s, the CO2 balance has
been disturbed and atmospheric greenhouse gas concentrations have increased as
a result of human interference. In fact, a variety of researchers have documented
an increase in the equilibrium atmospheric CO2 concentration from approximately
228 ppmv in the preindustrial era to about 364 ppmv in 1997 (Hansen et al., 1998;
Keeling and Whorf, 1998). Similar increases have been observed for atmospheric
concentrations of both CH 4 and nitrous oxide 1N2O2. Methane concentrations in
the preindustrial era averaged around 700 parts per billion volume (ppbv), and in
1994 they were about 1721 ppbv. During the same period, nitrous oxide increased
from about 275 to 312 ppbv (Houghton et al., 1996). In effect, this would allow
earth’s atmosphere to behave as a “thicker blanket,” causing the earth’s mean tem-
perature to rise.
Figure 11.2. provides a historical perspective of the previous 420,000 years
of global CO2 and CH 4 concentrations, as well as the temperature difference as
compared to the mean recent time average. These palaeoclimate data, derived
from ice cores drilled at the Russian Vostok station in East Antarctica, provide
documentation of the climate variability on Earth, punctuated by a series of
glacial–interglacial climate changes with cycles that last about 100,000 years.
These data confirm a strong correlation between greenhouse gases, such as CO2
and CH 4 , and temperatures in the Antarctic (Petit et al., 1999).
250
200
Temp diff ºC
150
5 Temp diff ºC (WRT mean recent time value)
0
5
10
400 350 300 250 200 150 100 50 0
Thousands of years before present (Kyr BP)
Section 11.5 Control of Particulate Matter from Stationary Sources 289
Among the various types of particulate control equipment are mechanical separa-
tors, typified by settling chambers and cyclones, electrostatic precipitators, fabric filters
such as baghouses, and wet scrubbers.The remainder of this section will briefly describe
how settling chambers and electrostatic precipitators work and provide general design
parameters and associated equations that can be used to predict removal efficiencies.
g1rp - r2d2
vs = B R (11.3)
18 m
where:
vs =
terminal settling velocity or Stokes’ settling velocity, m/s,
g =
gravitational acceleration, 9.81 m/s2,
rp =
particle density, kg/m3,
r =
density of the displaced fluid (in environmental applications, this will
frequently be air), kg/m3,
d = particle diameter, m, and
m = fluid viscosity, kg/1m # s2.
EXAMPLE 11.1
Stokes’ law application
Assume a point-source particulate emission having an effective stack height of 200 feet.
The plume contains particles having a density of 2.3 g/cm3, the stack-gas temperature is
80ºF, and the wind speed is constant at 5 mph. Assuming the terrain is flat, calculate the
distance downwind that a 5-, 10-, and 100-mm particle will travel.
Solution
Determine the Stokes’ settling velocity for each size particle using Equation (11.3).
At 80ºF, the viscosity and density for air are assumed as 6.66 * 10-2 kg/1m # hr2 and
0.0012 g/cm3, respectively. For the 5-mm particle, Stokes’ equation predicts:
g1rp - r2d2
vs = B R
18 m
m g g -6 1 kg 1003 cm3
9.81 ¢ 2.3 - 0.0012 ≤ 15 * 10 m22
* *
s2 cm3 cm3 1000 g 1 m3
vs 15 mm2 =
kg 1 hr
18a6.66 * 10-2 # b
m hr 3600 s
m
= 1.69 * 10-3
s
Section 11.5 Control of Particulate Matter from Stationary Sources 291
Similarly, Stokes’ velocity can be determined for the 10- and 100-mm particles:
1 hr 5280 ft 1m m
5 mph * * * = 2.235
3600 s 1 mi 3.281 ft s
1m
200 ft * L 61 m
3.281 ft
The time for each particle to drop is given by t = H/vs and the distance traveled
is equal to t times the average wind speed. Results are tabulated for each particle size
below.
H
Travel time, t =
Particle diameter vs Distance traveled,
( m) (sec) D = t * wind speed (m)
5 36,100 8.07 * 104
10 9,150 2.05 * 104
100 91.5 205
Settling chambers are used to remove the relatively large particles in a gas
stream and are often used as a precleaner. Particles with diameters greater than 50 μm
to 100 mm are effectively removed, and settling chambers are typically designed
having a velocity less than or equal to 3 m/s (10 fps), best results being obtained
with velocities less than 0.3 m/s (1 fps). The simple schematic of a settling cham-
ber shown in Figure 11.3 can be used to consider the fate of a particle in a settling
chamber and to determine the minimum particle size that can theoretically be
removed with 100% efficiency. For a particle that enters the top of the collector
and is removed, the time for the particle to fall the collector height, H, must be
less than or equal to the time of the horizontal movement within the collector
such that:
time for particle to fall H distance = time of horizontal movement
H L
t = =
vs V
VH
vs =
L
where L is the length of the hopper and V is the horizontal flow- through velocity. Sub-
stituting this value for Stokes’ velocity into Equation (11.3), neglecting the density of
292 Chapter 11 Air Pollution
air (since it is very small compared to the density of the solid), and solving for the par-
ticle diameter that is 100% removed yields:
18 mHV 0.5
D = B R (11.4)
gLrp
Notice that reducing the H/L ratio will result in removing smaller particles.
For particles sizes below that predicted by Equation (11.4), the removal effi-
ciency, h, for laminar-flow situations is determined by:
vsLW
h = 100 (11.5)
Q
Figure 11.3 L
Schematic of particle motion V
V
in a settling chamber.
Air inlet H
vs
Air outlet
Dust hopper
EXAMPLE 11.2
Settling chamber design
Design a settling chamber to collect particles 50 mm in diameter and 2000 kg/m3 in
density from an air stream with a volumetric flow of 1.5 m3/s. The chamber is to be
2.0 m in width and 2.0 m in height.
a. How long must the chamber be to give theoretical perfect collection
efficiency?
b. Determine the collection efficiency for particles of the same density that
are 25 mm in diameter.
Solution part a
Using Stokes’ law, determine the terminal settling velocity for the 50-mm particle.
Assume that the density and viscosity of air are 1.2 kg/m3 and 6.66 * 10-2 kg/1m # hr2,
respectively.
g1rp - r2d2
vs = B R
18 m
m kg kg
9.81 2
¢ 2000 3 - 1.2 3 ≤ 150 * 10-6 m22
s m m m
vs 150 mm2 = = 0.147
kg 1 hr s
18a6.66 * 10-2 ≤
m # hr 3600 s
Section 11.5 Control of Particulate Matter from Stationary Sources 293
Solve Equation (11.5) for the length of chamber required for theoretically
removing 100% of the 50-mm particles.
vsLW
h = 100
Q
m3
¢ 1.5 ≤ 11002
Qh s
L = = = 5.1 m
100vsW m
11002 ¢ 0.147 ≤ 12 m2
s
Solution part b
For the 25-mm particle, similarly, use Stokes’ law to determine the terminal settling
velocity.
g1rp - r2d2
vs = B R
18 m
m kg kg
9.81 2
¢ 2000 3 - 1.2 3 ≤ 125 * 10-6 m22
s m m m
vs 125 mm2 = = 0.037
kg 1 hr s
18a6.66 * 10-2 # b
m hr 3600 s
Use Equation (11.5) to determine the removal efficiency for the 25-mm particles.
m
a0.037 b15.1 m212 m2
vsLW s
h = 100 = 100 = 25%
Q m3
1.5
s
So, only 25% of the particles having a diameter of 25 mm are removed by the
settling chamber.
Figure 11.4
Schematic of an electrostatic
Dry gas in
precipitator.
(Source: U.S. EPA, Principles
and Practices of Air Pollution Grounded collecting plate
Control, 2003). with positive charge Hopper to discharge
30 ft (6.1 and 9.1 m), and collecting electrode height commonly ranges between 30
and 40 ft (9.1 and 12.1 m). A schematic of an ESP is shown in Figure 11.4.
Advantages associated with ESP technology that make it popular in industry
(especially coal-fired electric-power generators) include:
1. Ability to handle large gas volumes with small pressure drops, up to 4 * 106
scfm 11.1 * 105 m3/min2.
2. Ability to handle small gas volumetric flow rates, exemplified by household air
conditioning systems.
3. High removal of both wet and dry small-diameter particles (removal efficiencies
can be 99% to 99.9%).
4. Ability to operate within a wide range of temperature.
5. Low operation and maintenance (O&M) costs, a result of low power require-
ment because of relatively low pressure drop (0.1 to 0.5 in. of H 2O).
6. Acts only on the particle, not on the gas stream.
Disadvantages for ESPs include the following:
1. Certain types of dust cannot be removed efficiently. Particles with electrical
resistivity less than 104 ohm-cm or greater than 1010 ohm-cm are not effectively
removed. Particles with low resistivity, such as carbon dust, too readily give up
their negative charge to the collecting electrode, assuming a positive charge
which repels them back into the main gas stream (reentrainment). Particles with
high resistivity, such as powdered sulfur, will not give up their negative charge,
and a layer of dust builds up on the collecting electrode, acting as an insulator.
The potential drop across the layer builds up, causing a “back discharge” or
“back corona.” In these instances, removal may occur only if conditioning agents
such as water vapor, ammonia, or sulfur trioxide are added to change resistivity.
Section 11.5 Control of Particulate Matter from Stationary Sources 295
Av
h = 1 - expa - b (11.6)
Q
where:
A = area of collection electrodes, m2
v = drift velocity of particles towards the plates as estimated by Equation
(11.7) below, m/s
Q = volumetric flow rate, m3/s
Any internally consistent set of units must be used in the Deutsch-Anderson
equation.
