CHAPTER FOUR

Fundamentals of Water Quality

This chapter discusses the fundamental relationships for water quality. The
basis for all water quality analyses is conservation of a constituent mass that
was developed in Chapter 3. In this chapter, it will be applied to mixing at a
node and transport in a pipe. Constituent balance in a storage tank is discussed
in Chapter 7. A critical aspect of constituent mass balance is the constituent
reaction. Reaction relationships and estimating decay and growth coefficients
are also presented in this chapter.

4.1 CONSERVATION OF A CONSTITUENT MASS

As presented in Chapter 3, conservation of constituent mass (Eq. 3-18) is:

dmc d ( C V )
∑C
in flows
in Qin − ∑C
outflows
out Qout +
dt
=
dt
(4-1)

C is the volume concentration [Mc/L3], V is the volume of water in the control

volume and Q is the flow rate.
The right hand side is the rate of change in the mass of the constituent
within the control volume. The left hand side is the transport of constituent
mass into or out of the control volume. The first two terms are transport with
fluid. The last LHS term, dmc d t = [Mc/T], is a reaction term that accounts for
growth or decay transformations of the constituent in the control volume.
The concentration used in this equation is the mass of constituent per unit
volume of water or:

m ⎡M ⎤
C= =
V ⎢⎣ L3 ⎥⎦

Units of C in SI are typically given as g/m3 or mg/l where l is liters. Conversion

factors from g to mg and m3 to l are the same so the concentration value for
both units is the same. 1 g/m3 is also equivalent to 1 ppm (part per million).
Fluoride injections and chlorine are typically on the order of mg/l. Salinity or
total dissolved solids may be measured on the order of grams/liter (g/l). The
units of kg/m3 and ppt (parts per thousand) are identical to g/l. Bacteria are

4-1
4-2 CHAPTER FOUR

commonly in the range of micrograms/liter (µg/l). Equivalent measures to µg/l

are mg/m3 and ppb (parts per billion).
The constituent mass added to water per unit time is the loading rate, m& c =
m/t. In a distribution system, one method for adding constituent is injection of a
disinfectant mass. The loading rate will result in an increase in concentration,
∆C, in the volumetric flow rate, Q or:

dm ⎡ M L3 M ⎤
m& c = = Q ∆C = ⎢ = ⎥
dt ⎣T T L3 ⎦

Example 4.1

Problem: The chlorine concentration of water flowing at a rate of 0.3 m3/s is

0.03 mg/l. The desired concentration is 0.2 mg/l. What loading will be needed
to cause this increase? If the chlorine is injected continuously for a month, what
is the chlorine mass required?

Solution: The increase in concentration is 0.2 – 0.03 = 0.17 mg/l. The loading
rate is then:

m& Cl = Q ∆C = 0.3 m 3 / s ⋅ (0.2 − 0.03) g / m 3

= 0.051 mg / s = 184 mg / hr

The mass per month is the loading rate times the duration of injection or:

mCl = m& Cl ⋅ t = 0.051 mg / s ⋅ 3600 s / hr ⋅ 24 hr / d ⋅ 30 d / mo

= 132000 mg / mo = 132 g / mo

4.2 TRANSPORT AND MIXING IN THE PIPE NETWORK

As discussed in Chapter 3, the flow distribution in a water distribution network

is defined by conservation of mass and energy. We assume that any constituent
in the water does not affect the terms in these relationships. Thus, a hydraulic
analysis to determine the pipe flow velocities and nodal heads can be completed
without regard to water quality. However, since water quality transport is
directly related to the flow velocities a strong understanding of the network
hydraulics and a well-calibrated hydraulic model are necessary to perform and
evaluate a water quality analysis. All available water quality models first
 WATER QUALITY FUNDAMENTALS 4-3

perform a hydraulic analysis then provide the resulting flow distribution to a

water quality module to transport a constituent through the system.
The result of a water quality analysis in a pipe network is the constituent
concentration at all junction nodes. A temporal record or unsteady analysis is
generally desired. Time invariant or steady conditions are simpler to analyze
but are less realistic. In steady and unsteady analyses, two processes must be
considered when modeling water quality in a pipe network; mixing at nodes
and transport in pipes. Both processes are described by conservation of a
constituent mass (Eq. 4-1).
Nodal mixing accounts for the mixing of waters with different constituent
concentrations. No storage is provided at a node and water is assumed to pass
through the node instantaneously. If additional constituent is added to the water
system, it is assumed to occur at a node. Several types of injectors can provide
constituent.
Transport of water through a pipe introduces time dependency to water
quality analysis. The pipe travel time provides the time lags in the flows
between junction nodes. In addition as water travels through a pipe, a
constituent concentration may change due to decay, reactions, or growth. The
remainder of this section discusses the mixing and transport processes and their
mathematical formulations.

