Dilution of Pollutants

Dilution:

Polluters discharge chemicals into the environment to dispose of them. Environmental

pollution becomes a problem to society because such chemicals sometimes insert, or
persistent, to remain in the environment for many years.
However, discharging a chemical into the environment usually reduces its adverse effects
by reducing its concentration (quantity of chemical per unit volume).Concentration
reduction is achieved whenever a particular quantity of a chemical (the pollutant) mixes
with some other material (the carrier medium), thereby becoming diluted.

Dilution is the process by which the molecules of a substance become distributed over a
larger physical volume than they formerly occupied.

Dilution always accompanies the formal process of diffusion because the molecules in a
diffusion process tend to spread out and occupy an ever-increasing volume. However,
dilution also can occur in processes that do not primarily involve diffusion, such as the
simple mechanical mixing of one chemical liquid with another.

Dilution also appears in a variety of environmental phenomena. An effluent discharging

into a stream becomes diluted as it enters the receiving waters. Pesticides and other
chemicals sprayed on crops become diluted as they are carried away to streams as surface
runoff.
Chemical wastes dumped at sea become diluted as they are mixed and dispersed by ocean
currents.
Toxic chemicals stored in drums or underground tanks become diluted as they leak out
and leach through the soil.
Acids and other substances present in rain become diluted as the rainwater falls to earth,
ultimately passing to receiving waters. Water pollutants become diluted as they pass
through porous soils.
Air pollutants discharged from smokestacks become diluted as they are diffused and
transported by winds.
Even food additives, such as nitrates (which can ultimately form carcinogenic
nitrosamines under certain conditions), become diluted in the foods to which they are
added. Poisons and other chemicals absorbed by the body become diluted as they enter
the blood and other tissue.

Thus, dilution is an extremely ubiquitous process, occurring in a great variety if

phenomena in our bodies, our daily lives, and the environment about us.

Page 1 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
Dilution is the process by which one constituent is mixed with others, causing the ingredients
to spread out over a larger volume than before with a consequent reduction in concentration.

Deterministic Dilution:

Consider a pollutant present in some constituent prior to dilution. If v0 denote the initial
volume of the constituent with pollutant prior to dilution and c0 denotes the initial
concentration of the pollutant, then the total quantity of pollutant present initially will be
q0  c0v0
If the units of c0 are in grams/cubic meter, for example, then the units of q 0 will be
(grams/cubic meter)  cubic meter = grams.

Assumptions:
i) No-chemical reactions take place
ii) The total quantity of pollutant present after dilution is equal to the total
quantity of pollutant present before dilutions.

If v1 denotes the volume of the mixture after dilution and c1 denotes the concentration of
the pollutant in this mixture then the quantity of pollutant

The new concentration is proportional to the ratio of the initial volume v0 to the final
volume v1 .

Successive Deterministic Dilution:

Suppose that the dilution process has ended, and the pollutant concentration has become
uniform because the constituents are completely missed. Now suppose another dilution
takes place with this mixture. By adding more diluents, the volume of the mixture
changes from v1 to v2 and the concentration of the pollutant decrease further from c1 to
some value c2 , then the second dilution factor will be
v
2  1
v2

Page 2 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
 v1
Thus, c2   c1   2c1 ... ... ... 1
v2
The first dilution stage gave the concentration c1 , substitute into the above equation 1 ,
we get,
c2  1 2c0
It is seen that the final concentration c2 after two successive dilutions can be written as
the product of the dilution factors 1 and  2 and the initial concentration c0 .
If third dilution occurs, the resulting concentration c3 will be
c3  1  2 3 c0
In general, if a succession of n dilutions occurs
n
cn  1 2 ...  n c0  c0  i
i 1
It can be described as a “proportionate process” because the concentration in each
successive state is some constant proportion of the concentration in any previous state.
Because the proportion is always constant, the process is deterministic.

Example:

Suppose that five beakers are available. The first beaker contains 250 ml of water with a
dissolved chemical pollutant at a concentration of c0  1000 parts-per-million (ppm) by
volume.

