Professional Documents
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Environmental
Models
The Fugacity Approach
Second Edition
Multimedia
Environmental
Models
The Fugacity Approach
Second Edition
Donald Mackay
LEWIS PUBLISHERS
Boca Raton London New York Washington, D.C.
L1542 disclaimer Page 1 Saturday, January 20, 2001 10:47 AM
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Preface
This book is about the behavior of organic chemicals in our multimedia envi-
ronment or biosphere of air, water, soil, and sediments, and the diversity of biota
that reside in these media. It is a response to the concern that we have unwisely
contaminated our environment with a large number of chemicals in the mistaken
belief that the environment’s enormous capacity to dilute and degrade will reduce
concentrations to negligible levels. We now know that the environment has only a
finite capacity to dilute and degrade. Certain chemicals have persisted and accumu-
lated to levels that have caused adverse effects on wildlife and even humans. Some
chemicals have the potential to migrate from medium to medium, reaching unex-
pected destinations in unexpectedly high concentrations. We need to understand
these processes, not only qualitatively in the form of assertions that DDT evaporates
and bioaccumulates, but quantitatively as statements that DDT in a particular region
evaporates at a rate of 100 kg per year and bioaccumulates from water at a concen-
tration of 1 ng/L to fish at levels of 1 µg/g.
We have learned that chemical behavior in the complex assembly of environ-
mental media is not a random process like leaves blowing in the wind. The chemicals
behave in accordance with the laws of nature, which dictate chemical partitioning
and rates of transport and transformation. Most fundamentally, the chemicals are
subject to the law of conservation of mass, i.e., a mass balance exists for the chemical
that is a powerful constraint on quantities, concentrations, and fluxes. By coupling
the mass balance principle with expressions based on our understanding of the laws
of nature, we can formulate a quantitative accounting of chemical inputs and outputs.
This book is concerned with developing and applying these expressions in the form
of mathematical statements or “models” of chemical fate. These accounts or models
are invaluable summaries of chemical behavior. They can form the basis of remedial
and proactive strategies.
Such models can confirm (or deny) that we really understand chemical fate in
the environment. Since many environmental calculations are complex and repetitive,
they are particularly suitable for implementation on computers. Accordingly, for
many of the calculations described in this book, computer programs are described
and made available on the Internet with which a variety of chemicals can be readily
assessed in a multitude of environmental situations.
The models are formulated using the concept of fugacity, which was introduced
by G.N. Lewis in 1901 as a criterion of equilibrium and has proved to be a very
convenient and elegant method of calculating multimedia equilibrium partitioning.
It has been widely and successfully used in chemical processing calculations. In this
book, we exploit it as a convenient and elegant method of explaining and deducing
the environmental fate of chemicals. Since publication of the first edition of this
book ten years ago, there has been increased acceptance of the benefits of using
fugacity to formulate models and interpret environmental fate. Multimedia fugacity
models are now routinely used for evaluating chemicals before and after production.
Much of the experience gained in these ten years is incorporated in this second
edition. Mathematical simulations of chemical fate are now more accurate, compre-
Front Page vi Monday, January 15, 2001 1:46 PM
hensive, and reliable, and they have gained greater credibility as decision-support
tools. No doubt this trend will continue, especially as young environmental scientists
and engineers take over the reins of environmental science and continue to develop
new fugacity models.
This book has been written as a result of the author teaching graduate-level
courses at the University of Toronto and Trent University. It is hoped that it will be
suitable for other graduate courses and for practitioners of the environmental science
of chemical fate in government, industry, and the private consulting sector. The
simpler concepts are entirely appropriate for undergraduate courses, especially as a
means of promoting sensitivity to the concept that chemicals, which provide modern
society with so many benefits, must also be more carefully managed from their
cradle, in the chemical synthesis plant, to their grave of ultimate destruction.
At the end of most chapters is a “Concluding Example” in which a student may
be asked to apply the principles discussed in that chapter to one or more chemicals
of their choice. Necessary data are given in Table 3.5 in Chapter 3. I have found
this useful as a method of assigning different problems to a large number of students,
while allowing them to explore the properties and fate of substances of particular
interest to them.
We no longer regard the environment as a convenient, low-cost dumping ground
for unwanted chemicals. When we discharge chemicals into the environment, it must
be with a full appreciation of their ultimate fate and possible effects. We must ensure
that mistakes of the past with PCBs, mercury, and DDT are not repeated. This is
best guaranteed by building up a quantitative understanding of chemical fate in our
total multimedia environment, how chemicals will be transported and transformed,
and where, and to what extent they may accumulate. It is hoped that this book is
one step toward this goal and will be of interest and use to all those who value the
environment and seek its more enlightened stewardship.
Donald Mackay
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Acknowledgments
It is a pleasure to acknowledge the contribution of many colleagues. Much of
the credit for the approaches devised in this book is due to the pioneering work by
George Baughman, who saw most clearly the evolution of multimedia environmental
modeling as a coherent and structured branch of environmental science amid the
often frightening complexity of the environment and the formidable number of
chemicals with which it is contaminated. Brock Neely, Russ Christman, and Don
Crosby were instrumental in encouraging me to apply the fugacity concept to
environmental calculations.
I am indebted to my former colleagues at the University of Toronto, especially
Wan Ying Shiu and Sally Paterson, whose collaboration has been crucial in devel-
oping the fugacity approach. I am grateful to my more recent colleagues at Trent
University, and our industrial and government partners who have made the Canadian
Environmental Modelling Centre a successful focus for the development, validation,
and dissemination of mass balance models.
This second edition was written in part when on research leave at the Department
of Environmental Toxicology at U.C. Davis, where Marion Miller, Don Crosby, and
their colleagues were characteristically generous and supportive. At Trent, I was
greatly assisted by David Woodfine, Rajesh Seth, Merike Perem, Lynne Milford,
Angela McLeod, Adrienne Holstead, Todd Gouin, Alison Fraser, Ian Cousins, Tom
Cahill, Jenn Brimecombe, and Andreas Beyer. I am particularly grateful to Steve
Sharpe for the figures, to Matt MacLeod and Christopher Warren for their critical
review and comments, and to Eva Webster for her outstanding scientific and editorial
contributions.
Without the support and diligent typing of my wife, Ness, this book would not
have been possible. Thank you.
I dedicate this book to Ness, Neil, Ian, Julia, and Gwen, and especially to Beth,
who was born as this edition neared completion. I hope it will help to ensure that
her life is spent in a cleaner, more healthful environment.
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Front Page ix Monday, January 15, 2001 1:46 PM
Contents
Chapter 1
Introduction................................................................................................................1
Chapter 2
Some Basic Concepts.................................................................................................5
2.1 Introduction ...............................................................................................5
2.2 Units ..........................................................................................................5
2.3 The Environment as Compartments..........................................................9
2.4 Mass Balances.........................................................................................11
2.5 Eulerian and Lagrangian Coordinate Systems ........................................20
2.6 Steady State and Equilibrium..................................................................22
2.7 Diffusive and Nondiffusive Environmental Transport Processes...........25
2.8 Residence Times and Persistence............................................................26
2.9 Real and Evaluative Environments .........................................................27
2.10 Summary .................................................................................................28
Chapter 3
Environmental Chemicals and Their Properties ......................................................29
3.1 Introduction and Data Sources ................................................................29
3.2 Identifying Priority Chemicals................................................................31
3.3 Key Chemical Properties and Classes.....................................................40
3.4 Concluding Example...............................................................................54
Chapter 4
The Nature of Environmental Media .......................................................................55
4.1 Introduction .............................................................................................55
4.2 The Atmosphere ......................................................................................55
4.3 The Hydrosphere or Water......................................................................58
4.4 Bottom Sediments ...................................................................................60
4.5 Soils.........................................................................................................63
4.6 Summary .................................................................................................65
4.7 Concluding Example...............................................................................65
Chapter 5
Phase Equilibrium....................................................................................................69
5.1 Introduction .............................................................................................69
5.2 Properties of Pure Substances .................................................................75
5.3 Properties of Solutes in Solution.............................................................78
5.4 Partition Coefficients ..............................................................................83
5.5 Environmental Partition Coefficients and Z Values ...............................94
5.6 Multimedia Partitioning Calculations .....................................................99
5.7 Level I Calculations ..............................................................................111
5.8 Concluding Examples ...........................................................................113
Chapter 6
Advection and Reactions .......................................................................................117
6.1 Introduction ...........................................................................................117
6.2 Advection ..............................................................................................119
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CHAPTER 1
Introduction
Since the Second World War, and especially since the publication of Rachel Carson’s
Silent Spring in 1962, there has been growing concern about contamination of the
environment by “man-made” chemicals. These chemicals may be present in indus-
trial and municipal effluents, in consumer or commercial products, in mine tailings,
in petroleum products, and in gaseous emissions. Some chemicals such as pesticides
may be specifically designed to kill biota present in natural or agricultural ecosys-
tems. They may be organic, inorganic, metallic, or radioactive in nature. Many are
present naturally, but usually at much lower concentrations than have been estab-
lished by human activity. Most of these chemicals cause toxic effects in organisms,
including humans, if applied in sufficiently large doses or exposures. They may
therefore be designated as “toxic substances.”
There is a common public perception and concern that when these substances
are present in air, water, or food, there is a risk of adverse effects to human health.
Assessment of this risk is difficult (a) because the exposure is usually (fortunately)
well below levels at which lethal toxic effects and even sub-lethal effects can be
measured with statistical significance against the “noise” of natural population
variation, and (b) because of the simultaneous multiple toxic influences of other
substances, some taken voluntarily and others involuntarily. There is a growing
belief that it is prudent to ensure that the functioning of natural ecosystems is
unimpaired by these chemicals, not only because ecosystems have inherent value,
but because they can act as sensing sites or early indicators of possible impact on
human well-being.
Accordingly, there has developed a branch of environmental science concerned
with describing, first qualitatively and then quantitatively, the behavior of chemicals
in the environment. This science is founded on earlier scientific studies of the
condition of the natural environment—meteorology, oceanography, limnology,
hydrology, and geomorphology and their physical, energetic, biological, and chem-
ical sub-sciences. This newer branch of environmental science has been variously
termed environmental chemistry, environmental toxicology, or chemodynamics.
1
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It is now evident that our task is to design a society in which the benefits of
chemicals are enjoyed while the risk of adverse effects from them is virtually
eliminated. To do this, we must exert effective and cost-effective controls over the
use of such chemicals, and we must have available methods of calculating their
environmental behavior in terms of concentration, persistence, reactivity, and parti-
tioning tendencies between air, water, soils, sediments, and biota. Such calculations
are useful when assessing or implementing remedial measures to treat already-
contaminated environments. They become essential as the only available method for
predicting the likely behavior of chemicals that (a) may be newly introduced into
commerce or that (b) may be subject to production increases or introduction into
new environments.
In response to this societal need, this book develops, describes, and illustrates a
framework and procedures for calculating the behavior of chemicals in the environ-
ment. It employs both conventional procedures that are based on manipulations of
concentrations and procedures that use the concepts of activity and fugacity to
characterize the equilibrium that exists between environmental phases such as air,
water, and soil. Most of the emphasis is placed on organic chemicals, which are
fortunately more susceptible to generalization than metals and other inorganic chem-
icals when assessing environmental behavior.
The concept of fugacity, which was introduced by G.N. Lewis in 1901 as a more
convenient thermodynamic equilibrium criterion than chemical potential, has been
widely used in chemical process calculations. Its convenience in environmental
chemical equilibrium or partitioning calculations has become apparent only in the
last two decades. It transpires that fugacity is also a convenient quantity for describ-
ing mathematically the rates at which chemicals diffuse, or are transported, between
phases; for example, volatilization of pesticides from soil to air. The transfer rate
can be expressed as being driven by, or proportional to, the fugacity difference that
exists between the source and destination phases. It is also relatively easy to trans-
form chemical reaction, advective flow, and nondiffusive transport rate equations
into fugacity expressions and build up sets of fugacity equations describing the quite
complex behavior of chemicals in multiphase, nonequilibrium environments. These
equations adopt a relatively simple form, which facilitates their formulation, solution,
and interpretation to determine the dominant environmental phenomena.
We develop these mathematical procedures from a foundation of thermodynam-
ics, transport phenomena, and reaction kinetics. Examples are presented of chemical
fate assessments in both real and evaluative multimedia environments at various
levels of complexity and in more localized situations such as at the surface of a lake.
These calculations of environmental fate can be tedious and repetitive, thus there
is an incentive to use the computer as a calculating aid. Accordingly, computer
programs are made available for many of the calculations described later in the text.
It is important that the computer be viewed and used as merely a rather fast and
smart adding machine and not as a substitute for understanding. The reader is
encouraged to write his or her own programs and modify those provided.
The author was “brought up” to write computer programs in languages such as
FORTRAN, BASIC, and C. The first edition of this book was regarded as very
advanced by including a diskette of programs in BASIC. Such programs have the
CH01 Page 3 Monday, January 15, 2001 1:48 PM
INTRODUCTION 3
immense benefit that the sequence and details of calculations are totally transparent.
Executable versions can be run on any computer. Unfortunately, it is not always
easy to change input parameters or equations, and the output is usually printed tables.
The modern trend is to use spreadsheets, such as Microsoft EXCEL®, which have
improved input and output features, including the ability to draw graphs and charts.
Spreadsheets have the disadvantages that calculations are less transparent, there may
be problems when changing versions of the spreadsheet program, and not everyone
has the same spreadsheet.
Sufficient information is given on each mass balance model that readers can
write their own programs using the system of their choice. Microsoft Windows®
software for performing model calculations is available from the Internet site
www.trentu.ca/envmodel. Older DOS-based models are also available. They are
updated regularly and are subject to revision. In all cases, the equations correspond
closely to those in this book (unless otherwise stated), and they are totally transpar-
ent. Some are used in a regulatory context, thus the user is prevented from changing
the coding, although all code can be viewed.
Preparing a second edition of this book has enabled me to update, expand, and
reorganize much of the material presented in the first (1991) edition. I have benefited
greatly from the efforts of those who have sought to understand environmental
phenomena and who have applied the fugacity approach when deducing the fate of
chemicals in the environment. There is no doubt that, as we enter the new millen-
nium, environmental science is becoming more quantitative. It is my hope that this
book will contribute to that trend.
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CHAPTER 2
2.1 INTRODUCTION
Much of the scientific fascination with the environment lies in its incredible
complexity. It consists of a large number of phases such as air, soil, and water, which
vary in properties and composition from place to place (spatially) and with time
(temporally). It is very difficult to assemble a complete, detailed description of the
condition (temperature, pressure, and composition) of even a small environmental
system or microcosm consisting, for example, of a pond with sediment below and
air above. It is thus necessary to make numerous simplifying assumptions or state-
ments about the condition of the environment. For example, we may assume that a
phase is homogeneous, or it may be in equilibrium with another phase, or it may
be unchanging with time. The art of successful environmental modeling lies in the
selection of the best, or “least-worst,” set of assumptions that yields a model that is
not so complex as to be excessively difficult to understand yet is sufficiently detailed
to be useful and faithful to reality. The excessively simple model may be misleading.
The excessively detailed model is unlikely to be useful, trusted, or even understand-
able. The aim is to suppress the less necessary detail in favor of the important
processes that control chemical fate.
In this chapter, several concepts are introduced that are used when we seek to
compile quantitative descriptions of chemical behavior in the environment. But first,
it is essential to define the system of units and dimensions that forms the foundation
of all calculations.
2.2 UNITS
5
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give the derived units directly with no conversion factors. For example, energy
(joules) is variously the product of force (newtons) and distance (metres), or pressure
(pascals) and volume (cubic metres), or power (watts) and time (seconds). Thus, the
foot-pound, the litre-atmosphere, and the kilowatt-hour become obsolete in favor of
the single joule. Some key aspects of the SI system are discussed below. Conversion
tables from obsolete or obsolescent unit systems are available in scientific handbooks.
Length (metre, m)
Area
Square metre (m2). Occasionally, the hectare (ha) (an area 100 × 100 m or 104 m2)
or the square kilometre (km2) is used. For example, pesticide dosages to soils are
often given in kg/ha.
The litre (L) (0.001 m3) is also used because of its convenience in analysis, but
it should be avoided in environmental calculations. In the United States, the spellings
“meter” and “liter” are often used.
Kilogram (kg). The base unit is the kilogram (kg), but it is often more convenient
to use the gram (g), especially for concentrations. For large masses, the megagram
(Mg) or the equivalent metric tonne (t) may be used.
Concentration
The preferred unit is the mole per cubic metre (mol/m3) or the gram per cubic
metre (g/m3). Most analytical data are reported in amount or mass per litre (L),
because a litre is a convenient volume for the analytical chemist to handle and
measure. Complications arise if the litre is used in environmental calculations,
because it is not coherent with area or length. The common mg/L, which is often
ambiguously termed the “part per million,” is equivalent to g/m3. In some circum-
stances, the use of mass fraction, volume fraction, or mole fraction as concentrations
is desirable.
It is acceptable, and common, to report concentrations in units such as mol/L or
mg/L but, prior to any calculation, they should be converted to a coherent unit of
amount of substance per cubic metre.
Concentrations such as parts per thousand (ppt), parts per million (ppm), parts
per billion (ppb), and parts per trillion (also ppt) should not be used. There can be
confusion between parts per thousand and per trillion. The billion is 109 in North
America and 1012 in Europe. The air ppm is usually on a volume/volume basis,
whereas the water ppm is usually on a mass/volume basis. The mixing ratio used
for air is the ratio of numbers of molecules or volumes and is often given in ppm.
Concentrations must be presented with no possible ambiguity.
Density (kg/m3)
This has identical units to mass concentrations, but the use of kg/m3 is preferred,
water having a density of 1000 kg/m3 and air a density of approximately 1.2 kg/m3.
Force (newton, N)
The pascal or newton per square metre (N/m2) is inconveniently small, since it
corresponds to only 102 grams force over one square metre, but it is the standard
unit, and it is used here. The atmosphere (atm) is 101325 Pa or 101.325 kPa. The
torr or mm of mercury (mmHg) is 133 Pa and, although still widely used, should
be regarded as obsolescent.
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Energy (joule, J)
The joule, which is one N-m or Pa-m3, is also a small quantity. It replaces the
obsolete units of calorie (which is 4.184 J) and Btu (1055 J).
Temperature (K)
The hertz is one event per second (s–1). It is used in descriptions of acoustic and
electromagnetic waves, stirring, and in nuclear decay processes where the quantity
of a radioactive material may be described in becquerels (Bq), where 1 Bq corre-
sponds to the amount that has a disintegration rate of 1 Hz. The curie (Ci), which
corresponds to 3.7 × 1010 disintegrations per second (and thus 3.7 × 1010 Bq), was
formerly used.
This constant, which derives from the gas law, is 8.314 J/mol K or Pa-m3/mol K.
An advantage of the SI system is that R values in diverse units such as cal/mol K
and cm3·atm/mol K become obsolete and a single universal value now applies.
2.2.1 Prefices
Note that these prefices precede the unit. It is inadvisable to include more than one
prefix in a unit, e.g., ng/mg, although mg/kg may be acceptable, because the base
unit of mass is the kg. The equivalent µg/g is clearer. The use of expressions such
as an aerial pesticide spray rate of 900 g/km2 can be ambiguous, since a kilo(metre2)
is not equal to a square kilometre, i.e., a (km)2. The former style is not permissible.
CH02 Page 9 Monday, January 15, 2001 1:47 PM
Expressing the rate as 9 g/ha or 0.9 mg/m2 removes all ambiguity. The prefices deka,
hecto, deci, and centi are restricted to lengths, areas, and volumes. A common (and
disastrous) mistake is to confuse milli, micro, and nano.
We use the convention J/mol-K meaning J mol–1 K–1. Strictly, J/(mol-K) is correct
but, in the interests of brevity, the parentheses are omitted.
A reaction rate:
2.2.3 Logarithms
particles (aerosols), or biota in water]. In some cases, the phases may be similar
chemically but different physically, e.g., the troposphere or lower atmosphere, and
the stratosphere or upper atmosphere. It may be convenient to lump all biota together
as one phase or consider them as two or more classes each with a separate phase.
Some compartments are in contact, thus a chemical may migrate between them (e.g.,
air and water), while others are not in contact, thus direct transfer is impossible (e.g.,
air and bottom sediment). Some phases are accessible in a short time to migrating
chemicals (e.g., surface waters), but others are only accessible slowly (e.g., deep
lake or ocean waters), or effectively not at all (e.g., deep soil or rock).
Some confusion is possible when expressing concentrations for mixed phases
such as water containing suspended solids (SS). An analysis may give a total or bulk
concentration expressed as amount of chemical per m3 of mixed water and particles.
Alternatively, the water may be filtered to give the concentration or amount of
chemical that is dissolved in water per m3 of water. The difference between these
is the amount of chemical in the SS phase per m3 of water. This is different from
the concentration in the SS phase expressed as amount of chemical per m3 of particle.
Concentrations in soils, sediments, and biota can be expressed on a dry or wet weight
basis. Occasionally, concentrations in biota are expressed on a lipid or fat content
basis. Concentrations must be expressed unambiguously.
2.3.3 Summary
which can be translated as, “What can be done with fewer (assumptions) is done in
vain with more,” or more colloquially, “Don’t make models more complicated than
is necessary.”
This is the simplest class of equation. It describes how a given mass of chemical
will partition between various phases of fixed volume. The basic equation simply
expresses the obvious statement that the total amount of chemical present equals the
sum of the amounts in each phase, each of these amounts usually being a product of
a concentration and a volume. The system is closed or “sealed” in that no entry or
exit of chemical is permitted. In environmental calculations, the concentrations are
usually so low that the presence of the chemical does not affect the phase volumes.
CH02 Page 12 Monday, January 15, 2001 1:47 PM
A three-phase system consists of air (100 m3), water (60 m3), and sediment (3
3
m ). To this is added 2 mol of a hydrocarbon such as benzene. The phase volumes
are not affected by this addition, because the volume of hydrocarbon is small.
Subscripting air, water, and sediment symbols with A, W, and S, respectively, and
designating volume as V (m3) and concentration as C (mol/m3), we can write the
mass balance equation.
To proceed further, we must have information about the relationships between CA,
CW , and CS. This could take the form of phase equilibrium equations such as
Thus,
It follows that
The amounts in each phase (mi) mol are the VC products as follows:
This simple algebraic procedure has established the concentrations and amounts in
each phase using a closed system, steady-state, mass balance equation and equilib-
rium relationships. The essential concept is that the total amount of chemical present
CH02 Page 13 Monday, January 15, 2001 1:47 PM
must equal the sum of the individual amounts in each compartment. We later refer
to this as a Level I calculation. It is useful because it is not always obvious where
concentrations are high, as distinct from amounts.
Example 2.2
In this example, 0.04 mol of a pesticide of molar mass 200 g/mol is applied to
a closed system consisting of 20 m3 of water, 90 m3 of air, 1 m3 of sediment, and
2 L of biota (fish). If the concentration ratios are air/water 0.1, sediment/water 50,
and biota/water 500, what are the concentrations and amounts in each phase in both
gram and mole units?
Answer
Example 2.3
Answer
In this case, 8.3% is present in each of SS and biota and 83% in water with a
concentration in water of 39.8 µg/m3.
A 104 m3 thoroughly mixed pond has a water inflow and outflow of 5 m3/h. The
inflow water contains 0.01 mol/m3 of chemical. Chemical is also discharged directly
into the pond at a rate of 0.1 mol/h. There is no reaction, volatilization, or other
losses of the chemical; it all leaves in the outflow water.
CH02 Page 14 Monday, January 15, 2001 1:47 PM
(i) What is the concentration (C) in the outflow water? We designate this as an
unknown C mol/m3.
5 m3/h × 0.01 mol/m3 + 0.1 mol/h = 0.15 mol/h = 5 m3/h × C mol/m3 = 5 C mol/h
Thus,
C = 0.03 mol/m3
The total inflow and outflow rates of chemical are 0.15 mol/h.
(ii) If the chemical also reacts in a first-order manner such that the rate is
VCk mol/h where V is the water volume, C is the chemical concentration in the well
mixed water of the pond, and k is a first-order rate constant of 10–3 h–1, what will
be the new concentration?
The output by reaction is VCk or 104 × 10–3 C or 10 C mol/h, thus we rewrite
the equation as:
Thus,
C = 0.01 mol/m3
The total input of 0.15 mol/h is thus equal to the total output of 0.15 mol/h, consisting
of 0.05 mol/h outflow and 0.10 mol/h reaction.
An inherent assumption is that the prevailing concentration in the pond is con-
stant and equal to the outflow concentration. This is the “well mixed” or “continu-
ously stirred tank” assumption. It may not always apply, but it greatly simplifies
calculations when it does.
The key step is to equate the sum of the input rates to the sum of the output
rates, ensuring that the units are equivalent in all the terms. This often requires some
unit-to-unit conversions.
A lake of area (A) 106 m2 and depth 10 m (volume V 107 m3) receives an input
of 400 mol/day of chemical in an effluent discharge. Chemical is also present in the
inflow water of 104 m3/day at a concentration of 0.01 mol/m3. The chemical reacts
with a first-order rate constant k of 10–3 h–1, and it volatilizes at a rate of (10–5 C)
mol/m2s, where C is the water concentration and m2 refers to the air-water area. The
outflow is 8000 m3/day, there being some loss of water by evaporation. Assuming
that the lake water is well mixed, calculate the concentration and all the inputs and
outputs in mol/day. Use a time unit of days in this case.
CH02 Page 15 Monday, January 15, 2001 1:47 PM
Discharge =
400 mol/day
Inflow 104 m3/day × 0.01 mol/m3 = 100 mol/day
=
Total input =
500 mol/day
Reaction rate VCk = 107 m3 × C mol/m3 × 10–3 h–1 × 24 h/day = 24 × 104C
=
mol/day
Volatilization rate = 106 m2 × 10–5 C mol/m2 s × 3600 s/h × 24 h/day = 86.4 ×
104C mol/day
Outflow = 8000 m3/day × C mol/m3 = 0.8 × 104C mol/day
Thus,
Example 2.6
Answer
Example 2.7
Answer
Whereas the first two types of mass balances lead to simple algebraic equations,
unsteady-state conditions give differential equations in time. The simplest method
of setting up the equation is to write
The input and output rates should be in units of amount/time, e.g., mol/h or g/h.
The “contents” must be in consistent units, e.g., in mol or g, and dt, the time
increment, in units consistent with the time unit in the input and output terms, (e.g.,
h). The differential equation can then be solved along with an appropriate initial or
boundary condition to give an algebraic expression for concentration as a function
of time. The simplest example is the first-order decay equation.
Thus,
This differential equation is easily solved by separating the variables C and t to give
dC/C = –10–2 dt
Integrating gives
lnC = –10–2t + IC
CH02 Page 17 Monday, January 15, 2001 1:47 PM
ln(C/Co) = –10–2 t
or
C = Co exp (–10–2t)
Thus,
Input rate = 10 × 0.2 = 2 mol/s (we choose a time unit of seconds here)
Output by reaction = (106 m3)(10–2 h–1)(1 h/3600s)C mol/m3 = 2.78 C mol/s
Output by flow = 10 C mol/s
Thus,
CH02 Page 18 Monday, January 15, 2001 1:47 PM
or
or
IC = –ln(2)/12.78
and
or
or
Note that when t is zero, exp(0) is unity and C is zero, as dictated by the initial
condition. When t is very large, the exponential group becomes zero, and C
approaches (2/12.78) or 0.157 mol/m3. At such times, the input of 2 mol/s is equal
to the total of the output by flow of 10 × 0.157 or 1.57 mol/s plus the output by
reaction of 2.78 × 0.157 or 0.44 mol/s. This is the steady-state solution, which the
lake eventually approaches after a long period of time.
When t is 1 day or 86400s, C will be 0.105 mol/m3 or 67% of the way to its
final value. C will be halfway to its final value when 12.78 × 10–6 t is 0.693 or t is
54200 s or 15 h. This time is largely controlled by the residence time of the water
in the lake, which is
Input = 0
Output by flow = 0.5C
Output by reaction = VCk = 105 · C · 10–2h–1(1/3600) = 0.278C
Thus,
Example 2.11
If the concentration of CO2 in Example 2.6 has reached steady state of 3.1 g/m3,
and then the internal source is reduced to 100 g/h, deduce the equation expressing
the time course of CO2 concentration decay and the new steady-state value.
Answer
Example 2.12
Answer
30 days
Answer
Yes
CH02 Page 20 Monday, January 15, 2001 1:47 PM
What is the absolute minimum piscicide usage every 30 days to maintain 1 mg/m3?
Answer
It is usually best to define the mass balance envelope as being fixed in space.
This can be called the Eulerian coordinate system. When there is appreciable flow
through the envelope, it may be better to define the envelope as being around a certain
amount of material and allow that envelope of material to change position. This “fix
a parcel of material then follow it in time as it moves” approach is often applied to
rivers when we wish to examine the changing condition of a volume of water as it
flows downstream and undergoes various reactions. This can be called the Lagrangian
coordinate system. It is also applied to “parcels” of air emitted from a stack and
subject to wind drift. Both systems must give the same results, but it may be easier
to write the equations in one system than the other. The following example is an
illustration. It also demonstrates the need to convert units to the SI system.
CH02 Page 21 Monday, January 15, 2001 1:47 PM
Consider a river into which the 1.8 million population of a city discharges a
detergent at a rate of 1 pound per capita per year, i.e., the discharge is 1.8 million
pounds per year. The aim is to calculate the concentrations at distances of 1 and 10
miles downstream from a knowledge of the degradation rate of the detergent and
the constant downstream flow conditions, which are given below. This can be done
in Eulerian or Lagrangian coordinate systems. The input data are first converted to
SI units.
The river flow rate is Uhw, i.e., 18270 m3/h. The rate constant k is 0.693/τ1/2, i.e.
0.096 h–1. When the detergent mixes into the river, the concentration will be CO or
E/(Uhw) or 5.1 g/m3.
Lagrangian Solution
A parcel of water that maintains its integrity, i.e., it does not diffuse or disperse,
will decay according to the equation
C = CO exp(–kt)
where t is the time from discharge. At 1 mile (1609 m), the time t will be 1609/U
or 1.47 h, and at 10 miles, it will be 14.7 h.
Substituting shows that, after 1 and 10 miles, the concentrations will be 4.4 and
1.24 g/m3. The chemical will reach half its input concentration when t is 0.693/k or
7.2 h, which corresponds to 7900 m or 4.92 miles. This Lagrangian solution is
straightforward, but it is valid only if conditions in the river remain constant and
negligible upstream-downstream dispersion occurs.
Eulerian Solution
where CO and C1 are the input and output concentrations. C1 is also the concentration
in the segment. It follows that
CH02 Page 22 Monday, January 15, 2001 1:47 PM
Note the consistency of the dimensions, kL/U being dimensionless. The group (1 +
kL/U) has a value of 1.0175, thus C1 is 0.983CO. 1.7% of the chemical is lost in
each segment. The same equation applies to the second reach, thus C2 is 0.983C1
or 0.9832CO. In general, for the nth reach, Cn is (0.983)nCO or CO/(1 + kL/U)n.
One mile is reached when n is 8, and 10 miles corresponds to n of 80, thus C8
is 0.9838CO or 4.45, and C8 is 1.29. The half distance will occur when 0.983n is 0.5,
i.e., when n is log 0.5/log 0.983 or 40, corresponding to 8000 m or 5 miles.
The Eulerian answer is thus slightly different. It could be made closer to the
Lagrangian result by carrying more significant figures or by decreasing L and
increasing n. An advantage of the Eulerian system is that it is possible to have
segments with different properties such as depth, width, velocity, volume, and
temperature. There can be additional inputs. The general equation employing the
group (1 + kL/U)n will not then apply, each segment having a specific value of this
factor. The mathematical enthusiast will note that L/U is t/n, where t is the flow time
to a distance nL m. The Lagrangian factor is thus also (1 + kt/n)n, which approaches
exp(kt) when n is large. It is good practice to do the calculation in both systems
(even approximately) and check that the results are reasonable. Some water quality
models of rivers and estuaries can have several hundred segments, thus it is difficult
to grasp the entirety of the results, and mistakes can go undetected.
Figure 2.1 Illustration of the difference between equilibrium and steady-state conditions. Equi-
librium implies that the oxygen concentrations in the air and water achieve a ratio
or partition coefficient of 20. Steady state implies unchanging with time, even if
flow occurs and regardless of whether equilibrium applies.
the concentrations are not at a ratio of 4, the conditions are nonequilibrium, and,
since the concentrations are changing with time, they are also of unsteady-state in
nature.
This correspondence between equilibrium and steady state does not, however,
necessarily apply when flow conditions prevail. It is possible for air and water
CH02 Page 24 Monday, January 15, 2001 1:47 PM
containing nonequilibrium quantities of benzene to flow into and out of the tank at
constant rates as shown in Figure 2.1B. But equilibrium and a steady-state condition
are maintained, since the concentrations in the tank and in the outflows are at a
ratio of 1:4. It is possible for near equilibrium to apply in the vessel, even when
the inflow concentrations are not in equilibrium, if benzene transfer between air
and water is very rapid. Figure 2.1B thus illustrates a flow, equilibrium, and steady-
state conditions, whereas Figure 2.1A is a nonflow, equilibrium, and steady-state
situation.
In Figure 2.1C, there is a deficiency of benzene in the inflow water (or excess
in the air) and, although in the time available some benzene transfers from air to
water, there is insufficient time for equilibrium to be reached. Steady state applies,
because all concentrations are constant with time. This is a flow, nonequilibrium,
steady-state condition in which the continuous flow causes a constant displacement
from equilibrium.
In Figure 2.1D, the inflow water and/or air concentration or rates change with
time, but there is sufficient time for the air and water to reach equilibrium in the
vessel, thus equilibrium applies (the concentration ratio is always 4), but unsteady-
state conditions prevail. Similar behavior could occur if the tank temperature changes
with time. This represents a flow, equilibrium, and unsteady-state condition.
Finally, in Figure 2.1E, the concentrations change with time, and they are not
in equilibrium; thus, a flow, nonequilibrium, unsteady-state condition applies, which
is obviously quite complex.
The important point is that equilibrium and steady state are not synonymous;
neither, either, or both can apply. Equilibrium implies that phases have concentrations
(or temperatures or pressures) such that they experience no tendency for net transfer
of mass. Steady state merely implies constancy with time. In the real environment,
we observe a complex assembly of phases in which some are (approximately) in
steady state, others in equilibrium, and still others in both steady state and equilib-
rium. By carefully determining which applies, we can greatly simplify the mathe-
matics used to describe chemical fate in the environment.
A couple of complications are worthy of note. Chemical reactions also tend to
proceed to equilibrium but may be prevented from doing so by kinetic or activation
considerations. An unlit candle seems to be in equilibrium with air, but in reality it
is in a metastable equilibrium state. If lit, it proceeds toward a “burned” state. Thus,
some reaction equilibria are not achieved easily, or not at all.
Second, “steady state” depends on the time frame of interest. Blood circulation
in a sleeping child is nearly in steady state; the flow rates are fairly constant, and
no change is discernible over several hours. But, over a period of years, the child
grows, and the circulation rate changes; thus, it is not a true steady state when
viewed in the long term. The child is in a “pseudo” or “short-term” steady state.