The speed at which a charged particle migrates towards the collection elec-
trode is referred to as the particle-migration velocity or the drift velocity. Variables
influencing the magnitude of the drift velocity include particle size, the strength of
the electric field, and the viscosity of the gas. For standard air at 60ºF, the drift veloc-
ity can be estimated as:
where:
v = drift velocity, fps,
d = particle diameter, mm,
E = potential applied to discharge electrodes, kV/in., and
3k
P = , where k = dielectric constant for the particle
k + 2
EXAMPLE 11.3
Electrostatic precipitator design
Process exhaust gas with a volumetric flow rate of 500,000 cfm that contains 2 gr/ft3
(recall that gr is the abbreviation for grain; 1 lb = 7000 gr) of cement PM is to be
treated with an ESP. Regulatory requirements dictate that the outlet PM concen-
tration must be … 0.02 gr/ft3. Assume a plate-to-plate spacing of 8 inches and an
applied voltage of 12,000 volts. The smallest particles in the gas stream are 2 mm in
diameter, and all particles have a dielectric constant of 5. Estimate (a) the particle
296 Chapter 11 Air Pollution
drift velocity and (b) the required collection plate area to meet regulations. Assume
a system temperature of 60ºF.
Solution part a
Knowing the dielectric constant for the dust, calculate the constant P.
3k 3152
P = = = 2.14
k + 2 5 + 2
Use Equation (11.7) to estimate the drift velocity for 2-mm particles.
v = 8.42 * 10-3 E 2 dP
1 kV 1 2
= 8.42 * 10 -3 a12,000 V * * b 12 mm212.142
1000 V 4 in.
ft
v = 0.32
s
Solution part b
Use the Deutsch-Anderson equation [Equation (11.6)] to determine the required
collector-plate surface area.
First, determine the required removal efficiency using Equation (11.2):
gr
12 - 0.022
PM in - PM out ft3
h = = = 0.99 or 99%
PM in gr
2
ft3
Av
h = 1 - expa - b
Q
Av
1 - h = expa - b
Q
Av
ln11 - h2 = -
Q
ft
- 8,333
-Q s
A = 3ln11 - h24 = 3ln11 - 0.9924
v ft
0.32
s
If a plate length of 30 ft with height of 40 ft is used, the plate area can be calcu-
lated. Recognize that both sides of the plates are utilized as collectors:
119,922 ft2
number of plates required - 1 =
ft2
2400
plate
11.6.1 Incineration
Incineration is a high-efficiency process, occurring in the presence of oxygen, that
removes combustible pollutants (gases, vapors, or odors) from contaminated air and
other gas streams by raising the system temperature sufficiently high to autoignite
targeted pollutants, converting them primarily into carbon dioxide and water. It is
effective in streams containing either high or low concentration of contaminants.
Odorous pollutants (mercaptans, cyanide gases) and organic aerosol plumes, gases,
and vapors are effectively destroyed.
Thermal and catalytic are two common incinerator classes. Thermal incinera-
tors are also referred to as thermal oxidizers or direct-flame incinerators. If incin-
erators are properly designed, destruction efficiencies can be as high as 99.99%.
Critical design variables include combustion-chamber temperature, turbulence (or
degree of mixing), residence time, and concentration and type of contaminants
(U.S. EPA, 1992). Commonly, the factors affecting incinerator performance are
referred to as the 3 Ts (Time, Temperature, Turbulence). The EPA (1992) recom-
mends a residence time of 0.75 seconds combined with a chamber temperature of
1600ºF to effectively control a stream contaminated with VOCs. If halogenated
VOCs are present, the combustion temperature should be 2000ºF at a residence
time of 1 second. Use of a scrubber downstream of the incinerator to control the
acid gas effluent is desirable.
298 Chapter 11 Air Pollution
Figure 11.5
Typical packing material for
scrubbers.
(Source: U.S. EPA Air
Pollution Control Cost
Manual, 2002.)
Pall ring Tellerette Intalox saddle
Gas out
Mist eliminator
Spray nozzle
Packing
restrainer
Shell
Random
Packing
Liquid re-distributor
Packing support
Gas in
Figure 11.6
Schematic of packed tower
scrubber used for absorption
of gas contaminants.
(Source: U.S. EPA Air Liquid out
Pollution Control Cost
Manual, 2002.)
1. Capital cost, pressure drop, and space requirement are relatively low.
2. Highly corrosive environments can be treated if towers are constructed with
fiberglass-reinforced plastic (FRP).
3. High mass-transfer efficiencies can be achieved.
4. PM can be removed from gas streams as well as gases.
Disadvantages:
The following generalized reaction between SO2 and Ca1OH22, results in the
formation of calcium sulfite hemihydrate and occurs within the spray tower during
the removal of the acidic gas.
Disadvantages include:
1. High capital and O&M costs.
2. Wet wastes are generated.
3. Reactant product disposal is a significant cost.
S U M M A RY
Air pollution concerns related to anthropogenic emissions predate the modern era.
In the United States, the passage of the 1970 Clean Air Act provided the EPA with
statutory authority to establish and enforce guidelines for controlling air pollution.
Since the promulgation of the Act, national attention has been given to the estab-
lishment of criteria pollutant guidelines as well as to global issues such as acid rain,
stratospheric ozone, and the greenhouse effect. The chapter introduced end-of-pipe
pollution-control technologies used to mitigate gases containing particulates and
gas and vapors, and it provided preliminary operational and design criteria.
REFERENCES
Anderson, E. (1924). Report, Western Precipitator Co., Los Angeles, CA, 1919, Transactions
of the American Institute of Chemical Engineers, 16, 69.
AWMA (1992). Air & Waste Management Association, Air Pollution Engineering Manual,
Van Nostrand Reinhold, New York.
Cooper, C. David, and Alley, F.C. (1994). Air Pollution Control: A Design Approach, 2nd ed.,
Waveland Press, Inc., Prospect Heights, Illinois.
Deutsch, W. (1922). Annals of Physics (Leipzig), 68, 335.
EPA-CICA Fact Sheet, Catalytic Incinerator, EPA-452/F-03-018.
EPA-CICA Fact Sheet, Flue Gas Desulfurization (FGD), EPA-452/F-03-034.
EPA-CICA Fact Sheet, Packed-Bed/Packed-Tower Wet Scrubber, EPA-452/F-03-015.
EPA-CICA Fact Sheet, Thermal Incinerator, EPA-452/F-03-022.
Franek, W., and DeRose, L. (2003). Principles and Practices of Air Pollution Control Student
Manual, APTI Course 452, 2nd ed., Air Pollution Training Institute, Environmental
Research Center, MD, Research Triangle Park, NC.
Hansen, J., Sato Mki., Glascoe, J., and Ruedy, R. (1998). A Common Sense Climate Index: Is
Climate Changing Noticeably? Proc. Natl. Acad. Sci., 95, 4113–4120.
Exercises 303
Henderson-Sellers, A., and Robinson, P.J (1986). Contemporary Climatology, John Wiley &
Sons, New York, 439 pp.
Houghton, J.T., Filho, L.G.M., Callander, B.A., Harris, N., Kattenberg, A., and Maske, K.
(1996). Climate Change 1995: The Science of Climate Change, Intergovernmental Panel on
Climate Change, Cambridge University Press, Cambridge, GA, 1996, 572 pp.
Keeling, C.D., and Whorf, T.P. (1998). Atmospheric CO2 concentrations—Mauna Loa Obser-
vatory, Hawaii, 1958–1997 (revised August 1998). NDP-001. Carbon Dioxide Information
Analysis Center, Oak Ridge National Laboratory, Oak Ridge, TN.
Kellogg, W.K. (1996). Greenhouse Effect, in Encyclopedia of Climate and Weather, Ed.
S.H. Schneider, pp. 368–371, Oxford University Press, New York.
NASA (1991). Environmental Control and Life Support System Architectural Control Docu-
ment, SSP-30262, Revision D, National Aeronautics and Space Administration, Space Sta-
tion Freedom Program Office, Reston, Virginia, July 1991.
Peixoto, J.P., and Oort, A.H. (1992). Physics of Climate, American Institute of Physics,
New York, 530 pp.
Petit, J.R., Jouzel, J., Raynaud, D., Barkov, N.I., Barnola, J.-M., Basile, I., Benders, M., Chappellaz,
J., David, M., Delaygue, G., Delmotte, M., Kotlyakov,V.M., Legrand, M., Lipenkov,V.Y., Lorius,
C., Pépin, L., Ritz, C., Saltzman, E., and Stievenard, M. (1999). Climate and Atmospheric His-
tory of the Past 420,000 Years from the Vostok Ice Core,Antartica, Nature, 399, 429–436.
Shen, T.T. (1995). Industrial Pollution Prevention, Springer-Verlag, Berlin.
U.S. EPA (1992). Control Techniques for Volatile Organic Emissions from Stationary Sources,
U.S. EPA Research Triangle Park, NC, EPA-453/R-92-018.
U.S. EPA (1997). Exposure Factors Handbook, Volume 1, General Factors, August 1997,
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ment, Washington DC, EPA/600/P-95/002Fa.
U.S. EPA (2000). Estimated Per Capita Water Ingestion in the United States Based on Data
Collected by the United States Department of Agriculture’s 1994–96 Continuing Survey of
Food Intakes by Individuals, April 2007, U.S. Environmental Protection Agency, Office of
Water, Washington DC, EPA-822-R-00-008.
U.S. EPA (2002). Air Pollution Control Cost Manual, Office of Air Quality Planning and Stan-
dards, U.S. EPA Research Triangle Park, NC, EPA/452/B-02-001.
U.S. EPA (2003). Principles and Practices of Air Pollution Control, Student Manual, APTI
Course 452,Air Pollution Training Institute, Environmental Research Center, MD E142-01.
U.S. EPA (2007). Achievements in Stratospheric Ozone Protection, U.S. EPA Office of Air and
Radiation, Washington, DC, EPA-430-R-07-001.
Wark, K., Warner, C.F., and Davis, W.T. (1998). Air Pollution: Its Origin and Control, 3rd ed.,
Addison Wesley Longman, Inc.