Page 3 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
A person carefully measures out 50 ml of this solution and pours it into the next beaker
(beaker 1) add clean water to this beaker to bring its volume up to 250 ml and the
solution is thoroughly mixed up
v 50 1
1  0   ,
v1 250 5
1
and c1  1000  200 ppm
5
This process is repeated for beaker 2; one fifth of the quantity in beaker 1 is poured into
beaker 2 and clean water is added to bring the level up to 250 ml.

1
 c2   2c1   200  40 ppm
5
If the process is repeated in the remaing two beakers, the final concentration in beaker 4
will be
4
1
c4  1 2 3 4co    100  1.6 ppm
 5
In this example, it is assumed exactly 50 ml of the contents of a beaker is transferred on
each pouring that is four pouring is measured so exactly that no variation occurs in final
result.

In any real process, the individual pouring sometimes will be above 50 ml and some time
below 50 ml because the person will not always be able to measure the correct amount
exactly.

Question:

What effect will these pouring errors have in the final answer?

Answer:

To answer this question we must move from deterministic to the stochastic version of the
process.

Stochastic Dilution and the Theory of Successive Random Dilutions (SRD):

Suppose the entire experiment is repeated many times beginning with c0 and pouring
approximately 50 ml of mixed solution into each successive clean beaker.

Suppose that the investigator happens to shortchange every beaker by exactly c  1ml ,
causing 49 ml instead of 50 ml to be transferred. (The makes up the shortage by adding
and extra 1 ml of water).
For this set of 4 pouring

Page 4 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
 49
1   2   3   4   0.196
250
and c4   0.196  1000  1.476 ppm.
4

So in this case the final beaker will contain 1.6-1.476=0.124 ppm, less concentration that
it should.

Again suppose another pouring cycle occurs in which each of the 4 beakers receives an
excess of c  1 ml , causing 51 ml instead of 50 ml to be transferred.

Hence,
51
1   2   3   4   0.204
250
and c4   0.204  1000  1.732 ppm.
4

So the final beaker contains (1.732-1.6) = 0.132 ppm, more concentration than it should.

Although the error of the individual pouring varied as -1 ppm, +1 ppm about 50 ppm for
these two case, the error of the final result varied asymmetrically as -0.124 ppm, +0.132
ppm about the correct answer of 1.6 ppm.

Development of Successive Random Dilutions (SRD) theory:

Let Di be an independent random variable between 0 and 1 denoting the dilution factor
of the i th successive pouring such that 0  Di  1 .
The random variable cm denoting the final concentration after m successive pouring will
be the product of the initial concentration c0 and m individual dilution factors:
 cm  c0 D1 D2 ... Dm
m
 c0  Di
i 1
Taking logarithm in the both side we have,
m
log cm  log c0   log Di
i 1

The random variable D1 is assumed to be independent of the random variable D2 and Di

is assumed to be independent of Di 1 for all i .
Since 0  Di  1 for all i then the logarithms of the dilution factors will be random
variables ranging   log Di  0.

Let Ri  log Di

Page 5 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
 m
l og cm  log c0   Ri
i 1
m
or , log cm  const.   Ri
i 1

where log cm is the logarithm of the final concentration after the m successive
concentration and the right hand side is the sum of a constant and m independent random
variables.

The central limit theorem implies that the process of adding independent random
variables gives rise asymptotically to a normal distribution. In the limit as m approaches
infinity log cm will equal a normally distributed random variable plus a constant. Because
the logarithm of the concentration itself in the limit will be log-normally distributed. This
completes the formal argument.

Some words about the constant are appropriate. For each i , Ri  log Di is a negative
number, because Di ranges between 0 and 1. If the sum S  R1  R2  ...  Rm denotes the
stochastic part of the right-hand side of the above equation, then S will be asymptotically
normally distributed with negative mean   0 . The additive constant const  log c0 will
translate the mean of the normal distribution to the right side of the origin if the initial
concentration c0 is large enough such that log c0   . Thus, the initial concentration c0
affects the location parameter of the normally distributed random variable Y  log Cm .