In many cases, it is useful to assume steady state to apply for short periods,
knowing that it is not valid over long periods. Mathematically, a differential
equation that truly describes the system is approximated by an algebraic equation
by setting the differential or the d(contents)/dt term to zero. This can be justified
by examining the relative magnitude of the input, output, and inventory change
terms.
CH02 Page 25 Monday, January 15, 2001 1:47 PM
In the air-water example, it was argued that equilibrium occurs when the ratio
of the benzene concentrations in water and air is 4. Thus, if the concentration in
water is 4 mol/m3, equilibrium conditions exist when the concentration in air is 1
mol/m3. If the air concentration rises to 2 mol/m3, we expect benzene to transfer by
diffusion from air to water until the concentration in air falls, concentration in water
rises, and a new equilibrium is reached. This is easily calculated if the total amount
of benzene is known. In a nonflow system, if the initial concentrations in air and
water are CAO and CWO mol/m3, respectively, and the volumes are VA and VW , then
the total amount M is, as shown earlier,
Here, CAO is 2, and CWO is 4 mol/m3, and since the volumes are both 100 m3, M is
600 mols. This will distribute such that CW is 4CA or
Thus, CA is 1.2 mol/m3, and CW is 4.8 mol/m3. Thus, the water concentration rises
from 4.0 to 4.8, while that of the air drops from 2.0 to 1.2 mol/m3.
Conversely, if the concentration in water is increased to 10 mol/m3, there will
be transfer from water to air until a new equilibrium state is reached.
A worrisome dilemma is, “How does the benzene in the water know the con-
centration in the air so that it can decide to start or stop diffusing?” In fact, it does
not know or care. It diffuses regardless of the condition at the destination. Equilib-
rium merely implies that there is no net diffusion, the water-to-air and air-to-water
diffusion rates being equal and opposite. Chemicals in the environment are always
striving to reach equilibrium. They may not always achieve this goal, but it is useful
to know the direction in which they are heading.
Other transport mechanisms occur that are not driven by diffusion. For example,
we could take 1 m3 of the water with its associated 1 mol of benzene and physically
convey it into the air, forcing it to evaporate, thus causing the concentration of
benzene in the air to increase. This nondiffusive, or “bulk,” or “piggyback” transfer
occurs at a rate that depends on the rate of removal of the water phase and is not
influenced by diffusion. Indeed, it may be in a direction opposite to that of diffusion.
In the environment, it transpires that there are many diffusive and nondiffusive
processes operating simultaneously. Examples of diffusive transfer processes include
The mathematical expressions for these rates are quite different. For diffusion,
the net rate of transfer or flux is written as the product of the departure from
equilibrium and a kinetic quantity, and the net flux becomes zero when the phases
are in equilibrium. We examine these diffusive processes in Chapter 7. For nondif-
fusive processes, the flux is the product of the volume of the phase transferred (e.g.,
quantity of sediment or rain) and the concentration. We treat nondiffusive processes
in Chapter 6.
We use the word flux as short form for transport rate. It has units such as mol/h
or g/h. Purists insist that flux should have units of mol/h·m2, i.e., it should be area
specific. We will apply it to both. It is erroneous to use the term flux rate since flux,
like velocity, already contains the “per time” term.
The residence time is thus the reciprocal of a rate constant kF with units of h–1. The
half-time for recovery occurs when t/τF or kFt is ln 2 or 0.693, i.e., when t is 0.693τ
or 0.693/k.
If the chemical also undergoes a reaction with a rate constant kR h–1, it can be
shown that
Thus, the larger (faster) rate constant dominates. The characteristic times τF and τR
(i.e., 1/kF and 1/kR) combine as reciprocals to give the total time τT , as do electrical
resistances in parallel, i.e.,
Thus, the smaller (shorter) τ dominates. The term τR can be viewed as a reaction
persistence. Characteristic times such as τR and τF are conceptually easy to grasp
and are very convenient quantities to deduce when interpreting the relative impor-
tance of environmental processes. For example, if τF is 30 years and τR is 3 years,
τT is 2.73 years; thus, reaction dominates the chemical’s fate. Ten out of every 11
molecules react, and only one leaves the lake by flow.
2.10 SUMMARY
In this chapter, we have introduced the system of units and dimensions. A view
of the environment has been presented as an assembly of phases or compartments
that are (we hope) mostly homogeneous rather than heterogeneous in properties,
and that vary greatly in volume and composition. We can define these phases or
parts of them as “envelopes” about which we can write mass, mole, and, if necessary,
energy balance equations. Steady-state conditions will yield algebraic equations, and
unsteady-state conditions will yield differential equations. These equations may
contain terms for discharges, flow (diffusive and nondiffusive) of material between
phases, and for reaction or formation of a chemical. We have discriminated between
equilibrium and steady state and introduced the concepts of residence time and
persistence. Finally, the use of both real and evaluative environments has been
suggested.
Having established these basic concepts, or working tools, our next task is to
develop the capability of quantifying the rates of the various flow, transport, and
reaction processes.
CH03 Page 29 Tuesday, January 16, 2001 9:52 AM
CHAPTER 3
29
CH03 Page 30 Tuesday, January 16, 2001 9:52 AM
Table 3.1 Sources of information on chemical properties and estimation methods (See
Chapter 1.5 of Mackay, et al., Illustrated Handbooks of Physical Chemical
Properties and Environmental Fate for Organic Chemicals, cited below, for
more details)
3.2.1 Quantity
The first factor is the quantity produced, used, formed or transported, including
consideration of the fraction of the chemical that may be discharged to the environ-
ment during use. Some chemicals, such as benzene, are used in very large quantities
in fuels, but only a small fraction (possibly less than a fraction of a percent) is
emitted into the environment through incomplete combustion or leakage during
storage. Other chemicals, such as pesticides, are used in much smaller quantities
but are discharged completely and directly into the environment; i.e., 100% is
emitted. At the other extreme, there are chemical intermediates that may be produced
in large quantities but are emitted in only minuscule amounts (except during an
industrial accident). It is difficult to compare the amounts emitted from these various
categories, because they are highly variable and episodic. It is essential, however,
to consider this factor; many toxic chemicals have no significant adverse impact,
because they enter the environment in negligible quantities.
Central to the importance of quantity is the adage first stated by Paracelsus,
nearly five centuries ago, that the dose makes the poison. This can be restated in
the form that all chemicals are toxic if administered to the victim in sufficient
quantities. A corollary is that, in sufficiently small doses, all chemicals are safe.
Indeed, certain metals and vitamins are essential to survival. The general objective
of environmental regulation or “management” must therefore be to ensure that the
quantity of a specific substance entering the environment is not excessive. It need
not be zero; indeed, it is impossible to achieve zero. Apart from cleaning up past
mistakes, the most useful regulatory action is to reduce emissions to acceptable
levels and thus ensure that concentrations and exposures are tolerable. Not even the
EPA can reduce the toxicity of benzene. It can only reduce emissions. This implies
knowing what the emissions are and where they come from. This is the focus of
programs such as the Toxics Release Inventory (TRI) in the U.S.A. or the National
Pollutant Release Inventory (NPRI) system in Canada. There are similar programs
in Europe, Australia, and Japan. Regrettably, the data are often incomplete. A major
purpose of this book is to give the reader the ability to translate emission rates into
environmental concentrations so that the risk resulting from exposure to these con-
centrations can be assessed. When this can be done, it provides an incentive to
improve release inventories.
3.2.2 Persistence
The second factor is the chemical’s environmental persistence, which may also
be expressed as a lifetime, half-life, or residence time. Some chemicals, such as DDT
or the PCBs, may persist in the environment for several years by virtue of their
resistance to transformation by degrading processes of biological and physical origin.
They may have the opportunity to migrate widely throughout the environment and
reach vulnerable organisms. Their persistence results in the possibility of establishing
CH03 Page 35 Tuesday, January 16, 2001 9:52 AM
relatively high concentrations. This arises because, in principle, the amount in the
environment (kilograms) can be expressed as the product of the emission rate into
the environment (kilograms per year) and the residence time of the chemical in the
environment (years). Persistence also retards removal from the environment once
emissions are stopped. A legacy of “in place” contamination remains.
This is the same equation that controls a human population. For example, the
number of Canadians (about 30 million) is determined by the product or the rate at
which Canadians are born (about 0.4 million per year) and the lifetime of Canadians
(about 75 years). If Canadians were less persistent and lived for only 30 years, the
population would drop to 12 million.
Intuitively, the amount (and hence the concentration) of a chemical in the
environment must control the exposure and effects of that chemical on ecosystems,
because toxic and other adverse effects, such as ozone depletion, are generally a
response to concentration. Unfortunately, it is difficult to estimate the environmen-
tal persistence of a chemical. This is because the rate at which chemicals degrade
depends on which environmental media they reside in, on temperature (which
varies diurnally and seasonally), on incidence of sunlight (which varies similarly),
on the nature and number of degrading microorganisms that may be present, and
on other factors such as acidity and the presence of reactants and catalysts. This
variable persistence contrasts with radioisotopes, which have a half-life that is
fixed and unaffected by the media in which they reside. In reality, a substance
experiences a distribution of half-lives, not a single value, and this distribution
varies spatially and temporally. Obviously, long-lived chemicals, such as PCBs,
are of much greater concern than those, such as phenol, that may persist in the
aquatic environment for only a few days as a result of susceptibility to biodegra-
dation. Some estimate of persistence or residence time is thus necessary for priority
setting purposes. Organo-halogen chemicals tend to be persistent and are therefore
frequently found on priority lists. Later in this book, we develop methods of
calculating persistence.
3.2.3 Bioaccumulation
The third factor is potential for bioaccumulation (i.e., uptake of the chemical by
organisms). This is a phenomenon, not an effect; thus bioaccumulation per se is not
necessarily of concern. It is of concern that bioaccumulation may cause toxicity to
the affected organism or to a predator or consumer of that organism. Historically, it
was the observation of pesticide bioaccumulation in birds that prompted Rachel
Carson to write Silent Spring in 1962, thus greatly increasing public awareness of
environmental contamination.
As we discuss later, some chemicals, notably the hydrophobic or “water-hating”
organic chemicals, partition appreciably into organic media and establish high con-
centrations in fatty tissue. PCBs may achieve concentrations (i.e., they bioconcen-
trate) in fish at factors of 100,000 times the concentrations that exist in the water in
which the fish dwell. For some chemicals (notably PCBs, mercury, and DDT), there
is also a food chain effect. Small fish are consumed by larger fish, at higher trophic
levels, and by other animals such as gulls, otters, mink, and humans. These chemicals
CH03 Page 36 Tuesday, January 16, 2001 9:52 AM
may be transmitted up the food chain, and this may result in a further increase in
concentration such that they are biomagnified.
Bioaccumulation tendency is normally estimated using an organic phase-water
partition coefficient and, more specifically, the octanol-water partition coefficient.
This, in turn, can be related to the solubility of the chemical in the water. Clearly,
chemicals that bioaccumulate, bioconcentrate, and biomagnify have the potential to
travel down unexpected pathways, and they can exert severe toxic effects, especially
on organisms at higher trophic levels.
The importance of bioaccumulation may be illustrated by noting that, in water
containing 1 ng/L of PCB, the fish may contain 105 ng/kg. A human may consume
1000 L of water annually (containing 1000 ng of PCB) and 10 kg of fish (containing
106 ng of PCB), thus exposure from fish consumption is 1000 times greater than
that from water. Particularly vulnerable are organisms such as certain birds and
mammals that rely heavily on fish as a food source.
3.2.4 Toxicity
The fourth factor is the toxicity of the chemical. The simplest manifestation of
toxicity is acute toxicity. This is most easily measured as a concentration that will
kill 50% of a population of an aquatic organism, such as fish or an invertebrate (e.g.,
Daphnia magna), in a period of 24–96 hours, depending on test conditions. When
the concentration that kills (or is lethal to) 50% (the LC50) is small, this corresponds
to high toxicity. The toxic chemical may also be administered to laboratory animals
such as mice or rats, orally or dermally. The results are then expressed as a lethal
dose to kill 50% (LD50) in units of mg chemical/kg body weight of the animal.
Again, a low LD50 corresponds to high toxicity.
More difficult, expensive, and contentious are chronic, or sublethal, tests that
assess the susceptibility of the organism to adverse effects from concentrations or
doses of chemicals that do not cause immediate death but ultimately may lead to
death. For example, the animal may cease to feed, grow more slowly, be unable to
reproduce, become more susceptible to predation, or display some abnormal behav-
ior that ultimately affects its life span or performance. The concentrations or doses
at which these effects occur are often about 1/10th to 1/100th of those that cause
acute effects. Ironically, in many cases, the toxic agent is also an essential nutrient,
so too much or too little may cause adverse effects.
Although most toxicology is applied to animals, there is also a body of knowledge
on phytotoxicity, i.e., toxicity to plants. Plants are much easier to manage, and killing
them is less controversial. Tests also exist for assessing toxicity to microorganisms.
It is important to emphasise that toxicity alone is not a sufficient cause for concern
about a chemical. Arsenic in a bottle is harmless. Disinfectants, biocides, and pesti-
cides are inherently useful because they are toxic. The extent to which the organism
is injured depends on the inherent properties of the chemical, the condition of the
organism, and the dose or amount that the organism experiences. It is thus misleading
to classify or prioritize chemicals solely on the basis of their inherent toxicity, or on
the basis of the concentrations in the environment or exposures. Both must be
considered. A major task of this book is to estimate exposure. A healthy tension often
CH03 Page 37 Tuesday, January 16, 2001 9:52 AM
exists between toxicologists and chemists about the relative importance of toxicity
and exposure, but fundamentally this argument is about as purposeful as squabbling
over whether tea leaves or water are the more important constituents of tea.
Most difficult is the issue of genotoxicity, including carcinogenicity, and terato-
genicity. In recent years, a battery of tests has been developed in which organisms
ranging from microorganisms to mammals are exposed to chemicals in an attempt
to determine if they can influence genetic structure or cause cancer. A major difficulty
is that these effects may have long latent periods, perhaps 20 to 30 years in humans.
The adverse effect may be a result of a series of biochemical events in which the
toxic chemical plays only one role. It is difficult to use the results of short-term
laboratory experiments to deduce reliably the presence and magnitude of hazard to
humans. There may be suspicions that a chemical is producing cancer in perhaps
0.1% of a large human population over a period of perhaps 30 years, an effect that
is very difficult (or probably impossible) to detect in epidemiological studies. But
this 0.1% translates into the premature death of 30,000 Canadians per year from
such a cancer, and is cause for considerable concern. Another difficulty is that
humans are voluntarily and involuntarily exposed to many toxic chemicals, including
those derived from smoking, legal and illicit drugs, domestic and occupational
exposure, as well as environmental exposure. Although research indicates that mul-
tiple toxicants act additively when they have similar modes of action, there are cases
of synergism and antagonism. Despite these difficulties, a considerable number of
chemicals have been assessed as being carcinogenic, mutagenic, or teratogenic, and
it is even possible to assign some degree of potency to each chemical. Such chemicals
usually rank high on priority lists. As was discussed earlier, endocrine modulating
substances are of more recent concern. It seems likely that ingenious toxicologists
will find other subtle toxic effects in the future.
As lakes go, Lake Superior is fairly pristine, since there is relatively little industry
on its shores. In the U.S. part of this lake is an island, Isle Royale, which is a
protected park and is thus even more pristine. In this island is a lake, Siskiwit Lake,
which cannot conceivably be contaminated. No responsible funding agency would
waste money on the analysis of fish from that lake for substances such as PCBs.
Remarkably, perceptive researchers detected substantial concentrations of PCBs.
Similarly, surprisingly high concentrations have been detected in wildlife in the
Arctic and Antarctic. Clearly, certain contaminants can travel long distances through
the atmosphere and oceans and are deposited in remote regions.
This potential for long-range transport (LRT) is of concern for several reasons.
There is an ethical issue when the use of a chemical in one nation (which presumably
enjoys social or economic benefit from it) results in exposure in other downwind
nations that derive no benefit, only adverse effects. This transboundary pollution
issue also applies to gases such as SO2, which can cause acidification of poorly
buffered lakes at distant locations. A regulatory agency may then be in the position
of having little or no control over exposures experienced by its public. The political
implications are obvious.
CH03 Page 38 Tuesday, January 16, 2001 9:52 AM
Scheduled for
Scheduled for Elimination Scheduled for Restriction Reduction
Aldrin DDT PAHs
Chlordane Hexachlorocyclohexanes Dioxins/furans
DDT Polychlorinated biphenyls Hexachlorobenzene
Dieldrin
Endrin
Heptachlor
Hexabromobiphenyl
Hexachlorobenzene
Mirex
Polychlorinated biphenyls
Toxaphene
Finally, there is a variety of other adverse effects that are of concern, including
determine priority. This is a subjective process, and it becomes difficult for two
major reasons.
First, chemicals that are subject to quite different patterns of use are difficult to
compare. For example, chemical X may be produced in very large quantities, emitted
into the environment, and found in substantial concentrations in the environment,
but it may not be believed to be particularly toxic. Examples are solvents such as
trichloroethylene or plasticizers such as the phthalate esters. On the other hand,
chemical Y may be produced in minuscule amounts but be very toxic, an example
being the “dioxins.” Which deserves the higher priority?
Second, it appears that the adverse effects suffered by aquatic organisms and
other animals, including humans, are the result of exposure to a large number of
chemicals, not just to one or two chemicals. Thus, assessing chemicals on a case-
by-case basis may obscure the cumulative effect of a large number of chemicals.
For example, if an organism is exposed to 150 chemicals, each at a concentration
that is only 1% of the level that will cause death, then death will very likely occur,
but it cannot be attributed to any one of these chemicals. It is the cumulative effect
that causes death. The obvious prudent approach is to reduce exposure to all chem-
icals to the maximum extent possible. The issue is further complicated by the
possibility that some chemicals will act synergistically, i.e., they produce an effect
that is greater than additive; or they may act antagonistically, i.e., the combined
effect is less than additive. As a result, there will be cases in which we are unable
to prove that a specific chemical causes a toxic effect but, in reality, it does contribute
to an overall toxic effect. Indeed, some believe that this situation will be the rule
rather than the exception.
A compelling case can be made that the prudent course of action is for society
to cast a fairly wide net of suspicion (i.e., assemble a fairly large list of chemicals)
then work to elucidate sources, fate, and effects with the aim of reducing overall
exposure of humans, and our companion organisms, to a level at which there is
assurance that no significant toxic effects can exist from these chemicals. The risk
from these chemicals then becomes small as compared to other risks such as acci-
dents, disease, and exposure to natural toxic substances. This approach has been
extended and articulated as the “Precautionary Principle,” the “Substitution Princi-
ple,” and the “Principle of Prudent Avoidance.”
One preferred approach is to undertake a risk assessment for each chemical.
Formal procedures for conducting such assessments have been published, notably
by the U.S. Environmental Protection Agency (EPA). The process involves identi-
fying the chemical, its sources, the environment in which it is present, and the
organisms that may be affected. The toxicity of the substance is evaluated and routes
of exposure quantified. Ultimately, the prevailing concentrations or doses are mea-
sured or estimated and compared with levels that are known to cause effects, and
conclusions are drawn regarding the proximity to levels at which there is a risk of
effect. This necessarily involves consideration of the chemical’s behavior in an actual
environment. Risk is thus assessed only for that environment. Risk or toxic effects
are thus not inherent properties of a chemical; they depend on the extent to which
the chemical reaches the organism.
CH03 Page 40 Tuesday, January 16, 2001 9:52 AM
Table 3.5 Physical Chemical properties of Selected Organic Chemicals at 25°C Including Estimated Half-Lives Classified as in Table 3.4 and
Toxicity Expressed as Oral LD50 to the Rat. These data have been selected from a number of sources, including Mackay et al. (2000),
RTECS (2000), and the Hazardous Substances Data Bank (2000).
2-chloroethyl vinyl ether 106.55 3566 15000 1.28 –69.7 17 550 550 1700 210
bis(2-chloroethoxy)methane 173.1 21.6 8100 1.26 0 17 550 550 1700 65
1-pentanol 88.149 300 22000 1.5 –78.2 55 55 55 170 3030
1-hexanol 102.176 110 6000 2.03 –44.6 55 55 55 170 720
benzyl alcohol 108.14 12 80 1.1 –15.3 55 55 55 170 1230
cyclohexanol 100.16 85 38000 1.23 25.15 55 55 55 170 1400
benzaldehyde 106.12 174 3000 1.48 –55.6 5 55 55 170 1300
3-pentanone 86.135 4700 34000 0.82 –38.97 55 170 170 550 2410
2-heptanone 114.18 500 4300 2.08 –35 55 170 170 550 1670
cyclohexanone 98.144 620 23000 0.81 –32.1 55 170 170 550 1540
acetophenone 120.15 45 5500 1.63 19.62 550 170 170 550 815
45
46
octachlorodibenzofuran 443.8 5x10–10 1.16x10–6 8 258 550 5500 55000 55000 n/a
4-chlorophenol 128.56 20 27000 2.4 43 55 550 550 1700 500
2,4-dichlorophenol 163 12 4500 3.2 44 55 550 550 1700 2830
2,3,4-trichlorophenol 197.45 1 500 3.8 79 170 170 1700 5500 2800
2,4,6-trichlorophenol 197.45 1.25 434 3.69 69.5 170 170 1700 5500 2800
2,3,4,6-tetrachlorophenol 231.89 0.28 183 4.45 70 550 550 1700 5500 140
pentachlorophenol 266.34 0.00415 14 5.05 190 550 550 1700 5500 210
2,4-dimethylphenol 122.17 13.02 8795 2.35 26 17 55 170 550 2300
p-cresol 108.13 13 20000 1.96 34.8 5 17 55 170 207
ENVIRONMENTAL CHEMICALS AND THEIR PROPERTIES
dimethylphthalate (DMP) 194.2 0.22 4000 2.12 5 170 170 550 1700 2400
diethylphthalate (DEP) 222.26 0.22 1080 2.47 –40.5 170 170 550 1700 8600
dibutylphthalate (DBP) 278.34 0.00187 11.2 4.72 –35 55 170 550 1700 8000
butyl benzyl phthalate 312.39 0.00115 2.69 4.68 –35 55 170 550 1700 13500
di-(2-ethylhexyl)-phthalate 390.54 1.33x10–5 0.285 5.11 –50 55 170 550 1700 25000
(DEHP)
aldicarb 190.25 0.004 6000 1.1 99 5 550 1700 17000 0.5
aldrin 364.93 0.005 0.02 6.50 104 55 5500 17000 55000 39
carbaryl 201.22 0.0000267 120 2.36 142 55 170 550 1700 230
carbofuran 221.3 0.00008 351 2.32 151 5 170 550 1700 5
chloropyrifos 350.6 0.00227 0.73 4.92 41 17 170 170 1700 82
47
48
Figure 3.2 Plot of log KAW vs. log KOW for the chemicals in Table 3.5 on which dotted lines of
constant KOA line on the 45° diagonal. This graph shows the wide variation in
properties. Volatile compounds tend to lie to the upper left, water-soluble com-
pounds to the lower left, and hydrophobic compounds to the lower right. The thicker
lines represent constant percentages present at equilibrium in air, water, and
octanol phases, assuming a volume ratio of 656,000:1300:1, respectively. Modified
from Gouin et al. (2000).
CH03 Page 50 Tuesday, January 16, 2001 9:52 AM
3.3.2 Chemical Classes (see Fig. 3.1 for structures and Table 3.5 for
properties)
3.3.2.1 Hydrocarbons
Hydrocarbons are naturally occurring chemicals present in crude oil and natural
gas. Some are formed by biogenic processes in vegetation, but most contamination
comes from oil spills, effluents from petroleum and petrochemical refineries, and
the use of fuels for transportation purposes.
The alkanes can be separated into classes of normal, branched (or iso) species
and cyclic alkanes, which range in molar mass from methane or natural gas to waxes.
They are usually sparingly soluble in water. For example, hexane has a solubility
of approximately 10 g/m3. This solubility falls by a factor of about 3 or 4 for every
carbon added. The branched and cyclic alkanes tend to be more soluble in water,
apparently because they have smaller molecular areas and volumes.
Highly branched or cyclic alkanes such as terpenes are produced by vegetation.
They are often sweet smelling and tend to be very resistant to biodegradation.
The alkenes or olefins are not naturally occurring to any significant extent. They
are mainly used as petrochemical intermediates. The alkynes, of which ethyne or
acetylene is the first member, are also chemical intermediates that are rarely found
in the environment. These unsaturated hydrocarbons tend to be fairly reactive and
short-lived in the environment, whereas the alkanes are more stable and persistent.
Of particular environmental interest are the aromatics, the simplest of which is
benzene. The aromatics are relatively soluble in water, for example, benzene has a
solubility of 1780 g/m3. They are regarded as fairly toxic and often troublesome
compounds. A variety of substituted aromatics can be obtained by substituting
various alkyl groups. For example, methyl benzene is toluene.
When two benzene rings are fused, the result is naphthalene, which is also a
chemical of considerable environmental interest. Subsequent fusing of benzene rings
to naphthalene leads to a variety of chemicals referred to as the polycyclic aromatic
hydrocarbons or polynuclear aromatic hydrocarbons (PAHs). These compounds tend
to be formed when a fuel is burned with insufficient oxygen. They are thus present
in exhaust from engines and are of interest because many are carcinogenic.
Biphenyl is a hydrocarbon that is not of much importance as such, but it forms
an interesting series of chlorinated compounds, the PCBs or polychlorinated biphe-
nyls, which are discussed later.
chlorofluoro compounds are very stable and are used as refrigerants. Because these
molecules are quite small, they are fairly soluble in water and are therefore able to
penetrate the tissues of organisms quite readily. They are thus used as anaesthetics
and narcotic agents.
The chlorinated aromatics are a particularly interesting group of chemicals. The
chlorobenzenes are biologically active. 1,4 or paradichlorobenzene is widely used
as a deodorant and disinfectant. The polychlorinated biphenyls, or PCBs, and their
brominated cousins, the PBBs, are notorious environmental contaminants, as are
chlorinated terpenes such as toxaphene, which is a very potent and long-lived
insecticide. Many of the early pesticides, such as DDT, mirex, and chlordane, are
chlorinated hydrocarbons. They possess the desirable properties of stability and a
high tendency to partition out of air and water into the target organisms. Thus,
application of a pesticide results in protection for a prolonged time. As Rachel Carson
demonstrated in Silent Spring, the problem is that these chemicals persist long
enough to affect non-target organisms and to drift throughout the environment,
causing widespread contamination.
Fluorinated chemicals also possess considerable stability and, because the fluo-
rine atom is lighter than chlorine, they are generally more volatile. Polyfluorinated
substances are very stable in the environment as a result of the strong C-F bond.
Brominated chemicals are also stable, but with reduced volatility. A major use of
brominated substances is in fire retardants, specifically polybrominated diphenyl
ethers.
The most common oxygenated organic compounds are the alcohols, ethanol
being among the most widely used. Others are octanol, which is a convenient
analytical surrogate for fat, and glycerol is of interest because it forms the backbone
of fat molecules by esterification with fatty acids to form glycerides.
The phenols consist of an aromatic molecule in which a hydrogen is replaced
by an OH group. They are acidic and tend to be biologically disruptive. Phenol, or
carbolic acid, was the first disinfectant. Substituting chlorines on phenol tends to
increase the toxic potency of the substance and its tendency to ionize, i.e., its pKa
is reduced. Pentachlorophenol (PCP) is a particularly toxic chemical and has been
widely used for wood preservation.
The ketones such as acetone, and aldehydes such as formaldehyde, are fairly
reactive in the environment and can be of concern as atmospheric contaminants in
regions close to sources of emission. Much of the smog problem is attributable to
aldehydes formed in combustion processes.
Organic acids such as acetic acid are also fairly reactive. They are not usually
regarded as an environmental problem, but trifluoroacetic acid, which is formed by
combustion of freons and from some pesticides, is very persistent. Some chlorinated
organic acids, e.g., 2,4-D, are potent herbicides. Longer-chain acids, such as stearic
acid, are mainly of interest because they esterify with glycerol to form fats. Humic
and fulvic acids are of considerable environmental importance. These are substances
CH03 Page 52 Tuesday, January 16, 2001 9:52 AM
of complex and variable structure that are naturally present in soils, water, and
sediments. They are the remnants of living organic materials, such as wood, that
has been subjected to prolonged microbial conversion. These acids are sparingly
soluble in water, but the solubility can be increased at high pH.
The esters or “salts” or organic acids and alcohols tend to be relatively innocuous
and short-lived in most cases. A notable exception is the phthalate esters, which are
very stable oily substances and are invaluable additives (plasticizers) for plastics,
rendering them more flexible. Notable among the phthalate esters is diethylhexy-
lphthalate (DEHP), the ester with two molecules of 2 ethylhexanol. The other esters
of interest are the glycerides—for example, glyceryl trioleate, the ester of glycerine
and oleic acid. This chemical has similar properties to fat and has been suggested
as a convenient surrogate for measuring fat to water partitioning.
The “dioxins” and “furans” are two series of organic compounds that have
become environmentally notorious. The chlorinated dibenzo-p-dioxins were never
produced intentionally but are formed under combustion conditions when chlorine
is present. They form a series of very toxic chemicals, the most celebrated of which
is 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD). TCDD is possibly the most toxic
chemical to mammals. A dose of 2 µg of TCDD per kg of body weight is sufficient
to kill small rodents.
A related series of chemicals is the dibenzofurans, which are similar in properties
to the dioxins. It appears that molecules that are long and flat, with chlorine atoms
strategically located at the ends, are particularly toxic. Examples are the chloronaph-
thalenes, DDT, the PCBs, and chlorinated dibenzo-p-dioxins and dibenzofurans.
Other oxygenated compounds of interest include carbohydrates, cellulose, and
lignins, which occur naturally.
Sulfur compounds, including thiols, thiophenes, and mercaptans, are well known
because of their strong odor. One of the most prevalent classes of synthetic organic
chemicals is the alkyl benzene sulfonates, which are widely used in detergents.
3.3.2.8 Metals
Most metals are essential for human life in small quantities but can be toxic if
administered in excessive dosages. The metals of primary toxicological interest here
are those that form organo-metallic molecules. Notable is mercury, which can exist
as the element in various ionic and organometallic forms. Other metals such as lead
and tin behave similarly. A formidable literature exists on the behavior, fate, and
effects of the “heavy” metals such as lead, copper, and chromium. These metals
often have a complex environmental chemistry and toxicology that vary considerably,
depending on their ionic state as influenced by acidity and redox status.
Considerable quantities of drugs are used by humans and for veterinary purposes
on livestock. Antibiotics and steroids are examples. These substances are excreted
and may pass through sewage treatment plants or enter soils or groundwater follow-
ing agricultural use. There is a growing concern that these substances may have
adverse effects or may cause an increase in antibiotic resistance in bacteria. Among
personal care products of concern are detergents, fabric softeners, fragrances, and
certain solvents. They may evaporate or be discharged with sewage, which may or
may not be adequately treated.
It would be unwise to assume that current lists of priority chemicals are complete
and will remain static. It may be that the chemicals on the lists reflect our present
ability to detect and analyze them rather than their real environmental significance.
The prevalence of organo-chlorine chemicals on lists is in part the result of the
sensitive electron capture detector. As new analytical methods emerge, new chemi-
cals will presumably be found, and priorities will change. Happy hunting grounds
for environmental chemists include combustion gases, dyes, mine tailings, effluents
CH03 Page 54 Tuesday, January 16, 2001 9:52 AM
from pulp and paper operations (especially those involving chlorine bleaching),
landfill leachates, and a vast assortment of products of metabolic conversion in
organisms ranging from bacteria to humans.
Select five substances from Table 3.5 that range in their values of vapor pressure,
aqueous solubility, and log KOW.
Calculate KAW as
Calculate all the concentrations and amounts (which should add to 100 kg!) and
discuss briefly how each substance is behaving, i.e., its partitioning preference.
CH04 Page 55 Monday, January 15, 2001 1:49 PM
CHAPTER 4
4.1 INTRODUCTION
4.2.1 Air
The layer of the atmosphere that is in most intimate contact with the surface of
the Earth is the troposphere, which extends to a height of about 10 km. The tem-
perature, density, and pressure of the atmosphere fall steadily with increasing height,
55
CH04 Page 56 Monday, January 15, 2001 1:49 PM
through the tropopause to the stratosphere is a relatively slow process and is rarely
important in environmental calculations, except in the case of chemicals such as the
freons, which catalyze the destruction of stratospheric ozone, thus facilitating the
penetration of UV light to the Earth’s surface. A reasonable atmospheric volume
over our 1 km square world is thus 1000 × 1000 × 6000 or 6 × 109 m3.
If our environmental model is concerned with a localized situation (e.g., a state,
province, or metropolitan region), it is unlikely that most pollutants would manage
to penetrate higher than about 500 to 2000 m during the time the air resides over
the region. It therefore may be appropriate to reduce the height of the atmosphere
to 500 to 2000 m in such cases. In extreme cases (e.g., over small ponds or fields),
the accessible mixed height of the atmosphere may be as low as 10 m. The modeler
must make a judgement as to the volume of air that is accessible to the chemical
during the time that the air resides in the region of interest.
4.2.2 Aerosols
Aerosol particles have a very high surface area and thus absorb (or adsorb or
sorb) many pollutants, especially those of very low vapor pressure, such as the PCBs
or polyaromatic hydrocarbons. In the case of benzo(a)pyrene, almost all the chemical
present in the atmosphere is associated with particles, and very little exists in the
gas phase. This is important, because chemicals associated with aerosol particles
CH04 Page 58 Monday, January 15, 2001 1:49 PM
are subject to two important deposition processes. First is dry deposition, in which
the aerosol particle falls under the influence of gravity to the Earth’s surface. This
falling velocity, or deposition velocity, is quite slow and depends on the turbulent
condition of the atmosphere, the size and properties of the aerosol particle, and the
nature of the ground surface, but a typical velocity is about 0.3 cm/s or 10.8 m/h.
The result is deposition of 10.8 m/h × 2 × 10–11 (volume fraction) × 106 m2 or
0.000216 m3/h or 1.89 m3/year. Second, the particles may be scavenged or swept
out of the air by wet deposition with raindrops. As it falls, each raindrop sweeps
through a volume of air about 200,000 times its volume prior to landing on the
surface. Thus, it has the potential to remove a considerable quantity of aerosol from
the atmosphere. Rain is therefore often highly contaminated with substances such
as PCBs and PAHs. There is a common fallacy that rain water is pure. In reality, it
is often much more contaminated than surface water. Typical rainfall rates lie in the
range 0.3 to 1 m per year but, of course, vary greatly with climate. We adopt a figure
of 0.8 m/year for illustrative purposes. This results in the scavenging of 200,000 ×
0.8 m/year × 2 × 10–11 × 106 m2 or 3.2 m3/year, about twice the dry deposition. Snow
is an even more efficient scavenger of aerosol particles. It appears that one volume
of snow (as solid ice) may scavenge about one million volumes of atmosphere, five
times more than rain, presumably because of its flaky nature with a high surface
area and a slower, more tortuous downward journey.
In the four-compartment evaluative environment, we ignore aerosols, but we
include them in the eight-compartment version.