EXERCISES
11.1 Browse the portion of the U.S. EPA website focused on the Office of Air
and Radiation (http://www.epa.gov/air/) and provide (a) a list of the current
criteria pollutants listed in the National Ambient Air Quality Standards,
(b) a distinction between primary and secondary standards, (c) a definition
of nonattainment and attainment areas, and (d) a list of current nonattain-
ment areas near your home town, and (e) a summary of the EPA required
plan for areas deemed nonattainment.
11.2 Identify a locally operated industrial facility that is regulated under Title V of
the Clean Air Act. Find their permit online and briefly summarize their per-
mitting requirements.
11.3 Summarize the chemical equations primarily responsible for acid rain. Use
online resources to determine the average pH of rainfall in proximity to your
university. Has the pH of rainfall changed during the last several decades?
11.4 Using only reputable online resources, describe the “hole in the ozone layer.”
Items to consider as you conduct your research include: the chemical reactions
304 Chapter 11 Air Pollution
that occur, how ozone is measured, units for quantifying ozone, historical evi-
dence of ozone depletion, where the ozone layer is most impacted, associated
environmental and human health effects, and what predictions are made
regarding the future of stratospheric ozone recovery.
11.5 Using your own words, describe the greenhouse effect and global warming.
11.6 Air pollution can influence the limit of visibility by both absorbing and scat-
tering light. Using the library and internet resources, determine how the 1970
Clean Air Act impacted visibility within the United States. What are the pri-
mary pollutants that contribute to this phenomenon?
11.7 Consider particles characterized with a density of 1.5 g/cm3. At 25ºC and 1 atm,
determine the terminal settling velocity of particles falling in air that are (a) 15,
(b) 25, and (c) 150 mm in diameter.
11.8 Consider a settling chamber to treat a particulate ladened air stream having a
volumetric flow of 1.0 m3/s. Design a settling chamber to collect particles
10 mm in diameter having a density of 1700 kg/m3. The chamber is to be 1.5 m
in width and 1.5 m in height. (a) How long must the settling chamber be to give
theoretical perfect collection efficiency? (b) Using the length determined in
part (a), determine the collection efficiency for 5-mm particles with the same
density.
11.9 Design a settling chamber to collect particles 50 mm in diameter and 111 lb/ft3 in
density from an air stream with a volumetric flow of 8 ft3/s. The cross-sectional
area of the square inlet is 9 ft2. (a) How long must the chamber be to give theo-
retical perfect collection efficiency? (b) Determine the collection efficiency for
10-mm particles with the same density. Assume the gas-stream temperature is
70ºF, such that the gas density and viscosity are 0.075 lb/ft3 and 1.23 * 10-5
lb/1ft # s2, respectively.
11.10 Process exhaust gas with a volumetric flow rate of 100,000 cfm that contains
5 gr/ft3 of cement PM is to be treated with an ESP. Regulatory requirements
dictate that the outlet PM concentration must be … 0.02 gr/ft3. Assume a
plate-to-plate spacing of 10 inches and an applied voltage of 15,000 volts. The
smallest particles in the gas stream are 2 mm in diameter, and all particles
have a dielectric constant of 5.5. Estimate (a) the particle drift velocity and
(b) the required collection-plate area to meet regulations. (c) Assume that
plates with length and height of 30 ft are used. Estimate the number of plates
required. Assume standard temperature and pressure.
CHAPTER
Fundamentals
of Hazardous Waste Site
12
Remediation
from 1956 until 1972 in Stringfellow, California, where it accepted over 34 million
gallons (129 million liters) of industrial waste, primarily from metal finishing, elec-
troplating, and pesticide production. Aqueous-based wastes sent to the facility were
disposed of in evaporating ponds. Because of excessive rainfall in 1969, the ponds
overflowed into the town of Glen Avon and resulted in the contamination of Pyrite
Creek. In 1970, the EPA was created, and by 1972, DDT had been banned and the
Federal Insecticide, Fungicide, and Rodenticide Act enacted. Additional historical
highlights of hazardous waste history are given in Table 12.1.
CERCLA was created in 1980 in response to discoveries in the late 70s of
numerous abandoned, leaking, and hazardous waste dumps that threatened human
health and the environment. Possibly the most noted hazardous waste site associ-
ated with this time period was “Love Canal.” Located in Niagara Falls, New York,
the original intent of the canal, owned by Mr. William T. Love, was to provide hydro-
electricity to the region and to join the two sides of the Niagara River separated by
the Niagara Falls with a navigable waterway. When the project proved infeasible, the
land was acquired by Hooker Chemical and Plastics Corporation and was subse-
quently used as a hazardous waste repository. During a five-year span beginning in
1947, nearly 21,000 tons of hazardous material were buried in the area. Once the
canal was full, the land was sold to the City of Niagara Falls Board of Education. By
the late 70s, the land was surrounded by single-family and low-income housing as
well as three nearby schools. Public health concerns were realized in 1978 as a result
of reports published in the local newspaper and by the New York State Department
of Health. The publicity resulted in a school closure and demolition. Most residen-
tial dwellings in the impacted area were also demolished.
CERCLA, initially established as a five-year program, was created to identify
and take action to remedy hazardous waste sites, and to force responsible parties to
pay for the cleanup. In addition, CERCLA established a $1.6 billion “Superfund” to
support government cleanup actions and established guidelines for inclusion of sites
on the National Priorities List (NPL) based on the Hazardous waste site Ranking
System (HRS). The HRS ranks the hazardous character of sites based on risk. Risks
from the migration of toxic compounds through the air, groundwater, or surface
water, from direct contact with contaminated soils at the site, and from hazards asso-
ciated with potential fires or explosions are considered. In 1986, the Superfund
Reauthorization and Amendments (SARA) extended CERCLA five more years,
increased the fund to $8.5 billion, established the Leaky Underground Storage Tank
(LUST) trust fund, initiated the Emergency Planning and Community Right-to-
Know Act (EPCRA) and associated Toxic Release Inventory (TRI). EPCRA and TRI
were created in response to the 1984 release of methyl isocyanate (MIC) at the Union
Carbide pesticide production facility located in Bhopal, India. The MIC gas, a lung irri-
tant, caused up to 2,000 deaths and 350,000 injuries, leaving 100,000 people with per-
manent disabilities. As a consequence of EPCRA and the TRI, companies which
process more than 25,000 lb/year (11,340 kg/year) or use 10,000 lb/year (4536 kg/year)
of any of the 654 EPA listed hazardous chemicals must report all waste generated
and all releases and transfers of hazardous chemicals. Companies are also required to
develop an emergency response plan that allows the surrounding communities to pro-
tect themselves from catastrophic accidents associated with toxic chemical release.
Appropriations for SARA continue today.
Additional provisions of CERCLA include the National Contingency Plan
(NCP), developed as the federal government’s blueprint for responding to both oil
spills and the unintended release of hazardous substances. CERCLA also allows the
EPA to conduct or require both “Removal” and “Remedial” Actions. A CERCLA
Section 12.1 The Problem 307
Table 12.1 Historical Events Relevant to the History of Hazardous Wastes Management
Year Significant Event
1940s Increase in chemical production
1977 End of 30 years of PCB contamination in the Hudson River, during which the General Electric
Company (GE) discharged as much as 1.3 million pounds of PCBs directly into the river from
facilities located in Hudson Falls and Fort Edward, NY
1980 CERCLA (Superfund)—allowing the EPA to clean up, order abatement, and recover the cost of cleanup
1982 Times Beach, MO—largest civilian exposure to dioxin in the U.S. resulting from spraying oil to
control dust. The town was evacuated and registered as a Superfund site.
2002 Small Business Liability Relief and Brownfields Revitalization Act—provides relief from Superfund
liability for small businesses, and promotes the revitalization of ”brownfields,” properties where
redevelopment is hindered by the presence of contamination.
308 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
Table 12.2 Top 20 Environmental Contaminants Associated with the 2005 CERCLA Priority List of
Hazardous Substances
2005
Rank Substance Common current and historical uses and sources
1 Arsenic Wood preservative, pesticide
4 Vinyl chloride Used in the production of PVC, wire and cable coating, packaging
materials
7 Polycyclic aromatic hydrocarbons Incomplete combustion of fossil fuels and other organics
10 Benzo(b)fluoranthene Leaches from water-distribution system tanks lined with coal tar or
asphalt; from combustion of organic matter; no industrial use
12 p,p¿-DDT Pesticide
(dichlorodiphenyltrichlorethane)
18 Chromium, hexavalent Chrome plating, dyes, pigments, leather tanning, wood preserving
to the U.S. EPA RCRAInfo National Database, the quantity of RCRA hazardous
waste generated in the United States decreased by 29% between 1999 and 2003.
The National Biennial RCRA Hazardous Waste Report estimated that the United
States produced approximately 38.3 million tons of hazardous waste in 2005 (EPA
National Analysis, 2005). In that same year, 21.8 million tons of RCRA hazardous
wastes were disposed of by deep well or underground injection. The EPA has
projected that approximately 294,000 contaminated sites need to be remediated
within the United States and have an estimated cleanup cost of $209 billion. Most
of this cost will be assumed by the property owners and those deemed potentially
responsible for the contamination. Most sites are contaminated with solvents and
other organics, metals, and petroleum products (U.S. EPA, 2004). Table 12.2 lists
the top 20 hazardous substances on the CERCLA Priority List of Hazardous
Substances for 2005. The complete list can be obtained online at www.atsdr.cdc.
gov/cercla/05list.html.
Aliphatic Hydrocarbons
Aliphatic hydrocarbons contain either straight or branched chains of single-, double-,
or triple-bonded carbon atoms. If the backbone in the aliphatic contains only single-
bonded carbon atoms, the hydrocarbon is termed saturated and is referred to as an
alkane or paraffin. Alkanes can generically be described with the chemical formula
C nH 2n+2 , where n represents the number of carbon atoms in the chain. Figure 12.1a
Figure 12.1a
H H H H H Pentane is an example of a
H C C C C C H straight-chain aliphatic
hydrocarbon with chemical
H H H H H formula C5H12 .