So, E  log Cm   const  E  R1   E  R2   ...  E  Rm 

and var(logCm) = var(R1)+ var(R2)+ var(R3)+ … +var(Rm)

Application of Successive Random Dilution to Environmental Phenomena:

Air Quality:

When an air pollutant is emitted from a source, it is ordinarily transported by mechanical

air movements and by winds. Due to the many physical obstacles present in cities
(houses, walls, buildings and other edifices), the air movement will experience many
changes in direction. Due to these motions, a given parcel of air containing a pollutant is
likely to experience an erratic trajectory as it travels from the source to some measuring
point or receptor. A typical path might consist of several straight line segments, which is
shown in the following figure:

Page 6 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
Figure: Air pollutant trajectory in an atmospheric SRD process.

Beginning with the initial concentration c0 , the pollutant will be diluted as it travels along
the first segment, reaching concentration c1 , such that c1  c0 . The resulting conentratio0n
can be expressed as a function of the initial concentration and the dilution factor
c1  Di c0 .
If the wind suddenly changes direction at c1 , the parcel will undergo additional dilution as
it travels along a second segment, giving concentration c2  D2 c1  D2 D1c0 . As the parcel
travels along other segments, it will experience additional successive dilutions. After m
segments, the concentration cm  D1D2 ... Dm c0 will result.
If a concentration is observed some time later at the same monitoring location, it will be
the result of a different trajectory will apply. By the theory of successive random
Dilutions, the resulting distribution of concentrations observed at this monitoring location
will be approximately log-normal.

Page 7 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
Page 8 of 21 Dr.Rehena Parveen
Department of Statistics,
BSMRSTU
Page 9 of 21 Dr.Rehena Parveen
Department of Statistics,
BSMRSTU
Page 10 of 21 Dr.Rehena Parveen
Department of Statistics,
BSMRSTU
Page 11 of 21 Dr.Rehena Parveen
Department of Statistics,
BSMRSTU
Page 12 of 21 Dr.Rehena Parveen
Department of Statistics,
BSMRSTU
Indoor Air Quality:

The theory of successive random dilutions also can be applied to pollutants released into
other small micro-environments, such as houses, buildings and interior rooms. Many
pollutants inadvertently are released at relatively high concentrations into the air of
indoor dwellings and offices and the ordinary motion of the air causes the pollutants to
undergo successive dilutions as they travel through these mixing volumes, ultimately
reaching low concentrations as they mix with fresh air from out-doors.

The most general form of the model of indoor air quality takes all these factors into
account and contains five terms.
t t t t

 y u  wdu   g u  du   h u  wdu   c u  wdu  v c t 

0 0 0 0
where,
y  u  = pollutant concentration in the input flow stream  M 3 / T 
w = flow rate of air into system  L3 / T 
g  u  = internal pollutant source  M / T 
h  u  = internal pollutant sink  M / T 
c  t  = pollutant concentration in output flow steam  M / L3 
v = volume of chamber  L3 

If we examine each term in this equation, we can see that the two terms on the left side of
the equal sign represent the sources of pollutant entering the chamber:

a) the pollution contributed by the input part and

b) the source located inside the chamber.

Similarly, the three terms on the right side of the equal sign reflect the destination of
the pollutant among three components:

c) the amount absorbed by the interval sink,

d) the amount departed through the output port and

e) the amount currently inside the chamber.

The result is a general statement of the mass balance equation for indoor settings, the
quantity of pollutant generated by the sources must equal the quantity of pollutant
accounted for by the chamber (absorption plus contents) plus the quantity spilled out.

Page 13 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
Now we differentiate the above equation to obtain a general differential equation for
indoor settings and divide by w and then rearrange terms:

v d c t  g t  h t 
 c t   y t   
w dt w w

w
Here,   ordinarily is defined as the “air exchange rate” of the system, since it is the
v
“number of chamber volumes of air per unit time” entering the system though the input
port.