4.3.1 Water
Particulate matter in the water plays a key role in influencing the behavior of
chemicals. Again, we do not normally know if the chemical is absorbed or adsorbed
to the particles. We play it safe and use the vague term sorbed. A very clear natural
water may have a concentration of particles as low as 1 g/m3 or the equivalent 1 mg/L.
CH04 Page 59 Monday, January 15, 2001 1:49 PM
Fish are of particular interest, because they are of commercial and recreational
importance to users of water, and they tend to bioconcentrate or bioaccumulate
CH04 Page 60 Monday, January 15, 2001 1:49 PM
metals and organic chemicals from water. They are thus convenient monitors of the
contamination status of lakes. This raises the question, “What is the volume fraction
of fish in a lake?” Most anglers and even aquatic biologists greatly overestimate this
number. It is probably, in most cases, in the region of 10–8 to 10–9, but this is somewhat
misleading, because most of the biotic material in a lake is not fish—it is material
of lower trophic levels, on which fish feed. For illustrative purposes, we can assume
that all the biotic material in the water is fish, and the total concentration is about
1 part per million, yielding a volume of “fish” of about 7 m3. It proves useful later
to define a lipid or fat content of fish, a figure of 5% by volume being typical.
In summary, the water thus consists of 7 × 106 m3 of water containing 35 m3 of
particulate matter and 7 m3 of “fish” or biota.
In shallow or near-shore water, there may be a considerable quantity of aquatic
plants or macrophytes. These plants provide a substrate for a thriving microbial
community, and they possess inherent sorptive capacity. Their importance is usually
underestimated. Because of the present limited ability to quantify their sorptive
properties, we ignore them here.
The particulate matter in water is important, because, like aerosols in the atmo-
sphere, it serves as a vehicle for the transport of chemical from the bulk of the water
to the bottom sediments. Hydrophobic substances tend to partition appreciably on
to the particles and are thus subject to fairly rapid deposition. This deposition velocity
is typically 0.5 to 2.0 m per day or 0.02 to 0.08 m/h. This velocity is sufficient to
cause removal of most of the suspended matter from most lakes during the course
of a year. Thus, under ice-covered lakes in the winter, the water may clarify. Some
of the deposited particulate matter is resuspended from the bottom sediment through
the action of currents, storms, and the disturbances caused by bottom-dwelling fish
and invertebrates. During the summer, there is considerable photosynthetic fixation
of carbon by algae, resulting in the formation of considerable quantities of organic
carbon in the water column. Much of this is destined to fall to the bottom of the
lake, but much is degraded by microorganisms within the water column.
Assuming, as discussed earlier, 5 × 10–6 m3 of particles per m3 of water and a
deposition velocity of 200 m per year, we arrive at a deposition rate of 0.001 m3/m2
of sediment area per year or, for an area of 7 × 105 m2, a flow of 700 m3/year. We
examine this rate in more detail in the next section.
Inspection of the state of the bottom of lakes reveals that there is a fairly fluffy
or nepheloid active layer at the water–sediment interface. This layer typically con-
sists of 95% water and 5% particles and is often highly organic in nature. It may
consist of deposited particles and fecal material from the water column. It is stirred
CH04 Page 61 Monday, January 15, 2001 1:49 PM
by currents and by the action of the various biota present in this benthic region. The
sediment becomes more consolidated at greater depths, and the water content tends
to drop toward 50%. The top few centimetres of sediment are occupied by burrowing
organisms that feed on the organic matter (and on each other) and generally turn
over (bioturbate) this entire “active layer” of sediment. Depending on the condition
of the water column above, this layer may be oxygenated (aerobic or oxic) or depleted
of oxygen (anaerobic or anoxic). This has profound implications for the fate of
inorganic substances such as metals and arsenic, but it is relatively unimportant for
organic chemicals except in that the oxygen status influences the nature of the
microbial community, which in turn influences the availability of metabolic pathways
for chemical degradation. The deeper sediments are less accessible, and ultimately
the material becomes almost completely buried and inaccessible to the aquatic
environment above. Most of the activity occurs in the top 5 cm of the sediment, but
it is misleading to assume that sediments deeper than this are not accessible. There
remains a possibility of bioturbation or diffusion reintroducing chemical to the water
column.
Bottom sediments are difficult to investigate, can be unpleasant, and have little
or no commercial value. They are therefore often ignored. This is unfortunate,
because they serve as the depositories for much of the toxic material discharged into
water. They are thus very important, are valuable as a “sink” for contaminants, and
merit more sympathy and attention.
Fast-flowing rivers are normally sufficiently turbulent that the bottom is scoured,
exposing rock or consolidated mineral matter. Thus, their sediments tend to be less
important. Sluggish rivers have appreciable sediments.
It is possible to estimate the rate of deposition, i.e., the amount of material that
falls annually to the bottom of the lake and is retained there. This can be done by
sediment traps, which are essentially trays that collect falling particles, or by taking
a sediment core and assigning dates to it at various depths using concentrations of
various radioactive metals such as lead. Nuclear events provide convenient dating
markers for sediment depths. The measurement of deposition is complicated by the
presence of the reverse process of resuspension caused by currents and biotic activity.
It is difficult to measure how much material is rising and falling, since much may
be merely cycling up and down in the water column. Burial or net deposition rates
vary enormously, but a figure of about 1 mm per year is typical. Much of this is
water, which is trapped in the burial process.
Chemicals present in sediments are primarily removed by degradation, burial,
or resuspension back to the water column.
For illustrative purposes we adopt a sediment depth of 3 cm and suggest that it
consists of 67% water and 33% solids, and these solids consist of about 10% organic
matter or 5% organic carbon. Living creatures are included in this figure. Some of
this deposited material is resuspended to the water column, some of the organic
matter is degraded (i.e., used as a source of energy by benthic or bottom-living
organisms), and some is destined to be permanently buried. The low 5% organic
CH04 Page 62 Monday, January 15, 2001 1:49 PM
carbon figure for deeper sediments compared to high 17% for the depositing material
implies that about 75% of the organic carbon is degraded.
It is now possible to assemble an approximate mass balance for the sediment
mineral matter (MM) and organic matter (OM) and thus the organic carbon (OC).
This is given in Table 4.1.
Organic
Mineral matter Organic matter Total carbon
cm3 g cm3 g cm3 g g
Deposition 500 1200 500 500 1000 1700 250
Resuspension 200 480 200 200 400 680 100
OM conversion – – 233 233 233 233 117
Burial (solids) 300 720 67 67 367 787 33
On a 1 m2 basis, the deposition rate is 0.001 m3 per year or 1000 cm3 per year.
With a particle density of 1.7 g/cm3, this corresponds to 1700 g/year of which 500 g
is OM, and 1200 g is MM. We assume that 40% of this is resuspended, i.e., 200 g
of OM and 480 g of MM. Of the remaining 300 g OM, we assume that 233 g is
digested or degraded to CO2, and 67 g is buried along with the remaining 720 g of
MM. Total burial is thus 1420 g, which consists of 720 g of MM, 67 g of OM, and
633 g of water. The total volumetric burial rate of solids is 367 cm3/year. Now,
associated with these solids is 633 cm3 of pore water; thus, the total volumetric
burial rate of solids plus water is approximately 1000 cm3/year, corresponding to a
rise in the sediment-water interface of 1 mm/year. The mass percentage of OC in
the depositing and resuspending material is 15%, while in the buried material it is
4.2%. The bulk sediment density, including pore water, is 1420 kg/m3.
On a 7 × 105 m2 basis, the deposition rate is 700 m3/year, resuspension is
280 m3/year, burial is 257 m3/year, and degradation accounts for the remaining
163 m3/year. The organic and mineral matter balances are thus fairly complicated,
but it is important to define them, because they control the fate of many hydrophobic
chemicals.
It is noteworthy that the burial rate of 1 mm/year coupled with the sediment
depth of 3 cm indicates that, on average, it will take 30 years for sediment solids
to become buried. During this time, they may continue to release sorbed chemical
back to the water column. This is the crux of the “in-place contaminated sediments”
problem, which is unfortunately very common, especially in the Great Lakes Basin.
In the simple four-compartment environment, we treat only the solids but, in the
eight-compartment version, we include the sediment pore water. In the interests of
simplicity, we assign a density of 1500 kg/m3 to the sediment in the four-compart-
ment model.
CH04 Page 63 Monday, January 15, 2001 1:49 PM
4.5 SOILS
Soil is a complex organic matrix consisting of air, water, mineral matter (notably
clay and silica), and organic matter, which is similar in general nature to the organic
matter discussed earlier for the water column.
The surface soil is subject to diurnal and seasonal temperature changes and to
marked variations in water content, and thus in air content. At times it may be
completely flooded, and at other times almost completely dry. The organic matter
in the soil plays a crucial role in controlling the retention of the water and thus in
ensuring the viability of plants. The organic matter content is typically 1 to 5%, but
peat soils and forest soils can have much higher organic matter contents. Depletion
of organic matter through excessive agriculture tends to render the soil infertile,
which is an issue of great concern in agricultural regions. Soils vary enormously in
their composition and texture and consist of various layers, or horizons, of different
properties. There is transport vertically and horizontally by diffusion in air and in
water, flow, or advection in water and, of course, movement of water and nutrients
into plant roots and thence into stems and foliage. Burrowing animals such as worms
can also play an important role in mixing and transporting chemicals in soils.
A typical soil may consist of 50% solid matter, 20% air, and 30% water, by
volume. The dry soil thus has a porosity of 50%. The solid matter may consist of
about 2% organic carbon or 4% organic matter. During and after rainfall, water flows
vertically downward through the soil and may carry chemicals with it. During periods
of dry weather, water tends to return to the surface by capillary action, again moving
the chemicals.
Later, we set up equations describing the diffusion or permeation of chemicals
in soils. When doing so, we treat the soil as having a constant porosity. In reality,
there are channels or “macroporous” areas formed by burrowing animals and
decayed roots, and these enable water and air to flow rapidly through the soil,
bypassing the more tightly packed soil matrix. This phenomenon is very difficult to
address when compiling models of transport in soils and is the source of considerable
frustration to soil scientists.
Most soils are, of course, covered with vegetation, which stabilizes the soil and
prevents it from being eroded by wind or water action. Under dry conditions, with
poor vegetation cover, considerable quantities of soil can be eroded by wind action,
carrying with it sorbed chemicals. Sand dunes are an extreme example. In populated
regions, of more concern is the loss of soil in water runoff. This water often contains
very high concentrations of soil, perhaps as much as a volume fraction of 1 part per
thousand of solid material. This serves as a vehicle for the movement of chemicals,
especially agricultural chemicals such as pesticides, from the soils into water bodies
such as lakes.
In most areas, there is a net movement of water vertically from the surface soil to
greater depths into a pervious layer of rock or aquifer through which groundwater
CH04 Page 64 Monday, January 15, 2001 1:49 PM
flows. The quality of this groundwater has become of considerable concern recently,
especially to those who rely on wells for their water supply. This water tends to move
very slowly (i.e., at a velocity of metres per year) through the porous sub-surface strata.
If contaminated, it can take decades or even centuries to recover. Of particular concern
are regions in which chemical leachate from dumps or landfills has seeped into the
groundwater and has migrated some distance into rivers, wells, or lakes. It is quite
difficult and expensive to investigate, sample, and measure contaminant flow in ground-
water. It may not even be clear in which direction the water is flowing or how fast it
is flowing. Chemicals associated with groundwater generally move more slowly than
the velocity of the groundwater. They are retarded by sorption to the soil to an extent
expressed as a “retardation factor,” which is essentially the ratio of (a) the amount of
chemical that is sorbed to the solid matrix to (b) the amount that is in solution. Sorption
of organic chemicals is usually accomplished preferentially to organic matter; however,
clays also have considerable sorptive capacity, especially when dry. Polar, and espe-
cially ionic, substances may interact strongly with mineral matter. The characterization
of migration of chemicals in groundwater is difficult, and especially so when a chemical
is present in an non-aqueous phase, for example, as a bulk oil or emulsified oil phase.
Considerable effort has been devoted to understanding the fate of nonaqueous phase
liquids (NAPLs) such as oils, and dense NAPLs (DNAPLs) such as chlorinated sol-
vents that can sink in the aquifer and are very difficult to recover.
For illustrative purposes, we treat the soil as covering an area 1000 m × 300 m
× 15 cm deep, which is about the depth to which agricultural soils are plowed. This
yields a volume of 45,000 m3. This consists of about 50% solids, of which 4% is
organic matter content or 2% by mass organic carbon. The porosity of the soil, or
void space, is 50% and consists of 20% air and 30% water. Assuming a density of
the soil solids of 2400 kg/m3 and water of 1000 kg/m3 gives masses of 1200 kg
solids and 300 kg water per m3 (and a negligible 0.2 kg air), totaling 1500 kg,
corresponding to a bulk density of 1500 kg/m3. Rainwater falls on this soil at a rate
of 0.8 m per year, i.e., 0.8 m3/m2 year. Of this, perhaps 0.3 m evaporates, 0.3 m runs
off, and 0.2 m percolates to depths and contributes to groundwater flow. This results
in water flows of 90,000 m3/year by evaporation, 90,000 m3/year by runoff, and
60,000 m3/year by percolation to depths totaling 240,000 m3/year. With the runoff
is associated 90 m3/year of solids, i.e., an assumed high concentration of 0.1% by
volume. Again, it must be emphasized that these numbers are entirely illustrative.
This soil runoff rate of 90 m3/year does not correspond to the deposition rate of
700 m3/year, partly because of the contribution of organic matter generated in the
water column, but mainly because of the low ratio of soil area to water area.
species to another, and ultimately to humans. Plants play a critical role in stabilizing
soils and in inducing water movement from soil to the atmosphere, and they may
serve as collectors and recipients of toxic chemicals deposited or absorbed from the
atmosphere. They can also degrade certain chemicals and increase the level of
microbial activity in the root zone, thus increasing the degradation rate in the soil.
Amounts of vegetation, in terms of quantity of biomass per square metre, vary
enormously from near zero in deserts to massive quantities that greatly exceed
accessible soil volumes in tropical rain forests. They also vary seasonally. If it is
desired to include vegetation, a typical “depth” of plant biomass might be 1 cm.
This, of course, consists mainly of water, cellulose, starch, and ligneous material.
There is little doubt that future, more sophisticated models will include chemical
partitioning behavior into plants. But at the present state of the art, it is convenient
(and rather unsatisfactory) to regard the plants as having a volume of 3000 m3,
containing the equivalent of 1% lipid-like material and 50% water.
We ignore vegetation in the simple four-compartment model, treating the soil as
only a simple solid phase.
4.6 SUMMARY
These evaluative volumes, areas, compositions, and flow rates are summarized
in Table 4.2. From them is derived a simple four-compartment version. Also sug-
gested is an alternative environment that is more terrestrial and less aquatic, and it
reflects more faithfully a typical political jurisdiction. It is emphasized again that
the quantities are purely illustrative, and site-specific values may be quite different.
All that is needed at this stage is a reasonable basis for calculation.
Scientists who have devoted their lives to studying the intricacies of the structure,
composition, and processes of the atmosphere, hydrosphere, or lithosphere will
undoubtedly be offended at the simplistic approach taken in this chapter. The envi-
ronment is very complex, and it is essential to probe the fine detail present in its
many compartments. But, if we are to attempt broad calculations of multimedia
chemical fate, we must suppress much of the media-specific detail. When the broad
patterns of chemical behavior are established, it may be appropriate to revisit the
media that are important for that chemical and focus on detailed behavior in a specific
medium. At that time, a more detailed and site-specific description of the medium
of interest will be justified and required.
Our philosophy is that the model should be only as complex as is required to
answer the immediate question, not every question that could be asked. As questions
are answered, new questions will surface and new, more complex models can be
developed to answer these questions.
Select a region with which you are familiar; for example, a county, watershed,
state, or province. Calculate the volumes of air to a height of 1000 m; soil to a depth
CH04 Page 66 Monday, January 15, 2001 1:49 PM
C. Regional, 100,000 km2 environment as used in the EQC model of Mackay et al.
(1996b)
Volume (m3) Area (m2) Composition
Air 1014 100 × 109
Aerosols 2000 – (2 × 10–11 vol frn)
Water 2 × 10 11 10 × 10 9
of 10 cm; water and bottom sediment to a depth of 3 cm, and vegetation. Obtain
data on average temperature, rain rate, water flows, and wind velocity, and calculate
air and water residence times. Attempt to obtain information on typical concentra-
tions of aerosols, suspended solids in water, and the organic carbon contents of soils,
bottom, and suspended sediments. Prepare a summary table of these data similar to
Table 4.2.
These basic environmental data can be used in subsequent assessments of the
fate of chemicals in this region.
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CHAPTER 5
Phase Equilibrium
5.1 INTRODUCTION
There are two distinct tasks that must be addressed when predicting equilibrium
partitioning of chemicals in the environment. First, we must fully understand how
chemicals behave under ideal, laboratory conditions of controlled temperature and
well defined, pure phases. This is the task of physical chemistry. Second is the
translation of these partitioning data into the more complex and less defined condi-
tions of the environment where phases vary in composition and properties.
In both cases, we are concerned with the equilibrium distribution of a chemical
between phases as illustrated in the simple two-compartment system of Figure 5.1.
A small volume of nonaqueous phase (e.g., a particle of organic or mineral matter,
a fish, or an air bubble) is introduced into water that contains a dissolved chemical
such as benzene. There is a tendency for some of the benzene to migrate into this
new phase and establish a concentration that is some multiple of that in the water.
In the case of organic particles, the multiple may be 100 or, if the phase is air, the
multiple may be only 0.2. Equilibrium becomes established in hours or days between
the benzene dissolved in the water and the benzene in, or on, the nonaqueous phase.
Analytical measurements may give the total or average concentration that includes
the nonaqueous phase and may differ considerably from the actual dissolved water
concentration. The phase may subsequently settle to the lake bottom or rise to the
surface, conveying benzene with it. Clearly, it is essential to establish the capability
of calculating these concentrations and thus the fractions of the total amount of
benzene that remain in the water, and enter the second phase. In some cases, 95%
of the benzene may migrate into the phase, and in others only 5%. These systems
will behave quite differently.
The aim is to answer the question, “Given a concentration in one phase, what
will be the concentration in another phase that has been in contact with it long
enough to achieve equilibrium?” This task is part of the science of thermodynamics
69
CH05 Page 70 Monday, January 15, 2001 1:49 PM
that is fully described in several excellent texts such as those of Denbigh (1966),
Van Ness and Abbott (1982), Prausnitz et al. (1969), and for aquatic environmental
systems by Stumm and Morgan (1981) and Pankow (1991). It is assumed here that
the reader is familiar with the general principles of thermodynamics; therefore, no
attempt is made to derive all the equations. The aim is rather to extract from the
science of thermodynamics those parts that are pertinent to environmental chemical
equilibria and explain their source, significance, and applications.
CH05 Page 71 Monday, January 15, 2001 1:49 PM
PHASE EQUILIBRIUM 71
PHASE EQUILIBRIUM 73
5.1.3 Fugacity
Another useful quantity is the ratio of fugacity to some reference fugacity such
as the vapor pressure of liquid benzene. This is a dimensionless quantity and is
termed activity. Activity can also be used as an equilibrium criterion. This proves
to be preferable for substances such as ions, metals, or polymers that do not appre-
ciably evaporate and thus cannot establish vapor phase concentrations and partial
pressures.
Our task, then, is to start with a concentration of solute chemical in one phase,
from this deduce the chemical potential, fugacity, or activity, argue that these equi-
librium criteria will be equal in the other phase, and then calculate the corresponding
concentration in the second phase. We therefore require recipes for deducing C from
f and vice versa. This approach is depicted at the bottom of Figure 5.1.
The partition coefficient approach contains the inherent assumption that, what-
ever the factors are that are used to convert C1 to f1 and C2 to f2, the ratio of these
factors is constant over the range of concentration of interest. Thus, it is not actually
necessary to calculate the fugacities; their use is sidestepped. In the fugacity
approach, no such assumption is made, and the individual calculations are under-
taken. We can illustrate these approaches with an example.
Therefore,
1. Fugacity approach
Using techniques devised later, we find that, for water under these conditions,
Clearly, the problem is to determine the conversion factors Z2 and Z1, or K21,
which is their ratio. Care must be taken to avoid confusing K21 with its reciprocal
K12 or C1/C2, which in this case has a value of 5.
We therefore face the task of developing methods of estimating Z values that
relate concentration and fugacity, and partition coefficients that are ratios of Z values.
The theoretical foundations are set out in Section 5.3 and result in a set of working
equations applicable to the air-water-octanol system. The three solubilities (or
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PHASE EQUILIBRIUM 75
pseudo-solubilities) in these media and the three partition coefficients are then
discussed in more detail in Section 5.4. Armed with this knowledge we then address
how this “laboratory” information can be applied to environmental media such as
soils and aerosols.
ln P = A – B/T
lnP = A – B/(T + C)
Care must be taken to check the units of P, whether base e or base 10 logs are used,
and whether T is K or °C in the Antoine equation. Several other equations are used
as reviewed by Reid et al. (1987).
Correlations also exist for the vapor pressure of solids and supercooled liquids.
Of particular environmental interest is the relationship between these vapor pres-
sures, which can be used to calculate the unmeasurable supercooled liquid vapor
pressure from that of the solid. The reason for this is that, when a solid such as
naphthalene is present in a dilute, subsaturated, dissolved, or sorbed state at 25°C,
the molecules do not encounter each other with sufficient frequency to form a
crystal. Thus, the low-energy crystal state is not accessible. The molecule thus
behaves as if it were a liquid at 25°C. It “thinks” it is a liquid, because it has no
CH05 Page 77 Monday, January 15, 2001 1:49 PM
PHASE EQUILIBRIUM 77
access to information about the stability of the crystalline state, i.e., does not
“know” its melting point. As a result, it behaves in a manner corresponding to the
liquid vapor pressure. A similar phenomenon occurs above the critical point where
a gas such as oxygen, when in solution in water, behaves as if it were a liquid at
25°C, not a gas. No liquid vapor pressure can be measured for either naphthalene
or oxygen at 25°C; it can only be calculated. Later, we term this liquid vapor
pressure the reference fugacity. We may need to know this fictitious vapor pressure
for several reasons.
The ratio of the solid vapor pressure to the supercooled liquid vapor pressure is
termed the fugacity ratio, F. To estimate F, we need to know how much energy is
involved in the solid-liquid transition, i.e., the enthalpy of melting or fusion. The
rigorous equation for estimating F at temperature T(K) is (Prausnitz et al., 1986)
where ∆S (J/mol K) is the entropy of fusion at the melting point TM (K), ∆CP (J/mol
K) is the difference in heat capacities between the solid and liquid substances, and
R is the gas constant. The heat capacity terms are usually small, and they tend to
cancel, so the equation can be simplified to
ln F = –(∆S/R)(TM/T – 1)
The group ∆S/R is often assigned a value of 56/8.314 or 6.79. Thus, F is approxi-
mated as
F = exp[–6.79(TM/T – 1)]
Equations are needed to deduce the fugacity of a solute in solution from its
concentration. We first treat nonionizing substances that retain their structure when
in solution. It transpires that, at low concentrations, a substance’s fugacity and
concentration are linearly related, i.e., fugacity is proportional to concentration. This
suggests using a relationship of the following form:
C = Zf
f = y φ PT
Here, n is the total number of moles present, R is the gas constant, V is volume
(m3), and T is absolute temperature (K). Now the concentration of the solute in the
gas phase CA will be yn/V or P/RT mol/m3.
PHASE EQUILIBRIUM 79
and partial pressure are not equal, and (2) there is some conceptual difficulty about
referring to a “partial pressure of DDT in a fish” when there is no vapor present for
a pressure to be present in—even partially.
The fugacity equation (Prausnitz et al., 1986) for solute i in solution is given in
terms of mole fraction xi activity coefficient γi and reference fugacity fR on a Raoult’s
law basis.
fi = xiγifR
Now, xi, the mole fraction of solute, can be converted to concentration C mol/m3
using molar volumes v (m3/mol), amounts n (mol), and volumes V (m3) of solute
(subscript i) and solution (subscript w for water as an example). Assuming that the
solute concentration is small, i.e., Vi<<VW, we can write
But
VW = nwvw
and
Thus,
Thus,
fi = CivwγifR
and
Ci = (1/vwγifR)fi = Zwf
Hence,
ZW = (1/vWγifR)
The reference fugacity fR is by definition the fugacity that the solute will have
(or tend to) when in the pure liquid state when xi is 1.0 and γi is also (by definition)
CH05 Page 80 Monday, January 15, 2001 1:49 PM
1.0. This, then, is the fugacity or vapor pressure of pure liquid solute at the temper-
ature (and strictly the pressure) of the system.
The activity coefficient γ is defined here on a “Raoult’s law” basis such that γ is
1.0 when x is 1.0. In most cases, γ values exceed 1.0 and, for hydrophobic chemicals,
values may be in the millions.
An alternative convention, which we do not use here, is to define γ on a Henry’s
law basis such that γ is 1.0 when x is zero.
The activity coefficient is thus a very important quantity. It can be viewed as the
ratio of the activity or fugacity of the solute to the activity or fugacity that the solute
would have if it were in a solution consisting entirely of its own kind. It depends
on the concentration of the solute with a dependence of the type
where γO is the activity coefficient at infinite dilution, i.e., when x the mole fraction
approaches zero.
Another useful way of viewing activity coefficients is that they can be regarded
as an inverse expression of solubility, i.e., an insolubility. A solute that is sparingly
soluble in a solvent will have a high activity coefficient, an example being hexane
in water. For a liquid solute such as hexane, at the solubility limit, when excess pure
hexane is present, the fugacity equals the reference fugacity fR and
fi = fR = xiγifR
Therefore,
xi = 1/γi or γi = 1/xi
The activity coefficient is thus the reciprocal of the solubility when expressed as a
mole fraction. For solids at saturation, fi is the fugacity of the pure solid fS. Thus,
fS = xiγifR
and
xi = (fS/fR)/γi = F/γi
where F is the fugacity ratio discussed earlier. Solid solutes of high melting point
thus tend to have low solubilities, because F is small.
It is more common to express solubilities in units such as g/m3. Under dilute
conditions, the solubility Si mol/m3 is xi/vS, where vS is the molar volume of the
solution (m3/mol) and approaches the molar volume of the solvent. Si is thus 1/γivS
for liquids and F /γivS for solids. In the gas phase, the solubility is essentially the
vapor pressure in disguise, i.e.,
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PHASE EQUILIBRIUM 81
Si = n/V = PS/RT
Ka = H+ A–/HA
where
PHASE EQUILIBRIUM 83
If we have two immiscible phases or media (e.g., air and water or octanol and
water), we can conduct experiments by shaking volumes of both phases with a small
amount of solute such as benzene to achieve equilibrium, then measure the concen-
trations and plot the results as was shown in Figure 5.1. It is preferable to use
identical concentration units in each phase of amount per unit volume but, when
one phase is solid, it may be more convenient to express concentration in units such
as amounts per unit mass (e.g., µg/g) to avoid estimating phase densities. The plot
of the concentration data is often linear at low concentrations; therefore, we can write
C2/C1 = K21
and the slope of the line is K21. Some nonlinear systems are considered later. Now,
since C2 is Z2f2 and C1 is Z1f1, and at equilibrium f1 equals f2, it follows that K21 is
Z2/Z1. A Z value can be regarded as “half” a partition coefficient. If we know Z for
one phase (e.g., Z1 as well as K21), we can deduce the value of Z2 as K21Z1. This
proves to be a convenient method of estimating Z values.
The line may extend until some solubility limit or “saturation” is reached. In
water, this is the aqueous solubility, but, for some substances such as lower alcohols,
there is no “solubility,” because the solute is miscible with water. In air, the “solu-
bility” is related to the vapor pressure of the pure solute, which is the maximum
partial pressure that the solute can achieve in the air phase.
Partition coefficients are widely available and used for systems of air-water,
aerosol-air, octanol-water, lipid-water, fat-water, hexane-water, “organic carbon”-
water, and various minerals with water.
Applying the theory that was developed earlier and noting that, at equilibrium,
the solute fugacities will be equal in both phases, we can define partition coefficients
for air-liquid and liquid-liquid systems.
For air-water as an example at a total atmospheric pressure PT ,
f = xiγifR = yiPT = Pi
Thus,
yi/xi = γifR/PT
In terms of solubilities, SiA and SiW, KAW is simply SiA/SiW, the ratio of the two
solubilities.
The pioneering work on air-water partitioning was done by Henry, who measured
Pi as a function of xi and discovered that the solubility in water was proportional to
the partial pressure Pi. The proportionality constant H´ is γifR and has units of pressure
(Pa). Interestingly, for super-critical gases such as oxygen, fR cannot be measured,
but γifR can be measured. If concentration is expressed as mol/m3, i.e., Ci instead of
mole fraction xi, another and more convenient Henry’s law constant H can be defined
as Pi/Ci and is γivWfR. KAW is then obviously H/RT, and it is also ZA/ZW . Note that
H is also PSL/SiW and is 1/ZW , as was shown earlier. KAW is sometimes (wrongly)
referred to as a Henry’s law constant. Atmospheric scientists, who are concerned
with partitioning from air to water (e.g., into rain) use KWA, the reciprocal of KAW ,
and often refer to it as a Henry’s law constant. Extreme care thus must be taken
when using reported values of Henry’s law constants because of these different
definitions.
For a liquid solute in a liquid-liquid system such as octanol-water,
xiO/xiW = γiW/γiO
and
If the solute is solid the same final equation applies because F, like fR, cancels.
Because vW and vO are relatively constant, the variation in KOW between solutes
is a reflection of variation in the ratio of activity coefficients γiW/γiO. Hydrophobic
substances such as DDT have very large values of γiW and low solubilities in water.
The solubility in octanol is usually fairly constant for organic solutes, thus KOW is
approximately inversely proportional to SiW . Numerous correlations have been pro-
posed between log KOW and log SiW , which are based on this fundamental relation-
ship.
Finally, for completeness, the octanol-air partition coefficient can be shown to be
where γi applies to the octanol phase. It can be shown that ZO is 1/γi vO PSL and that
KOA is ZO/ZA.
Measurements of solubilities and partition coefficients are subject to error, as is
evident by examining the range of values reported in handbooks. An attractive
approach is to measure the three partition coefficients, KAW , KOW , and KOA, and
CH05 Page 85 Monday, January 15, 2001 1:49 PM
PHASE EQUILIBRIUM 85
perform a consistency check that, for example, KOA is KOW/KAW. Further checks are
possible if solubilities can be measured to confirm that KAW is SA/SW or PS/SWRT.
These checks are also useful for assessing the “reasonableness” of data. For example,
if an aqueous solubility SW is reported as 1 part per million or 1 g/m3 or (say)
10–2 mol/m3, and KOW is reported to be 107, then the solubility in octanol must be
SWKOW or 100,000 mol/m3. Octanol has a solubility in itself, i.e., a density of about
820 kg/m3 or 6300 mol/m3. It is inconceivable that the solubility of the solute in
octanol exceeds the solubility of octanol in octanol by a factor of 100,000/6300 or
16; therefore, either SW or KOW or both are likely erroneous.
The relationships between the three solubilities and the partition coefficients are
shown in Figure 5.3. Two points worthy of note.
There are numerous correlations for quantities such as KAW, KOW, SW, SA as a
function of molecular structure and properties. They are generally derived indepen-
dently, so it is possible to estimate SW, SA, and KAW and obtain inconsistent results,
i.e., KAW will not equal SA/SW. It is preferable, in principle, to correlate SA, SW , and
SO independently and use the values to estimate KAW, KOW , and KOA. There is then
no possible inconsistency. It must be easier to correlate S (which depends on
interactions in only one phase) than K (which depends on interactions in two phases).
Finally, all activity coefficients, solubilities, and partition coefficients are tem-
perature dependent.
Figure 5.3 Illustration of the relationships between the three solubilities, CA, CW, and CO, and
the three partition coefficients, KAW, KOW, and KOA, with values for four substances.
Note the wide substance variation in concentrations corresponding to unit con-
centration in the air phase.
CH05 Page 86 Monday, January 15, 2001 1:49 PM
The temperature coefficient is the enthalpy of phase transfer, e.g., pure solute to
solution for solubility or from solution to solution for partition coefficients. The
enthalpies must be consistent around the cycle air-water-octanol such that their sum
is zero. This provides another consistency check. It should be noted that the enthalpy
change refers to the solubility or partition coefficient variation when expressed in
mole fractions, not mol/m3 concentrations. This is particularly important for parti-
tioning to air, where a temperature increase causes a density decrease, thus C or S
will fall while x remains constant. For details of the merits of applying the “three
solubility” approach, the reader is referred to Cole and Mackay (2000). We discuss
these partition coefficients individually in more detail in the following sections.
The nature of air-water partition coefficients or Henry’s law constants has been
reviewed by Mackay and Shiu (1981), and estimation methods have been described
by Mackay et al. (2000) and Baum (1997), and only a brief summary is given here.
Several group contribution and bond contribution methods have been developed,
and estimation methods are available from websites such as the EPIWIN programs
of the Syracuse Research Corporation site at www.syrres.com. As was discussed
above, the simplest method of estimating Henry’s law constants of organic solutes
is as a ratio of vapor pressure to water solubility. It must be recognized that this
contains the inherent assumption that water is not very soluble in the organic
material, because the vapor pressure that is used is that of the pure substance
(normally the pure liquid) whereas, in the case of solubility of a liquid such as
benzene in water, the solubility is not actually that of pure benzene but is inevitably
of benzene saturated with water. When the solubility of water in a liquid exceeds a
few percent, this assumption may break down, and it is unwise to use this relation-
ship. If a solute is miscible with water (e.g., ethanol), it is preferable to determine
the Henry’s law constant directly; that is, by measuring air and water concentrations
at equilibrium. This can be done by various techniques, e.g., the EPICS method
described by Gossett (1987) or a continuous stripping technique described by
Mackay et al. (1979). A desirable strategy is to measure vapor pressure PS, solubility
CS, and H or KAW and perform an internal consistency check that H is indeed PS/CS
or close to it. KAW is, of course, ZA/ZW.
Care must be taken when calculating Henry’s law constants to ensure that the
vapor pressures and solubilities apply to the same temperature and to the same phase.
In some cases, reported vapor pressures are estimated by extrapolation from higher
temperatures. They may be of a liquid or subcooled liquid, whereas the solubility
is that of a solid. As was discussed earlier, subcooled conditions are not experimen-
tally accessible but prove to be useful for theoretical purposes.
Henry’s law constants vary over many orders of magnitude, tending to be high
for substances such as the alkanes (which have high vapor pressures, low boiling
points, and low solubilities) and very low for substances such as alcohols (which
have a high solubility in water and a low vapor pressure). There is a common
misconception that substances that are “involatile,” such as DDT, will have a low
Henry’s law constant. This is not necessarily the case, because these substances also
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PHASE EQUILIBRIUM 87
have very low solubilities in the water, i.e., they are very hydrophobic; thus, their
low vapor pressure is offset by their very low water solubility, and they have relatively
large Henry’s law constants. They may thus partition appreciably from water into
the atmosphere through evaporation from rivers and lakes.