310 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
Table 12.3a Names, Structures, and Properties of Short-Chain Aliphatic Hydrocarbons Commonly Found at
Contaminated Sites (Chlorinated Alkanes and Alkenes are Emphasized)
Compound name Molecular Henry’s law constant
(Acronym) Structure weight (unitless) Log K OW T (°C)
Vinyl chloride (VC) Cl H 62.5 3.35 1.38 25
C C
H H
Figure 12.1b
Both ring structures shown are commonly used to represent benzene, the base for all aromatic
and polycyclic aromatic hydrocarbons. The benzene ring contains six carbon atoms joined by
alternating single and double bonds and the molecule contains six hydrogen atoms. The posi-
tions of the bonds are known to change, resulting in benzene often being depicted as a hexa-
gon with an internal ring that represents the shifting bond positions, causing all the bonds to
have an equal length.
alternating single and double bonds. Other aromatic compounds are formed by the
addition of functional groups onto the aromatic ring. Table 12.3b shows several aro-
matic compounds that are commonly found at contaminated sites. Benzene, Toluene,
Ethyl benzene, and Xylene (BTEX) are often associated with petroleum products and
typically enter the environment as a result of LUSTs. Many states use the concentra-
tion of BTEX compounds for cleanup standards of petroleum-contaminated sites. In
addition to its prominence in petroleum-based products, benzene is used by a variety
of other industries to manufacture plastics, resins, detergents, pesticides, and synthetic
fibers; it is ranked sixth on the 2005 CERCLA NPL list and is believed to be a human
carcinogen. Aromatics are less dense than water, have a high vapor pressure and are
thus considered volatile, and are sparingly soluble in water.
Table 12.3b Names, Structures, and Properties of Aromatic Hydrocarbons Commonly Found at Contaminated Sites
Molecular Henry’s law constant
Compound name Structure weight (unitless) Log K OW T (°C)
Benzene 78.1 0.227 2.13 25
CH3
312 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
Figure 12.1C
Napthalene and phenan-
threne are common two- Naphthalene
and three-ring polycyclic
Phenanthrene
aromatic hydrocarbons.
Table 12.3c Names, Structures, and Properties of Polycyclic Aromatic Hydrocarbons Commonly Found at
Contaminated Sites
Henry’s
law
Molecular constant
Compound name Structure weight (unitless) Log K OW T (°C)
Naphthalene 128.2 1.977 * 10-2 3.36 25
Biphenyl
X represents possible Cl sites
Figure 12.1d
Possible sites for chlorine atoms to be bonded to a biphenyl molecule are shown. From 1 to 10
chlorine atoms can be bonded to a biphenyl molecule for a total of 209 possible congeners.
314 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
Explosives are usually made of aliphatic or aromatic ring compounds that con-
tain a nitro functional group 1-NO22. Environmental contamination from this
group of compounds is associated primarily with military production and storage,
but it is also widely used by the mining and construction industries. Explosives tend
to be environmentally persistent and they are considered toxic. One of the most
common bulk explosives is 2,4,6-trinitrotoluene (TNT). TNT has been an important
military explosive since World War I because of its relative safety during manufac-
turing, loading, transportation, and storage. It is often mixed with other explosives,
such as Royal Demolition Explosive (RDX) and High Melting Explosive (HMX).
Wastewaters from munitions programs, often referred to as “pink water,” may be
difficult to remediate and are often colored pink as a result of the presence of TNT
and RDX. TNT is known to be poisonous and is listed as a possible human carcino-
gen. Prolonged exposure may result in anemia and abnormal liver functions, and it
is thought to be harmful to the immune system if ingested or breathed. Skin contact
causes irritation that turns the skin a bright yellow-orange color.
As a result of the promulgation of the 1970 Clean Air Act (CAA), additives
were blended with gasoline in an effort to reduce pollution from vehicles by burning
cleaner fuels. Additives included octane enhancers, antiknock compounds, corrosion
inhibitors, detergents, and oxygenates. Reformulated gasoline (RFG) also contained
a higher concentration of benzene, a carcinogenic compound. RFG is required
in cities exhibiting the worst smog problems and is now used in 17 states and the
District of Columbia. Two of the most common fuel oxygenates are acetone and
methyl tertiary butyl ether (MTBE). It was anticipated that with the reduction of
HC emissions caused by the addition of oxygenates to the mixture, the production
of the secondary air pollutant, ozone, would be diminished. The anticipated drop in
tropospheric ozone concentrations was not realized in most regions. Also, as a
result of MTBE’s high aqueous solubility, it travels farther and faster in water than
other gasoline constituents and it now contaminates many subsurface waters and
drinking water supplies.
Representative chemical structures and characteristics for pesticides, explo-
sives, and fuel additives are shown in Table 12.3d.
Inorganics of Concern
Metal contamination is commonly found in both solid and aqueous environments.
The 2005 CERCLA NPL ranks arsenic, lead, and mercury as the top three contam-
inants most frequently found at hazardous waste sites. Metals are used in a variety
of industrial activities and therefore have varied pathways into the environment.
Organic arsenic is used to make herbicides and fungicides and is used in semicon-
ductor production, while inorganic arsenic in the form of copper chromated arsenic
(CCA) is used during the preservation process of pressure-treated wood.
Lead is ubiquitous to the environment. Much lead contamination is a result of
the burning of gasoline in vehicles before the forced phase-out by the CAA of the
organometallic compound tetraethyl lead (TEL). Water pipes in some older houses
may contain lead solder, and deteriorating lead-based paints are of concern. Lead is
also commonly used in the production of auto batteries, ammunition, electronics,
and plastics.
Mercury is found in three forms, including elemental, inorganic, and organic.
Metallic and inorganic mercury compounds enter the environment as a result of mining,
burning coal, and waste disposal from manufacturing facilities. Metallic mercury is used
to produce chlorine gas and caustic soda and is also used in thermometers and batteries.
Section 12.2 Contaminant Characteristics and Phase Distribution 315
Table 12.3d Names, Structures, and Properties of Additional Organic Compounds Commonly Found at
Contaminated Sites. Structures Include PCBs, Explosives, Gasoline Additives, and Insecticides
Henry’s
law
Compound name Molecular constant Log T
(acronym) Structure weight (unitless) K OW (°C)
Aroclor® 1254 n.a.* n.a. 0.155 6.03 20
NO2
…
n.a.—not applicable, as Aroclors contain a mixture of PCBs, not just a single compound.
Metals such as arsenic, lead, and mercury are potentially toxic to the kidneys,
decrease mental capabilities, and can cause weakness, headaches, abdominal cramps,
diarrhea, and anemia (U.S. EPA, 2004). While these compounds cannot be destroyed
through a bioremediation process in the environment, they can be transformed by
methylation, complexation, sorption, and change of valence state to affect their solu-
bility (and therefore their mobility and bioavailability) or toxicity.
Transport medium
(ground water)
Ground-water flow
Figure 12.2
Cartoon depicting a leaky underground storage tank and resulting contaminant fate in the environment.
(Source: U.S. EPA. 1989.)
form on the water table and provide a continual source of contamination to the
aquifer if not removed. Similarly, compounds that have a specific gravity greater
than one, such as TCE and PCE, will tend to sink to a nonpervious layer within the
subsurface and form a dense nonaqueous-phase liquid (DNAPL) pool.
Partitioning Coefficients
Partition coefficients are used to describe how organic compounds distribute
between the solid, liquid, and gas phases of the environment. Many compounds
released into the environment are bound or sorbed in the soil and sediment present.
The octanol-water partition coefficient, KOW , describes a compound’s hydrophobic-
ity and how it partitions between the organic and aqueous phase. The KOW is deter-
mined by quantifying the ratio of the compound in both phases of an immiscible
mixture of octanol and water.
Values of KOW are unitless, vary widely from 10-3 to 107, and tend to increase
with the size of the molecule. Large KOW values indicate that the compound is rela-
tively hydrophobic and tends to partition to the organic phase. Organic compounds
with low KOW values are hydrophilic and thus tend to stay in the aqueous phase,
showing minimal soil adsorption.
Soil-Distribution Coefficient
The sorption, or the distribution of nonpolar hydrophobic organic compounds to a par-
ticular soil matrix can often be well characterized by a linear relationship (recognize
Section 12.2 Contaminant Characteristics and Phase Distribution 317
s
KSD = (12.2)
CL
where:
KSD = soil-distribution coefficient (often referred to as the partition
coefficient), L/mg or m3/g,
s = mass of solute sorbed per unit mass of dry soil, unitless, and
CL = liquid-phase equilibrium concentration of the targeted compound,
mg/L or g/m3.
The soil-distribution coefficient is strongly dependent on the hydrophobicity
of the solute as well as the organic content of the soil, such that the partition coeffi-
cient is not the same for every soil. Eweis et al., (1998), provide a relationship for the
partition coefficient that requires knowledge of the KOW and the mass fraction of
organic carbon in the soil, fOC .
mass of carbon
where fOC = fraction of organic carbon in solids, a b
mass of solid
EXAMPLE 12.1
Estimation of sorption to soil
Groundwater is contaminated with 150 mg/L (150 ppb) TCE. Assume the aquifer
solids contain 1% organic carbon (i.e., fOC = 0.01) and that sorption is adequately
described by a linear model. Estimate the mass of TCE sorbed to the solid material.
Solution
From Table 12.3a, the log KOW for TCE is 2.38. Use Equation (12.3) to estimate the
soil-distribution coefficient, KSD .
L
KSD = 6.3 * 10-7 fOCKOW = 6.3 * 10-7 10.0121102.382 = 1.51 * 10-6
mg
L 106 mg L
KSD = ¢ 1.51 * 10-6 ≤¢ ≤ = 1.51
mg kg kg
Using Equation (12.2), which describes linear sorption, and the KSD value
obtained from Equation (12.3), determine the equilibrium TCE concentration
sorbed to the solid phase in the aquifer.