If all the sources on the right side of the equation suddenly stop generating pollution at
time t  0 and the right side becomes zero, this equation has an exponential solution with
c0 as the initial concentration at time t  0 ,

c  t   c0 et for t  0

w
Where   = air exchange rate of system 1/ T 
v

c  t  = pollutant concentration as a function of time

c0 = initial concentration at time t  0

Water Quality:

Pollutants often are released into water bodies at relatively high concentrations and
undergo numerous stages of dilution. A simple example is an effluent discharged from a
pipe into a pond. If the pipe discharges the pollutant at high concentration over a very
short time and if fresh water is flowing into the pond, the pond will cause the pollutant to
become well-mixed.

The fresh water entering the pond from up stream. The pollutant has been released; the
concentration in the stream will decline exponentially, following the exponential solution
of the mass balance equation. If the process were repeated many times over and the fresh
water added were allowed to vary then the pollutant concentration in the stream after a
sequence of these dilutions would approach very nearly a two-parameter log-normal
distribution.

Considerable mixing and dilution occurs and one can imagine the pollutant concentration
after many points downstream to be some fraction of the initial concentration. Each of
these dilution stages along the path can be viewed as a stage of a SRD process.

Page 14 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
For example, if the source has released an effluent with pollutant concentration c0 at point
A , then the concentration at point B will be diluted and can be expressed as c1  D1c0
where 0  D1  1 .

Figure: Network of tributaries and streams illustrating a SRD process. Similarly, the
concentration at point C will be c2  D2c1  D1D2 c0 and so on.

Such that the final concentration cm after m dilutions is given by the usual result for a
SRD process:
m
cm  c0  Di
i 1

The SRD process results from the cascading effect of these dilution stages as well as the
effect of the stochastic mass balance action when ever water containing the pollutant
encounters fresh water and a mixing volume. In summary, one can expect the resulting
downstream concentrations measured after pollutant discharges on different dates to be
approximately log-normally distribution.

Page 15 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
Continuous Mass Balancer Model:

Because continuous pouring can be represented as a large number of step that are infinite
small, the dilution process in the continuous model can be described by a differential
equation.

To derive this differential equation, consider a slightly modified experiment. The beaker
begins completely full with water containing pollutant concentration c0 . Instead of
pouring off the excess liquid at each dilution step, the experimenter pours the diluent
continuously into the beaker. As soon as the pouring begins, the beaker begins to
overflow, and the concentration inside the beaker gradually declines. The continuous
pouring case can be viewed as the continuous version of many small dilutions in the two
discrete cases.

Derivation of the continuous model describing the system begins by considering two
states in time: the original state (at t  0) and a subsequent state after some time has
elapsed (at t  T ) . Just as pouring is about to start, at t  0 , the total mass of pollutant in
the system is contained entirely within the beaker as qoriginal  c0v . Instead of adding very
small quantities of diluent in successive increments, the investigator pours the diluent
into the beaker continuously and the contents spill over the edges of the beaker. At the
elapsed time t  T , if we take a “snapshot” of the system we will find that the total mass
of the pollutant is distributed in two places: the contents present in the beaker at time T ,
qspilled T  .

If we consider the mass balance before and after the passage of time T , we set the
original mass in the beaker equal to the sum of the quantity that is present at the two
locations at time T . The following is the “mass balance equation” for this system:

The mass balance equation accounts for all mass everywhere in the system

Original mass  Mass Inside at TimeT  Mass Spilled at TimeT

qoriginal  qinside T   qspilled T 

at time T . The original mass of pollutant in the system prior to pouring was qoriginal  c0v .
Because mass cannot be created or destroyed in this system, the sum of the pollutant
mass inside the compartment at time T and the pollutant mass that has spilled out must
be equal to the original total.