The solubility and activity of a solute in water are affected by the presence of
electrolytes and other co-solvents; thus, the Henry’s law constant is also affected.
The magnitude of the effect is discussed later in Section 5.4.5.
Deduce H and KAW for benzene, DDT, and phenol given the following data at
25°C:
In each case, the solubility CS in mol/m3 is the solubility in g/m3 divided by the
molar mass, e.g., 1780/78 or 22.8 mol/m3 for benzene. H is then PS/CS or 556 Pa
m3/mol for benzene. KAW is H/RT or 556/(8.314 × 298) or 0.22.
H KAW
benzene 556 0.22
DDT 1.29 5.2 × 10–4
phenol 0.050 2 × 10–5
Note that these substances have very different H and KAW values because of their
solubility and vapor pressure differences. The vapor pressure of DDT is about 600
million times less than that of benzene, but H is only 400 times less, because of
DDT’s very low water solubility. Phenol has a much higher vapor pressure than
DDT, but it has a much lower H and KAW. Benzene tends to evaporate appreciably
from water into air, and DDT less so but still to a significant extent, while phenol
does not evaporate significantly. Inherent in this calculation for phenol is the assump-
tion that it does not ionize appreciably.
(1982), Baum (1997) and Leo (2000). Extensive databases are also available as
reviewed by Baum (1997). Octanol was selected because it has a similar carbon to
oxygen ratio as lipids, is readily available in pure form, and is only sparingly soluble
in water (4.5 mol/m3). The solubility of water in octanol of 2300 mol/m3, however,
is quite large (Baum, 1997). The molar volumes of these phases are 18 × 10–6 m3/mol
and 120 × 10–6 m3/mol, a ratio of 0.15. It follows that KOW is 0.15 γW/γO.
KOW is a measure of hydrophobicity, i.e., the tendency of a chemical to “hate”
or partition out of water. As was discussed earlier, it can be viewed as a ratio of
solubilities in octanol and water but, in most cases of liquid chemicals, there is no
real solubility, because octanol and the liquid are miscible. The “solubility” of
organic chemicals in octanol tends to be fairly constant in the range 200 to 2000
mol/m3, thus variation in KOW between chemicals is primarily due to variation in
water solubility. It is therefore misleading to assert that KOW describes lipophilicity
or “love for lipids,” because most organic chemicals “love” lipids equally, but they
“hate” water quite differently. Viewed in terms of Z values, KOW is ZO/ZW . ZO is
(relatively) constant for organic chemicals; however, ZW varies greatly and is very
small (relatively) for hydrophobic substances.
Because KOW varies over such a large range, from approximately 0.1 to 107, it
is common to express it as log KOW. It is a disastrous mistake to use log KOW in a
calculation when KOW should be used!
KOW is usually measured by equilibrating layers of water and octanol containing
the solute of interest at subsaturation conditions and analyzing both phases. If KOW
is high, the concentration in water is necessarily low, and even a small quantity of
emulsified octanol in the aqueous phase can significantly increase the apparent
concentration. A “slow stirring” method is usually adopted to avoid emulsion for-
mation. An alternative is to use a generator column in which water is flowed over
a packing containing octanol and the dissolved chemical.
PHASE EQUILIBRIUM 89
(2000) and Baum (1997). Extensive databases are available, for example, the hand-
books by Mackay et al. (2000), which also give details of methods of experimental
determination.
It is important to appreciate that solubility in water is affected by temperature
and the presence of electrolytes and other solutes in solution. It is often convenient
to increase the solubility of a sparingly soluble organic substance by addition of a
cosolvent to the water. Methanol and acetone are common cosolvents. To a first
approximation, a “log-linear” relationship applies in that, if the solubility in water
is SW and that in pure cosolvent is SC , then the solubility in a mixture SM is given by
There are relatively few data on this solubility, and for many substances, espe-
cially liquids, the low activity coefficients render the solute-octanol system miscible;
thus, no solubility is measurable. Pinsuwan and Yalkowsky (1995) have reviewed
available solubility data and the relationships between KOW and solubilities in octanol
and water.
The fugacity of a pure solute is its vapor pressure PS, and its “concentration” is
the reciprocal of its molar volume vS (m3/mol) (typically, 10–4 m3/mol). Thus,
and
ZP = 1/PS vS
CH05 Page 90 Monday, January 15, 2001 1:49 PM
Chemicals tend to adsorb from air or water to the surface of solids. An extensive
literature exists on this subject as reviewed in texts in chemistry and environmental
processes. A good review with environmental applications is given by Valsaraj (1995)
in which the fundamental Gibbs equation is developed into the commonly used
adsorption isotherms. These isotherms relate concentration at the surface to concen-
tration in the bulk phase. Examples are the Langmuir, BET, and Freudlich isotherms.
Generally, a linear isotherm applies at low concentrations as are usually encountered
in the environment in relatively uncontaminated situations. Nonlinear behavior
occurs at high concentrations in badly contaminated systems and in process equip-
ment such as carbon adsorption units.
It is often not realized that partitioning also occurs at the air-water interface,
where an excess concentration may exist. This is exploited in the solvent sublation
process for removing solutes from water using fine bubbles.
If an area of the surface is known, a surface concentration in units of mol/m2
can be calculated, but more commonly the concentration is given in mol/mass of
sorbent, which is essentially the product of the surface concentration and a specific
area expressed in m2 surface per unit mass of sorbent. Solids such as activated carbon
have very high specific areas and are thus effective sorbents. Partitioning to the air-
water interface can become very important when the area of that interface is large
compared to the associated volume of air or water. This occurs in fog droplets and
snow where the ratio of area to water volume is very large, or in fine bubbles where
the ratio of area to air volume is large. These ratios are (6/diameter) m2/m3.
A Z value can be defined on an area basis (mol/m2 Pa) or for the bulk phase by
including the specific area.
Schwarzenbach et al. (1993) have reviewed mechanisms of sorption and have
summarized reported data. This partitioning is important for ionizing substances
but less important for nonpolar compounds, which sorb more strongly to organic
matter.
CH05 Page 91 Monday, January 15, 2001 1:49 PM
PHASE EQUILIBRIUM 91
This and other correlations have been reviewed and discussed by Veith et al. (1983),
Kaiser (1984, 1987), Karcher and Devillers (1990), and Abernethy et al. (1986,
1980). The fundamental relationship expressed by this correlation is best explained
by an example.
Consider two chemicals of log KOW 3 and 5. The LC50 values will be 182 and
3.3 µmol/L, a factor of 55 different. If the target site is similar to octanol in solvent
properties, and equilibrium is reached, then the concentrations at the target site will
be the product LC50 × KOW or 182,000 and 330,000 µmol/L, only a difference of a
factor of 1.8. The chemical of lower KOW appears to be less toxic (it has a higher
LC50) when viewed from the point of view of water concentration. When viewed
from the target site concentration, it is slightly more toxic. The chemicals in the
correlation display similar toxicities when evaluated from the target site concentra-
tions. The correlation therefore expresses two processes, partitioning and toxicity,
with most of the chemical-to-chemical variation being caused by partitioning dif-
ference. Such chemicals are referred to as narcotics in which the effect seems to be
induced by high lipid concentrations.
5.4.10 Summary
The key properties of a pure substance for our purposes are its vapor pressure
(i.e., its solubility in air), its solubility in water, its solubility in octanol, and the
three partition coefficients KAW , KOW , and KOA. The magnitudes of these quantities
are controlled by vapor pressure and activity coefficients.
92
CH05 Page 92 Monday, January 15, 2001 1:49 PM
Figure 5.4 Illustration of quantitative structure property relationships for benzene and the chlorobenzenes showing the systematic changes in properties
with chlorine substitution.
MULTIMEDIA ENVIRONMENTAL MODELS AND FUGACITY
CH05 Page 93 Monday, January 15, 2001 1:49 PM
PHASE EQUILIBRIUM 93
We can also relate equilibrium concentrations in these phases using the three Z
values and fugacity. The partition coefficients are simply the ratio of the respective
Z values; e.g., KAW is ZA/ZW. The use of Z values at this stage brings little benefit,
but they become very useful when we calculate partitioning to environmental media.
We use ZA, ZW , and ZO to calculate Z in phases such as soils, sediments, fish, and
aerosol particles, and it proves useful to have ZP as a reference point when examining
the magnitude of Z values. It is enlightening to calculate all the physical chemical
properties of a solid and a liquid substance as shown in the following example.
Benzene
5.5.1 Introduction
Our aim is now to use the physical chemical data to predict how a chemical will
partition in the environment. Information on air-water-octanol partitioning is invalu-
able and can be used directly in the case of air and pure water, but the challenge
remains of treating other media such as soils, sediments, vegetation, animals, and
fish. The general strategy is to relate partition coefficients involving these media to
partitioning involving octanol. We thus, for example, seek relationships between
KOW and soil-water or fish-water partitioning.
KP = y KOC
PHASE EQUILIBRIUM 95
variety of chemicals show that KOC is related to KOW as discussed above. KOW is
dimensionless, thus the constant 0.41 has dimensions of L/kg. Care must be taken
to use consistent units in these calculations. For example, if the water concentration
has units of mol/m3, and KP is applied, the soil concentration will be in mol/Mg,
i.e., moles per 106 grams. The usual units used are mg/L in water and mg/kg in soil.
Units of either mass (g) or amount (mol) of solute can be used, but they must be
consistent in both water and soil.
The relationship between KOW and KOC has been the subject of considerable
investigation, and it appears to be variable. For example, DiToro (1985) has sug-
gested that, for suspended matter in water, KOC approximately equals KOW. Other
workers, notably Gauthier et al. (1987), have shown that the sorbing quality of the
organic carbon varies and appears to be related to its aromatic content as revealed
by NMR analysis.
Gawlik et al. (1997) have recently reviewed some 170 correlations between KOC
and KOW, solubility in water, liquid chromatographic retention time, and various
molecular descriptors. They could not recommend a single correlation as being
applicable to all substances. Seth et al. (1999) analyzed these data and suggested
that KOC is best approximated as 0.35 KOW (a coefficient slightly lower than Karick-
hoff’s 0.41) but that the variability is up to a factor of 2.5 in either direction. It is
thus expected that, depending on the nature of the organic carbon, KOC can be as
high as 0.9 KOW and as low as 0.14 KOW. Values outside this range may occur because
of unusual combinations of chemical and organic matter. Doucette (2000) has given
a very comprehensive review of this issue, and Baum (1997) has reviewed estimation
methods.
In summary, Z values can be calculated for soils and sediments containing
organic carbon of 0.35 ZOy(ρ/1000) or 0.41 ZOy(ρ/1000), where ZO is for octanol,
y is the organic carbon content, and ρ is the solid density, typically 2500 kg/m3. If
an organic matter content is given, the organic carbon content can be estimated as
56% of the organic matter content.
These relationships provide a very convenient method of calculating the extent
of sorption of chemicals between soils or sediments and water, provided that the
organic carbon content of the soil and the chemical’s octanol-water partition coef-
ficient are known. This is illustrated in Example 5.4 below.
Estimate the partition coefficient between a soil containing 0.02 g/g of organic
carbon for benzene (KOW of 135) and DDT (log KOW of 6.19), and the concentrations
in soil in equilibrium with water containing 0.001 g/m3, using the Karickhoff (0.41)
correlation.
KP and KOC have units of L/kg or m3/Mg, i.e., reciprocal density thus when
applying the equation below CS the soil concentration will have units of g/Mg or µg/g.
CH05 Page 96 Monday, January 15, 2001 1:49 PM
Note the much higher DDT concentration because of its hydrophobic character.
The concentrations in the organic carbon are CWKOC or 0.055 µg/g for benzene
and 635 µg/g for DDT. If octanol was exposed to this water, similar concentrations
of CWKOW or 0.135 µg/cm3 for benzene and 1549 µg/cm3 for DDT would be estab-
lished in the octanol.
This can be viewed as containing the assumption that fish is about 4.8% lipid.
Lipid contents vary considerably, and it is certain that there is some sorption to non-
lipid material, but it appears that, on average, the fish behaves as if it is about 4.8%
octanol by volume.
In summary, Z for lipids can be equated to ZO for octanol. For a phase such as
a fish of lipid volume fraction L, ZF is LZO.
PHASE EQUILIBRIUM 97
be coated with organic matter probably of bacterial origin. They thus may be shielded
from the solute by a layer of highly sorbing organic material. It is thus a fair (and
very convenient) assumption that the sorptive capacity of clays and other mineral
surfaces can be ignored. Notable exceptions to this are subsurface environments in
which there may be extremely low organic carbon contents and when the solute
ionizes. In such cases, the inherent sorptive capacity of the mineral matter may be
controlling.
One of the most difficult, and to some extent puzzling, sorption partition coef-
ficients is that between air and aerosol particles. These particles have very high
specific areas, i.e., area per unit volume. They also appear to be very effective
sorbents. The partition coefficient is normally measured experimentally by passing
a volume of air through a filter then measuring the concentrations before and after
filtration, and also the concentrations of the trapped particles. Relationships can then
be established between the ratio of gaseous to aerosol material and the concentration
of total suspended particulates (TSP).
There has been a profound change over the years in our appreciation of this
partitioning phenomenon. The pioneering work was done by Junge and later by
Pankow resulting in the Junge-Pankow equation, which takes the form
φ = C θ/(PSL + C θ)
where φ is the fraction on the aerosol, θ is the area of the aerosol per unit volume
of air, C is a constant, and PSL is the liquid vapor pressure. This is a Langmuir type
of equation, which implies that sorption is to a surface, and the maximum extent of
sorption is controlled by the available area.
Experimental data were better correlated by calculating KP. It can be shown that
φ = KP TSP/(1 + KP TSP)
from which
KP = φ/[TSP(1 – φ)]
The units of TSP are usually µg/m3, thus it is convenient to express KP in units
of m3/µg. KP is usually correlated against PSL for a series of structurally similar
chemicals using the relationship
where m and b are fitted constants, and m is usually close to –1 in value. Bidleman
and Harner (2000) list 21 such correlations and present a more detailed account of
this theory.
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KQA = 6 × 106/PSL
where vQ is the volume fraction of aerosol and is 10–12 TSP/(ρ/1000) when TSP has
units of µg/m3. TSP is typically about 30 µg/m3, plus or minus a factor of 5; thus,
vQ is about 20 × 10–12, plus or minus the same factor. Equipartitioning between air
and aerosol phases occurs when ϕ is 0.5 or KP·TSP and KQAvQ equals 1.0. This
implies a chemical with a KP of 0.03 m3/µg or KQAof 0.05 × 1012 and a vapor pressure
of about 10–4 Pa.
It is noteworthy that ZQ has a value of KQAZA or about (6 × 106/PSL)(4 × 10–4)
or 2400/PSL. This is comparable to ZP , the pure substance Z value of 1/v PSL, where
v is the chemical’s molar volume and is typically 100 cm3/mol or 10–4 m3/mol, giving
a ZP of about 10,000/PSL. This implies that the solute is behaving near-ideally in the
aerosol, i.e., the solubility in the aerosol is about 24% of the solubility of a substance
in itself. This casts doubt on the surface sorption model, since it seems a remarkable
coincidence that the area is such that it gives this near-ideal behavior. It further
suggests that ZQ may correlate well with ZO for octanol.
This was explored by Finizio et al. (1997), Bidleman and Harner (2000), and
Pankow (1998), leading ultimately to a suggestion that
where 820 kg/m3 is the density of octanol, and y is the fraction organic matter in
the aerosol, which is typically 0.2.
This reduces to
the use of KOA is advantageous, because it eliminates the need to deduce the fugacity
ratio, F, when calculating the subcooled liquid vapor pressure. It is also possible
that, for a series of chemicals, the activity coefficients in octanol and aerosol organic
matter are similar, or at least have a fairly constant ratio.
This approach is appealing, because it mimics the Karickhoff method of calcu-
lating soil-water partitioning, except that partitioning is now to air instead of water;
thus, KOA replaces KOW.
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PHASE EQUILIBRIUM 99
KQA = yKOA(ρ/1000)
In principle, partition coefficients can be defined and correlated for any phase
of environmental interest, usually with respect to the fluid media air or water. For
example, vegetation or foliage-air partition coefficients KFA can be measured and
correlated against KOA. Since KFA is ZF/ZA and KOA is ZO/ZA, the correlation is
essentially of ZF versus ZO. Hiatt (1999) has suggested that, for foliage, KFA is
approximately 0.01 KOA, implying that ZF is about 0.01 ZO, or foliage has a content
of octanol-equivalent material of 1%.
It is thus possible to estimate Z values for chemicals in any phase of environ-
mental interest, provided that the appropriate partition coefficient has been measured
or can be estimated. Figure 5.5 summarizes the relationships between fugacity,
concentrations, partition coefficients, and Z values.
The calculation of one phase concentration from another by the use of a simple
partition coefficient is the most direct and convenient method. Care must be taken
that the concentration units and the partition coefficient dimensions are consistent,
especially when dealing with solid phases. There may also be inadvertent inversion
of a partition coefficient, i.e., the use of K12 instead of K21. It is also possible to
deduce certain partition coefficients from others; e.g., if an air/water and a soil/water
partition coefficient are available, then the air/soil or soil/air partition coefficient can
be deduced as follows:
KAS = KAW/KSW
Figure 5.5 Relationships between Z values and partition coefficients and summary of Z value
definitions.
chemical M mol into this hypothetical environment, then we can argue that M must
be the sum of the concentration-volume products as follows:
It is thus possible to calculate the concentrations in each phase, the amounts in each
phase, and the percentages, and obtain a tentative picture of the behavior of this
chemical at equilibrium in an evaluative environment. This is best illustrated by an
example.
VA = 1000 VW = 20 VS = 10 VF = 0.05 m3
KAW = 0.2 KSW = 15 KFW = 20
Therefore,
from which the percentages are, respectively, 53.9, 5.4, 40.4, and 0.3.
It is clear that, in this system, benzene partitions primarily into air, mainly
because of the large volume of air. The concentration in the air is lower than in any
other phase; thus, we must discriminate between phases where the amount is large,
which depends on the product CV, and where the concentration is large. There is a
CH05 Page 102 Monday, January 15, 2001 1:49 PM
high concentration in the fish, but only a negligible fraction of the benzene is
associated with fish. Such calculations are invaluable, because they establish the
dominant medium into which the chemical is likely to partition, and they even give
approximate concentrations.
We now repeat these calculations using the fugacity concept and replacing C by
Zf. We know that Z will depend on
We have developed procedures by which Z values can be estimated for any given
environmental situation. Equilibrium concentrations can then be deduced using f as
a common criterion of equilibrium. We can repeat the previous partitioning example
using the fugacity method and demonstrate the equivalence of the two approaches
as before, but now applying the same fugacity to each phase.
Therefore,
from which each C can be calculated as Zf, and the amount in each phase m is CV
or VZf.
In general,
Using the data in Example 5.5, recalculate the distribution using fugacity and
assuming that ZA is 4 × 10–4 mol/m3 Pa.
ZW = ZA/KAW = 0.002
ZS = KSWZW = 0.03
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ZF = KFWZW = 0.04
= 10/0.742 = 13.48
heat content (J) = mass of phase (kg) × heat capacity (J/kg K) × temperature (K)
For example, water has a heat capacity of 4180 J/kg K, which is more familiar as
1 cal/g°C. We can rearrange this equation in terms of volumes instead of masses to
give
This new volumetric heat capacity for water is 4,180,000 J/m3 K. The use of mass
rather than volume in heat capacities is an “accident” resulting from the greater ease
and accuracy of mass measurements compared to volume measurements, and the
complication that volumes change on heating, while mass remains constant.
The equilibrium criterion used above is temperature (K), whereas we are con-
cerned with fugacity (Pa). The quantity that partitions above is heat (J), whereas we
are concerned with amount of matter (moles). Replacing K by Pa and J by mol leads
to the analogous fugacity equation,
heat capacity of 0.38 J/g°C requires absorption of only 0.38 J to cause the same rise
in temperature. Hydrogen gas has a large heat capacity of 14.3 J/g°C and thus
requires a great deal of heat to raise its temperature. These substances differ markedly
in their temperature response when heat is added. If 1000 J are added to equal masses
of 1 g of these substances, the copper becomes much hotter by 263°C (or 100/0.38),
while the water only heats up by 24°C (or 100/4.2) and the hydrogen by only 7°C
(or 100/14.3). Hydrogen and water can thus absorb or “soak up” larger quantities
of heat without becoming much hotter.
The fugacity capacity is similar. Phases of high Z (possibly sediments or fish)
are able to absorb a greater quantity of solute yet retain a low fugacity. It follows
that solutes will tend to partition into these high Z phases and build up a substantial
concentration yet retain a relatively low fugacity. Conversely, phases with low Z
values will tend to experience a large increase in f following absorption of a small
quantity of solute. A substance such as DDT is readily absorbed by fish and achieves
a high concentration at low fugacity. The Z value of DDT in fish is large. On the
other hand, DDT is not readily absorbed by water; indeed, it is hydrophobic or
“water hating.” Its Z value in water is very low.
This analogy between heat and fugacity capacity is perhaps best illustrated by
the following pair of numerically identical examples, the fugacity quantities being
given in parentheses.
Thus, the total will be the summation over the three phases, i.e.,
Thus,
Phase Z V VZ C = Zf VC %
Therefore,
Again, a large value of Z or C does not necessarily imply a large quantity. Quantity
is controlled by VZ. Concentration is controlled by Z.
• The volumes (m3) are denoted VA and VB, and usually VA is much greater than VB.
• The equilibrium concentrations are denoted CA and CB mol/m3.
• The dimensionless partition coefficient KBA is CB/CA.
• The total amount of solute M moles is distributed between the two phases.
where CT is the total concentration. It can be assumed that VT , the total volume is
approximately VA. Now,
CB = KBACA
Therefore,
Therefore,
where vB is the volume fraction of phase B and is approximately VB/VA. The fraction
dissolved (i.e., in the continuous phase) is
CH05 Page 107 Monday, January 15, 2001 1:49 PM
The key quantity is thus KBAvB or the product of the dimensionless partition coeffi-
cient and the volume fraction of the dispersed sorbing phase. When this product is
1.0, half the solute is in each state. When it is smaller than 1.0, most is dissolved,
and when it exceeds 1.0, more is sorbed. When the phase B is solid, it is usual to
express the concentration CB in units of moles or grams per unit mass of B in which
case KBA has units of volume/mass or reciprocal density. For example, it is common
to use mg/L for CA, mg/kg for CB, and L/kg for KP; then, with M in mg and VA in
L, then it can be shown that
where XB is the concentration of sorbent in kg/L. The units of the partition coefficient
KBA or KP and concentration of sorbent vB or XB do not matter as long as their
product is dimensionless and consistent, i.e., the amounts of sorbing phase, contin-
uous phase, and chemical are the same in the definition of both the partition coef-
ficient and the sorbent concentration.
Care must be taken when interpreting sorbed concentrations to ascertain if they
represent the amount of chemical per unit volume or mass of sorbent, or the per
unit volume of the environmental phase such as water.
The analogous fugacity equations are simply
ϕA = VAZA/(VAZA + VBZB)
ϕB = VBZB/(VAZA + VBZB)
VTZTf = ΣviZif
Thus,
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ZT = Σ(Vi/VT)Zi =ΣviZi
where vi is the volume fraction of each phase. The key point is that the component
Z values add in proportion to their volume fractions.
The use of bulk Z values helps to simplify calculations by reducing the number
of compartments, but it does assume that equilibrium exists within the bulk com-
partment.
An aquarium contains 10 m3 of water and 200 fish, each of volume 1 cm3. How
will 0.01 g (i.e., 10 mg) of benzene and the same mass of DDT partition between
water and fish, given that the fish are 5% lipids, and log KOW is 2.13 for benzene
and 6.19 for DDT?
KFW will be 0.05 KOW or 6.7 for benzene and 77440 for DDT.
CT is 0.001 g/m3 or 1 mg/m3 in both cases.
The fraction dissolved ϕ2 is 1/(1 + KFWvF), where vF is the volume fraction of fish,
i.e., 200 × 10–6/10 = 2 × 10–5.
For benzene, KFWvF is 0.00013.
For DDT, KFWvF is 1.55.
The fractions dissolved are 0.99987, essentially 1.0, for benzene and 0.39 for DDT.
The dissolved concentrations are thus 0.00099987 g/m3 or 0.99987 mg/m3 (benzene)
and 0.00039 g/m3 or 0.39 mg/m3 (DDT), and the sorbed concentrations (per m3 of
water) are 0.00013 mg/m3 and 0.61 mg/m3, respectively. The sorbed concentrations
per m3 of fish are 0.0067 g/m3 and 30 g/m3, respectively.
Example 5.10
Answer
When fugacities are calculated, it is advisable to check that the value deduced
is lower than the fugacity of the pure phase, i.e., the solid or liquid fugacity or, in
the case of gases, of atmospheric pressure. If these fugacities are exceeded, super-
saturation has occurred, a “maximum permissible fugacity” has been exceeded, and
the system will automatically “precipitate” a pure solute phase until the fugacity
drops to the saturation value. It is possible to calculate inadvertently and use (i.e.,
CH05 Page 109 Monday, January 15, 2001 1:49 PM
A problem arises when calculating values of the fugacity and fugacity capacity
of solutes that have a negligible or zero vapor pressure. Thermodynamically, the
problem is that of determining the reference fugacity. The practical problem may
be that no values of vapor pressure or air-water partition coefficients are published
or even exist. Examples are ionic substances, inorganic materials such as calcium
carbonate or silica and polymeric, or high-molecular-weight substances including
carbohydrates and proteins. Intuitively, no vapor pressure determination is needed
(or may be possible), because the substance does not partition into the atmosphere,
i.e., its “solubility” in air is effectively zero. Ironically, its air fugacity capacity can
still be calculated as (1/RT), but all the other (and the only useful) Z values cannot
be calculated, since H cannot be determined and indeed may be zero. Apparently,
the other Z values are infinite or at least are indeterminably large.
This difficulty is more apparent than real and is a consequence of the selection
of fugacity rather than activity as an equilibrium criterion. There are two remedies.
The first method, which is convenient but somewhat dishonest, is to assume a
fictitious and reasonable, but small, value for vapor pressure (such as 10–6 Pa) and
proceed through the calculations using this value. The result will be that Z for air
will be very small compared to the other phases, and negligible concentrations will
result in the air. It is obviously essential to recognize that these air concentrations
are fictitious and erroneous. The relative values of the other concentrations and Z
values will be correct, but the absolute fugacity will be meaningless.
The second method, which is less convenient but more honest, is to select a new
equilibrium criterion. We can illustrate this for air, water, and another phase(s) by
equating fugacities as follows:
A saturated solution thus has an activity of 1.0. A zero or near-zero vapor pressure
can be used to calculate Z for air as zero or near zero.
In some cases, we may have to go farther, because we are uncertain about the
solubility CS. The simple expedient is then to multiply through by CS to give a new
equilibrium criterion A as
We are now using the water concentration or the equivalent equilibrium water
concentration as the criterion of equilibrium. This has been termed the aquivalent
concentration (Mackay and Diamond, 1989) and can be used for metals in ionic
form when the solubility is meaningless.
The essential procedure is that, for most organic substances, Z is defined in air
as 1/RT, then all other Z values are deduced from it. In the “aquivalence” approach,
Z is arbitrarily set to 1.0 in water, and all other Z values are deduced from this basis
using partition coefficients. This approach is used in the EQC model for involatile
substances (Mackay et al., 1996).
concentrations are likely to be large and thus easier to determine accurately. When
monitoring for PCBs in lakes, it is thus common to sample sediment or fish rather
than water, since the expected concentrations in water are very low. Likewise, those
concerned with PCB behavior in the atmosphere may measure the PCBs on aerosols
or in rainfall containing aerosols, since concentrations are higher than in the air.
In general, when assessing the likely environmental behavior of a new chemical,
it is useful to calculate the various Z values and from them identify the larger ones,
since it is likely that the high Z compartments are the most important. It is no
coincidence that solutes such as halogenated hydrocarbons, about which there is
great public concern, have high Z values in humans!
It should be borne in mind that, when calculating the environmental behavior of
a solute, Z values are needed only for the phases of concern. For example, if no
atmospheric partitioning is considered, it is not necessary to know the air-water
partition coefficient or H. An arbitrary value of H can be used to define Z for water
and other phases, because H cancels. Intuitively, it is obvious that H, or vapor
pressure, play no role in influencing water-fish-sediment equilibria.
In summary, in this chapter we have introduced the concept of equilibrium
existing between phases and have shown that this concept is essentially dictated by
the laws of thermodynamics. Fortunately, we do not need to use or even understand
the thermodynamic equations on which equilibrium relationships are based. How-
ever, it is useful to use these relationships for purposes such as correlation of partition
coefficients. It transpires that there are two approaches that can be used to conduct
equilibrium calculations. First is to develop and use empirical correlations for par-
tition coefficients. Using these coefficients, it is possible to calculate the partitioning
of the chemical in a multimedia environment.
The second approach, which we prefer, is to use an equilibrium criterion such
as fugacity or, in the case of involatile chemicals, an aquivalent concentration. The
criterion can be related to concentration for each chemical and for each medium
using a proportionality constant or Z value. The Z value can be calculated from
fundamental equations or from partition coefficients. We have established recipes
for the various Z values in these media using information on the nature of the media
and the physical chemical properties of the substance of interest. This enables us to
undertake simple multimedia partitioning calculations.
Table 5.1 Table 5.1 Summary of Definitions of Z Values and Equations Used in Level
I Calculations
Definitions of Z values
ZA = 1/RT
ZO = ZW KOW (octanol)
ZQ = ZAKQA (aerosols)
Note that the Z value of a bulk phase consisting of continuous and dispersed material, e.g.,
water plus suspended solids, is given by the volume fraction weighted Z values.
ZT = Σ viZi
Fugacity equation
f = M/ΣViZi
The concepts presented in this chapter are best grasped by working through
examples. A chemical can be selected from those listed in Chapter 3 and the
properties used with assumed media volumes to deduce the distribution of a defined
quantity of the substance between these media.
Select two nonionizing substances from Table 3.5, one a liquid and the other a
solid, preferably with a melting point exceeding 100°C, and with log KOW in the
range 3 to 6.
CH05 Page 116 Monday, January 15, 2001 1:49 PM
Assume KOC to be 0.41 KOW and all solid densities to be 2000 kg/m3.
Using Fugacity Form 2, calculate the fugacity, concentrations, and distribution
of 100 kg of each chemical in an environment consisting of these volumes:
air 109 m3
water 106 m3
soil solids 104 m3
suspended sediment solids 50 m3
bottom sediment solids 103 m3
aerosols 1 m3
fish 5 m3
Alternatively, use the environment that was deduced in the concluding example from
Chapter 4.
Write a short account of the partitioning behavior of these substances. Where
would you analyze for monitoring purposes? Why? At what fraction of the saturation
conditions is the chemical present, i.e., the ratio of fugacity to vapor pressure? In
the water and atmosphere, what fractions of the total concentration are present in
each of the dispersed phases of aerosols, suspended sediment, and fish?
CH06 Page 117 Monday, January 15, 2001 1:50 PM
CHAPTER 6
6.1 INTRODUCTION
117
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A key concept in this discussion that was introduced earlier, and is variously
termed persistence, lifetime, residence time, or detention time of the chemical.
In a steady-state system, as shown in Figure 6.1a, if chemical is introduced at a
rate of E mol/h, then the rate of removal must also be E mol/h. Otherwise, net
accumulation or depletion will occur. If the amount in the system is M mol, then,
on average, the amount of time each molecule spends in the steady-state system will
be M/E hours. This time, τ, is a residence time and is also called a detention time
or persistence. Clearly, if a chemical persists longer, there will be more of it in the
system. The key equation is
τ = M/E or M = τ E
This concept is routinely applied to retention time in lakes. If a lake has a volume
of 100,000 m3, and if it receives an inflow of 1000 m3 per day, then the retention
time is 100,000/1000 or 100 days. A mean retention time of 100 days does not imply
Figure 6.1 Diagram of a steady-state evaluative environment subject to (a) advective flow, (b)
degrading reactions, (c) both, and (d) the time course to steady state.
CH06 Page 119 Monday, January 15, 2001 1:50 PM
that all water will spend 100 days in the lake. Some will bypass in only 10 days,
and some will persist in backwaters for 1000 days but, on average, the residence
time will be 100 days.
The reason that this concept is so important is that chemicals exhibit variable
lifetimes, ranging from hours to decades. As a result, the amount of chemical present
in the environment, i.e., the inventory of chemical, varies greatly between chemicals.
We tend to be most concerned about persistent and toxic chemicals, because rela-
tively small emission rates (E) can result in large amounts (M) present in the
environment. This translates into high concentrations and possibly severe adverse
effects. A further consideration is that chemicals that survive for prolonged periods
in the environment have the opportunity to make long and often tortuous journeys.
If applied to soil, they may evaporate, migrate onto atmospheric particles, deposit
on vegetation, be eaten by cows, be transferred to milk, and then consumed by
humans. Chemicals may migrate up the food chain from water to plankton to fish
to eagles, seals, and bears. Short-lived chemicals rarely survive long enough to
undertake such adventures (or misadventures).
This lengthy justification leads to the conclusion that, if we are going to discharge
a chemical into the environment, it is prudent to know
This latter knowledge is useful, because it is likely that situations will occur in
which a common removal mechanism does not apply. For example, a chemical may
be potentially subject to rapid photolysis, but this is not of much relevance in long,
dark arctic winters or in deep, murky sediments.
In the process of quantifying this effect, we will introduce rate constants, advec-
tive flow rates and, ultimately, using the fugacity concept, quantities called D values,
which prove to be immensely convenient. Indeed, armed with Z values and D values,
the environmental scientist has a powerful set of tools for calculation and interpre-
tation.
It transpires that there are two primary mechanisms by which a chemical is
removed from our environment: advection and reaction, which we discuss individ-
ually and then in combination.
6.2 ADVECTION
N = GC mol/h
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Thus, if there is river flow of 1000 m3/h (G) from A to B of water containing 0.3
mol/m3 (C) of chemical, then the corresponding flow of chemical is 300 mol/h (N).
Turning to the evaluative environment, it is apparent that the primary candidate
advective phases are air and water. If, for example, there was air flow into the 1
square kilometre evaluative environment at 109 m3/h, and the volume of the air in
the evaluative environment is 6 × 109 m3, then the residence time will be 6 hours,
or 0.25 days. Likewise, the flow of 100 m3/h of water into 70,000 m3 of water results
in a residence time of 700 hours, or 29 days. It is easier to remember residence
times than flow rates; therefore, we usually set a residence time and from it deduce
the corresponding flow rate.
Burial of bottom sediments can also be regarded as an advective loss, as can
leaching of water from soils to groundwater. Advection of freons from the tropo-
sphere to the stratosphere is also of concern in that it contributes to ozone depletion.