L mg mg mg TCE sorbed
s = KSDCL = a1.51 b a 150 b a b = 0.23
kg L 1000 mg kg soil
318 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
Cg = kH,A CL (12.4)
where:
kH,A = dimensionless Henry’s constant,
Cg = equilibrium gas-phase concentration, mg/L, and
CL = equilibrium liquid-phase concentration, mg/L.
Care should be taken when using Henry’s law constants, as their values
depend on the concentration units for the gas and liquid phases.
EXAMPLE 12.2
U s i n g H e n r y ’s l a w t o e s t i m a t e e q u i l i b r i u m c o n c e n t r a t i o n s
Results from a soil-vapor study showed a soil-vapor concentration for toluene of
1000 ppmv. Use Henry’s law to estimate the surrounding liquid-phase toluene con-
centration. The dimensionless kH,A for toluene is 0.279.
Solution
The molecular formula for toluene is C 7H 8 . Determine the molecular weight for
toluene as shown.
MW = 71122 + 8112 = 92
Use the equation shown below to convert the volume-based vapor-phase con-
centration to a mass-per-unit volume basis when the gas temperature is 20°C.
mg ppmv * MW * 103
3
= 1at 20°C2
m 24
mg ppmv * MW * 103 1000 * 92 * 103 mg mg
= = = 3.83 * 106 3 = 3.83
m3 24 24 m L
Use Henry’s law to calculate the aqueous-phase concentration,
Cg = kH,A CL
mg
Cg 3.83
L mg
CL = = = 13.7 toluene in the aqueous phase
kH,A 0.279 L
Volume Mass
relationships relationships
Va Air
Ww
Vv Water
Vw rw 1.0 g/cm3
Wt
Vt
Figure 12.3
Vs Solids Phase diagram for a par-
Ws
rs 2.65 g/cm3 tially saturated soil. Volume
and mass relationships are
identified.
each property, its Greek symbolic reference, and a mathematical description. From
the figure, notice that the total weight of the soil is equal to the weight of the water
plus the weight of the solids. The weight of air is neglected, such that the total weight
is given mathematically as Wt = Ww + Ws . The void volume in the soil is equal to
the sum of the volumes of air and water, such that Vv = Va + Vw . The total soil vol-
ume can be represented as Vt = Vv + Vs = Va + Vw + Vs .
EXAMPLE 12.3
Determine mass and volume relationships in soil
A sample of moist soil having a wet weight of 1000 g and volume of 650 cm3 was
oven dried and found to have a dry mass of 800 g. Determine the soil’s dry bulk den-
sity and porosity and the volumetric water content.
Solution
From the problem statement, recognize that:
Mt = 1000 g, Ms = 800 g, and Vt = 650 cm3
320 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
Assume a soil density of rs = 2.65 g/cm3. Given that the mass of the solid is
800 g, the volume of the soil is Vs = 1800 g2/12.65 g/cm32 = 301.9 cm3.
Assume that the mass of the air is negligible, so Ma = 0. The mass of the water
present in the sample can be determined as Mw = 11000 - 8002g = 200 g. Assuming
the density of water is 1 g/cm3, the volume of water in the sample is Vw = 200 cm3.
Recognize that the total sample volume is Vt = 650 cm3 = Va + Vw + Vs .
Knowing the volumes of the water and solid phases, we can algebraically determine
Va = 148.1 cm3.
With Vt = 650 cm3, Vw = 200 cm3, Vs = 301.9 cm3, and Va = 148.1 cm3, we
can determine the unknown mass and volume soil relationships. Use Figure 12.3 and
Table 12.4 to determine appropriate definitions and equations.
Ms 800 g g
dry bulk density = rb = = 3
= 1.23 3
Vt 650 cm cm
Vv Va + Vw 1148.1 + 2002cm3
porosity = h = = = = 0.54
Vt Vt 650 cm3
Vw 200 cm3
volumetric water content = ® = = = 0.31
Vt 650 cm3
dh
q = KC (12.5)
dL
where:
q = Darcy flux along the flow path (often called the superficial velocity,
discharge velocity, specific discharge, or Darcy’s velocity), m/s,
KC = hydraulic conductivity, m/s, and
dh
= hydraulic gradient, dimensionless.
dL
Section 12.2 Contaminant Characteristics and Phase Distribution 321
The porosity 1h2 relates the actual pore velocity (v) to the Darcy flux (q). The
flux is divided by the porosity in recognition that the flow through the subsurface is
limited by the available pore space in the matrix, such that the average velocity
through the porous media is larger than the Darcy flux. The pore velocity, v (also
referred to as the average linear velocity and the seepage velocity), is equal to
Darcy’s velocity (q) divided by porosity 1h2, shown as:
q
v = (12.6)
h
v
R = (12.7)
vp
Flow of a conservative, inert material that travels at the speed of the seepage
velocity has an R value equal to 1. In a given environment, the plume of a hydropho-
bic compound with R = 2 is estimated to travel at half the groundwater seepage
velocity. If the flow system is assumed to be at equilibrium and sorption can be char-
acterized as linear and reversible, the retardation coefficient can be estimated as:
rb
R = 1 + K (12.8)
h SD
EXAMPLE 12.4
G ro u n d w a t e r m i g r a t i o n a n d r e t a r d a t i o n o f c o n t a m i n a n t s
Assume a leak in a 200-L underground storage tank containing water contaminated
with methyl tertiary-butyl ether, benzene, and benzo(b)fluoranthene. Estimate how
far each contaminant will travel in one year. Assume the following hydrogeologic
characteristics:
Solution
Use Equation (12.5) to calculate the Darcy velocity:
dh cm ft cm
q = KC = a 0.0001 b a0.05 b = 5 * 10-6
dL s ft s
322 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
cm
5 * 10-6
q s cm
v = = = 1 * 10-5
h 0.5 s
Calculate the KSD for each compound using Equation (12.3). For example, the
KSD for MTBE is found as follows:
L
KSD = 6.3 * 10-7 fOCKOW = 16.3 * 10-7210.0121101.242 = 1.09 * 107
mg
Use Equation (12.8) to determine the retardation factor for each compound. The
calculation is demonstrated with MTBE.
g 1000 ml L 1000 mg
a1.25 ba b a1.09 * 10-7 ba b
rb ml L mg g
R = 1 + K = 1 +
h SD 0.5
= 1.27
Relying on Equation (12.7), calculate the velocity of each contaminant. For MTBE:
cm
1 * 10-5
v s cm
vp = = = 7.9 * 10-6
R 1.27 s
Now, determine an estimate of the distance traveled in one year. Again, MTBE is
used as an example:
distance = vp * time
cm 365 d 24 hr 60 min 60 s
distance = a7.9 * 10-6 b11 yr2a ba ba ba b = 250 cm
s yr d hr min
Notice the role sorption plays for benzo(b)fluoranthene! Recognize that due to sub-
surface heterogeneities, assumptions of uniform fOC , differences in sorption of dif-
ferent soil organics, and the linear sorption assumption in the retardation-factor
formula, these results are simply estimates. Therefore, do not report too many sig-
nificant figures when providing your answers.
Section 12.3 Overview of Microbial Processes 323
Figure 12.4
Typical pump-and-treat
ee
k Treatment system.
Cr Discharge pipe
building (Source: U.S. EPA, 2001.)
Extraction wells
Plume
326 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
employ both vertical and horizontal wells to enhance contaminant extraction, with
air bubbles traveling both horizontally and vertically through the subsurface. Sys-
tems should be designed such that the uncontrolled release of volatiles into the
atmosphere is minimized. The treatment of offgas may be required.
Sites contaminated with VOCs and fuels are often amenable to air sparging.
The lower-molecular-weight constituents in gasoline, such as BTEX, are generally
mitigated well with this technology, while less volatile, heavier mixtures such as
diesel fuel do not respond adequately. Appropriate geologic and hydrogeologic site
conditions are crucial to the application of an air-sparging system. Site considera-
tions dictate the ability to effectively deliver air to the treatment area. In general,
site conditions that favor air sparging include a moderate to high permeability, often
correlating to relatively coarse-grained materials. Low-permeability (fine-grained)
soils limit the migration of air into the subsurface and reduce the effectiveness of
the treatment strategy. A typical air-sparging system is shown in Figure 12.5.
Groundwater
extraction wells
Vadose zone
Contaminated
Injection well groundwater
Saturated zone
Submersible
pump
Section 12.4 Introduction to Engineered Remediation Processes 327
Clean air
Vacuum Vapor
blower treatment
(5)
(4)
Extracted
vapor Vapor- Process residual
liquid
separator
(3)
Clean water
Extraction Liquid
well treatment
(6)
(1)
Process residual
Air vent or
Air vent or injection well
injection well
(2) Impermeable cap (7) Ground surface
Contaminated
vadoss
zone
Water table
Figure 12.6
Generic soil-vapor extraction system.
(Source: U.S. EPA, 1991.)
Most SVE systems are installed to treat shallow contamination, where the site
targeted for cleanup is less than 10 m deep. Typical vacuums of 0.1 to 0.2 atm (1.5 to
2.9 psi) are applied, resulting in extraction flow rates between 1 to 6 m3/min (35 to
212 ft3/min). In the vadose zone, recall that the contaminant is partitioned between
three phases (possibly four phases, if pure product is available). Soils with high
organic content tend to sorb VOCs, making SVE much more difficult, and desorp-
tion from the solid phase is considered rate limiting. SVE in the preferential path-
ways will be achieved primarily due to advection, while in the dead-end pores
removal will be achieved primarily due to diffusion. Soil conditions should be dry
enough so that air moves freely. However, the drier the soil, the more the compound
will partition to the solid phase. Also recognize that many spills contain multiple
compounds, each having a different vapor pressure. Typically, the more volatile com-
pounds evaporate first, leaving the less volatile ones. This fractionalization process is
sometimes called “weathering” the product.