We can represent the the quantity that has spilled over the beaker’s edges mathematically
by integrating the product of the time varying concentration c  t  and the flow rate w  t 
between time t  0 and t  T :

Page 16 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
 q T spilled   c  t  w  t  dt
T

where q T spilled  total quantity spilled over edge of single beaker after time T  M 

c  t  = time varying concentration spilling over beaker’s edges [typically M / L3

w  t  = flow rate of liquid spilling over beaker’s edges  L3 / T 

Assume that the flow rate is held constant in a particular experiment: that is, w  t   w . If the
beaker remains well-mixed as the diluent is added, then the quantity inside the compartment will
be the product of the concentration at time T and the volume of the beaker,
or qinside T   c T v . If we substitute both this expression for qinside T  and the above
expression for qspilled T  into the mass balance equation of the system with qoriginal  c0v , we
obtain the following specific mass balance equation;

c0v  c T  v   c  t  wdt
T

Differentiating this equation, we obtain

v d c t 
 c t   0
w dt

if we rearrange the terms, this equation can be written as

d c t  w
  c t 
dt v

and, integrating this equation to obtain a solution we obtain:

w
ln c  t    tB
v

Here, B is constant of integration and substituting the constant A  e B then obtains the following
solution:
w w
 t  t
c t   e v
.e B  Ae v

the initial conditions require that c  0   c0 at t  0 , and therefore A  c0 .

w
 t
Hence, c  t   c0 e v
 c0 et

Page 17 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
If we represent the ratio of the flow rate to the volume as a single parameter   w / v , the
 will be the number of “beaker volumes” per unit time of fresh water that is added.

Page 18 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
Page 19 of 21 Dr.Rehena Parveen
Department of Statistics,
BSMRSTU
Concentrations in Soils, Plants, and Animals:
The Theory of Successive Random Dilutions (SRD), applies to a pollutant that is released
at initially high concentrations into a carrier medium and then undergoes dilution in
successive, independent stages. If a mixing stage occurs between each independent
dilution stage, the final concentration will be the product of the initial concentration and a
series of independent dilution factors. As the number of successive random dilutions
becomes large, the distribution of the final concentration will be approximately
lognormal. The Theory of Successive Random Dilutions is a special application of the
Law of Proportionate Effect. It is especially appropriate for modeling substances released
into environmental carrier media (e.g., air, water, soil) experiencing considerable
physical movement and agitation. Real-world conditions are likely to meet the
requirements for the Theory of Successive Random Dilutions only approximately.
Nevertheless, distributions with a characteristic lognormal appearance have been
observed in a variety of fields as for examples outdoor air pollutants; indoor air

Page 20 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU
pollutants; water pollutants measured in streams, lakes, and ground waters; radionuclides
in soils, plants, fishes, birds, and mammals; additives in foods; radionuclides and trace
metals in human tissue, blood, and feces; and precious metals in the earth.

Pollutants released into the soil from point sources are apt to experience successive
random dilutions, giving rise to concentration distributions that are right-skewed and
appear lognormal. Little and Whicker studied the distributions of plutonium
concentrations in the soil of Rocky Flats, a nuclear facility about 12 miles northeast of
Denver, CO. The contamination occurred after a fire at the site and was attributed to
leakage from drums containing plutonium-laden cutting oil that had been stored outdoors.
They believed that the mechanism responsible for transport of the pollutant was
movement from the surface soil by wind, followed by weathering, microdispersal, and
penetration into the soil. They cite several other investigators who have reported
lognormal radionuclide distributions in soils: “Generally, radionuclide contamination of
the environment results in lognormal distributions. As the concentrations of trace
contaminants in soils are taken up by plants, they undergo additional dilutions, becoming
dispersed throughout the plant fibre. Cattle and other animals may graze on these plants,
absorbing a small proportion of the original substance in their tissue. As the pollutant
moves through the food chain, it undergoes additional successive dilutions, and the
concentration distribution in plants and animals should show a tendency toward
lognormality. However, for some substances, bioaccumulation may occur, reducing the
skewness of the distribution and its tendency toward lognormality.

Page 21 of 21 Dr.Rehena Parveen

Department of Statistics,
BSMRSTU