If we decree that our evaluative environment is at steady state, then air and water
inflows must equal outflows; therefore, these inflow rates, designated G m3/h, must
also be outflow rates. If the concentrations of chemical in the phase of the evaluative
environment is C mol/m3, then the outflow rate will be G C mol/h. This concept is
often termed the continuously stirred tank reactor, or CSTR, assumption. The basic
concept is that, if a volume of phase, for example air, is well stirred, then, if some
of that phase is removed, that air must have a concentration equal to that of the
phase as a whole. If chemical is introduced to the phase at a different concentration,
it experiences an immediate change in concentration to that of the well mixed, or
CSTR, value. The concentration experienced by the chemical then remains constant
until the chemical is removed. The key point is that the outflow concentration equals
the prevailing concentration. This concept greatly simplifies the algebra of steady-
state systems. Essentially, we treat air, water, and other phases as being well mixed
CSTRs in which the outflow concentration equals the prevailing concentration. We
can now consider an evaluative environment in which there is inflow and outflow
of chemical in air and water. It is convenient at this stage to ignore the particles in
the water, fish, and aerosols, and assume that the material flowing into the evaluative
environment is pure air and pure water. Since the steady-state condition applies, as
shown in Figure 6.1a, the inflow and outflow rates are equal, and a mass balance
can be assembled. The total influx of chemical is at a rate GACBA in air, and GWCBW
in water, these concentrations being the “background” values. There may also be
emissions into the evaluative environment at a rate E. The total influx I is thus
This enables us to conceive of, and define, our first Level II calculation in which
we assume equilibrium and steady state to apply, inputs by emission and advection
are balanced exactly by advective emissions, and equilibrium exists throughout the
evaluative environment. All the phases are behaving like individual CSTRs.
Of course, starting with a clean environment and introducing these inflows, it
would take the system some time to reach steady-state conditions, as shown in Figure
6.1d. At this stage, we are not concerned with how long it takes to reach a steady
state, but only the conditions that ultimately apply at steady state. We can therefore
develop the following equations, using partition coefficients and later fugacities.
But
CA = KAWCW
Therefore,
Other concentrations, amounts (m), and the total amount (M) can be deduced
from CW. The extension to multiple compartment systems is obvious. For example,
if soil is included, the concentration in soil will be in equilibrium with both CA and
CW.
f = I/(GAZA + GWZW)
or, in general,
f = I/ΣGiZi
from which the fugacity and all concentrations and amounts can be deduced.
An evaluative environment consists of 104 m3 air, 100 m3 water, and 1.0 m3 soil.
There is air inflow of 1000 m3/h and water inflow of 1 m3/h at respective chemical
concentrations of 0.01 mol/m3 and 1 mol/m3. The Z values are air 4 × 10–4, water
CH06 Page 122 Monday, January 15, 2001 1:50 PM
0.1, and soil 1.0. There is also an emission of 4 mol/h. Calculate the fugacity
concentrations, persistence amounts and outflow rates.
CA = 0.012 CW = 3 CS = 30 mol/m3
τ = 450/15 =30 h
In this example, the total amount of material in the system, M, is 450 mol. The
inflow rate is 15 mol/h, thus the residence time or the persistence of the chemical
is 30 hours. This proves to be a very useful time. Note that the air residence time
is 10 hours, and the water residence time is 100 hours; thus, the overall residence
time of the chemical is a weighted average, influenced by the extent to which the
chemical partitions into the various phases. The soil has no effect on the fugacity
or the outflow rates, but it acts as a “reservoir” to influence the total amount present
M and therefore the residence time or persistence.
6.2.3 D values
The group G Z, and other groups like it, appear so frequently in later calculations
that it is convenient to designate them as D values,
i.e.,
G Z = D mol/Pa h
The rate, N mol/h, then equals D f. These D values are transport parameters, with
units of mol/Pa h. When multiplied by a fugacity, they give rates of transport. They
are thus similar in principle to rate constants, which, when multiplied by a mass of
chemical, give a rate of reaction. Fast processes have large D values. We can write
the fugacity equation for the evaluative environment in more compact form, as shown
below:
where DAA = GAZA, DAW = GWZW, and the first subscript A refers to advection.
Recalculating Example 6.1,
Therefore,
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f = 15/0.5 = 30
and the rates of output, Df, are 12 and 3 mol/h, totaling 15 mol/h as before.
It is apparent that the air D value is larger and most significant. D values can be
added when they are multiplied by a common fugacity. Therefore, it becomes
obvious which D value, and hence which process, is most important. We can arrive
at the same conclusion using partition coefficients, but the algebra is less elegant.
Note that how the chemical enters the environment is unimportant, all sources
being combined or lumped in I, the overall input. This is because, once in the
environment, the chemical immediately achieves an equilibrium distribution, and it
“forgets” its origin.
It also transpires that there are several advective processes which can apply to
chemical movement within the evaluative environment. Notable are rainfall, water
runoff from soil, sedimentation, and food consumption, but we delay their treatment
until later.
In situations 1 through 4, there is no difficulty in deducing the rate as GC or Df,
where G is the flowrate of the phase in question, C is the concentration of chemical
in that phase, and the Z value applies to the chemical in the phase in which it is
dissolved or sorbed.
For example, aerosol may be transported to an evaluative world in association
with the inflow of 1012 m3/h of air. If the aerosol concentration is 10–11 volume
fraction, then the flowrate of aerosol GQ is 10 m3/h. The relevant concentration of
chemical is that in the aerosol, not in the air, and is normally quite high, for example,
100 mol/m3. Therefore, the rate of chemical input in the aerosol is 1000 mol/h. This
can be calculated using the D and f route as follows, giving the same result.
If ZQ = 108, then
Therefore,
DAS dominates. A residence time of solids in the mixed layer can be calculated as
the volume of solids in the mixed layer divided by GS. For example, if the depth of
the mixed layer is 3 cm, and the solids concentration is 25%, then the volume of
solids is 75,000 m3 and the residence time is 260,000 hours, or 30 years. The
residence time of water is probably longer, because the water content is likely to be
higher in the active sediment than in the buried sediment. In reality, the water would
exchange diffusively with the overlaying water during that time period.
As discussed in Chapter 5, there are occasions in which it is convenient to
calculate a “bulk” Z value for a medium containing a dispersed phase such as an
aerosol. This can be used to calculate a “bulk” Z value, thus expressing two loss
processes as one. D is then GZ where G is the total flow and Z is the bulk value.
The word reaction requires definition. We regard reactions as processes that alter
the chemical nature of the solute, i.e., change its chemical abstract system (CAS)
number. For example, hydrolysis of ethyl acetate to ethanol and acetic acid is
definitely a reaction, as is conversion of 1,2-dichlorobenzene to 1,3-dichlorobenzene,
or even conversion of cis butene 2 to trans butene 2. In contrast, processes that
merely convey the chemical from one phase to another, or store it in inaccessible
form, are not reactions. Uptake by biota, sorption to suspended material, or even
uptake by enzymes are not reactions. A reaction may subsequently occur in these
locations, but it is not until the chemical structure is actually changed that we
consider reaction to have occurred. In the literature, the word reaction is occasionally,
and wrongly, applied to these processes, especially to sorption.
We have two tasks. The first is to assemble the necessary mathematical frame-
work for treating reaction rates using rate constants, and the second is to devise
methods of obtaining information on values of these rate constants.
We prefer, when possible, to use a simple first-order kinetic expression for all
reactions. The basic rate equation is
where V is the volume of the phase (m3), C is the concentration of the chemical
(mol/m3), M is the amount of chemical, and k is the first-order rate constant with
units of reciprocal time. The group VCk thus has units of mol/h.
The classical application of this equation is to radioactive decay, which is usually
expressed in the forms
The use of C instead of M implies that V does not change with time.
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Rate constants have units of frequency or reciprocal time and are therefore not
easily grasped or remembered. A favorite trick question of examiners is to ask a
student to convert a rate constant of 24 h–1 into reciprocal days. The correct answer
is 576 days–1, so beware of this conversion! It is more convenient to store and
remember half-lives, i.e., the time, τ1/2, which is the time required for C to decrease
to half of CO. This can be related to the rate constant as follows.
Unfortunately, there are many situations in which the real reaction rate is not a
first-order reaction. Second-order rate reactions occur when the reaction rate is
dependent on the concentration of two chemicals or reactants. For example, if
A+B→D+E
then the rate of the reaction is dependent on the concentration of both A and B.
Therefore, the reaction rate is as follows:
N = Vk CA CB
N = Vk CACB
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and
kP = k CB
Therefore,
N = VkP CA
which has the form of a simple first-order reaction. Examples of pseudo first-order
reactions include photolysis reactions where reactant “B” is the solar radiation
intensity (I, in photons/s) or microbial degradations processes where “B” is the
populations of microorganisms. Reactions between two chemicals can also be con-
sidered a pseudo first-order reaction when CA << CB, so the concentration of B does
not change as the reaction proceeds.
Second-order rate expressions also arise when a chemical reacts with itself,
giving rise to a messy quadratic equation. Thus, if A + A → D, the rate equation is
N = Vk CACA = Vk CA2
Fortunately, most pollutants are present at low concentrations and tend not to react
with themselves, so these types of reactions are rare.
Zero-order expressions occasionally occur in which the rate is independent of
the concentration of the chemical and is thus proportional to concentration to the
power zero. Including zero-order expressions in mass balance models is potentially
dangerous, because the equations can now predict a positive rate of reaction, even
when there is no chemical present. It is embarrassing when computer models cal-
culate negative concentrations of chemicals.
Our strategy is to use every reasonable excuse to force first-order kinetics on
systems by lumping parameters in k. The dividends that arise are worth the effort,
because subsequent calculations are much easier.
Perhaps most worrisome are situations in which we treat the kinetics of microbial
degradation of chemicals. It is possible that, at very low concentrations, there is a
slower or even no reaction, because the required enzyme systems are not “turned
on.” At very high concentrations, the enzyme may be saturated; therefore, the rate
of degradation ceases to be controlled by the availability of the chemical and becomes
controlled by the availability of enzyme. In other cases, the rate of conversion may
be influenced by the toxicity of the chemical to the organism or by the presence of
co-metabolites, chemicals that the enzyme recognizes as being similar to that of the
chemical of interest. Microbiologists have no difficulty conceiving of a multitude
of situations in which chemical kinetics become very complicated and very difficult
to predict and express. They seem to obtain a certain perverse delight in finding
these situations.
Saturation kinetics is usually treated by the Michaelis–Menten equation, which
can be derived from first principles or, more simply, by writing down the basic first-
order equation and multiplying the rate expression by the group shown below.
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When C is small compared to CM, the rate reduces to VCk. When C is large compared
to CM, it reduces to VCMk, which is independent of C, is constant, and corresponds
to the maximum, or zero-order rate. The concentration, CM, therefore corresponds
to the concentration that gives the maximum rate using the basic expression. When
C equals CM, the rate is half the maximum value. This can be (and usually is)
expressed in terms of other rate constants for describing the kinetics of the associ-
ation of the chemical with the enzyme.
The rate expression is usually written in biochemistry texts in the form
E = ΣViCwKiwki = CwΣViKiwki
Therefore,
air = 0.38
water = 9.61
soil = 0.01
We can now follow the same process as used when treating advection and define
D values for reactions. If the rate is V C k or V Z f k, it is also DRf, where DR is V
Z k. Note that DR has units of mol/m3 Pa identical to those of DA or G Z, discussed
earlier. If there are several reactions occurring to the same chemical in the same
phase, then each reaction can be assigned a D value, and these D values can be
added to give a total D value. This is equivalent to adding the rate constants. The
Level II mass balance becomes
The rate constants in each case are 0.693/half-life. The sum of the V Z k terms
or D values is 0.2587, thus,
f = E/ΣD = 96.6 Pa
Thus, each C is Z f and each amount m is VC, totaling 2318 mol. Each rate is V C
k or D f, totaling 25 mol/h.
It is clear that the D value V Z k controls the overall importance of each process.
Despite its low volume and relatively slow reaction rate, the soil provides a fairly
fast-reacting medium because of its large Z value. It is not until the calculation is
completed that it becomes obvious where most reaction occurs. The overall residence
time is 2318/25 or 93 hours.
Note that the persistence or M/E is a weighted mean of the persistence or
reciprocal rate constants in each phase. It is also ΣVZ/ΣD.
This can be solved either by substituting KiWCW for all concentrations and solving
for CW, or calculating the advective D values as GZ and adding them to the reaction
D values. The equivalence of these routes can be demonstrated by performing both
calculations.
The environment in Example 6.3 has advective flows of 1000 m3/h in air and
1 m3/h in water as in Example 6.1 and reaction D values as in Example 6.3, with a
total input by advection and emission of 40 mol/h. Calculate the fugacity concen-
trations, amounts, and chemical residence time.
Rate
Volume DA DR C m (mol/h)
Phase (m3) Z (advection) (reaction) (mol/m3) (mol) f(DA + DR)
Air 10000 4 × 10–4 0.4 0.0277 0.021 210 22.55
Water 100 0.1 0.1 0.0924 5.27 527 10.14
Soil 10 1.0 0.0 0.1386 52.7 527 7.31
Total 0.5 0.2587 1264 40
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E = 40
Therefore,
f = 40/ΣD = 52.7
The total amount is 1264 mols, giving a mean residence time of 31.6 hours. The
most important loss process is advection in air, which accounts for 21.08 mol/h.
Next is soil reaction at 7.31 mol/h, the water advection at 5.27 mol/h, etc. Each
individual rate is D f mol/h.
Examination of these equations shows that the group G/V plays the same role
as a rate constant having identical units of h–1. It may, indeed, be convenient to
regard advective loss as a pseudo reaction with this rate constant and applicable to
the phase volume of V. Note that the group V/G is the residence time of the phase
in the system. Frequently, this is the most accessible and readily remembered quan-
tity. For example, it may be known that the retention time of water in a lake is 10
days, or 240 hours. The advective rate constant, k, is thus 1/240 h–1, and the D value
is V Z k, which is, of course, also G Z.
It is noteworthy that this residence time is not equivalent to a reaction half-time,
which is related to the rate constant through the constant 0.693 or ln 2. Residence
time is equivalent to 1/k.
I = ΣDAif + ΣDRif
But I = M/τO, where M is the amount of chemical and τO is the overall residence
time. Furthermore, M = ΣVZf or fΣVZ. Thus, dividing both sides by M and can-
celling f gives
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= 1/τA + 1/τR
The key point is that the advective and reactive residence times τA and τR add as
reciprocals to give the reciprocal overall time. These are the residence times that
would apply to the chemical if only that process applied. Clearly, the shorter resi-
dence time dominates, corresponding, of course, to the faster rate constant. It can
be shown that the ratio of the amounts removed by reaction and by advection are in
the ratio of the overall rate constants or the reciprocal residence times.
Example 6.5
Calculate the individual and overall residence times in Example 6.4. Each resi-
dence time is VZ/D and the rate constant is D/VZ.
The advection residence time is 1/0.0209 or 47.8 h, and for reaction it is 1/0.0108
or 92.6 h. Each residence time (e.g., 60, 866, etc.) contributes to give the overall
residence time of 31.5 hours, reciprocally.
In mass balance models of this type, it is desirable to calculate the advection,
reaction, and overall residence times. An important observation is that these resi-
dence times are independent of the quantity of chemical introduced; in other words,
they are intensive properties of the system. Concentrations, amounts, and fluxes are
dependent on emissions and are extensive properties.
These concepts are useful, because they convey an impression of the relative
importance of advective flow (which merely moves the problem from one region to
another) versus reaction (which may help solve the problem). These are of particular
interest to those who live downwind or downstream of a polluted area.
it to decay in concentration with time, but maintain equilibrium between all phases
at the same time. This is analogous to a batch chemical reaction system. Although
it is possible to include emissions or advective inflow, we prefer to treat first the
case in which only reaction occurs to an initial mass M. We assume that all volumes
and Z values are constant with time.
But,
M = ΣViZif = fΣViZi
Solving gives
f = fO exp(–kOt)
where kO = ΣViZiki/ΣViZi = ΣDRi/ΣViZi, and fO is the initial fugacity. Note that kO,
the overall rate constant, is the reciprocal of the overall residence time.
Calculate the time necessary for the environment in Example 6.3 to recover to
50%, 36.7%, 10%, and 1% of the steady-state level of contamination after all
emissions cease.
Here, ΣVZ is 24 and ΣD is 0.2587. Thus,
6.6.1 Biodegradation
Microbiologists are usually quick to point out that the process of microbial
conversion of chemicals in the environment is exceedingly complex. The rate of
conversion depends on the nature of the chemical compound; on the amount and
condition of enzymes that may be present in various organisms in various states of
activation and availability to perform the chemical conversion; on the availability
of nutrients such as nitrogen, phosphorus, and oxygen; as well as pH, temperature,
and the presence of other substances that may help or hinder the conversion process.
Virtually all organic chemicals are susceptible to microbial conversion or biodegra-
dation. Notable among the slowly degrading or recalcitrant compounds are high-
molecular-weight compounds such as the humic acids, certain terpenes that appear
to have structures that are too difficult for enzymes to attack, and many organo-
halogen substances. Generally, water-soluble organic chemicals are fairly readily
biodegraded. Over evolutionary time, enzymes have adapted and evolved the capa-
bility of handling most naturally occurring organic compounds. When presented
with certain synthetic organic compounds that do not occur in nature (notably the
CH06 Page 136 Monday, January 15, 2001 1:50 PM
6.6.2 Hydrolysis
Structure activity approaches can be used to correlate and predict these rate constants.
Often, the best approach is to seek data on a structurally similar substance.
Other useful references on hydrolysis include the Wolfe (1980), Pankow and
Morgan (1981), Zepp et al. (1975), Wolfe et al. (1977), and Jeffers et al. (1989).
6.6.3 Photolysis
light. Sunburn and photosynthesis are examples of such reactions. This process is
primarily of interest when considering the fate of chemicals in solution in the
atmosphere and in water. The radiation that is most likely to effect chemical change
is high-energy, short-wavelength photons at the blue and near UV end of the spec-
trum, i.e., shorter than 400 nm. The relationships between energy, wavelength, and
frequency are readily deduced using the fundamental constants of the speed of light
c (3.0 × 108 m/s), Planck’s constant h (6.6 × 10–34 Js), and Avogadro’s Number N
(6.0 × 1023). The energy of a photon of wavelength λ nm (frequency c/λ Hz) is hc/λ
J/molecule or hcN/λ J/mol or Einsteins. A photon of wavelength 307 nm has a
frequency of 9.8 × 1014Hz and energy of 387,000 J/mol or Einsteins. This is approx-
imately the dissociation energy of the tertiary C-H bond in isobutane (2 methyl
propane); thus, in principle, if the energy in such a photon could be applied to that
bond, dissociation would occur. Short-wavelength photons are more energetic and
are more likely to induce chemical reactions.
There are two general concerns. Will the photon be absorbed such that reaction
will occur? Will the quantity of photons be such that the reaction rate will be
significant?
To be absorbed directly, the molecule must have a chromophore that imparts
suitable absorption characteristics. These properties can be measured using a spec-
trophotometer. As discussed later, there may be indirect absorption of the energy
from another species that absorbs the photon then passes on the energy to the
substance of interest.
The issue of quantity can be assessed by calculating the amount of energy
absorbed, recognizing that there are competitive absorbing substances such as natural
organic matter present in the environment. The extent of absorption can be calculated
from the Beer–Lambert Law such that
to Zepp and Cline (1977) for the original work in this area; to Leifer (1988) for an
update; and to Calvert and Pitts (1966), Mill (2000), and Schwarzenbach et al.
(1993) for more details and examples of photochemical reactions and computer
programs.
For our purposes, it is sufficient to appreciate that, knowing the absorbance
properties of the molecule, the quantum yield and the local insolation conditions, it
is possible to calculate a rate constant and a half-life for direct photolysis.
Relatively simple experiments can be conducted in which the chemical is dis-
solved in distilled or natural water in a suitable container and exposed to natural
sunlight or to artificial light for a period of time, and the concentration decay is
monitored. Test methods have been described by Svenson and Bjarndahl (1988),
Lemaire et al. (1982), and Dulin and Mill (1982).
The issue is complicated by the presence of photosensitizing molecules or
substances. These substances absorb light then pass on the energy to the chemical
of interest, resulting in subsequent chemical reaction. It is therefore not necessary
for the chemical to absorb the photon directly. It can receive it second hand from a
photosensitizer. This is a troublesome complication, because it raises the possibility
that chemicals may be subject to photolysis due to the unexpected presence of a
photosensitizer. Of particular interest are the naturally occuring organic matter pho-
tosensitizers that are present in water and give it its characteristic brown color,
especially in areas in which there is peat and decaying vegetation.
A chemical present in the atmosphere may react with oxygen, an activated form
of oxygen such as singlet oxygen, ozone, hydrogen peroxide, or with various radicals,
notably OH radicals. Fortunately, we live in a world with an abundance of oxygen,
and it is not surprising that a suite of oxygen compounds exists that are eager to
oxidize organic chemicals. The rates of these reactions can be estimated by con-
ducting conventional chemical kinetic experiments in which the substance is con-
tacted with known concentrations of the oxidant, the decay of chemical is followed,
and a kinetic law and rate constant established.
The most important oxidative process is the reaction of hydroxyl radicals with
chemical species in the atmosphere. The concentration of sunlight-induced hydroxyl
radicals is exceedingly small, averaging only about 1 million molecules per cubic
centimetre. Peak concentrations approach 8 million per cm3 in urban areas. Concen-
trations in rural or remote areas are much lower. They are extremely reactive and
are responsible for the reaction of many organic chemicals in the environment that
would otherwise be persistent.
Ozone is produced by UV radiation in the stratosphere and by certain high-
temperature and photolytic processes in the troposphere. The average mixing ratio,
i.e., the ratio of ozone to non-ozone molecules, is in the range of 10 to 40 × 10–9.
Oxides of nitrogen produced at high temperature include NO, NO2, and the
reactive NO3 radical. The latter has an average concentration of about 500 million
molecules per cm3 and peaks in concentration at night.
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Natural oxidizing agents include oxygen, hydrogen peroxide, ozone, and “engi-
neered” oxidants include chlorine, hypochlorite, chlorine dioxide, permanganate,
chromate, and ferrate. Natural reducing agents include sulphide, ferrous and man-
ganous ion, and organic matter, while “engineered” reductants include dithionite
and zero-valent (metal) iron. Oxidation usually involves the addition of oxygen but,
in more general terms, it is the removal of or abstraction of an electron. Reduction
involves electron addition. The potential or feasibility of such a reaction occurring
can be readily evaluated from the standard potential of the half reactions.
The kinetics are usually expressed using a second-order expression including
the concentration of the substance and the oxidant or reductant. In some cases, the
reactant is a solid (e.g., zero-valent iron), and an area-normalized value can be used.
Tratnyek and Macalady (2000) provide an excellent review of this literature and
give several examples of oxidation and reduction processes. Again, for our purposes,
a first-order rate constant can be estimated that includes the concentration of the
oxidising or reducing agent. This can be used to calculate the corresponding half-
life and D value.
6.6.6 Summary
It has been possible to provide only a brief account of the vast literature relating
to chemical reactivity in the environment. The air pollution literature is particularly
large and detailed. References have been provided to give the reader an entry to the
literature.
The susceptibility of a chemical in a specific medium to degrading reaction
depends both on the inherent properties of the molecule and on the nature of the
medium, especially temperature and the presence of candidate reacting molecules
or enzymes. In this respect, environmental chemicals are fundamentally different
from radioisotopes, which are totally unconcerned about external factors. Translation
and extrapolation of reaction rates from environment to environment and laboratory
to environment is therefore a challenging and fascinating task that will undoubtedly
keep environmental chemists busy for many more decades.
CH06 Page 141 Monday, January 15, 2001 1:50 PM
6.8 SUMMARY
Chemical: Hypothene
For the two substances selected from Table 3.5, which were the subject of the
concluding example in Chapter 5, perform a Level II calculation for the air, water,
soil, and bottom sediment phases either as defined in that example or using the
environment deduced in the concluding example from Chapter 4. Use Fugacity Form
3 and ignore other phases. Assume reasonable residence times in air, water, and
bottom sediment for the purpose of calculating advection rates. There is no advection
from soil. Use the degradation half-lives from Table 3.5.
Assume first a total input by emission of 100 kg/h and calculate the fugacity,
concentrations, amounts, and the three chemical residence times (overall, reaction,
and advection).
Second, recalculate this Level II example assuming that the inflow air and water
both contain the chemical at a concentration that is 20% of the air and water
concentrations calculated above.
Discuss the results and present them in a diagrammatic form. Discuss which
reaction and advection processes are most important. Are the residence times in
these two examples equal or not? Explain why they are equal or different.
CH07 Page 145 Monday, January 15, 2001 1:51 PM
CHAPTER 7
Intermedia Transport
7.1 INTRODUCTION
145
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Figure 7.1 Illustration of nonequilibrium behavior in an air-water system. In the lower diagram,
the rate of reaction in air is constrained by the rate of evaporation.
material that has decided, for reasons unrelated to the presence of the chemical, to
make this journey. Examples include advective flows in air, water, or particulate
phases, as discussed in Chapter 6; deposition of chemical in rainfall or sorbed to
aerosols from the atmosphere to soil or water; and sedimentation of chemical in
association with particles that fall from the water column to the bottom sediments.
These are usually one-way processes. The rate of chemical transfer is simply
the product of the concentration C mol/m3 of chemical in the moving medium, and
the flowrate of that medium, G, m3/h. We can thus treat all these processes as
advection and calculate the D value and rate as follows:
N = GC = GZf = Df mol/h
The second group of processes are diffusive in nature. If we have water containing
1 mol/m3 of benzene and add some octanol to it as a second phase, the benzene will
CH07 Page 147 Monday, January 15, 2001 1:51 PM
diffuse from the water to the octanol until it reaches a concentration in octanol that
is KOW, or 135, times that in the water. We could rephrase this by stating that, initially,
the fugacity of benzene in the water was (say) 500 Pa, and the fugacity in the octanol
was zero. The benzene then migrates from water to octanol until both fugacities
reach a common value of (say) 200 Pa. At this common fugacity, the ratio CO/CW
is, of course, ZO/ZW or KOW. We argue that diffusion will always occur from high
fugacity (for example, fW in water) to low fugacity (fO in octanol). Therefore, it is
tempting to write the transfer rate equation from water to octanol as
This equation has the correct property that, when fW and fO are equal, there is no
net diffusion. It also correctly describes the direction of diffusion.
In reality, when the fugacities are equal, there is still active diffusion between
octanol and water. Benzene molecules in the water phase do not know the fugacity
in the octanol phase. At equilibrium, they diffuse at a rate, DfW, from water to
benzene, and this is balanced by an equal rate, DfO, from octanol to water. The
escaping tendencies have become equal, and N is zero. The term (fW – fO) is termed
a departure from equilibrium group, just as a temperature difference represents a
departure from thermal equilibrium. It quantifies the diffusive driving force.
Other areas of science provide good precedents for using this approach. Ohm’s
law states that current flows at a rate proportional to voltage difference times
electrical conductivity. Electricians prefer to use resistance, which is simply the
reciprocal of conductivity. The rate of heat transfer is expressed by Fourier’s law as
a thermal conductivity times a difference in temperature. Again, it is occasionally
convenient to think in terms of a thermal resistance (the reciprocal of thermal
conductivity), especially when buying insulation. These equations have the general
form
or
1. Evaporation of chemical from water to air and the reverse process of absorption.
Note that we consider the chemical to be in solution in water and not present as
a film or oil slick, or in sorbed form.
2. Sorption from water to suspended matter in the water column, and the reverse
desorption.
3. Sorption from the atmosphere to aerosol particles, and the reverse desorption.
4. Sorption of chemical from water to bottom sediment, and the reverse desorption.
CH07 Page 148 Monday, January 15, 2001 1:51 PM
Armed with these D values, we can set up mass balance equations that are similar
to the Level II calculations but allow for unequal fugacities between media.
To address these tasks, we return to first principles, quantify diffusion processes
in a single phase, then extend this capability to more complex situations involving
two phases. Chemical engineers have discovered that it is possible to make a great
deal of money by inducing chemicals to diffuse from one phase to another. Examples
are the separation of alcohol from fermented liquors to make spirits, the separation
of gasoline from crude oil, the removal of salt from sea water, and the removal of
metals from solutions of dissolved ores. They have thus devoted considerable effort
to quantifying diffusion rates, and especially to accomplishing diffusion processes
inexpensively in chemical plants. We therefore exploit this body of profit-oriented
information for the nobler purpose of environmental betterment.
N = –B A dC/dy
CH07 Page 149 Monday, January 15, 2001 1:51 PM
Here, N is the flux of chemical (mol/h), B is the diffusivity (m2/h), A is area (m2),
C is concentration of the diffusing chemical (for example, benzene in water)
(mol/m3), and y is distance (m) in the direction of diffusion. The group dC/dy is
thus the concentration gradient and is characteristic of the degree to which the
solution is unmixed or heterogeneous. The negative sign arises because the direction
of diffusion is from high to low concentration, i.e., it is positive when dC/dy is
negative. Here, we use the symbol B for diffusivity to avoid confusion with D values.
Most texts sensibly use the symbol D. The equation is really a statement that the
rate of diffusion is proportional to the concentration gradient and the proportionality
constant is diffusivity. When the equation is apparently not obeyed, we attribute this
misbehavior to deviations or changes in the diffusivity, not to failure of the equation.
As was discussed earlier, there are differences of opinion about the word flux.
We use it here to denote a transfer rate in units such as mol/h. Others insist that it
should be area specific and have units of mol/m2h. We ignore their advice. Occa-
CH07 Page 150 Monday, January 15, 2001 1:51 PM
sionally, the term flux rate is used in the literature. This is definitely wrong, because
flux contains the concept of rate just as does speed. Flux rate is as sensible as speed
rate.
It is worthwhile digressing to examine how the mixing process leads to diffusion
and eventually to Fick’s first law. This elucidates the fundamental nature of diffu-
sivity and the reason for its rather strange units of m2/h. Much of the pioneering
work in this area was done by Einstein in the early part of this century and arose
from an interest in Brownian movement—the erratic, slow, but observable motion
of microscopic solid particles in liquids, which is believed to be due to multiple
collisions with liquid molecules.
Note that CyA is the product of concentration and volume and is thus an amount
(moles).
The concentration gradient that is causing this net diffusion from left to right is
(C3 – C4)/y or, in differential form, dC/dy. The negative sign below is necessary,
because C decreases in the direction in which y increases. It follows that
which is referred to as Fick’s first law. The diffusivity B is thus (y2/2t), where y is
the molecular displacement that occurs in time t.
In a typical gas at atmospheric pressure, the molecules are moving at a velocity
of some 500 m/s, but they collide after traveling only some 10–7 m, i.e., after 10–7/500
or 2 × 10–10 s. It can be argued that y is 10–7 m, and t is 2 × 10–10; therefore, we
CH07 Page 151 Monday, January 15, 2001 1:51 PM
expect a diffusivity of approximately 0.25 × 10–4 m2/s or 0.25 cm2/s or 0.1 m2/h,
which is borne out experimentally. The kinetic theory of gases can be used to
calculate B theoretically but, more usefully, the theory gives a suggested structure
for equations that can be used to correlate diffusivity as a function of molecular
properties, temperature, and pressure.
In liquids, molecular motion is more restricted, collisions occur almost every
molecular diameter, and the friction experienced by a molecule as it attempts to
“slide” between adjacent molecules becomes important. This frictional resistance is
related to the liquid viscosity µ (Pa s). It can be shown that, for a liquid, the group
(Bµ/T) should be relatively constant and (by the Stokes-Einstein equation) approx-
imately equal to R/(6πNr), where N is Avogadro’s number, R is the gas constant,
and r is the molecular radius (typically 10–10 m). B is therefore T R/(µ6πNr), where
the viscosity of water µ is typically 10–3 Pa s. Substituting values of R, T, µ, and r
suggests that B will be approximately 2 × 10–9 m2/s or 2 × 10–5 cm2/s or 7 × 10–6
m2/h, which is also borne out experimentally. Again, this equation forms the foun-
dation of correlation equations.
The important conclusion is that, during its diffusion journey, a molecule does
not move with a constant velocity related to the molecular velocity. On average, it
spends as much time moving backward as forward, thus its net progress in one
direction in a given time interval is not simply velocity/time. In t seconds, the distance
traveled (y) will be 2tB m. Taking typical gas and liquid diffusivities of 0.25 ×
10–4 m2/s and 2 × 10–9 m2/s respectively, a molecule will travel distances of 7 mm
in a gas and 0.06 mm in a liquid in one second. To double these distances will
require four seconds, not two seconds. It thus may take a considerable time for a
molecule to diffuse a “long” distance, since the time taken is proportional to the
square of the distance. The most significant environmental implication is that, for a
molecule to diffuse through, for example, a 1 m depth of still water requires (in
principle) a time on the order of 3000 days. A layer of still water 1 m deep can thus
effectively act as an impermeable barrier to chemical movement. In practice, of
course, it is unlikely that the water would remain still for such a period of time.
The reader who is interested in a fuller account of molecular diffusion is referred
to the texts by Reid et al. (1987), Sherwood et al. (1975), Thibodeaux (1996), and
Bird et al. (1960). Diffusion processes occur in a large number of geometric con-
figurations from CO2 diffusion through the stomata of leaves to large-scale diffusion
in ocean currents. There is thus a considerable literature on the mathematics of
diffusion in these situations. The classic text on the subject is by Crank (1975), and
Choy and Reible (2000) have summarized some of the more environmentally useful
equations.
N = AB∆C/∆y mol/h
Combining B and ∆y in one term kM, equal to B/∆y, with dimensions of velocity
thus appears to decrease our ignorance, since we now do not know one quantity
instead of two. Hence we write
N = AkM∆C mol/h
Term kM is termed a mass transfer coefficient, has units of velocity (m/h), and is
widely used in environmental transport equations. It can be viewed as the net
diffusion velocity. The flux N in one direction is then the product of the velocity,
area, and concentration.
For example, if, as in the lower section of Figure 7.2, diffusion is occurring in
an area of 1 m2 from point 1 to 2, C1 is 10 mol/m3, C2 is 8 mol/m3, and kM is 2.0
m/h, we may have diffusion from 1 to 2 at a velocity of 2.0 m/h, giving a flux of
kMAC1 of 20 mol/h. There is an opposing flux from 2 to 1 of kMAC2 or 16 mol/h.
The net flux is thus the difference or 4 mol/h from 1 to 2, which of course equals
kMA(C1 – C2). The group kMA is an effective volumetric flowrate and is equivalent
to the term G m3/h, introduced for advective flow in Chapter 6.
D = BAZ/∆y or D = kMAZ
Thus,
This flux of 0.002 mol/s can be regarded as a net flux consisting of kMAC1 or
0.003 mol/s in one direction and kMAC2 or 0.001 mol/s in the opposing direction.
Note that the “amount” unit in N and C need not be moles. It can be another quantity
such as grams, but it must be consistent in both. In this example, the 2 mm thick
film is controlled by the air speed over the pan. Increasing the air speed could reduce
this to 1 mm, thus doubling the evaporation rate. This ∆y is rather suspect, so it is
more honest to use a mass transfer coefficient, which, in the example above is
0.09/0.002 or 45 m/h. This is the actual net velocity with which water molecules
migrate from the water surface into the air phase.
Sc = µ/ρB
N = –A(BM + BT)dC/dy
Figure 7.3 The nature of turbulent or eddy diffusion in which chemical is conveyed in eddies
within a fluid to a surface.