Bioventing (BV) treats contaminants in the unsaturated zone and, like SVE,
forces air through the treatment area. But, as the focus in SVE is removal by
volatilization followed by above-ground treatment, BV is designed to treat contami-
nants through bioremediation in situ. A BV system is designed to enhance the activ-
ity of indigenous bacteria, effectively stimulating the natural in situ biological
degradation of hydrocarbons. To encourage biodegradation rather than removal
through volatilization, bioventing systems are generally operated at vapor extrac-
tion or injection rates lower than those used for SVE systems, in an effort to provide
only enough oxygen to sustain microbial activity. Bioventing can be used to treat all
328 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
Atomospheric
Vapor discharge
treatment
(if needed)
Nutrient tank
UST Blower
Legend:
Vapor phase
Optional depending
on the site conditions
Groundwater
gradient
Figure 12.7
Typical bioventing system using vapor extraction.
(Source: U.S. EPA, 2004.)
Section 12.4 Introduction to Engineered Remediation Processes 329
Form Windrow
Excavate Periodic
windrows Windrow Compost disassembly
and screen turning of
w/soil and monitoring analysis and
soils windrow
amendments disposition
Figure 12.8
Typical windrow composting process.
(Source: FRTR, 2002.)
330 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
Exiting
ground Microbes
surface nutrients
Waste
Manhole
Concrete
1% Slope retaining
wall footing
Polyethylene
Compacted sand geomembrane
Leachate
collection
pipe
To wastewater Compacted
treatment subgrade
plant surface
Figure 12.9
Typical landfarming treatment unit.
(Source: FRTR, 2002.)
References 331
S U M M A RY
There are an estimated 294,000 CERCLA and RCRA contaminated sites in the
United States. Cleanup costs are predicted to reach $209 billion. This chapter pro-
vided a brief historical perspective and presented regulatory requirements associated
with hazardous waste. An introduction to organic chemistry was given to provide
context for the significant compounds contributing to hazardous waste. Contaminant
partitioning was introduced and its effect on the fate and transport of targeted com-
pounds within the environment was discussed. An overview was given of microbial
systems and environmental factors that affect metabolism. Both in situ and ex situ
treatment schemes for soil and groundwater were presented.
REFERENCES
Alvarez, P.J., and Illman, W.A. (2006). Bioremediation and Natural Attenuation Process Fun-
damental and Mathematical Models, Eds. J.L. Schnoor and A. Zehnder, Wiley-Interscience,
Hoboken, NJ.
EPA National Analysis (2005). The National Biennial RCRA Hazardous Waste Report:
Based on 2005 Data. Available online at http://www.epa.gov/epaoswer/hazwaste/data.
Eweis, J.B., Ergas, S.J., Chang, D.P.Y., and Schroeder, E.D. (1998). Bioremediation Principles,
WCB/McGraw-Hill.
Federal Remediation Technology Roundtable (FRTR) (2002). Remediation Technologies Screen-
ing Matrix and Reference Guide, 4th ed., prepared by J. Van Deuren, T. Lloyd, S. Chhetry,
R. Liou, and J. Peck of Platinum International, Inc., for U.S. Army Environmental Center,
SFIM-AEC-ET-CR-97053.Available online at www.frtr.gov.
Kuo, J. (1999). Practical Design Calculations for Groundwater and Soil Remediation, Lewis
Publishers, Boca Raton, FL.
LaGrega, M.D., Buckingham, P.L., and Evans, J.C. (1994). Hazardous Waste Management,
McGraw-Hill, New York.
Mackay, D., Shiu, W. Y., and Ma, K. C. (1997). Illustrated Handbook of Physical and Chemical
Properties and Environmental Fate for Organic Chemicals, Volumes I, II, and V, Lewis
Publishers, New York.
UNEP (United Nations Environment Programme): UNEP 1999 Report.
332 Chapter 12 Fundamentals of Hazardous Waste Site Remediation
U.S. EPA (1989). Risk Assessment Guidance for Superfund, Volume 1, Human Health Evalua-
tion Manual (Part A), Interim Final, EPA/540/1-89/002, Office of Emergency and Remedial
Response, Washington, DC, December, 1989.
U.S. EPA (1990). CERCLA Site Discharges to POTWs Treatability Manual, EPA 540/2-90-007,
Office of Water, U.S. EPA, Washington, DC.
U.S. EPA (1991). Guide for Conducting Treatability Studies Under CERCLA: Soil Vapor Extrac-
tion, Office of Solid Waste and Emergency Response, Office of Emergency and Remedial
Response Quick Reference Fact, Hazardous Site Control Division OS-220, September 1991,
EPA/540/2-91/019B.
U.S. EPA (2001). Groundwater Pump and Treat Systems: Summary of Selected Cost and Per-
formance Information at Superfund-financed Sites, Office of Solid Waste and Emergency
Response. EPA 542-R-01-021b. Available online at www.clu-in.org.
U.S. EPA (2004). How to Evaluate Alternative Cleanup Technologies for Underground Storage
Tank Sites. A Guide for Corrective Action Plan Reviewers. Solid Waste and Emergency
Response, EPA 510-B-94-003; EPA 510-B-95-007; and EPA 510-R-04-002, May 2004,
Available online at www.epa.gov/oust/pubs/tums.htm.
EXERCISES
12.1 Visit the Office of Solid Waste and Emergency Response EPA website (http://
www.epa.gov/superfund/) and research CERCAL NPL sites within your state
of residence. Review the information provided online and write a summary
paragraph describing your findings.
12.2 From Table 12.2, select a metal, a chlorinated aliphatic, and a PAH compound
of choice. Use the internet or library to write a paragraph summary describing
potential uses, contamination sources, and health effects for each compound.
12.3 Describe the difference between a CERCLA removal and remedial action.
12.4 Research the regulations associated with deep-well injection of hazardous
waste. Write a paragraph outlining these provisions that includes your opin-
ion of this type of disposal practice.
12.5 Groundwater is contaminated with 300 mg/L (300 ppb) of toluene. Assume
that the aquifer solids contain 1.5% organic carbon and that sorption is ade-
quately described by a linear model. Estimate the mass of toluene sorbed to
the solid material.
12.6 Results from a soil-vapor study showed a soil-vapor concentration for vinyl
chloride of 1500 ppmv. Use Henry’s law to estimate the surrounding liquid-
phase VC concentration.
12.7 A sample of moist soil having a wet weight of 1500 g and volume of 1000 cm3
was oven dried and found to have a dry mass of 1150 g. Determine the soil: dry
bulk density, porosity, and volumetric water content. Assume a soil density of
rs = 2.65 g/cm3.
12.8 Assume a leak in a 500-gal underground storage tank containing water conta-
minated with Aroclor® 1254 and acetone. Estimate how far each contaminant
will travel in one year. Assume the following hydrogeologic characteristics:
Introduction to Solid
13
Waste Management
13.1 INTRODUCTION
Objectives
Western world civilizations realized as early as 500 B.C.E. the importance of
In this chapter, you will solid waste disposal. The Greeks knew that garbage attracted rats and other
learn about: vectors that contributed to the spread of disease, and in 320 B.C.E they passed
Municipal solid waste the first known refuse-disposal decree, banning disposal in the streets of
(MSW) management Athens. Athenian citizens were required to dispose of their waste at least one
options mile from the city walls. The Romans learned from the Greeks and followed a
The magnitude of MSW similar waste management plan. Interestingly, the fall of the Roman Empire
issues coincided with an increased mismanagement of waste disposal. During the mid-
dle ages, septic wastes and their inherent disease threat were routed directly to
Federal regulations
a moat that surrounded the inhabitants of the castle. In colonial America, peo-
pertinent to solid waste
ple pushing west had few possessions and therefore not much waste was pro-
management
duced. People in towns and cities of America and Europe, however, tossed
Quantification of MSW their garbage out of windows and doors. The consequences of this practice
Components of a landfill were heightened by the industrial revolution, as a relatively large number of
people moved to the city and for the first time in history were able to buy
products made in mass quantity. Tossing trash from windows and doors contin-
ued through the mid 1800s, until piled garbage began to hinder access to cities,
and citizens finally became concerned about unsanitary and malodorous con-
ditions. By the early 1900s, several hundred solid waste incinerators were used
in the United States. Industrial growth in the U.S. during WWII increased solid
waste emissions. Plastics were developed and their many uses exploited, lead-
ing to new disposal problems. Postwar waste emissions became a national
concern, resulting in a federal government response. In 1965, the first solid
waste regulation directed at protecting public health in the United States was
passed, the Solid Waste Disposal Act. In 1979, the Environmental Protection
Agency (EPA) prohibited open dumping, and initial standards for landfills were
mandated.Ten years later, the EPA initiated a goal to reduce waste nationally by
25% and to concentrate on recycling. This chapter provides an overview of
municipal solid waste (MSW) management options, current regulations, and
related issues.
334 Chapter 13 Introduction to Solid Waste Management
population in millions
handling trends. 250
(Source for waste generation
trends: Municipal Solid 200
Waste in the United States: 150
2005 Facts and Figures;
Source for historical 100
population trends: www. 50
census.gov; Source for
population projections in 0
1950 1960 1970 1980 1990 2000 2010
years beyond 2000: Census
Time (year)
Release-T1, 2000)
Durable
Other wastes
goods Containers &
1.5%
16.4% packaging
Yard 31.2% Figure 13.3
trimmings Waste generated by product
13.1% category in the United
States, 2005.
Food scraps (Source: Municipal Solid
11.9% Nondurable
goods Waste in the United States:
25.9% 2005 Facts and Figures.)
Wood Wood
Textiles
Source: Municipal Solid Waste in the United States: 2005 Facts and Figures.
Federal act
1. A LISTED RCRA hazardous waste. (These are wastes from various industrial
processes, wastes from specific sectors of industry, or wastes in the form of spe-
cific chemical formulations.)