CH07 Page 155 Monday, January 15, 2001 1:51 PM
is much greater than BM, and the molecular processes can be ignored. In stagnant
regions, such as thermoclines or in deep sediments, BT may be small or zero, and
BM dominates. As we move closer to a phase boundary, BT tends to become smaller;
thus, it is possible that much of the resistance to diffusion lies in the layer close
to the interface. The roughness of the interface plays a role in determining the
thickness of this layer. For example, grass may damp out wind eddies and retard
the rate of diffusion from soil to air. Animal fur retards both diffusion of heat and
water vapor.
A complicating factor is that we have no guarantee that BT is isotropic, i.e., that
the same value applies vertically and horizontally. In Figure 7.3, we postulate that
some eddies may be constrained to form elongated “roll cells.” The horizontal BT
will therefore exceed the vertical value. In practice, this nonisotropic situation is
common and even leads to conditions in rivers where three BT values must be
considered: vertical, upstream-downstream, and cross-stream.
To give an order of magnitude appreciation of turbulent diffusivities, it is
observed that a vertical eddy diffusivity in air is typically 3600 m2/h plus or minus
a factor of 3, thus the time for moving a distance of 1 m is of the order of 1 s.
Molecular diffusion is clearly negligible in comparison. In lakes, a vertical eddy
diffusivity may be 36 m2/h near the surface, corresponding to a velocity over a
distance of 1 m of 1 cm/s. At greater depths, diffusion is much slower, possibly by
a factor of 100. To estimate eddy diffusivities, one can watch a buoyant particle and
time its transport over a given distance. The diffusivity is then that distance squared,
divided by the time.
Turbulent processes in the environment are thus quite complex and difficult to
describe mathematically. The interested reader can consult Thibodeaux (1996) or
Csanady (1973) for a review of the mathematical approaches adopted. We sidestep
this complex issue here, but certain generalizations that emerge from the study of
turbulent diffusion are worth noting.
In the bulk of most fluid masses (air and water) that are in motion, turbulent
diffusion dominates. We can measure and correlate these diffusivities. Generally,
vertical diffusion is slower than horizontal diffusion. Often, diffusion is so fast that
near-homogeneous conditions exist, which is fortunate, because it eliminates the
need to calculate diffusion rates.
In the atmosphere and oceans, there is a spectrum of eddies of varying size and
velocity. The larger eddies move faster. Consequently, when a plume in the atmo-
sphere or a dye patch in an ocean expands in size, it becomes subject to dispersion
by larger, faster eddies, and the diffusivity increases. If the velocity of expansion of
the plume or patch is constant, this implies that diffusivity increases as the square
of distance.
At phase interfaces (e.g., air-water, water-bottom sediment), turbulent diffusion
is severely damped or is eliminated, thus only molecular diffusion remains. One can
even postulate the presence of a “stagnant layer” in which only molecular diffusion
occurs and calculate its diffusion resistance. This model is usually inherently wrong
in that no such layer exists. It is more honest (and less trouble) to avoid the use of
diffusivities and stagnant layer thicknesses close to the phase interfaces and invoke
mass transfer coefficients that combine the varying eddy diffusivities, the molecular
CH07 Page 156 Monday, January 15, 2001 1:51 PM
diffusivity, and some unknown layer thickness, into one parameter, kM. We then
measure and correlate kM as a function of fluid conditions (e.g., wind speed) and
seek advice from the turbulent transport theorists as to the best form of the correlation
equations.
In some diffusion situations, such as bottom sediments, the eddy diffusion may
be induced by burrowing worms or creatures that “pump” water. This is termed
bioturbation and is difficult to quantify. Its high variability and unpredictability is
a source of delight to biologists and irritation to physical scientists.
The study of turbulent diffusion in the atmosphere includes aspects such as the
micrometeorology of diffusion near the ground as it influences evaporation of pes-
ticides, the uptake of contaminants by foliage, and the dispersion of plumes from
stacks, in which case the plume is treated by the Gaussian dispersion equations. In
lakes, rivers, and oceans it is important to calculate concentrations near sewage and
industrial outfalls and in intensively used regions such as harbors. In each case, a
body of specialized knowledge and calculation methods has evolved.
Those who dislike calculus, and especially partial differential equations, can skip
this section, but the two concluding paragraphs should be noted.
In certain circumstances, we are interested in the transient or unsteady-state
situation, which exists when diffusion starts between two volumes that are brought
into contact. This is shown conceptually in Figure 7.4, in which a “shutter” is
removed, exposing a concentration discontinuity. The two regions proceed to mix
and chemical diffuses, eventually achieving homogeneity. Environmentally, this
situation is encountered when a volume of fluid (e.g., water) moves to an interface
and there contacts another phase (e.g., air) containing a solute with a different
fugacity. Volatilization may then occur over a period of time.
There are now three variables: concentration (C), position (y), and time (t). If
we consider a volume of A∆y, as shown in Figure 7.4, then the flux in is –BA dC/dy,
and the flux out is –BA(dC/dy + ∆yd2C/dy2), while the accumulation is A∆y∆C in
the time increment ∆t. It follows that
Bd2C/dy2 = dC/dt
This is Fick’s second law. Solution of this partial differential equation requires two
boundary conditions, usually initial concentrations at specified positions. A partic-
ularly useful solution is the “penetration” equation, which describes diffusion into
a slab of fluid that is brought into contact with another slab of constant concentration
CS. The boundary conditions are
CH07 Page 157 Monday, January 15, 2001 1:51 PM
C = CS at y = 0 at all times
C = 0 for y > 0 at t = 0
where
X = y/ 4Bt
which is quite accurate when X exceeds 0.75. When X is less than 0.5, erf(X) is
approximately 1.1X. The penetration solution shown in Figure 7.4 illustrates the
very rapid initial transfer close to the interface, followed by slower penetration that
occurs later as the concentration gradient becomes smaller. Now the transfer rate at
the boundary (y = 0) can be shown to be
CSA 4Bt/π
But, since the average flux is CSAkM, the average mass transfer coefficient kM, which
applies over this time, must be 4B/π t .
The mass transfer coefficient, kM, under these transient conditions, thus depends
on the time of exposure (short exposures giving a large kM) and on the square root
of diffusivity. This contrasts with the steady-state solution, in which kM is indepen-
dent of time and proportional to diffusivity. The reason for this behavior is that kM
is apparently very large initially, because the concentration gradient is large. It falls
in inverse proportion to t , thus the average also falls in this proportion. The lower
dependence on diffusivity (to the power of 0.5 instead of 1.0) arises, because not
all the transferring mass has to diffuse the total distance; much of it goes into
“storage” during the transient concentration buildup.
A problem now arises in environmental calculations: which definition of kM
applies, B/∆y or 4B/π t ? Contact time is the key determinant. If the contact time
between phases is long, and the amount transferred exceeds the capacity of the
phases, it is likely that a steady-state condition applies, and we should use B/∆y.
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Conversely, if the contact time is short, we can expect to use 4B/π t . If we measure
the transfer rates at several temperatures, and thus different diffusivities, or measure
the transfer rate of different chemicals of different B, then plot kM versus B on log-
log paper, the slope of the line will be 1.0 if steady-state applies, and 0.5 if unsteady-
state applies. In practice, an intermediate power of about 2/3 often applies, suggesting
that we have mostly penetration diffusion followed by a period of near-steady-state
diffusion.
Figure 7.5 Diffusion in a porous medium in which only part of the area is accessible, and the
diffusing molecule must take a longer, tortuous path.
CH07 Page 160 Monday, January 15, 2001 1:51 PM
fraction of the total volume that is fluid, and thus is accessible to diffusion. It can
be argued that the tortuousity factor, FY, is related to void fraction, v, raised possibly
to the power –0.5; therefore, in total, we can postulate that the effective diffusivity
in the porous medium, BE, is related to the molecular diffusivity, B, by
BE = BFA/FY = Bv1.5
where BA and BW are the molecular diffusivities, and BAE and BWE are the effective
diffusivities. Inspection of these equations shows that they reduce to a similar form
to that presented earlier. If vW is zero, BAE is proportional to vA to the power 1.33
instead of 1.5.
Occasionally, there is confusion when selecting the concentration driving force
that is to be multiplied by BE. This should be the concentration in the diffusing
medium, not the total concentration including sorbed form. In sediments, the pore
water concentration may be 0.01 mol/m3, but the total sorbed plus pure water, i.e.,
bulk concentration, is 10 mol/m3. BE should then be multiplied by 0.01 not 10. In
some situations (regrettably), the total concentration (10) is used, in which case BE
must be redefined to be a much smaller “effective diffusivity,” i.e., by a factor of
1000. The problem is that diffusivity is then apparently controlled by the extent of
sorption.
In sediments, it is suspected that much of the chemical present in the pore or
interstitial water, and therefore available for diffusion, is associated with colloidal
organic material. These colloids can also diffuse; consequently, the diffusing chem-
ical has the option of diffusing in solution or piggy backing on the colloid. From
the Stokes–Einstein equation, the diffusivity B is approximately inversely propor-
tional to the molecular radius. A typical chemical may have a molecular mass of
200 and a colloid an equivalent molar mass of 6000 g/mol, i.e., it is a factor of 30
CH07 Page 161 Monday, January 15, 2001 1:51 PM
larger in mass and volume, but only a factor of 300.33 or about 3 in radius. The colloid
diffusivity will thus be about one-third that of the dissolved molecule. But if 90%
of the chemical is sorbed, the colloidal diffusion rate will exceed that of the dissolved
form. As a result, is necessary to calculate and interpret the component diffusion
processes, since it may not be obvious which route is faster.
So far in this discussion, we have treated diffusion in only one phase, but in
reality, we are most interested in situations where the chemical is migrating from
one phase to another. It thus encounters two diffusion regimes, one on each side of
the interface. Environmentally, this is discussed most frequently for air-water
exchange, but the same principles apply to diffusion from sediment to water, soil to
water and to air, and even to biota-water exchange.
An immediate problem arises at the interface, where the chemical must undergo
a concentration “jump” from one equilibrium value to another. The chemical may
even migrate across the interface from low to high concentration. Clearly, whereas
concentration difference was a satisfactory “driving force” for diffusion within one
phase, it is not satisfactory for describing diffusion between two phases. When
diffusion is complete, the chemical’s fugacities on both sides of the interface will
be equal. Thus, we can use fugacity as a “driving force” or as a measure of “departure
from equilibrium.” Indeed, fugacity is the fundamental driving force in both cases,
but it was not necessary to introduce it for one-phase systems, because only one Z
applies, and the fugacity difference is proportional to the concentration difference.
Traditionally, interphase transfer processes have been characterized using the
Whitman Two-Resistance mass transfer coefficient (MTC) approach (Whitman,
1923), in which departure from equilibrium is characterized using a partition coef-
ficient, or in the case of air-water exchange, a Henry’s law constant. We derive the
flux equations for air-water exchange using the Whitman approach and following
Liss and Slater (1974), who first applied it to transfer of gases between the atmo-
sphere and the ocean, and Mackay and Leinonen (1975), who applied the same
principles to other organic solutes. We will later derive the same equations in fugacity
format. Unfortunately, the algebra is lengthy, but the conclusions are very important,
so the pain is justified.
Figure 7.6 illustrates an air-water system in which a solute (chemical) is diffusing
at steady-state from solution in water at concentration CW (mol/m3) to the air at
concentration CA mol/m3, or at a partial pressure P (Pa), equivalent to CART. We
assume that the solute is transferred relatively rapidly in the bulk of the water by
eddies, thus the concentration gradient is slight. As it approaches the interface,
however, the eddies are damped, diffusion slows, and a larger concentration gradient
is required to sustain a steady diffusive flux. A mass transfer coefficient, kW, applies
over this region. The solute reaches the interface at a concentration CWI, then abruptly
changes to CAI, the air phase value. The question arises as to whether there is a
162
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Figure 7.6 Mass transfer at the interface between two phases as described by the two-resistance concept. Note the concentration
discontinuity on the right, whereas, in the equivalent fugacity profile on the left, there is no discontinuity.
MULTIMEDIA ENVIRONMENTAL MODELS AND FUGACITY
CH07 Page 163 Monday, January 15, 2001 1:51 PM
and
CAI/KAW = CWI
The solute then diffuses in the air from CAI to CA in the bulk air with a mass
transfer coefficient kA. We can write the flux equations for each phase, noting that
the fluxes N must be equal, otherwise there would be net accumulation or loss at
the interface.
or more conveniently,
CW – CWI = N/kWA
CAI – CA = N/kAA
or
which is
or
where
The term kOW is an “overall” mass transfer coefficient that contains the individual
kW and kA terms and KAW. It should not be confused with KOW, the octanol-water
CH07 Page 164 Monday, January 15, 2001 1:51 PM
RW = 1/(kW A)
Thus,
RO = RW + RA = 1/(kOW A)
and
It follows that
If H is low, kOA approaches kA, and when P/H is small, the flux approaches
kACWKAW or kACWH/RT. In such cases, volatilization becomes proportional to H and
may be negligible if H is very small. In the limit, when H is zero (as with sodium
chloride), volatilization does not occur at all.
Figure 7.7 is a plot of log vapor pressure, PS, versus log solubility in water on
which the location of certain solutes is indicated. Recalling that H or KAWRT is the
ratio of these solubilities, compounds of equal H or KAW will lie on the same 45°
diagonal. Compounds of H > 250 Pa m3/mol lie to the upper left, are volatile, and
are water phase diffusion controlled. Those of H < 2.5 or KAW < 0.001 lie to the
lower right, are relatively involatile, and are air phase diffusion controlled. There is
an intermediate band in which both resistances are important.
It is interesting to note that a homologous series of chemicals, such as the
chlorobenzenes or PCBs, tends to lie along a 45° diagonal of constant KAW . Substi-
tuting methyl groups or chlorines for hydrogen tends to reduce both vapor pressure
and solubility by a factor of 4 to 6, thus KAW tends to remain relatively constant,
Figure 7.7 Plot of log vapor pressure versus log solubility in water for selected chemicals.
The diagonals are lines of constant Henry’s law constant. The dashed line corre-
sponds to a Henry’s law constant of 25 Pa m3/mol at which there are approximately
equal resistances in the water and air phases.
CH07 Page 166 Monday, January 15, 2001 1:51 PM
and the series retains a similar ratio of air and water resistances. Paradoxically,
reducing vapor pressure as one ascends such a series does not reduce evaporation
rate from solution, since it is KAW that controls the rate of evaporation, not vapor
pressure.
It is noteworthy that oxygen and most low-molecular-weight hydrocarbons lie
in the water phase resistant region, whereas most oxygenated organics lie in the air
phase resistant region. The H for water can be deduced from its vapor pressure of
2000 Pa at 20°C and its concentration in the water phase of 55,000 mol/m3 to be
0.04 Pa m3/mol. If a solute has a lower H than this, it may concentrate in water as
a result of faster water evaporation but, of course, humidity in the air alters the water
evaporation rate. Water evaporation is entirely air phase resistant, because the water
need not, of course, diffuse through the water phase to reach the interface. It is
already there.
Certain inferences can be made concerning the volatilization rate of one solute
from another, provided that (1) their H values are comparable, i.e., the same resis-
tance or distribution of resistances applies, and (2) corrections are applied for
differences in molecular diffusivity. For example, rates of oxygen transfer can be
estimated using noble gases or propane as tracers, because all are gas phase con-
trolled. Particularly elegant is the use of stable isotopes and enantiomers as tracers,
since the partition coefficients and diffusivities are nearly identical.
We can use D values instead of mass transfer coefficients and diffusivities. These
two-resistance equations can be reformulated in fugacity terms to yield an algebraic
result equivalent to the concentration version. The derivation is less painful when
fugacity is used. If the water and air fugacities are fW and fA and the interfacial
fugacity is fI, then replacing C by Zf in the steady-state Fick’s law equation yields
and
where
fW – fI = N/DW
CH07 Page 167 Monday, January 15, 2001 1:51 PM
and
fI – fA = N/DA
Adding gives
and
N = DV(fW – fA)
where
The groups 1/DA and 1/DW are effectively resistances that add to give the total
resistance 1/DV. It can be shown that
DV = kOWAZW = kOAAZA
Thus,
as before.
The net volatilization rate, DV(fW – fA), can be viewed as the algebraic sum of
an upward volatilization rate, DVfW, and a downward absorption rate, DVfA.
Expressions for intermedia diffusion become very simple and transparent when
written in fugacity form. The selection of one of two possible overall MTCs is
avoided. Each conductivity is expressed in identical units containing its own Z value.
The conductivities add reciprocally, as do electrical conductivities in series.
ments of resuspension rates are particularly difficult, because the resuspension event
may be triggered periodically by a storm or flood or by an especially energetic fish
chasing prey at the bottom of the lake. Regrettably, the sediment-water interface is
not easily accessible, thus measurements are few, difficult, and expensive.
Measurement of diffusion D values usually involves setting up a system in which
there is a known fugacity driving force (f1 – f2) and the capacity to measure N,
leaving the overall transport D value as the only unknown in the flux equation. A
difficulty arises because, for a two-resistance in series system, it is impossible to
measure the concentrations or fugacity at the interface; therefore, it is not possible
to deduce the individual D values that combine to give the overall D value. The
subterfuge adopted is to select systems in which one of the resistances dominates
and that resistance can be equated to the total resistance. Guidance on chemical
selection can be obtained from the location of the substance on Figure 7.7.
Air phase mass transfer coefficients (MTCs) can be determined directly by
measuring the evaporation rate of a pool of pure liquid, or even the sublimation rate
of a volatile solid. The interfacial partial pressure, fugacity, or concentration of the
solute can be found from vapor pressure tables. The concentration some distance
from the surface can be zero if an adequate air circulation is arranged, thus ∆C or
∆f is known. The pool can be weighed periodically to determine N, and area A can
be measured directly, thus the MTC or evaporation D value is the only unknown.
A tray (50 × 30 cm in area) contains benzene at 25°C (vapor pressure 12,700 Pa).
The benzene is observed to evaporate into a brisk air stream at a rate of 585 g/h.
What are D and kM, the mass transfer coefficient?
Since the molecular mass is 78 g/mol, N is 585/78 or 7.5 mol/h.
∆f = (12700 – 0) Pa
A is 0.5 × 0.3 or 0.15 m2. ZA is 1/RT or 4.04 × 10–4. Since D is kMAZ, kM is 9.7 m/h.
In conventional units, ∆C is 12,700/RT or 5.13 mol/m3.
N = kMA∆C
where CA and CW are concentrations in air and water and kOW the overall MTC.
Assuming CA to be zero, integrating gives
or
fW = fWO exp(–DVt/VZW)
Plotting CW on semilog paper vs. linear time gives a measurable slope of –kOW/Y,
hence kOW can be estimated. A system of this type has been described by Mackay
and Yuen (1983) and is illustrated in Figure 7.8.
A very useful quantity is the evaporation half-life, which is 0.693Y/kOW and
0.693 VZW/DV. Often, an order of magnitude estimate of this time is sufficient to
show that volatilization is unimportant or that it dominates other processes, such as
reaction.
As noted earlier, measurement of the individual contributing air and water D
values or MTCs is impossible, because the interfacial concentrations cannot be
measured. If, however, the evaporation rates of a series of chemicals of different
KAW are measured, it is possible to deduce kW and kA or DW and DA.
The relationship 1/kOW = 1/kW + 1/kAKAW suggests plotting, as in Figure 7.8,
1/kOW versus 1/KAW for a series of chemicals. The intercept will be 1/kW and the
slope 1/kA.
A correction may be necessary for molecular diffusivity differences. kW or DW
is measured by selecting chemicals of high KAW for which the term 1/kAKAW or 1/DA
is negligible. Alkanes, oxygen, or inert gases are convenient. kA or DA is measured
by choosing chemicals of low KAW such that 1/kAKAW or 1/DA is large compared to
1/kW or 1/DW. Alcohols are convenient for this purpose.
Figure 7.8 Movement of air phase (kA), water phase (kW), and overall (kOV) mass transfer
coefficients by following the volatilization of substances with different air-water
partition coefficients, KAW.
This equation can be written twice, once for benzene and once for naphthalene,
using the specific values of kOW and KAW . The two equations can be solved for kW
and kA, giving
kW = 0.20 kA = 15 m/h
In fugacity format, ZA is 4.04 × 10–4 for both substances, and ZW is 1.836 × 10–3
for benzene and 23.7 × 10–3 for naphthalene, thus the fugacities are initially 54 and
4.22 Pa, falling to 25 and 2.72 Pa. The DV values are obtained from
CH07 Page 171 Monday, January 15, 2001 1:51 PM
fW = fWO exp(–DVt/VZW)
Now, 1/DV equals (1/DA + 1/DW), the DA value being common to both chemicals.
DW contains the variable ZW; therefore, DW for naphthalene is DW for benzene times
23.7 × 10–3/1.836 × 10–3 or 12.9.
Example 7.5
Ten kilograms each of benzene, 1,4 dichlorobenzene, and p cresol are spilled
into a pond 5 m deep with an area of 1 km2. If kW is 0.1 m/h, and kA is 10 m/h,
what will be the times necessary for half of each chemical to be evaporated? Use
the property data from Chapter 3, and ignore other loss processes.
Answer
rates can thus be used to estimate mass transfer coefficients for other solutes having
similar (large) H such as alkanes. Indeed, an ingenious experimental approach for
determining k2 for oxygen is to use a volatile hydrocarbon, such as propane, as a
tracer, thus avoiding the complications of biotic oxygen consumption or generation,
which confound environmental measurements of oxygen concentration change. It is
erroneous to use k2 to estimate the rate of volatilization of a chemical with low H,
since k2 contains negligible air phase resistance information. A correction should
also be applied for the effect of molecular diffusivity, preferably using the dimen-
sionless form of diffusivity, the Schmidt number raised to a power such as –0.5 or
–0.67.
This technique of probing interfacial MTCs by measuring N for various chem-
icals can be applied in other areas. When chemical is taken up by fish, it appears
that it passes through one or more water layers and one or more organic membranes
in series. By analogy with air-water transfer, we can write an organic membrane-
water transfer equation simply by replacing subscript A by subscript M, giving
N = kOWA(CW – CM/KOW)
where
N = kOMA(CWKMW – CM)
where
where VF is fish volume and CO is CF/L, where L is the volume fraction lipid
(equivalent to octanol) in the fish. It follows that
1/k2 versus KOW to obtain quantities containing kM and kW. Such a plot was compiled
by Mackay and Hughes (1984), yielding estimates of the two-resistances expressed
as characteristic uptake times.
Another example is the penetration of chemicals through the waxy cuticles of
leaves in which there are air and wax resistances in series. Kerler and Schonherr
(1988) have measured such penetration rates for a variety of chemicals, and Schramm
et al. (1987) have attempted to model chemical uptake by trees using this two-
resistance approach. A plant’s principal problem in life is to manage its water budget
and avoid excessive loss of water through leaves. It accomplishes this by forming
a waxy layer through which water has only a very slow diffusion rate. Diffusivities
are very low, leading to very low MTCs and D values for water. The plant thus
exploits this two-resistance approach to conserve water. If only governments could
manage their budgets with the same efficiency!
Having introduced these transport D values and shown how they combine when
describing resistances in series, it is useful to set out the general flux equation for
any combination of transport processes in series or parallel.
Each transport process is quantified by a D value (deduced as GZ, kAZ, or
BAZ/Y) that applies between two points in space such as a bulk phase and an
interface, or between two bulk phases. It is helpful to prepare an arrow diagram of
the processes showing the connections, as illustrated in Figure 7.9. Diffusive pro-
cesses are reversible, so they actually consist of two arrows in opposing directions
with the same D value but driven by different source fugacities.
When processes apply in parallel between common points, the D values add. An
example is wet and dry deposition from bulk air to bulk water.
When processes apply in series, the resistances add or, correspondingly, the recip-
rocal D values add to give a reciprocal total.
An example is the addition of air and water boundary layer resistances, which in
total control the rate of volatilization from water.
It is possible to assemble numerous combinations of series and parallel processes
linking bulk phases and interfaces. These situations can be viewed as electrical
analogs, with voltage being equivalent to fugacity, resistance equivalent to 1/D, and
current equivalent to flux (mol/h). Figure 7.9 gives some examples.
In air-water exchange, there can be deposition by the parallel processes of (1)
dry particle deposition, (2) wet particle deposition, (3) rain dissolution, and (4)
diffusive absorption-volatilization.
CH07 Page 174 Monday, January 15, 2001 1:51 PM
Figure 7.9 Combination of D values and resistances in series, parallel, and combined con-
figurations.
The soil-air exchange example involves parallel diffusive transport from bulk
soil to the interface in water and air, followed by a series air boundary layer diffusion
step.
The sediment-water example is similar, having parallel diffusive paths for chem-
ical transport in water and in association with organic colloids. The difficulty is to
estimate the diffusivity of the colloids.
Even more complex combinations can be compiled for transport processes into
and within organisms, this being essentially the science of pharmacokinetics.
CH07 Page 175 Monday, January 15, 2001 1:51 PM
In this chapter, we have examined the nature of molecular and eddy diffusivity,
introduced the concept of mass transfer coefficients (k), and treated the problem of
resistances occurring in series and parallel as material diffuses from one phase to
another. Two new D values have been introduced, a kAZ product and a BAZ/∆Y
product. We can treat situations in which various D values apply in series and in
parallel.
In some situations, diffusion D values may be assisted or countered by advective
transfer D values. For example, PCB may be evaporating from a water surface into
the atmosphere only to return by association with aerosol particles that fall by wet
or dry deposition. We can add D values when the fugacities with which they are
multiplied are identical, i.e., the source is the same phase. This is convenient, because
it makes the equations algebraically simple and enables us to compare the rates at
which materials move by various mechanisms between phases.
We thus have at our disposal an impressive set of tools for calculating transport
rates between phases. We need Z values, mass transfer coefficients, diffusivities,
path lengths, and advective flow rates. Quite complicated models can be assembled
describing transfer of a chemical between several media by a number of routes. In
general, the total D value for movement from phase A to phase B will not be the
same as that from B to A. The reason is that there may be an advective process
moving in only one direction. Diffusive processes always have identical D values
applying in each direction. D values for loss by reaction can also be included in the
mass balance expression. We are now able to use these concepts to perform a Level
III calculation.
These calculations were suggested and illustrated in a series of papers on fugacity
models (Mackay, 1979; Mackay and Paterson 1981, 1982; and Mackay et al. 1985).
It is important to emphasize that these models will give the same results as other
concentration-based models, provided that the intermedia transport expressions are
ultimately equivalent. A major advantage of the fugacity approach is that an enor-
mous amount of detail can be contained in one D value, which can be readily
compared with other D values for different processes. It is quite difficult, on the
other hand, to compare a reaction rate constant, a mass transfer coefficient, and a
sedimentation rate and identify their relative importance.
Figure 7.10 depicts the simple four-compartment evaluative environment with
the intermedia transport processes indicated by arrows. In addition to the reaction
and advection D values, which were introduced in Level II, there are seven intermedia
D values. The emission rates of chemicals must now be specified on a medium-by-
medium basis whereas, in Level II, only the total emission rate was needed.
Table 7.1 lists the intermedia D values and gives the equations in terms of
transport rate parameters. Subscripts are used to designate air, 1; water, 2; soil, 3;
and sediment, 4.
Table 7.2 gives order-of-magnitude values for parameters used to calculate inter-
media transport D values. These values depend on the environmental conditions and
CH07 Page 176 Monday, January 15, 2001 1:51 PM
where U* is the friction velocity, which characterizes the drag of the wind on the
water surface. ScA is the Schmidt number in air and ranges from 0.6 for water to
about 2.5, and ScW applies to the water phase and is generally about 1000. U10 is
the wind velocity at 10 m height.
Changing the velocity units to m/h, substituting typical values for the Schmidt
number, and taking into account other studies, the following correlations are sug-
gested.
CH07 Page 177 Monday, January 15, 2001 1:51 PM
These correlations will underestimate the mass transfer coefficients under turbulent
conditions of breaking waves or in rivers where there is “white water.”
Sedimentation rates can be estimated by assuming a deposition velocity of about
1 m/day. Therefore, a lake containing 15 g/m3 of suspended solids is probably
depositing 15 g/m2 day of solids, which corresponds to about 10 cm3/m2 day if the
density is 1.5 g/cm3. This corresponds to 0.4 cm3/m2 h or 40 × 10–8 m3/m2 h or 40
× 10–8 m/h. Of this, a fraction is buried, and the remainder is resuspended. In waters
of lower solids concentration, the deposition rate is correspondingly slower.
The air-to-water D value (D12) consists of diffusive absorption (DV) and nondif-
fusive wet and dry aerosol deposition. Each D value can be estimated and summed
to give D12.
CH07 Page 178 Monday, January 15, 2001 1:51 PM
The water-to-air D value (D21) is DV for diffusive volatilization and is, of course, the
same DV as for absorption.
The air-to-soil D value (D13) is similar to D12, but the areas differ, and the absorption-
volatilization D value is also different.
The soil-to-air D value (D31) is for volatilization.
The water-to-sediment D value (D24) represents diffusive transfer plus nondiffusive
sediment deposition.
The sediment-to-water D value (D42) represents diffusive transfer plus nondiffusive
resuspension.
Finally, the soil-to-water D value (D32) consists of nondiffusive water and particle
runoff.
We now write the mass balance equations for each medium as follows.
CH07 Page 179 Monday, January 15, 2001 1:51 PM
Air (subscript 1)
Water (subscript 2)
Soil (subscript 3)
Sediment (subscript 4)
In each case, Ei is the emission rate (mol/h), GA is the advective inflow rate (m3/h),
CBi is the advective inflow concentration (mol/m3), DRi is the reaction rate D value,
and DAi is the advection rate D value. DTi is the sum of all loss D values from
medium i. Sediment burial and air-to-stratospheric transfer can be included as an
advection process or as a pseudo reaction.
These four equations contain four unknowns (the fugacities), thus solution is
possible. After some algebra, it can be shown that
f1 = (J1 + f2J2)/J3
f3 = (I3 + f1D13)/DT3
f4 = (I4 + f2D24)/DT4
where
J1 = I1/DT1 + I3D31/(DT3DT1)
J2 = D21/DT1
J3 = 1 – D31D13/(DT1DT3)
J4 = D12 + D32D13/DT3
and
Ii = Ei + GAiCBi
i.e., the total of emission and advection inputs into each medium.
CH07 Page 180 Monday, January 15, 2001 1:51 PM
Unlike the Level II calculation, it is now necessary to specify the emissions into
each compartment separately. Different mass distributions, concentrations, and res-
idence times result if 100 mol/h is emitted to air, water, or soil; thus, “mode of
entry” is an important determinant of environmental fate and persistence.
Having obtained the fugacities, all process rates can be deduced as Df, and a
steady-state mass balance should emerge in which the total inputs to each medium
equal the outputs. The amounts and concentrations can be calculated.
An overall residence time can be calculated as the sum of the amounts present
divided by the total input (or output) rate. A reaction residence time can be calculated
as the amount divided by the total reaction rate, and a corresponding advection
residence time can also be deduced. Doubling emissions simply doubles fugacities,
masses, and concentrations, but the residence times are unchanged.
An important property of this model is its linear additivity. This is also called
the principle of superposition. Because all the equations are linear, the fugacity in,
for example, water, deduced as a result of emissions to air, water, and soil, is simply
the sum of the fugacities in water deduced from each emission separately. It is thus
possible to attribute the fugacity to sources, e.g., 50% is from emission to water,
30% is from emission to soil, and 20% from emission to air. The masses and fluxes
are also linearly additive.
Figure 7.11 is a schematic representation of the results corresponding to the
computed output in Figure 7.12. This is a comprehensive multimedia picture of
chemical emission, advection, reaction, intermedia transport, and residence time or
persistence. The important processes are now clear, and it is possible to focus on
them when seeking more accurate rate data. Figure 7.11 contains information about
21 processes, some of which, such as air-water transfer, consist of several contrib-
uting processes. The human mind is incapable of making sense of the vast quantity
of physical chemical and environmental data without the aid of a conceptual tool
such as a Level III program.
It is possible to add more compartments and to subdivide the existing compart-
ments. It may be advantageous to add vegetation as a separate compartment. The
atmosphere or water column could be segmented vertically. The soil can be treated
as several layers. If information is available to justify these changes, they can be
implemented, albeit at the expense of greater algebraic complexity. If the number
of compartments becomes large and highly connected, it is preferable to solve the
equations by matrix algebra.
Computer programs are provided on the Internet, as discussed in Chapter 8, that
undertake the Level III calculation of the multimedia fate of a specified chemical.
The user must provide physical chemical (partitioning) properties, reaction half-
lives, and sufficient information to deduce intermedia transport D values. Assembly
of an entire Level III model for a chemical is a fairly demanding task, since there
are numerous areas, flows, mass transfer coefficients, and diffusivities to be esti-
mated. To assist in this task, Table 7.2 gives suggested order-of-magnitude values
for the various parameters. Such values are included as defaults in some programs,
but they can be modified as desired.
The user is encouraged to conduct Level III calculations for chemicals of interest,
or those specified in Chapter 3. It is instructive to prepare a mass balance diagram,
CH07 Page 181 Monday, January 15, 2001 1:51 PM
check that the balance is correct (i.e., input equals output for each compartment)
and identify the primary processes which control environmental fate. It may then
be appropriate to examine these processes in more detail, seeking more accurate
parameter values. Usually, the chemical’s fate is controlled by a few key processes,
but these are not always obvious until a Level III calculation is performed.
where Vi is volume, Zi is bulk Z value, Ii is the input rate (which may be a function
of time), each term Djifj represents intermedia input transfers, and DTifi is the total
output. If an initial fugacity is defined for each medium, these four equations can
be integrated numerically to give the fugacities as a function of time, thus quantifying
the time response characteristics of the system.
It is noteworthy that the characteristic response time of a compartment is ViZi/DTi,
which can be deduced from the Level III steady-state version. These characteristic
times provide advance insight into how a Level IV system should respond to chang-
ing emissions. This calculation is most useful for estimating recovery times of a
contaminated system that is now experiencing zero or reduced emissions.
Hand Calculation
Using only air, water, and sediment from the four-compartment environments
and the chemicals treated in the Level II example at the conclusion of Chapter 6,
draw a Level III diagram similar to Figure 7.11, showing the compartments, the VZ
values for each, and the advection and reaction D values. Write in somewhat arbitrary
values for the six intermedia transport D values, but assigning values that lie in the
range of 0.1 to 1% of VZ of the source phase. This gives rate constants for transport
of 10–3 to 10–2 h–1. Feel free to round off all VZ and D values to facilitate calculation.
Assume total inputs into air of 100 mol/h, and into water of 20 mol/h.
Write down the three mass balance equations and solve by hand for the three
fugacities. Calculate all the fluxes and check the mass balance for each compartment
and the system as a whole. Calculate the three chemical residence times. Confirm
the validity of the linear additivity assertion by calculating the fugacity in water for
emissions only to air, and only to water, and show that their sum is the fugacity
calculated when both emissions apply simultaneously. Do the residence times depend
on the chemicals’ mode of entry to the environment?
Computer Calculation
Using the Level III program described in Chapter 8, compile a Level III mass
balance diagram for a chemical using data from Table 3.5 and postulated emission
rates in the range of 0.1 to 10 g per hour per square kilometre into air, water, and
soil. Discuss the results, including the primary media of accumulation, the important
processes, the relative media fugacities, and the residence times.
EQC Calculation
Using the EQC model described in Chapter 8, compile Level I, II, and III mass
balances for a chemical and discuss the results.
CH07 Page 184 Monday, January 15, 2001 1:51 PM
CH08 Page 185 Monday, January 15, 2001 1:52 PM
CHAPTER 8
The ability to define Z values for a variety of media, and D values for processes
such as advection, reaction, and intermedia transport, enables us to set up mass
balance equations and then deduce fugacities, concentrations, fluxes, and amounts.
We thus have the capability of addressing a series of environmental modeling
problems in addition to the Level I, II, and III calculations described earlier.
The aim of this chapter is to provide the reader with a description of the
calculation of chemical fate in a variety of environmental situations in the expectation
that the parameter values describing the environment and the chemical can be
modified to simulate specific situations. It may be desirable to add or delete processes
or change the model structure to suit individual requirements. Many of the models
apply to steady-state conditions and can be reformulated to describe time-varying
conditions by writing differential rather than algebraic equations. These differential
equations can be solved algebraically or integrated numerically, depending on their
complexity.
Some of the most satisfying moments in environmental science come when a
model is successfully fitted to experimental or observed data and it becomes apparent
that the important chemical transport and transformation processes are being repre-
sented with fidelity. Even more satisfying is the subsequent use of the model to
predict chemical fate in as yet uninvestigated situations leading to gratifying and
successful “validation.” Failure of the model may be disappointing, but it is a positive
demonstration that our fundamental understanding of environmental processes is
flawed and further investigation is needed. For a review of the history of environ-
mental mass balance models, the reader is referred to Wania and Mackay (1999).
8.1.1 Scope
185
CH08 Page 186 Monday, January 15, 2001 1:52 PM
applications. Citations are given to enable the reader to download these models from
the internet site of the Canadian Environmental Modelling Centre at Trent University,
namely http://www.trentu.ca/envmodel. Included are DOS and Windows Level I,
Level II, and Level III models, the EQC (EQuilibrium Criterion) model, the Generic
model, and ChemCAN, a Level III model that has data for regions of Canada but
can be (and has been) adapted to other regions.
The next group of models is used to explore how a chemical is migrating or
exchanging across the interface between two media, given the concentrations or
fugacity in both. No mass balance is necessarily sought—merely a knowledge of
how fast, and by what mechanism, the chemical is migrating. Compartment volumes
are not necessary, but they may be included for the purpose of calculating half-lives.
An example is air-water exchange in which both concentrations are defined and the
aim is to deduce in what direction and at what rate the chemical is moving. Often,
it is not clear if a substance in a lake is experiencing net input or output as a result
of exchange with the atmosphere. An important conclusion is that zero net flux does
not necessarily correspond to equilibrium or equifugacity. We refer to these as
intermedia exchange models.
The simplest mass balance model is a one-compartment “box” that receives
various defined inputs either as an emission term or as the product of a D value and
a fugacity from an adjoining compartment. The various D values for output or loss
processes are then calculated. The steady-state fugacity at which inputs and outputs
are equal is then deduced. An unsteady-state version of the model can also be devised.
Examples are a “box” of soil to which sludge or pesticide is applied, a one-com-
partment fish with input of chemical from respired water and food, and a mass
balance for the water in a lake.
The complexity can be increased by adding more connected compartments. The
QWASI (Quantitative Water, Air, Sediment Interaction) model includes mass bal-
ances in two compartments (water and sediment), the concentration in air being
defined. A river, harbour, or estuary can be treated as a series of connected Eulerian
QWASI boxes or using Lagrangian (follow a parcel of water as it flows) coordinates.
A sewage treatment plant (STP) model is described in which the compartments are
the three principal vessels in the activated sludge process. This illustrates that the
modeling concepts can also be applied to engineered systems. Indeed, such systems
are often easier to model, because they are well defined in terms of volumes, flows,
and other operating conditions such as temperature.
This multicompartment approach can be applied to chemical fate in organisms
ranging from plants to humans and whales. These are physiologically based phar-
macokinetic (PBPK) models.
Fairly complex models containing multiple compartments can be assembled,
an example being the POPCYCLING–BALTIC model of chemical fate in the
Baltic region. The ultimate model is one of chemical fate in the entire global
environment, GloboPOP. These models are available from a website at the Uni-
versity of Toronto, to which a link is provided from the Trent University address
given earlier.
Where possible, references are given to published studies in which the models
have been applied. These reports give more detail than is possible here.
CH08 Page 187 Monday, January 15, 2001 1:52 PM
The general model-building strategy is first to evaluate the system being simu-
lated, then to decide how many compartments and thus mass balances are required.
There is a compelling incentive to start with a simple model then build up complexity
only when justified. The volumes and bulk Z values are deduced for each compart-
ment. All inputs and outputs are identified, preferably as arrows on a mass balance
diagram. Equations are written for each flux, either as an emission or a Df product.
For a steady-state model, the inputs are equated to outputs for each of the n com-
partments, leading to n equations with n unknown fugacities. These equations are
solved, either algebraically or using a matrix method.
For a dynamic system, the differential equations for each medium are written in
the form
These equations are then solved, either analytically or numerically, for a defined
initial condition and defined inputs. The integration time step can be selected as 5%
of the shortest half-time for transport or transformation and the stability of the result
checked by decreasing the time step systematically. Integration is best done using
a Runge–Kutta method, but the simple Euler’s method may be adequate.
Results should be checked for a mass balance. For steady-state models, this is
simply a comparison of inputs and outputs for each compartment. For dynamic
models, the initial mass plus the cumulative inputs should equal the final mass and
the cumulative outputs. To gain a pictorial appreciation of the results, a mass balance
diagram should be drawn listing all inputs and outputs beside the appropriate arrows.
The dominant processes then become apparent.
It is often useful to play “sensitivity games” with the model to gain an appreci-
ation of how variation in an input quantity such as an emission rate, Z value, or D
value propagates through the calculation and affects the results. An input quantity
can be increased by 1% and the effect on the desired output quantity determined.
The best way to quantify this sensitivity S is to deduce
S = (∆output/output)/(∆input/input)
For example, if the input quantity of 100 is increased to 101 and the output
quantity changes from 1000 to 1005, then S is (5/1000)/(1/100) or 0.5. This is
actually an estimate of the partial derivative of log output with respect to log input,
and it is dimensionless. For linear systems of the types treated here, all values of S
should be less than 1.0. It may be useful to list the input parameters, deduce S for
each, then rank them in order of decreasing S. The most sensitive parameters, for
which the most accurate data are necessary, are then identified. Often, the sensitivity
of a parameter is surprisingly small, and only a rough estimate is needed. It may be
desirable to revisit and improve the accuracy of the estimates of most sensitive
parameters.
CH08 Page 188 Monday, January 15, 2001 1:52 PM
Another approach is to employ Monte Carlo analysis and run the model repeat-
edly, allowing the input data to vary between prescribed limits and deducing the
variation in the output quantities. This gives an impression of the likely variability
in the output, but it does not necessarily reveal the individual quantitative sources
of this variability.
The model results can then be compared with measured values to achieve a
measure of validation. Complete validation is impossible, because chemicals or
conditions can always be found for which the model fails. For a philosophical
discussion of the feasibility of validation, the reader is referred to a review by Oreskes
et al. (1994). A model can be useful, even if not validated, because it can give reliable
results for a restricted set of conditions.
A final note on transparency. It is unethical for an environmental scientist to
assert that a chemical experiences certain fate characteristics as a result of model
calculations unless the full details of the calculations inherent in the model are made
available. The scientific basis on which the conclusions are reached must be fully
transparent. For various reasons, the modeler may elect to prevent the user from
modifying the code, but the calculations themselves must be readable. For this
reason, all model calculations described here are fully transparent.
To aid in formulating models, Table 8.1 summarizes the expressions for estimat-
ing Z values, and Table 8.2 summarizes equations for estimating D values.
Bulk Z values are ΣviZi, where vi is the volume fraction of phase i, and Zi is its
Z value. For example, for bulk air,
For a solid phase (subscript s) containing organic carbon of mass fraction yOC, in
which sorption to mineral matter is negligible and the partitioning coefficient with
respect to water is KD L/kg,
CH08 Page 189 Monday, January 15, 2001 1:52 PM
Advection or flow D = GZ = UAZ G is medium flow rate (m3/h) and may be given
as a product of velocity U (m/h) and area A m2.
Reaction D = VZk V is volume (m3) and k is rate constant (h–1).
Diffusion D = BAZ/Y B is molecular or effective diffusivity (m2/h).
A is area (m2) and Y is path length (m).
Mass transfer D = kAZ k is mass transfer coefficient or velocity (m/h).
Growth dilution D = ZdV/dt = VZk dV/dt is growth rate (m3/h), and k is the growth
rate constant (h–1) or (dV/dt)/V.
In all cases, Z refers to the medium in which the process occurs.
The rate is Df (mol/h).
For series processes 1/D = Σ1/Di.
For parallel processes D = ΣDi.
Characteristic times are VZ/D (h) where V and Z refer to the source phase.
Half–times are 0.693 VZ/D (h).
Rate constants are D/VZ (h–1).
KOC can be estimated as 0.41 KOW (Karickhoff, 1981) or as 0.35 KOW plus or minus
a factor of 2.5 (Seth et al., 1999). Note that KOM is typically 0.56 KOC, i.e., OM is
typically 56% OC. KQA can be estimated as 6 × 106/PS, where PS is the liquid vapor
pressure, or from other correlations using vapor pressure or KOA as described in
Chapter 5.
These models have been described earlier in Chapters 5, 6, and 7. These programs
are available from http://www.trentu.ca/envmodel in two formats. First are BASIC
models, which can be run directly on DOS systems or using GWBASIC or QBASIC.
Second are more user-friendly Windows® models in which input parameters are
more easily changed, and output is available on the screen, and it can be printed or
saved to a file. The code of the BASIC models can be changed, and they can serve
as a template for building other models. The calculations in the Windows models
cannot be modified by the user. In all cases, the code can be inspected; it is fully
transparent.
The following BASIC models are available.
LEVEL1A
LEVEL1B
LEVEL2A
LEVEL2B
LEVEL3A
A four-compartment Level III program that requires all the Level II data and
prompts for D values in the form of transfer half-lives.
LEVEL3B
Level I
Level II
Level III
The DOS-based Generic model contains all the Level I, II, and III calculations.
It is described in a paper by Mackay et al. (1992). It is also described in Chapter 1
of the five-volume Illustrated Handbook of Physical Chemical Properties and Envi-
ronmental Fate of Organic Chemicals, by Mackay, Shiu, and Ma, which is also
available in CD ROM format.
The EQC (EQuilibrium Criterion) model is described in a series of papers by
Mackay et al. (1996). It applies to a 100,000 km2 land area (about the size of Ohio).
It is a Windows model and has been used in several assessments of the likely behavior
of a chemical in an evaluative context. An example is the application to the chlo-
robenzenes in Ontario by MacLeod and Mackay (1999). Booty and Wong (1996)
have also applied the model to the same region for a variety of chemicals.
The Level III ChemCAN model is in Windows format and contains databases of
24 regions of Canada and a number of chemicals. It can be applied to other regions,
and it has been modified to apply to regions of France (Devillers and Bintein, 1995),
Germany (Berding et al., 2000), and the U.K.
The CalTOX model of McKone, which is available from the California Environ-
mental Protection Agency (http://www.cwo.com/~herd1/), is a Level III model that
CH08 Page 191 Monday, January 15, 2001 1:52 PM
8.3.1 Introduction
The situation treated here, and the resulting model, are largely based on the
study of air-water exchange by Mackay et al. (1986) as is depicted in Figure 8.1.
The water phase area and depth (and hence volume) are defined, it being assumed
that the water is well mixed. The water contains suspended particulate matter, to
CH08 Page 192 Monday, January 15, 2001 1:52 PM
which the chemical can be sorbed, and which may contain mineral and organic
material. The concentration (mg/L or g/m3) of suspended matter is defined, as is its
organic carbon (OC) content (g OC per g dry particulates). By assuming a 56% OC
content of organic matter, the masses of mineral and organic matter can be deduced.
Densities of 1000, 1000, and 2500 kg/m3 are assumed for water, organic matter,
and mineral matter respectively, thus enabling the volumes and volume fractions to
be deduced.
The air phase is treated similarly, having the same area as the water and a defined
(possibly arbitrary) height and containing a specified concentration (ng/m3) of aero-
sols or atmospheric particulates to which the chemical may sorb. By assuming an
aerosol density of 1500 kg/m3, the volume fraction of aerosols can be deduced. No
information on aerosol composition, size distribution, or area is sought or used. If
the concentration of aerosols or total suspended particulates is TSP ng/m3, this
corresponds to 10–12 TSP kg/m3 and to a volume fraction vQ of 10–12 TSP/ρQ, where
ρQ is the aerosol density (1500 kg/m3). Thus, a typical TSP of 30,000 ng/m3 or 30
µg/m3 is equivalent to a volume fraction of 20 × 10–12.
The volumes of particles can be calculated as the product of total volume V, and
respective volume fractions.
Physical chemical properties of the chemical are requested.
The total or bulk concentrations in the water and air phases are requested in
mass/volume units. These are converted to mol/m3 and divided by the bulk Z values
to give the water and air fugacities. The quantities and concentrations in dissolved,
or gaseous, and sorbed form are then calculated, i.e., the input concentrations are
apportioned to sorbed and nonsorbed forms. Z and D values are calculated using
the expressions in Tables 8.1 and 8.2.
CH08 Page 193 Monday, January 15, 2001 1:52 PM
A check should be made of the magnitude of f/PS, where PS is the solid or liquid
vapor pressure. When this ratio equals 1, saturation is achieved. When the ratio
exceeds 1, the chemical will precipitate as a pure phase, i.e., its solubility in air or
water is exceeded, and the fugacity will drop to the saturation value indicated by
the vapor pressure. Normally, the ratio is much less than unity.
Four processes are considered as shown in Figure 8.1: (1) diffusive exchange by
volatilization and the reverse absorption, (2) dry deposition of aerosols, (3) wet
dissolution of chemical, and (4) wet deposition of aerosols. In each case, a D value
(mol/Pa h) is used to characterize the rate, which is Df mol/h.
For diffusion, the two-resistance approach is used, and D values are deduced for
the air and water boundary layers,
DA = kA A ZA DW = kW A ZW
where kA and kW are mass transfer coefficients with units of m/h, and A is area (m2).
Illustrative values of 5 m/h for kA and 5 cm/h for kW can be used, but it should be
appreciated that environmental values can vary widely, especially with wind speed,
and a separate calculation may be needed for the situation being simulated.
The overall resistance (1/DV) is obtained by adding the series resistances (1/D) as
The rate of vaporization is then fWDV, the rate of absorption is fADV, and the net rate
of vaporization is DV(fW – fA). An overall mass transfer coefficient is also calculated.
For dry deposition, a dry deposition velocity UD of particles is used, a typical
value being 0.3 cm/s or 10 m/h. The total dry deposition rate is thus UDvQA m3/h,
the corresponding D value DD is UDvQAZQ, and the rate is DDfA mol/h.
For wet dissolution, a rain rate is defined, usually in units of m/year, a typical
value being 0.5 m/year or 6 × 10–5 m/h, designated UR. The total rain rate is then
URA (m3/h), the D value, DR, is URAZW, and the rate is DRfA mol/h.
For wet aerosol deposition, a scavenging ratio Q is used, representing the volume
of air efficiently scavenged by rain of its aerosol content, per unit volume of rain.
A typical value of Q is 200,000. The volume of air scavenged per hour is thus URAQ
(m3/h), which will contain URAQvQ (m3/h) of aerosol (vQ is the volume fraction of
aerosol). The D value DQ is thus URAQvQZQ, and the rate is DQfA (mol/h).
A washout ratio is often employed in such calculations. This is the dimensionless
ratio of concentration in rain to total concentration in air, usually on a volumetric
(g/m3 rain per g/m3 air) basis, but occasionally on a gravimetric (mg/kg per mg/kg)
basis. The total rate of chemical deposition in rain is (DR + DQ)fA; thus, the concen-
tration in the rain is (DR + DQ)fA/URA or fA(ZW + QvQZQ) mol/m3. The total air
concentration is fA(ZA + vQZQ), and therefore the volumetric washout ratio is (ZW +
QvQZQ)/(ZA + vQZQ). The gravimetric ratio is smaller by the ratio of air to water
densities, i.e., approximately 1.2/1000. If the chemical is almost entirely aerosol
associated, as is the case with metals such as lead, the volumetric washout ratio
approaches Q. These washout ratios are calculated and can be compared to reported
values.
CH08 Page 194 Monday, January 15, 2001 1:52 PM
fWDV = fADT
The steady-state water fugacity and concentration with respect to the air, and the
steady-state air fugacity and concentration with respect to the water, can thus be
calculated to give an impression of the extent to which the actual concentration
departs from the steady-state values, as distinct from the equilibrium (equifugacity)
value. It is noteworthy that, because DT exceeds DV, the fugacity in water will tend
to exceed the fugacity in air; however, this will be affected by removal processes in
water.
8.3.3 Model
The AirWater model is available from the website as Windows software and in
the older DOS-based BASIC format. In both cases, the calculations can be viewed
by the user, and sufficient comments are included to enable the logic to be followed.
A sample chemical and set of air and water properties are included as an example
for the user. Given the concentrations in the air and water, the steady-state fluxes
are calculated.
8.4.1 Introduction
leakage. It is often useful to assess the likely fate of the chemical, i.e., how fast the
rates of degradation, volatilization, and leaching in water are likely to be, and how
long it will take for the soil to “recover” to a specified or acceptable level of
contamination. Persistence is an important characteristic for pesticide selection.
Remedial measures such as excavation may be needed when recovery times are
unacceptably long.
Most modeling efforts in this context have been for agrochemical purposes, the
most comprehensive recent effort being described in a series of publications by Jury,
Spencer, and Farmer (1983, 1984a, 1984b, 1984c). Other notable models are
reviewed in these papers. The Soil model is essentially a very simplified version of
the Jury model (1983) and is a modification of a published herbicide fate model
(Mackay and Stiver, 1990). The reader is referred to the texts by Sposito (1989) and
Sawhney and Brown (1989) and the chapter by Green (1988) for fuller accounts of
chemical fate in soils. Cousins et al. (1999) have reviewed and modeled these
processes.
In the Soil model, only soil-to-air processes are treated; no air-to-soil transport
is considered. A second, more complex fugacity model SoilFug was developed by
DiGuardo et al. (1994a), which allows the user to calculate the fate of the pesticide
in a defined agricultural area over time with changing rainfall. The model gave
satisfactory predictions of pesticide runoff in agricultural regions in Italy and the
U.K. (Di Guardo et al., 1994a, 1994b). Both models are available from the website.
Only the Soil model is described here.
In the Soil model, the soil matrix illustrated in Figure 8.2 is considered to consist
of four phases: air, water, organic matter, and mineral matter. The organic matter is
considered to be 56% organic carbon. The volume fractions of air and water are
defined, either by the user or by default values, as is the mass fraction organic carbon
(OC) content on soil basis. Assuming densities of 1.19, 1000, 1000, and 2500 kg/m3
for air, water, organic matter, and mineral matter, respectively, enables the mass and
volume fractions of each phase, and the overall soil density, to be calculated.
The soil area and depth are specified, thus enabling the total volumes and mass
of soil and its component phases to be deduced. The amount of chemical present in
the soil is specified as a concentration or as an amount in units of kg/ha, which is
convenient for agrochemicals. The chemical is assumed to be homogenously dis-
tributed throughout the entire soil volume.
The individual phase Z values are calculated, then the bulk Z value of the soil
ZTS is deduced. From the concentration, the fugacity is deduced, and the individual
phase quantities and concentration are calculated.
It is prudent to examine the fugacity to check that it is less than the vapor
pressure. If it exceeds the vapor pressure, phase separation of pure chemical will
occur; i.e., the capacity of all phases to “dissolve” chemical is exceeded. This can
occur in heavily contaminated soils that have been subject to spills, or when there
is heavy application of a pesticide. Essentially, the “solubility” of the chemical in
the soil is exceeded. This calculation of partitioning behavior provides an insight
CH08 Page 196 Monday, January 15, 2001 1:52 PM
into the amounts present in the air and water phases. It also shows the extent to
which organic matter dominates the sorptive capacity of the soil.
Three loss processes are considered: degrading reactions, volatilization, and
leaching, each rate being characterized by a D value.
An overall reaction half-life τ(h) is specified from which an overall rate constant
kR (h–1) is deduced as 0.693/τ. The reaction D value DR is then calculated from the
total soil volume and the bulk Z value as kRVTZTS. In principle, if a rate constant ki
is known for a specific phase in the soil, the phase-specific D value can be deduced
as kiViZi, but normal practice is to report an overall rate constant applicable to the
total amount of chemical in the entire soil matrix. If no reaction occurs, an arbitrarily
large value for the half-life, such as 1010 hours, should be input.
A water leaching rate is specified in units of mm/day. This may represent rainfall
(which is typically 1 to 2 mm/day) or irrigation. This rate is converted into a total
water flow rate GL (m3/h), which is combined with the water Z value to give the
advection leaching D value DL as GLZW. This assumes that the concentration of
chemical in the water leaving the soil is equal to that in the water in the soil; i.e.,
local equilibrium has become established, and no bypassing or “short circuiting”
occurs. The “solubilizing” effect of dissolved or colloidal organic matter in the soil
water is ignored, but it could be included by increasing the Z value of the water to
account for this extra capacity.
CH08 Page 197 Monday, January 15, 2001 1:52 PM
Volatilization is treated using the approach suggested by Jury et al. (1983). Three
contributing D values are deduced.
An air boundary layer D value, DE, is deduced as the product of area A, a mass
transfer coefficient kV, and the Z value of air, i.e., A kV ZA.
Jury has suggested that kV be calculated as the ratio of the chemical’s molecular
diffusivity in air (0.43 m2/day or 0.018 m2/h being a typical value), and an air
boundary layer thickness of 4.75 mm (0.00475 m); thus, kV is typically 3.77 m/h.
Another kV value may be selected to reflect different micrometerological conditions.
An air-in-soil diffusion D value characterizes the rate of transfer of chemical
vapor through the soil in the interstitial air phase. The Millington–Quirk equation
is used to deduce an effective diffusivity BEA from the air phase molecular diffusivity
BA as outlined in Chapter 7, namely,
where vA is the volume fraction of air, and vW is the volume fraction of water. If vW
is small, this reduces to a dependence on vA to the power 1.33. A diffusion path
length Y must be specified, which is the vertical distance from the position of the
chemical of interest to the soil surface; i.e., it is not the “tortuous” distance. The air
diffusion D value DA is then BEA A ZA/Y
A similar approach is used to calculate the D value for chemical diffusion in the
water phase in the soil, except that the molecular diffusivity in water BW is used (a
value of 4.3 × 10–5 m2/day being assumed), and the water volume fraction and Z
value being used, namely,
DW = BEWAZW/Y
where
Since the diffusion D values DA and DW apply in parallel, the total D value for
chemical transfer from bulk soil to the soil surface is (DA + DW). The boundary layer
D value then applies in series so that the overall volatilization D value, DV, is given
as illustrated in Figure 8.2 as
mean. For chemical between depths of 1 and 10 cm, a log mean depth of 3.9 cm is
more appropriate than the arithmetic mean of 5.5 cm. It may be useful to consider
layers of soil separately, e.g., 2 to 4 cm, 4 to 6 cm, etc., and calculate separate
volatilization rates for each. Chemical present at greater depths will thus volatilize
more slowly, leaving the remaining chemical more susceptible to other removal
processes. It is acceptable to specify a mean Y of, say, 10 cm to examine the fate
of chemical in the 2 cm depth region from 9 to 11 cm. This depth issue is irrelevant
to reaction or leaching, but it must be appreciated that, if the soil is treated as separate
layers, the leaching rate is applicable to the total soil, not to each layer independently.
The total rate of chemical removal is then f DT , where the total D value is:
DT = DR + DL + DV
the individual rates being f DR, f DL, and f DV. The overall rate constant kO is thus
DT/VTZT, where VTZT is the sum of the ViZi products, and the overall half-life τO is
0.693/kO hours. The half-life τi attributable to each process individually is
0.693VTZT/Di, thus,
It is illuminating to calculate the rates of each process, the percentages, and the
individual half-lives. Obviously, the shorter half-lives dominate. The situation being
simulated is essentially the first-order decay of chemical in the soil by three simul-
taneous processes, thus the amount remaining from an initial amount M (mol) at
any time t (h) will be
This relatively simple calculation can be used to assess the potential for volatilization
or for groundwater contamination.
Implicit in this calculation is the assumption that the chemical concentration in
the air, and in the entering leaching water, is zero. If this is not the case, an appropriate
correction must be included. In principle, it is possible to estimate atmospheric
deposition rates as was done in the air-water example and couple these processes
to the soil fate processes in a more comprehensive air-soil exchange model.
It may prove desirable to segment the soil into multiple layers, especially if
evaporation or input from the atmosphere is important. Models of this type have
been reported by Cousins et al. (1999) for PCBs in soils.
8.4.3 Model
The Soil model is available from the website in both Windows software and in
the older DOS-based BASIC format, similarly to the AirWater model. The SoilFug
model is also available and can be used to explore the effects of varying precipitation
on soil runoff.
CH08 Page 199 Monday, January 15, 2001 1:52 PM
Users are encouraged to modify the various parameter values and are cautioned
that the values given are not necessary widely applicable. It should be noted again
that varying the input temperature will not vary physical chemical properties such
as vapor pressure. Temperature dependence must be entered “by hand.”
8.5.1 Introduction
The water phase area and depth (and hence volume) are defined, it being assumed
that the water is well mixed. The water contains suspended particulate matter, which
may contain mineral and organic material. The concentration (mg/L or g/m3) of
suspended matter is defined, as is its organic carbon (OC) content (g OC per g dry
particulates). The volume fractions are calculated similarly to those for air-water
exchange.
The sediment phase is treated similarly, having the same area, a defined well
mixed depth, and a specified concentration of solids and interstitial or pore water.
Rates of sediment deposition, resuspension, and burial are specified, as are first-
order reaction rates in the sediment phase. Allowance is made for infiltration of
ground water through the sediment in either vertical direction. Lipid contents of
organisms present in the water and sediment are specified for later illustrative
bioconcentration calculations.
The equilibrium partitioning distribution is calculated using Z values for the water
and sediment phases using specified total chemical concentrations (g/m3 or mg/L) in
the water, and µg/g of dry sediment solids in the sediment. Since no air phase appears
in the calculation, the vapor pressure is not strictly necessary. Identical concentration,
but not fugacity, results are obtained when an arbitrary vapor pressure is used.
Illustrative biotic Z values can be deduced for both water and sediment as KBZW,
where the bioconcentration factor KB is estimated from the product of lipid content
LB (e.g., 0.05) and KOW, i.e., LBKOW. Biota are included only for illustrative purposes
and are not included in the mass balance.
The total and contributing concentrations in all phases and the fugacities can
thus be deduced. From the biotic Z values, the corresponding concentrations can
also be deduced for biota resident in water and sediment.
Several transport and transformation processes are considered: (1) sediment
deposition, (2) sediment resuspension, (3) sediment burial, (4) diffusive exchange
of water between the water column and the pore water, and (5) sediment reaction.
Irrigation, i.e., net flow of groundwater into or out of the sediment, could be added
as a sixth process.
The individual and total rates of transfer can be calculated as the D f products.
CH08 Page 201 Monday, January 15, 2001 1:52 PM
8.5.3 Model
The Sediment model is available from the website in Windows- and DOS-based
versions. Input data are requested on the properties of the chemical, the dimensions
and properties of the media, and the prevailing concentrations. The Z and D values
are calculated, followed by fugacities and fluxes. It is also of interest to calculate
the overall steady-state mass balance, which is given by
The steady-state water and sediment fugacities corresponding to the defined sediment
and water fugacities are deduced. Response times can be calculated for each medium
if the volumes are known.
It is noteworthy that, for a persistent, hydrophobic substance, it is likely that the
steady-state sediment fugacity will exceed that of the water. The principal loss
process of a persistent chemical from the sediment is likely to be DR, which must
be less than DD, because some sediment is buried, and the organic carbon content
of the resuspended material will be less than the deposited material because of
mineralization. As a result, a benthic organism that respires sediment pore water
may reach a higher fugacity and concentration than a corresponding organism in
the water column above. A compelling case can be made for monitoring benthic
organisms, because they are less mobile than fish and they are likely to build up
higher tissue concentrations of contaminants.
These sediment-water calculations can be invaluable for estimating the rate at
which “in-place” sediment concentrations, resulting from past discharges of persis-
tent substances, are falling. Often, the memory of past stupidities lingers longer in
sediments than in the water column.
8.6.1 Introduction
learn the benefits of using fugacity. This RateConstant model is available from the
Trent University website, but only in DOS format. In principle, the QWASI model
can be applied to any well mixed body of water for which the hydraulic and
particulate flows are defined.
Figure 8.4 shows the transport and transformation processes treated, and Table
8.3 lists the D values and the corresponding fugacity in the rate expressions. Figure
8.5 gives the mass balance equations in steady-state and unsteady-state or differential
form. The steady-state solution describes conditions that will be reached after pro-
longed exposure of the lake to constant input conditions, i.e., emissions, air fugacity,
and inflow water fugacity. Also given in Figure 8.5 is the solution to the differential
equations from a defined initial condition, assuming that the input terms remain
constant with time. If it is desired to vary these inputs, or any other terms, as a
function of time, the differential equations must be solved numerically. The subscript
refers to the steady-state solution, which applies at infinite time.
Since D values add, simple inspection reveals which are important and control the
overall chemical fate. For example, if DV greatly exceeds DQ, DC, and DM, it is apparent
that most transfer from air is by absorption. The relative magnitudes of the processes
of removal from water are particularly interesting. These occur in the denominator of
the fW equation as volatilization (DV), reaction (DW), water outflow (DJ), particle
outflow (DY), and a term describing net loss to the sediment. The gross loss to the
sediment is (DD + DT), but only a fraction of this (DS + DB)/(DR + DT + DS + DB) is
Figure 8.4 Transport and transformation processes treated in the QWASI model, consisting
of a defined atmosphere with water and sediment compartments.
CH08 Page 203 Monday, January 15, 2001 1:52 PM
Table 8.3 D Values in the QWASI Model and Their Multiplying Fugacity
Definition of D Multiplying
Process D Value Value Fugacity
Sediment burial DB GBZS fS
Sediment transformation DS V SZ Sk S fS
Sediment resuspension DR G RZ S fS
Sediment to water diffusion DT kTASZW fS
Water to sediment diffusion DT kTASZW fW
Sediment deposition DD G DZ P fW
Water transformation DW VWZWkW fW
Volatilization DV kVAWZW fW
Absorption DV kVAWZW fA
Water outflow DJ G JZ W fW
Water particle outflow DY GYZP fW
Rain dissolution DM GMZW fA
Wet particle deposition DC G CZ Q fA
Dry particle deposition DQ GQZQ fA
Water inflow DI GIZW fI
Water particle inflow DX GXZP fI
Direct emissions — EW
Nomenclature and Explanation
The rate (mol/h) is the product of the D Value and the multiplying fugacity, e.g., DBfS.
G values are flows (m3/h) of a phase, e.g., GB is m3/h of sediment that is buried.
fW, fS, fA, and fI are the fugacities of water, sediment, air and water inflow.
Z values are fugacity capacities (mol/m3 Pa), the subscript being S sediment, W water, A
air, Q aerosol, P water particles.
The advective flows are subscripted I water inflow, X water particle inflow, J water outflow,
and Y water particle outflow.
kS and kW are sediment and water transformation rate constants (h–1).
kT is a sediment–water mass transfer coefficient and kV an overall (water–side) air–water
mass transfer coefficient (m/h).
AW and AS are air–water and water–sediment areas (m2).
VW and VS are water and sediment volumes (m3).
retained in the sediment, with the remaining fraction (DR + DT)/(DR + DT + DS + DB)
being returned to the water. The three terms in the numerator of the fW equation give
the inputs from emissions, inflow, and transfer from air.
When the equations are solved, the concentrations, amounts, and fluxes can be
calculated. An illustration of such an output is given in Figure 8.6 for PCBs in Lake
Ontario (Mackay, 1989). Such mass balance diagrams clearly show which processes
are most important for the chemical of interest.
Windows- and DOS-based BASIC programs are provided that process the var-
ious Z values, volumes, areas, flows, D values, and the chemical input parameters
to give the steady-state solution. The conditions simulated in the BASIC program
CH08 Page 204 Monday, January 15, 2001 1:52 PM
QWASI Equations
Steady-state solutions (i.e., derivatives are equal to zero)
Since Sum of all input rates = sum of all output rates
The sediment mass balance is
fW(DD + DT) = fS(DR + DT + DS + DB)
and can be rewritten as
fS = fW (DD + DT)/(DR + DT + DS + DB)
DR + DT
I 2 = ---------------------
V W Z BW
DV + DW + DJ + DY + DD + DT
I 3 = --------------------------------------------------------------------------------
V W Z BW
DD + DT
I 4 = ----------------------
V S Z BS
DR + DT + DS + DB
I 5 = -------------------------------------------------
V S Z BS
The solution with the initial conditions fSO and fWO and final conditions fS∞ and fW∞ is
f W = f W∞ + I 8 exp [ – ( I 6 – I 7 )t ] + I 9 exp [ – ( I 6 + I 7 ) t ]
( I 3 – I 6 + I 7 )I 8 exp [ – ( I 6 – I 7 )t ] + ( I 3 – I 6 – I 7 )I 9 exp [ – ( I 6 + I 7 )t ]
f S = f S∞ + ---------------------------------------------------------------------------------------------------------------------------------------------------------------------
I 2
where
fW∞ = I1I5/(I3I5 – I2I4), as in the steady-state solution above
fS∞ = I1I4/(I3I5 – I2I4), as in the steady-state solution above
I6 = (I3 + I5)/2
I7 = [(I3 – I5)2 + 4I2 I4]0.5/2
I8 = [–I2(fS∞ – fSO) + (I3 – I6 – I7)(fW∞ – fWO)]/2I7
I9 = [+I2(fS∞ – fSO) – (I3 – I6 + I7)(fW∞ – fWO)]/2I7
Figure 8.6 Illustrative results from a QWASI model calculation of steady-state behavior of PCBs in Lake Ontario (Mackay,
1989).
205
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are similar to those described by Mackay (1989) for the fate of PCBs in Lake Ontario.
To obtain unsteady-state solutions requires programming the equations in Figure 8.5
or solving the differential equations by a numerical method.
For chemical X, determine for both water and sediment, the D values, total inputs
and outputs, fugacities at steady state, concentrations, total amounts, and residence
times. Also estimate the concentration of chemical X in fish and benthos.