• F list—wastes from certain common industrial or manufacturing processes.
Because the processes producing these wastes can occur in different sec-
tors of industry, the F list wastes are known as wastes from nonspecific
sources.
• K list—wastestreams from certain specific industries. K list wastes are known
as wastes from specific sources.
• P list and U list—pure or commercial-grade formulations of certain specific
unused chemicals.
Section 13.3 Waste Generation (Quantifying MSW Generation) 337
where:
generated waste = all solid waste materials generated,
disposed waste = solid waste materials collected and taken to ultimate
disposal (landfill or waste incinerator),
338 Chapter 13 Introduction to Solid Waste Management
EXAMPLE 13.1
Solid waste generation
(Example adapted from Tchobanoglous et al., 1993.) Use the following informa-
tion to estimate the unit waste generation rate per week and the recycling effi-
ciency for a residential area consisting of 1200 homes. The average occupancy is
3.5 persons per home. Two observation locations were used, each for a period of
one week. The local transfer station collected all of the waste for disposal, and a
recycling facility was also monitored. According to estimates by the local waste-
water treatment facility, 7,350 pounds of food waste is disposed of in home food
grinders every week.
Additional Data from the Transfer Station:
Solution
Develop a computation table to estimate the total weight of waste disposed during
this week.
Average 3.5
Japan 2.5
Sweden 2.7
Finland 2.8
Italy 3.0
France 3.1
Germany 3.3
Belgium 3.3
Country
United Kingdom 3.4
Ireland 3.4
Australia 3.4
Netherlands 3.7
Norway 3.7
Canada 3.9
Switzerland 3.9
Denmark 4.0
Figure 13.5 Austrailia 4.2
Municipal waste-generation United States 4.6
rates of major countries. 0.0 1.0 2.0 3.0 4.0 5.0
(Source: OECD, 2002.) lb MSW generated per capita per day
lb/(capita-day)
250 4
200
3
Figure 13.6 150
MSW generation in the 100 2
United States.
50 1
(Source: Municipal Solid 1950 1960 1970 1980 1990 2000 2010
Waste in the United States: Time (years)
2005 Facts and Figures.)
and other sources characterized as having a high rate of waste generation. In the
HCS, large containers are used to store waste at the generation site, and the con-
tainer with its waste contents is then transported to the disposal site, emptied, and
returned into service. In the Stationary Container System (SCS) operation, the con-
tainers used to store the waste remain at the generation site, except when moved to
the curb or elsewhere to be emptied. Both residential and some commercial genera-
tors use the SCS process.
13.4.2 Equipment
Vehicles and containers are required for both HCS and SCS collection systems.
When the HCS is used, only one truck and a driver are required to accomplish col-
lection. Each pickup, however, requires a trip to the disposal site underlying the
importance of container size and utilization to the economic viability of this process.
Three types of vehicles are used in HCS collection:
1. Hoist trucks are generally used to handle commercial wastes, in what is often
characterized as a small operation with a few pickup locations that generate con-
siderable amounts of waste. Scrap metal, construction debris, and other bulky
items are also often picked up by hoist trucks. Containers used in conjunction
with hoist trucks may vary in size from 2 to 12 yd3 (1.5 to 9.2 m3).
2. Vehicles equipped with a tilt frame are frequently used to collect solid waste
from dumpsters, the large steel containers commonly used at apartment com-
plexes and commercial sites.
3. Large dumpsters, often referred to as roll-off containers, are used to collect
heavy rubbish and are often observed at construction and demolition sites.
Roll-off container size can vary from 10 to 40 yd3 (7.6 to 30.6 m3). Trash-trailer
systems equipped with a tilt frame are used for this type of collection.
Packer trucks are commonly used in the SCS process for pickup of residential
waste. Although packers can vary in design, most are covered vehicles having inter-
nal compactors. Packers vary in size from 16 to 20 yd3 (12.2 to 15.3 m3) and most are
rear loaded, although some designs now incorporate side loading. Once loaded, the
waste is compacted to approximately 600 to 700 lb/yd3 (357 to 416 kg/m3). On aver-
age, packers usually service approximately 200 customers before the truck is full and
a trip is made to the landfill (Vesilind et al., 2002).
EXAMPLE 13.2
Solid waste collection
Assume that each pickup location produces 75 lb of waste per week and the packer
vehicle can compact the waste to a density of 750 lb/yd3. Estimate the number of cus-
tomers that have their waste collected prior to making a trip to the landfill. Assume
the truck capacity is 20 yd3.
Section 13.5 Landfill Containment and Monitoring Systems 343
Solution
Determine the weight of waste on the truck when full:
lb
20 yd3 * 750 = 15,000 lb
yd3
Then the number of customers served can be calculated as:
15,000 lb
= 200 customers
lb
75
customer
EXAMPLE 13.3
Solid waste collection
Assume a truck and crew are observed to service customers at a rate of 1.25 customers
per minute, and the actual time spent per day collecting waste is 5 hours (recognizing
that some time is spent each 8-hr day traveling to and from the garage and taking
breaks). Estimate the number of customers that can be served per day.
Solution
If 1.25 customers are served per minute, then the number of customers served in
5 hours can be estimated as:
customers 60 min 5 collection hr customers
a1.25 b * a b * a b = 375
min hr d d
• Leachate collection and removal systems—rests on top of the composite liner and
removes leachate from the landfill for treatment and disposal.
• Operating practices—that help protect public health, include compacting and
covering waste frequently with several inches of soil to help reduce odors; control
litter, insects, and rodents; and decrease leachate formation by increasing runoff.
• Groundwater monitoring requirements—requires testing groundwater wells to
determine whether waste materials have escaped from the landfill.
• Closure and postclosure care requirements—include covering landfills and provid-
ing long-term care of closed landfills.
• Corrective-action provisions—control and clean up landfill releases and achieve
groundwater protection standards.
• Financial assurance—provides funding for environmental protection during and
after landfill closure (i.e., closure and postclosure care).
Site selection for a landfill is paramount. The site should be large enough to
accommodate the SW needs of the area it serves for a lifetime of approximately
10 years. It must be compatible with the local SW management programs, such that
public health, safety, welfare, and the environment are protected. Every effort is
made during site selection to minimize adverse impacts on the surrounding area,
property value, and traffic flow. When selecting the site, the potential for fire, spills,
and accidents must be realized. The site must be located outside of the 100-year
flood plain and far from airports, because of the increased risk of birds in the land-
fill area and potential impact on planes. Landfills must be sited at least 10,000 ft
(3050 m) from jetports and 5,000 ft (1524 m) from other airports. Other factors
affecting site selection include land availability, haul distance, soil conditions, and
topography. Geological restrictions on landfill sites require that no landfill should
exist within 200 ft (61 m) of a fault or unstable area characterized by seismic activity.
Leachate concerns dictate hydrological conditions associated with surface water
and groundwater issues. Also considered are climate (rainfall and wind), environ-
mental, and ecological conditions, public input and concerns, as well as the potential
use for the site after closure are considered.
Landfills can be classified as either wet or dry. A dry landfill is designed to keep
waste dry in an effort to limit biological activity, while a wet landfill, often called a
bioreactor, uses leachate recirculation to moisten and facilitate microbial degrada-
tion of the waste. Landfills are designed to accept either municipal (sanitary) or haz-
ardous wastes. Controlled landfills may be used for co-disposal of both municipal and
hazardous wastes.
Three construction techniques used for landfills include excavation, above
ground, and canyon/depression. The excavation method can be used only when the
groundwater table (GWT) is distant from the surface. Trenches with typical dimen-
sions of length = 100- 400 ft 130.5- 122 m2, width = 15- 25 ft 14.6 -7.6 m2, and
depth = 10-15 ft 13-4.6 m2 are excavated, and the SW is dumped into the trenches
for disposal. Tractors and compactors spread and compact the refuse by pushing it up
the working face. Multiple passes are made with compaction equipment to maxi-
mize compaction density. Soil cover, obtained from excavation, is placed on the
refuse. When the excavation method is not feasible, the above-ground method is
used. SW is unloaded and spread in long narrow strips (15–30 inches or 38–76 cm
thick). SW placement in strips is repeated multiple times until a predetermined cell
thickness is reached (usually 5–20 ft or 1.5–6.1 m). Cover soil is applied (6–12 inches
or 15–30 cm) at the end of each day. Geotextiles, foams, ground tires, compost, and
other materials are also often used as cover. The embankment (working face) slope
for a landfill is limited by the capabilities of the equipment used and is typically
References 345
S U M M A RY
This chapter provided an overview of solid waste management issues, options, and
current governing regulations. Historical data were presented, providing insight
concerning yearly increases in refuse production and the need for well-engineered
solutions for disposal and reuse. RCRA characteristics for hazardous waste were
presented and the concept of MSW generation (quantification) was introduced.
The hauled container and stationary container systems were introduced as com-
mon collection schemes. Municipal solid waste landfill operations and basic design
concepts were discussed. An overview was given of appropriate regulatory infor-
mation regarding landfill siting, design, operation, and closure.
REFERENCES
Census Release -T1 (2000). ”Annual Projections of the Total Resident Population as of July;
Lowest, Middle, High Series: 1999 to 2100,” Population Estimates Program, Population
Division, U.S. Census Bureau, Washington, D.C. 20233, February 14, 2000.
Municipal Solid Waste in the United States: 2005 Facts and Figures. United States Environ-
mental Protection Agency, Office of Solid Waste (5306P) EPA530-R-06-011 October 2006,
www.epa.gov.
OECD, 2002. OECD Environmental Data. Waste. Compendium 2002. Environmental Perfor-
mance and Information Division, Environment Directorate, Organization for Economic
Cooperation and Development (OECD), Working Group on Environmental Information
and Outlooks. URL: http://www.oecd.org
Repa, E.W. NSWMA’s 2005 Tip Fee Survey, NSWMA Research Bulletin 05-3 March 2005.