Volumes
D values
Transformation: D = VZk
Inputs
Emissions EW = 1 mol/h
fA (air) = 10–4 Pa
Calculation of D values
Rates Multiplying
(mol/h) Fugacity
DB = GBZS = 0.1 × 600 = 60 0.149 fS
DR = GRZS = 0.2 × 600 = 120 0.300 fS
DT = GTZW = 50 × 0.8 = 40 0.100 fS (sediment to water)
0.054 fW (water to sediment)
DD = GDZP = 0.3 × 1600 = 480 0.643 fW
DW = VWZWkW = 106 × 0.8 × 10–4 = 80 0.107 fW (water phase only, not on particles)
DV = GVZW = 500 × 0.8 = 400 0.536 fW (evaporation)
0.040 fA (absorption)
DJ = GJZW = 400 × 0.8 = 320 0.429 fW
DY = GYZP = 0.01 × 1600 = 16 0.021 fW
DM = GMZW = 0.1 × 0.8 = 0.08 8 × 10–6 fA
DC = GCZQ = 0.001 × 5000 = 5 5 × 10 –4 fA
DQ = GQZQ = 0.0005 × 5000 = 2.5 2.5 × 10–4 fA
DI = GIZW = 400 × 0.8 = 320 0.320 fI
DX = GXZP = 0.02 × 1600 = 32 0.032 fI
DS = VSZSkS = 104 × 600 × 10–5 = 60 0.149 fS
EW = 1.0 fI = 10–3 fA = 10–4
Calculation of fugacities
Concentrations
Total Amounts
Residence Times
Total input to water is 1.393 mol/h from emissions, advective inflow and the
atmosphere and 0.4 mol/h from sediment. Total input from sediment is by deposition
and diffusion from water.
Total inputs to and outputs from both water and sediment and the entire system
balance within round-off error.
This example, while tedious to do by hand, is readily implemented on a spread-
sheet, or the software available on the internet can be used. It gives a clear quanti-
fication of all the fluxes and demonstrates which processes are most important. A
mass balance diagram such as Figure 8.6 illustrates the process rates clearly.
The QWASI lake equations can be modified to describe chemical fate in rivers
by one of two methods.
The river can be treated as a series of connected lakes or reaches, each of which
is assumed to be well mixed, with unique water and sediment concentrations. There
can be varying discharges into each reach, and tributaries can be introduced as
desired. The larger the number of reaches, the more closely simulated is the true
“plug flow” condition of the river. Figure 8.7 illustrates the approach.
The second approach is to set up and solve the Lagrangian differential equation
for water concentration as a function of river length, as was discussed when com-
paring Eulerian and Lagrangian approaches in Chapter 2. This has been discussed
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Figure 8.7 Chemical fate in a river, as treated by QWASI models in series with no downstream-to-upstream flows.
209
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by Mackay et al. (1983), and an application to surfactant decay in a river has been
described by Holysh et al. (1985).
A differential equation is set up for the water column as a function of flow
distance or time, and steady-state exchange with the sediment is included. The
equation can then be solved from an initial condition with zero or constant inputs
of chemical. The practical difficulty is that changes in flow volume, velocity, or river
width or depth cannot be easily included, therefore the equation necessarily applies
to idealized conditions.
This equation may be useful for calculating a half-time or half-distance of a
substance in a river as the concentration decays as a result of volatilization or
degradation. A version is the oxygen sag equation. This contains an additional term
for oxygen consumption by organic matter added to the river. This model was first
developed by Streeter and Phelps in 1925 and is described in texts such as that of
Thibodeaux (1996). This is historically significant as being among the first successful
applications of mathematical models to the fate of a chemical (oxygen) in the aquatic
environment.
A lake, river, or estuary rarely can be treated as a single well mixed “box” of
water, and a more accurate simulation is obtained if the system is divided into a
series of connected boxes. In the case of a river, it may be acceptable to use the
output from one box as input to the next downstream box and treat any downstream-
upstream flow as being negligible compared to upstream-downstream flow. In slowly
moving water, this will be invalid if there are significant flows in both directions.
In principle, if there are n water and n sediment boxes, there are 2n mass balance
equations containing 2n fugacities, and the equations can be solved algebraically
for steady-state conditions or numerically for dynamic conditions.
In the case of steady-state conditions, a major simplification is possible if it is
assumed that there is no direct sediment-sediment transfer between reaches; i.e., all
transfer is via the water column. Each sediment mass balance equation then can be
written to express the sediment fugacity as a function of the fugacity in the overlying
water. The fugacity in sediment then can be eliminated entirely, leaving only n water
fugacities to be solved. This is equivalent to calculating the water fugacity as in the
QWASI model by including loss to the sediment in the denominator. A total loss D
value can thus be calculated for the water and sediment.
Algebraic solution of the equations is straightforward, provided the number of
boxes is small and there is minimal branching.
For a set of boxes connected in series with both “upstream and downstream”
flows, the solution becomes simple, elegant, general, and intuitively satisfying
because of its transparency. This is illustrated in Figure 8.8. For a given box, the
numerator consists of a series of terms, each reflecting inputs (designated I) to this
box and Q, including input from other boxes. For each box, the input I (by discharge
and from the atmosphere) is included directly. For adjacent boxes, the input to that
box is multiplied by the fraction that migrates to the box in question. This fraction,
CH08 Page 211 Monday, January 15, 2001 1:52 PM
Figure 8.8 Steady-state mass balance equations for a series of four QWASI models with
flows in both directions.
accordingly, but the final solution can still be inspected to reveal the significance
of each term.
If the number of boxes is very large (above about 8) and there is appreciable
branching, it may be easier to set up the equations in differential form and solve
them numerically in time, with constant inputs to reach a steady-state solution.
Details of how this can be accomplished are given in Figure 8.9.
The dynamic version allows the user to observe changes in concentrations with
time. The steady-state version gives the concentrations when the system has reached
a nonchanging condition with respect to time. If a long enough integration period
is used for the dynamic version, the concentrations approach those in the steady-
state version.
It is best to use the steady-state version if the user is concerned only with the
end result, and the dynamic version if it is desired to track changes in the system
over time or how long it will take the system to approach a steady state.
It is good practice to check the consistency between steady-state and dynamic
solutions by comparing the steady-state output with the dynamic output obtained
after integrating for a prolonged period at constant input rates, such that a steady
state has been achieved.
The following papers are examples of multi-QWASI model applications. Lun et
al. (1998) describe the fate of PAHs in the Saguenay River in Quebec. Ling et al.
(1993) treat the fate of chemicals in a harbor including vertical segmentation. Hickie
Changes in fugacity in water (dfW) and sediment (dfS) as a function of time for each
reach, as pseudocode.
For I = 1 to 4
dfW(I) = DTIM ((I(I) + fA(I) (DM(I) + DQ(i) + DC(I) + DV(I)) +
fS(I)(DT(I) + DR(I)) + fW(I + 1) D(I + 1, I) + fW(I – 1) D(I – 1, I)) –
fW(I)(DW(I) + DV(I) + DD(I) + DT(I) + D(I, I – 1) + D(I, I + 1))}/(VW(I) ZWT(I))
dfS(I) = DTIM ((fW(I) (DD(I) + DT(I))) – fS(I) (DB(I) + DS(I) + DR(I) + DT(I)))/(VS(I) ZST(I))
Next I
For I = 1 to 4
fW(I) = fW(I) + dfW(I)
fS(I) = fS(I) + dfS(I)
Next I
Note: VW is volume of water, VS is volume of sediment, ZWT is Z for bulk water, and ZST
is Z for bulk sediment.
Figure 8.9 Dynamic mass balance equations for a four-reach multi-QWASI system.
CH08 Page 213 Monday, January 15, 2001 1:52 PM
and Mackay (2000) describe the fate of PAHs from atmospheric sources to Lac Saint
Louis in the St. Lawrence River. Diamond et al. (1994) treat the fate of a variety of
organic chemicals and metals in a highly segmented model of the Bay of Quinte
which is connected to Lake Ontario.
8.9.1 Introduction
Here, we treat the fish as one “box.” The conventional concentration expression
for uptake of chemical by fish from water, through the gills only under laboratory
conditions, was first written by Neely et al. (1974) as
where CF and CW are concentrations in fish and water, k1 is an uptake rate constant
and k2 is the clearance rate constant. The fish is regarded as a single compartment.
CH08 Page 214 Monday, January 15, 2001 1:52 PM
Apparently, the chemical passively diffuses into the fish along much the same route
as oxygen. In the laboratory, it is usual to expose a fish to a constant water concen-
tration for a period of time during which the concentration in the fish should rise
from zero to CF according to the integrated version of the differential equation with
CF initially zero and CW constant.
CF = (k1/k2)CW[1 – exp(–k2t)]
After prolonged exposure, when k2t is large, i.e., >4, CF approaches (k1/k2)CW or
KFWCW where KFW is the bioconcentration factor. The fish is then placed in clean
water, and loss or clearance or depuration is followed, the corresponding equation
being
CF = CFO exp(–k2t)
If the fish is growing, there will be growth dilution, which can be included as
an additional loss rate constant kG, which is the fractional increase in fish volume
per hour.
At steady-state conditions, the left side is zero, and
Gobas (1993) has suggested correlations for these rate constants as a function of
fish size. The mass balance around the fish can be deduced and the important
processes identified. The rate constant k1 is much larger than kA, typically by a factor
of 5000. Thus, uptake from water and food become equal when CA is about 5000
times CW, which corresponds to a KOW of about 105 and 5% lipid. For lower KOW
chemicals, uptake from water dominates whereas, for higher KOW chemicals, uptake
from food dominates.
fF = fW(1 – exp[–DVt/VFZF)]
fF = fFO exp(–DVt/VFZF)
The following expressions relate the rate constants and D values, showing that
the two approaches are ultimately identical algebraically.
k1 = DV/VFZW
k2 = DV/VFZF
KFW = ZF/ZW
The nature of the processes controlling DW and DO is not precisely known, but
it is suspected that they are a combination of flow (GZ) and mass transfer (kAZ)
resistances. If we substitute GZ for each D, recognizing that G may be fictitious,
we obtain
= τWKOW + τO
By plotting 1/k2 against KOW for a series of chemicals taken up by goldfish, Mackay
and Hughes (1984) estimated that τW was about 0.001 hours and τO 300 hours. This
is another example of probing the nature of series or “two-film” resistances using
chemicals of different partition coefficient as discussed in Chapter 7.
The times τW and τO are characteristic of the fish species and vary with fish size
and their metabolic or respiration rate, as discussed by Gobas and Mackay (1989).
The uptake and clearance equilibria and kinetics, i.e., bioconcentration phenomena,
of a conservative chemical in a fish are thus entirely described by KOW, L, τW, and τO.
The bioconcentration equation can be expanded as before to include uptake from
food with a D value DA, loss by egestion (DE) and loss by metabolism (DM), giving
that the uptake efficiency EA from food in the gastrointestinal tract of a “clean” fish
can also be described by a two-film approach yielding
1/EA = AWKOW + AO
where AW and AO are water and organic resistance terms similar in principle to τW
and τO, but are dimensionless. AO appears to have a magnitude of about 2, and AW
a magnitude of about 10–7, thus, for all but the most hydrophobic chemicals, EA is
about 50%. When KOW exceeds 107, the efficiency drops off, because of a high water
phase resistance in the gut.
A major difficulty is encountered when describing the loss of chemical in feces
and urine. In principle, D values can be defined, but it is quite difficult and messy
to measure G and Z; therefore, neither are known. It is probable that the digestion
process, which removes both mass and lipid content to provide matter and energy
to the fish, reduces both GA and ZA so that DE for egestion is smaller than DA. The
simplest expedient is to postulate that it is reduced by a factor Q, thus we estimate
DE for loss by egestion as DA/Q or DAE/Q, i.e., DE or DEE. The resistances causing
EA for uptake are assumed to apply to loss by egestion. This assumption is probably
erroneous, but it is acceptable for most purposes, especially because there is presently
an insufficiency of data to justify different values for uptake and loss.
The steady-state solution to the differential equation for the entire fish becomes
biomagnification is more significant for these animals, rendering them more vulner-
able to toxic effects of persistent chemicals.
Input data
fW = 10–6
DV = 10–4
DA = 10–3
DM = 10–4
Q =4
= 4.67 × 10–6 Pa
In both cases, because fugacity in the fish exceeds that of the water, there is net loss
by respiration. The presence of biomagnification depends on whether the fish can
clear the chemical fast enough to maintain a fugacity less than that of the food. In
this case, if the metabolic rate was zero, the fish would reach a fugacity of 6 ×
10–6 Pa, 3 times that of the food, losing 0.6 to water and 1.5 by egestion.
CH08 Page 219 Monday, January 15, 2001 1:52 PM
8.9.4 Model
Available on the website are Windows- and DOS-based Fish models that calcu-
late the fish fugacity, concentration and the various flux terms from input data on
the chemical’s properties, concentration in water, and various physiological con-
stants. They include a “bioavailability” calculation in the water by estimating sorp-
tion to organic matter in particles. The models are particularly useful for exploring
how variation in KOW and metabolic half-life affect bioaccumulation, and they show
the relative importance of food and water as sources of chemical. An overall resi-
dence time is calculated that indicates the time required for contamination or decon-
tamination to take place.
The fish bioaccumulation model can be applied to an aquatic food web starting
with water and then moving successively to phytoplankton, zooplankton, inverte-
brates, small fish, and to various levels of larger fish. Each level becomes food for
the next higher level. If KOW is relatively small, i.e., <105, the DV terms dominate,
and equifugacity is probable throughout the web; i.e., fA, fW and fF will be equal.
For larger KOW chemicals, biomagnification is likely. For “superhydrophobic”
chemicals of KOW>107, the EA term becomes small, uptake is slowed, and the growth
and metabolism terms become critical. Association with suspended organic matter
in the water column becomes important, i.e., “bioavailability’ is reduced. A fall-
off in observed BCFs is (fortunately) observed for such chemicals; thus, there
appears to be a “window” in KOW of about 106 to 107 in which bioaccumulation is
most significant and most troublesome. Chemicals such as DDT and PCBs lie in
this “window.” This issue has been discussed in detail and modeled by Thomann
(1989).
Several features of food web biomagnification are worthy of note. Humans
usually eat creatures close to the top of food webs, and strive to remain at the top
of food webs, avoiding being eaten by other predators. Fish consumption is often
the primary route of human exposure to hydrophobic chemicals. Creatures high
in food webs are invaluable as bioindicators or biomonitors of contamination of
lakes by hydrophobic chemicals. But to use them as such requires knowledge of
the D values, especially the D value for metabolism. A convincing argument can
be made that, if we live in an ecosystem in which wildlife at all trophic levels is
thriving, we can be fairly optimistic that we humans are not being severely affected
by environmental chemicals. This is a (selfish) social incentive for developing,
testing, and validating better environmental fate models, especially those employ-
ing fugacity.
A food web model treating multiple species can be written by applying the
general bioaccumulation equation to each species (with appropriate parameters).
The final set of equations for n organisms has n unknown fugacities that can be
solved sequentially, starting at the base of the food web and proceeding to other
species, with smaller animals becoming food for larger animals.
CH08 Page 220 Monday, January 15, 2001 1:52 PM
An alternative and more elegant method is to set up the equations in matrix form
as described by Campfens and Mackay (1997) and solve the equations by a routine
such as Gaussian elimination. This permits complex food webs to be treated with
no increase in mathematical difficulty.
A DOS-based BASIC model Foodweb is available that performs these calcula-
tions as described in detail by Campfens and Mackay (1997). It is an expansion of
the Fish model, and it treats any number of aquatic species that consume each other
according to a dietary preference matrix. A steady-state condition is calculated using
matrix algebra. All organism-to-organism fluxes (i.e., food consumption rates) are
given. The model is also useful as a means of testing how concentrations in top
predators respond to changes in food web structure. It is essentially a multibox
model with one-way transfers from box to box.
An obvious extension is to include nonaquatic species such as birds and mam-
mals. This has been discussed by Clark et al. (1989), who showed that fish-eating
birds could be included in an aquatic food web model. In the long term, it may be
possible to build models containing all relevant biota, including fish, birds, mammals,
insects, and vegetation. A framework for accomplishing this has been described by
Sharpe and Mackay (2000). The primary difficulties are in the development of
species-specific mass balance equations, determining appropriate parameters for the
organisms and obtaining validation data. There is little doubt that comprehensive
food web models will be developed and validated in the future, even models includ-
ing humans.
Many chemicals are discharged to sewers and are subsequently treated biologi-
cally in sewage treatment plants (STPs), also called publicly owned treatment works
(POTWs). Treatment configurations vary from simple lagoons to more complex
systems in which the concentration and activity of the biomass are optimized by
recycling the biomass or sludge. Such activated sludge STPs essentially consist of
a series of connected vessels, the contents of which are well mixed, having contact
with air either at the surface (as in a lake) or by forced aeration. A typical STP flow
diagram is shown in Figure 8.11 with illustrative chemical fluxes. The influent
sewage is settled by primary sedimentation, followed by secondary treatment under
aeration conditions with subsequent settling and recycling.
The flows of water, solids, and air are defined by the plant operating conditions.
The task is then to deduce the corresponding fluxes of the chemical present in the
influent. Steady-state mass balance equations can be set up for each vessel and solved
for the three fugacities, from which all chemical fluxes can be deduced. This requires
that D values be defined for flows of chemical in water, biomass solids, and air, for
both degradation and surface volatilization.
Clark et al. (1995) have described such a model, and Windows software and a
BASIC program (STP) are available. The model is particularly useful not only for
estimating the overall treatment efficiency but also the fraction of the chemical input
that is volatilized, degraded, left in the sludge, or remains in the effluent.
CH08 Page 221 Monday, January 15, 2001 1:52 PM
Figure 8.11 Transport and transformation processes in a typical activated sludge plant repre-
sented as three well mixed compartments. The relative chemical fluxes, e.g. (100),
are illustrative.
8.11.1 Introduction
We present here a very simple model of chemical fate in indoor air. Numerous
studies have shown that humans are exposed to much higher concentrations of certain
chemicals indoors than outdoors. Notable are radon, CO, CO2, formaldehyde, pes-
ticides, and volatile solvents present in glues, paints, and a variety of consumer
products.
The key issue is that, whereas advective flow rates are large outdoors, they are
constrained to much smaller values indoors. Attempts to reduce heating costs often
result in reduced air exchange, leading to increased chemical “entrapment.” A nuclear
submarine or a space vehicle is an extreme example of reduced advection. Fairly
complicated models of chemical emission, sorption, reaction, and exhaust in multi-
chamber buildings have been compiled [e.g., Nazaroff and Cass (1986, 1989) and
Thompson et al. (1986)], but we treat here only the simple model developed by
Mackay and Paterson (1983), which shows how D values can be used to estimate
indoor concentrations caused by evaporating pools or spills of chemicals.
An example of the effective use of fugacity for compiling mass balances indoors
is the INPEST model, developed in Japan by Matoba et al. (1995, 1998). This model
successfully describes the changing concentration of pyrethroid pesticides applied
indoors in the hours and days following their application. Because of the reduced
advection, there is a potential for high concentrations and exposures immediately
following pesticide use, and it may be desirable to evacuate the room or building
for a number of hours to allow the initial peak concentration in air to dissipate. The
INPEST fugacity model, which is in the form of a spreadsheet, can be used to suggest
effective strategies for avoiding excessive exposure. It can be used to compare
pesticides and explore the effects of different application practices.
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Thus, DT is essentially D1, most resistance lying in the slow evaporation process
from the small spill area. The molar mass is 260 g/mol, and the evaporation rate N
is then
CH08 Page 223 Monday, January 15, 2001 1:52 PM
The intermediate fugacities and concentrations are 3.6 × 10–5 Pa (3800 ng/m3)
and 11 × 10–5 Pa (11500 ng/m3). The time for evaporation of 1 g of PCB will be 65
days. The amount of PCB in an air volume of 500 m3 would be on the order of
0.004 g, a small fraction of the small amount of PCB spilled.
The significant conclusion is that, despite appreciable ventilation at an ACH of
0.5 h–1, the indoor air concentrations are over 1000 times those outdoors. Fortunately,
the indoor fugacity is still very much lower than the pool fugacity. Similar behavior
applies to other solvents, pesticides, and chemicals that may be used and released
indoors. Although the amounts spilled or released are small, the restricted advective
dilution results in concentrations that are much higher than are normally encountered
outdoors. In many cases, this phenomenon is suspected to be the cause of the “sick
building” problem in which residents complain repeatedly about headaches, nausea,
and tiredness. The cure is to eliminate the source or increase the ventilation rate.
Fugacity calculations can contribute to understanding such problems.
Uptake of chemicals by plants is one of the most important but still poorly
understood processes. It is important because plants are at the base of food chains.
Thus, a chemical such as a dioxin absorbed by grass can be transported to the cow,
then to dairy and meat products, and thus to humans. Plants can be valuable monitors
of the presence of chemicals in the environment, but they are only of quantitative
value if the plant-environment partitioning phenomena are fully understood. Plants
may also affect the overall environmental fate of a substance by removing it from
the atmosphere or absorbing it from soils. An attractive “phyto-remediation” option
is to use plants to reduce concentrations in contaminated sites.
Ironically, although plants are much simpler organisms than animals on the scale
of biological evolution, they are more difficult to model. A major difficulty is that
plants grow quickly relative to animals, and their circulatory system is not as efficient
as those of animals. There are flows in xylem and phloem channels, but these are
not as well characterized as blood flows. Foliage, which is the primary contact area
with the atmosphere, is very complex and variable from species to species. It consists
of an external often waxy cuticle, but with access to the interior by stomata that are
designed to ensure entry of CO2. The root, which is in contact with soil, presents a
complex barrier to uptake of chemicals. It is not clear how the wood or bark of trees
should be treated. Much of the mass of a tree is inaccessible to contaminants. Often,
the consumed material is fruit, nuts, or seeds that form rapidly, but processes of
chemical transport to them from foliage, roots, and stem are not yet well understood.
These and other issues have been discussed in the texts by Nobel (1991) and
Trapp and MacFarlane (1995). McLachlan (1999) has set out a framework for
assessing uptake of chemicals by grasses from the atmosphere. Severinson and Jager
(1998) have discussed the need for including plants in multimedia models. Actual
fugacity or related models of uptake have been developed by Trapp et al. (1990),
CH08 Page 224 Monday, January 15, 2001 1:52 PM
Paterson et al. (1991), and Hung and Mackay (1997). This topic is the focus of
considerable research, and improved models will no doubt be developed in the near
future.
of chemical contamination in vulnerable tissues with levels that are believed to cause
adverse effects.
There is clearly a need to link environmental and pharmacokinetic modeling
efforts to build up a comprehensive capability of assessing the journey of the
chemical from source to environment to organism and ultimately to the target site.
CH08 Page 226 Monday, January 15, 2001 1:52 PM
8.14.1 Introduction
Concentrations
Medium Predicted Level Effect Level Quotient
Air (µ/m3) 3 60 20
Water (µg/L) 10 3000 300
Fish (µg/g) 2 10 5
Soil (µg/g) 1 100 100
Whereas simple lethality experiments can be designed using air, water, or food as
vehicles for chemical exposure, it is not always clear how concentrations in the solid
matrices of soils and sediments relate to exposure or intake of chemical by organisms.
It is difficult to design meaningful bioassays involving interactions between organ-
isms, soils, and sediments. One approach is to decree that whatever target fugacity
is developed for water be applied to sediment. This effectively links the target
concentrations by equilibrium partition coefficients.
A second method is to use concentrations to estimate exposure or dosage in units
such as µg/day of chemical to an organism, which for selfish reasons is usually a
human. Individual and total dosages can be estimated to reveal the more important
routes. This calculation of dose is enlightening, because it reveals which medium
or route of exposure is of most importance. Presumably, steps can then be taken to
reduce this route by, for example, restricting fish consumption.
Table 8.5 lists representative exposure quantities for several human age classes.
Table 8.5 Representative Exposure Rates for Four Human Age Classes Derived
Principally from the EPA Exposure Factors Handbook
Age Classes
Route <1 1–5 6–19 20+ Units
Air inhalation 4.5 6 10 13.5 m3/day
Drinking water 300 694 904 1500 mL/day
Foodstuffs
fruit 135.6 145.1 161.6 166.9 g/day
vegetables 61.9 108.0 209.1 271.3 g/day
grains 155.1 143.7 227.7 219.0 g/day
meat 26.1 59.1 113.8 123.3 g/day
fish — 4 6 14 g/day
dairy 570.9 339.6 438.7 249.6 g/day
human milk 775 0 0 0 g/day
Soil ingestion — 0.11* 0.087 0.065 g/day
Dermal contact
soil
area — 0.43 0.62 0.70 m2
duration — 1440 600 320 h/yr
water
area — 0.65 1.25 1.81 m2
duration — 82.4 82.4 82.4 h/yr
*A pica child may ingest up to 10g/day
An average human inhales some 14 m3 of air per day. If the concentration in air
is known in µg/m3, the amount of chemical inhaled in this air is readily calculated
as the product with units of µg/day. Not all this chemical may be absorbed, but at
least a maximum dosage can be deduced. The same human may consume 1.5
litres/day of water containing dissolved chemical, enabling this dosage to be esti-
CH08 Page 228 Monday, January 15, 2001 1:52 PM
mated again in µg/day. Food, the other vehicle, is more difficult to estimate. A typical
diet may consist of 1 kg/day of solids broken down as shown in Table 8.5. Fish
concentrations can be estimated directly from water concentrations, but meat, veg-
etable, and dairy product concentrations are still poorly understood functions of the
concentrations of chemical in air, water, soil, and animal feeds, and of agrochemical
usage. Techniques are emerging for calculating food-environment concentration
ratios, but at present the best approach is to analyze a typical purchased “food
basket.” This issue is complicated by the fact that much food is grown at distant
locations and imported. Beverages, food, and water may also be treated for chemical
removal commercially or domestically by washing, peeling, or cooking. An example
illustrates this method of estimating dose.
A chemical of molar mass 181.5 g/mol has partitioned into the air, water, soil,
and sediment resulting in the concentrations given in Table 8.6 below. As a result
of contact with these abiotic media, fish, vegetation, and meat (and correspondingly,
dairy products) are estimated to have the concentrations tabulated.
Using these data and the exposure rates from Table 8.5 for an adult, calculate
the dose to an adult human. Assume that the density of food is 1000 kg/m3.
Amount
Concentration Intake Rate Consumed Amount Consumed
C (mol/m3) I (m3/day) (C*I) (mol/day) (C*I*181.5) (g/day)
Vegetation × 10–7
4.02 6.57 × 10–4 2.64 × 10–10 4.79 × 10–8
Fish 2.75 × 10 –6 1.40 × 10–5 3.85 × 10 –11 6.99 × 10–9
Meat 1.02 × 10 –9 1.23 × 10–4 1.26 × 10–13 2.28 × 10–11
Dairy 3.23 × 10–10 2.50 × 10–4 8.06 × 10–14 1.46 × 10–11
Water 1.16 × 10 –9 1.50 × 10–3 1.74 × 10–12 3.16 × 10–10
Soil 1.69 × 10 –7 6.50 × 10–8 1.10 × 10–14 1.99 × 10–12
Air 6.80 × 10 –11 13.5 × 100 9.18 × 10–10 1.67 × 10–7
Total dose = 2.22 × 10–7 g/day = 0.222 µg/day
In this case, inhalation in air causes 75% of the dose, and consumption of
vegetation causes another 21%.
Significant chemical exposure may also occur in occupational settings (e.g.,
factories), in institutional and commercial facilities (e.g., schools, stores, and cine-
mas), and at home, but these exposures vary greatly from individual to individual
and depend on lifestyle.
There emerges a profile of relative exposures by various routes from which the
dominant route(s) can be identified. If desired, appropriate measures can be taken
to reduce the largest exposures. The advantage of this approach is that it places the
spectrum of exposure routes in perspective. There is little merit in striving to reduce
an already small exposure.
CH08 Page 229 Monday, January 15, 2001 1:52 PM
models. Most interest is in LRT in the atmosphere but, in some cases, oceans and
rivers can play a significant role. Even migrating biota can contribute to LRT. The
most promising approach is to consider the fate of chemical in a parcel of Lagrangian
air passing over soil or water and subject to degradation, deposition, and reevapo-
ration. Such systems have been suggested by Van Pul (1998), Bennett et al. (1999),
and Beyer et al. (2000). Beyer et al. (2000) showed that a LRT distance in air can
be deduced from a simple Level III model as the product of the wind velocity, the
overall persistence or residence time of the chemical, and the fraction of the chemical
in the atmosphere.
A model, TaPL3 (Transport and Pesistence Level 3), can be used for a Level III
evalution of persistence and LRT. It is available on the website.
It is expected that new models will be developed to assist in the evaluation of
these attributes, especially in situations where there is no easy method of obtaining
the required information from environmental monitoring data.
The ultimate mass balance model of chemical fate is one that describes the
dynamic behavior of the substance in the entire global environment. At present, only
relatively simplistic treatments of chemical fate at this scale have been accomplished,
but it is likely that more complex and accurate models will be produced in the future.
Meteorologists can now describe the dynamic behavior of the atmosphere in some
detail. Oceanographers are able to describe ocean currents. Ultimately, there may
be linked meteorological/oceanographic/terrestrial models in which the ultimate fate
of 100 kg of DDT applied in Mexico can be predicted over the decades in which it
migrates globally.
The obvious ethical implication is that a nation should not use a substance in
such a way that other nations suffer significant exposure and adverse effects. These
situations have already occurred with acid rain and Arctic and Antarctic contamina-
tion by persistent organic substances.
The construction of global-scale models opens up many new and interesting
prospects. It appears that there is a global fractionation phenomenon as a result of
chemicals migrating at different rates and tending to condense at lower temperatures.
Chemicals that do reach cold regions may be better preserved there because of the
reduced degradation rates. Chemicals appear to be subject to “grasshopping” (or
“kangarooing” in the Southern Hemisphere) as they journey, deposit, evaporate, and
continue hopping from place to place until they are ultimately degraded as shown
in Figure 8.13.
Accounts of these phenomena, and models that attempt to quantify them, are
given in a series of papers by Wania and Mackay (1993, 1996, 1999) and Wania et
al. (1996). The most successful modeling to date has been of α-HCH, which was
produced as an impurity in the insecticide, technical lindane (Wania and Mackay,
1999) but is no longer produced. An interesting insight from that study is an assertion
that, despite α-HCH never having been used in the Arctic, about half the remaining
mass on this planet now resides in the arctic oceans. This GloboPOP model is
CH08 Page 231 Monday, January 15, 2001 1:52 PM
available from the University of Toronto. A link is maintained from the Trent website,
at which other models are available.
As better models of global fate become available, they will provide an invaluable
tool with which humanity can design, select, and use chemicals on our planet with
no fear of adverse consequences. Whether we will be sufficiently enlightened to
achieve this is a question only time will answer.
8.17 CLOSURE
Perhaps the task addressed by this book is best summarized by Figure 8.14,
which depicts many of the environmental processes to which chemical contaminants
are subject. The aim has been to develop methods of calculating partitioning, trans-
port, and transformation in the wide range of media that constitute our environment.
Ultimately of primary concern to the public, and thus to regulators, is the effect that
these chemicals may have on human well-being. But there are sound practical and
ethical reasons for protecting wildlife, and indeed all fellow organisms in our eco-
system.
It is not yet clear how severe the effects of chemical contaminants are, nor is it
likely that the full picture will become clear for some decades. Undoubtedly, there
are chemical surprises or “time bombs” in store as analytical methods and toxicology
improve and new chemicals of concern are identified.
Regardless of the incentive nurtured by public fear of “toxics,” environmental
science has a quite independent and noble objective of seeking, for its own sake, a
fuller quantitative understanding of how the biotic and abiotic components of our
multimedia ecosystem operate; how chemicals that enter this system are transported,
transformed, and accumulate; and how they eventually reach organisms and affect
their well-being.
Modern society now depends on a wide variety of chemicals for producing
materials, as components of fuels, for maintaining food production, for ensuring
sanitary conditions and reducing the incidence of disease, for use in domestic and
personal care products, and for use in medical and veterinary therapeutic drugs. We
enjoy enormous benefits from these chemicals. Our industrial, municipal, and
domestic activities also generate chemicals inadvertently by processes such as incin-
eration and waste treatment. The challenge is to use chemicals wisely and prudently
by reducing emissions or discharges to a level at which there is assurance that there
are no adverse effects on the quality of life from chemicals, singly or in combination.
It is hoped that the tools developed in these chapters can contribute to this process.
CH08 Page 233 Monday, January 15, 2001 1:52 PM
Figure 8.14 An illustration of a chemical’s sources, environmental fate, human exposure, and human pharmacokinetics.
233
CH08 Page 234 Monday, January 15, 2001 1:52 PM
Appendix Page 235 Monday, January 15, 2001 1:54 PM
Appendix
Fugacity Forms
235
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Index Page 257 Thursday, January 18, 2001 11:29 AM
Index*
A bioaccumulation/bioconcentration 35,
59, 213, 229
absorption 94 biochemical oxygen demand 136
adsorption 90 BIODEG 137
acids 51, 81 biodegradation 135
activity coefficients 80 BIOLOG 137
advection 117, 123, 119 biomagnification 217
aerobic conditions 136 bioturbation 156
aerosol-air partition coefficient 97 biphenyls 50, 51
activity 71 bulk Z values 107
aerosols 57, 192 burial from sediments 61, 199
air changes per hour 222
air inhalation 227
air phase control 165 C
air-water exchange 191 California EPA 190
Air-water model 194 CalTOX model 190
air-water partitioning 49, 84, 86 Canadian Environmental Modelling
alcohols 51 Centre 186
aldehydes 51 carcinogenicity 37
alkenes 50 Carson, Rachel 1, 35, 51
anaerobic conditions 136 characteristic times 27
Antoine equation 76 ChemCAN model 190
aquatic biota 59 chemical potential 71, 73
aquivalence 110 chemical properties 30, 40
area factor 159 chromophore 138
aromatics 50 Clapeyron-Clausius equation 76
arsenic compounds 53 closed systems 11
atmosphere 55 Colborn, Theo 31
atmospheric oxidation 139 colloid 199
co-metabolites 127
B concentration units 7
conductivity 147
Beer-Lambert Law 138 critical-point temperature 76
* Specific mass balance models are in bold italic.
257
Index Page 258 Thursday, January 18, 2001 11:29 AM
INDEX 259
NAPLs 64
J nitrogen compounds 52
Junge-Pankow equation 97 non-diffusive processes 25, 145
K O
ketones 51 Occam 11
occupational 233
L octanol-air partition coefficient 49, 84,
88
Lagrangian coordinates 20 octanol-water partition coefficients 44,
Lake Ontario 203, 205 49, 84, 87
lakes 201 open systems 13
Lavoisier 11
organic carbon-water partition
leaching 196
coefficients 94
Level I models 111, 113, 189, 190
organic matter and carbon 59
Level II models 121, 128, 130, 141, 142,
Our Stolen Future 31
143, 190
oxidation 140
Level III models 175, 178, 182, 190
oxides of nitrogen 139
Level IV models 181
ozone 139
Lewis G.N. 73
linear additivity 180
lipids 96 P
lipid-water partition coefficients 96
lipophilicity 40 PAHs 50
long-range transport 37, 229 Paracelsus 34
parallel D values 173
parallel resistances 174
M
particulate matter 58
macropores 63 partitioning phenomena 69
mass balances 11 partition coefficients 70, 83, 85
Index Page 260 Thursday, January 18, 2001 11:29 AM
INDEX 261
U Z