National Solid Waste Management Association, Washington, DC, www.nswma.org.
Tchobanoglous, G., Theisen, H., and Vigil, S. (1993). Integrated Solid Waste Management Engi-
neering Principles and Management Issues, McGraw-Hill, New York.
Vesilind, P.A., Worrell, W.A., and Reinhart, D.R. (2002). Solid Waste Engineering, Brooks/Cole,
Pacific Grove, CA.
346 Chapter 13 Introduction to Solid Waste Management
EXERCISES
13.1 Use your text and online information available from the U.S. EPA Office of Solid
Waste (http://www.epa.gov/epaoswer/osw/) to answer the following questions:
(a) Define the acronym RCRA. Describe the difference between RCRA-
subtitle C and RCRA-subtitle D.
(b) Which federal agency is responsible for enforcing RCRA?
(c) If an RCRA solid waste material is reused, is it still considered an RCRA
solid waste?
(d) Do RCRA regulations and verbiage address only hazardous and non-
hazardous solid wastes? Provide examples to support your answer.
(e) List the four physical characteristics which may result in a waste being
categorized as hazardous.
(f) Define the acronym CERCLA and briefly describe the main focus of this
federal regulation.
(g) In the early 2000s, the amount of hazardous waste generated in the United
States was (greater than, the same as, or less than) the amount of municipal
solid waste generated in the United States today. Please provide the data
and source(s) used to support your response.
(h) In 2005, approximately how many tons of waste did the United States
generate? Please provide source(s) used.
(i) How much waste is generated on a percapita basis in the United States?
How does this generation rate correspond to the rates observed in other
major countries?
(j) What is the main component of waste generated in the United States?
13.2 The terms generated, disposed, recycled, and diverted wastes are commonly
used in relation to solid waste management. Briefly define these terms in your
own words.
13.3 The EPA recognizes a variety of waste management methods, including:
(1) source reduction, (2) composting, (3) waste combustion, (4) landfilling, and
(5) recycling. (a) Briefly define each of these methods and (b) identify the
EPA’s preferred method for waste management.
13.4 Consider the most recent waste-generation and waste-management data
available to you. Using the 2004 national average landfill tipping fee, reported
as $34.29 per ton, estimate the amount of money the United States spends on
waste disposal by landfilling every year.
13.5 For both your home state and the state in which you reside while in college,
determine the name of the state agency that enforces the rules for solid waste
management.
13.6 What is the difference between a listed and a characteristic hazardous waste?
13.7 The accompanying table contains information on the composition of the resid-
ual (disposed) waste stream generated by a community and the recycling effi-
ciencies achieved for various components in the waste stream. Calculate the
overall recycling efficiency achieved by the community to one decimal place.
Metal 3 60
Textiles 7 0
Wood 8 0
Yard waste 25 30
Sum 100
[Hint: Use Equation (13.1) and assume 0% diverted.]
13.8 Assume that each pickup location produces 125 lb of waste per week, and the
packer vehicle can compact the waste to a density of 800 lb/yd3. Estimate the
number of customers that have their waste collected before the vehicle makes
a trip to the landfill. Assume the truck capacity is 20 yd3.
13.9 Assume that a truck and crew are observed to service customers at a rate of
1.32 customers per minute, and the actual time spent per day collecting waste
is 6 hours (recognizing that some time is spent each 8-hr day traveling to and
from the garage and taking breaks). Estimate the number of customers that
can be served per day.
13.10 A community needs to decrease the amount of waste being sent to the local
landfill. A city engineer has proposed the installation of food grinders and the
implementation of a recycling program. Using the following information, deter-
mine the reduction (as a percentage) in the waste being disposed (give your
answer to one decimal place). Consider that food grinders will be installed in
70% of the homes. It is estimated that, through the food grinder, these homes
will dispose of 45% of the food waste currently generated. [Note: Initially, the
amount of waste disposed is the same as the amount of waste generated. Both
the food grinders and recycling reduce the quantity of waste disposed.]
349
350 Index
Radioactivity: Risk:
sources of, 161 calculating (example), 99–100
units of, 161–162 defined, 98, 116
Radionuclides, 159 Risk assessment, 98–119
half-lives of, 163 data collection and evaluation, 102
Radium-226 and radium-228, 195 defined, 101, 116
Raoult’s law, 54–56 dose-response assessment, 102–103
Rapid-mix basin design (example), 212–213 environmental impact statement (EIS),
Rapid mixing, of coagulants, 210 12, 113–116
Raschig rings, 299 exposure, 101
RCRA, See Resource Conservation and Recovery exposure assessment, 107–109
Act (RCRA) hazard identification, 102
Reaction order, 121–122 hazards, 101
and k determination (example), 126–128 and pollution prevention, 156
Reaction stoichiometry, 38–42 risk characteristics, 110–111
Reactive unit, 34 risk management, 112–113
Reactivity, wastes, 337 toxicology, 102
Reactors, 134–142 Risk management, 101
batch reactors, 134–137 Roentgen equivalent man (rem), 162
completely mixed batch-reactor design Roentgen (R), 161–162
(example), 137 Roll-off containers, 341
completely mixed flow reactor (CMFR), 137–139 Rotating biological contactors (RBCs), 245
completely mixed reactor design (example), Rotifers, 66
139–140 Royal Demolition Explosive (RDX), 314
defined, 134
first-order removal reaction, 137–139 S
plug flow reactor (PFR), 140–142 Safe Drinking Water Act, 194
second-order removal reaction, 137 Safety, defined, 98
zero-order removal reaction, 135–137 Saltwater, 202
Reaeration, 87 Saprophytes, 63
coefficients, 87 Screening, 248
Reasonable maximum exposure (RME), 107–109 Second law of thermodynamics, 144
Recreational exposure factors, 109 Second-order reactions, 125–126
Recycle flow, 253 Second-order removal reaction, 137, 140–142
Reference dose (RfD), 104–105, 111 Secondary clarifier design protocol, 262–263
Regulatory agencies, 5 example, 263
Rem, 162 Secondary consumers, 71
Reproducibility, 28 Secondary drinking water standards, 195–196
Residence time, 27–28 Secondary effluent, 253
calculating (example), 28 Secondary pollutants, 282
Residential exposure, 109 Secondary wastewater treatment, 245–246, 252–258
Residential exposure equations, for various trickling filters, 260–261
pathways, 108 Seconds (s), 15
Resource Conservation and Recovery Act (RCRA), Sedimentation, 220–226
305, 335–337 flocculent settling, 221
hazardous waste definition, 336–337 free/discrete settling, 220–221
nonhazardous waste definition, 337 overflow rate, 222
Retention time, See Residence time settling basin, 221–222
Return activated sludge (RAS) flow, 253 settling-basin design criteria, 224–225
Reverse osmosis treatment, 206–207 settling velocity, 222–224
Ribonucleic acid (RNA), 66 weir loading rate, 224
Index 361
Streams: Tera-, 16
calculating the critical deficit point in (example), Teratogens, 102
90–92 Tetrachloroethylene (PCE/Perc), 310
dissolved-oxygen depletion in, 85–87 Tetraethyl lead (TEL), 314
Streeter-Phelps DO depletion model, 88–90, 93 Theoretical oxygen demand, calculating (example),
Streptococcus, 62 185–186
Strong acids and bases vs. weak acids and bases, 45–46 Thermal discharges to river (example), 145–146
Substrate adsorption and utilization, 253 Thermal incinerators (oxidators), 297–298
Substrate utilization, 255 Thermodynamics, 143
Sugars, 59 Thermoelectric power, 175
Sulfur cycle, 80–81 water for, 175
acid mine drainage, 81 Thorium-232 (Th-232), 163
sulfur dioxide emissions, 81 Thorium (Th), 161
Sulfur dioxide emissions, 81 Threshold number (FTN), 182
Sulfur oxides, 284–285 Threshold odor number (TON), 182
Summer stratification, 85 TNT, 314
Superficial velocity, 320 Total dissolved solids (TDS), 179, 182
Superfund Reauthorization and Amendments Total energy (E), 143
(SARA), 306 Total Kjeldahl nitrogen (TKN), 183
Surface water quality standards, 196 Total maximum daily loads (TMDLs), 176
Surface water treatment processes, 207–238 Total nitrogen (TN), 245
coagulation, 207–210 Total phosphorus (TP), 245
filtration, 225–233 Total reaction order, 122
flocculation tanks, 213–215 Total solids (TS), 179
mixing, 210–213 Total suspended solids (TSS), 179, 245
sedimentation, 220–226 Total trihalomethanes (TTHMs), 195, 234
water softening, 215–220 Toxic Release Inventory (TRI), 306
Surface Water Treatment Rule (SWTR), 234 Toxic Substance Control Act (1976), 289
Surface water treatment systems, 203–205 Toxicants, 102
conventional, 203–204 Toxicity Characteristic Leaching Procedure (TCLP),
membrane treatment, 205 337
Suspended solids (SS), 3, 179 Toxicity, wastes, 337
removal, 221 Toxicology, 102
Sustainability, 156 Trichloroethylene (TCE), 310
Sustainable development, 154–171 Trickling filters, 260–261
defined, 155 Trihalomethanes (THMs), 233, 237, 264
design, 155 Trimedia filters, 227
material selection, 156–158 Trophic level, 59
Sweep coagulation, 210 True color, 181
Synthesis reactions, 37 Turbidity, 178, 208
Synthetic organic compounds (SOCs), 5 nephelometric turbidity units (NTUs), 178
Systems of units, 15 Typhoid fever, 233
T U
Taste, water, 182 U-235, 164
Teacup system (EUTEK Systems), 249 U-238/U-239, 162–163, 164
Temperature: U list (RCRA), 336
conversion factors, 18 Ultimate BOD, 187–188
water, 183 Uncertainty, in calculating risk, 98
Temperature corrections, 128–130 Underground storage tanks (USTs), 335
example, 129–130 Uniformity coefficient, 230
Index 363