4.2.1 Mixing at Junctions

4.2.1.1 Simple Junctions

At junction nodes within a pipe network, water quality changes due to dilution
and injection. Conservation of mass is applied at junctions to determine the
effect of combining flow with different constituent concentrations. Full and
complete mixing is assumed to occur resulting in concentrations that are
uniform across the downstream pipe section. Since a node cannot store water,
the mass of constituent at the node is constant and the left-hand side of Eq. 4-1
equals zero. Also since pipe lengths at the junction are very small, no time is
spent at the node so no constituent growth or decay can occur. For a simple
junction, no constituent is supplied at the node. The last two statements imply
that dmc dt equals zero. Under these conditions, Eq. 4-1 becomes:

d ( CV ) dmc
dt
= ∑ in
C Q− ∑ out
CQ +
dt
⇒ ∑
in
C Q− ∑ out
CQ =0
(4-2)

Consider a junction with three pipes carrying flow to the node, two carrying
flow away from the node and a lumped withdrawal at the node (Figure 4-1).
4-4 CHAPTER FOUR

Applying conservation of a constituent mass with no storage, we can write Eq.

4-2 as:

C1 Q1 + C 2 Q2 + C 3 Q3 - C 4 Q4 - C5 Q5 - C out q out = 0

Figure 4-1: Junction node with three inputs and three withdrawals.

The signs correspond to inflows and outflows from the node. Pipes 4 and 5
carry flow away from the node. During a water quality analysis, these flow
directions and the flow rates are known from a prior hydraulic analysis. The
concentrations of constituents input at the node are also known.
Assuming that complete and instantaneous mixing occurs at the node, the
concentrations in pipes 4 and 5 and the nodal withdrawal are the same, Cout, or:

C1 Q1 + C 2 Q2 + C 3 Q3 - C out Q4 - C out Q5 - C out q out = 0

Since the inflow concentrations are known, this equation can be solved for
Cout or:

C1 Q1 + C 2 Q2 + C 3 Q3 4 (1.5) + 3 (2.5) + 5 (2)

C out = = ⇒ C out = 3.92
Q4 + Q5 + q out
3 + 2 +1

Eq. 4-2 can be written for a general node as:

 WATER QUALITY FUNDAMENTALS 4-5

∑C
l ∈ J in
l Ql + C in q in
C out = (4-3)
q out + ∑Q
l ∈ J out
l

Here, flow enters the node through Jin pipes and as an externally supplied
flow, q in . Each of these flows may have a different constituent concentration,
Cl and Cin, respectively. Outgoing flow consists of the nodal withdrawal, qout,
and the flow in the set of Jout pipes carrying flow from the node. With the
complete mixing assumption, all outflows have the same concentration, Cout.
Equation 4-3 shows that the outgoing concentration is a flow weighted average
of the incoming concentrations.

4.2.1.2 Junctions with Injected Constituent

In most models, a constituent can be introduced to the system in five ways.

First, for a dynamic simulation, the initial constituent concentrations, C0, must
be defined for all locations. Second, constituents may be added to the system
with water entering the network as source contributions. The last three methods
are injections of a constituent at a node without water, such as a tracer or
disinfection booster injection. Three types of boosters are commonly used:
mass, setpoint and flow paced. For these cases, dmc dt in Eq. 4-1 is not equal
to zero.
A common injection approach is municipal chlorinators (Figure 4-2) that
can be used within the water treatment plant or at booster locations. Chlorine is
available in gas, liquid or solid forms. For safety reasons, tablets are most often
used away from the plant. In the injector, water is drawn from a distribution
system pipe into the unit. Water flows through the contact chamber containing
chlorine tables. The flow rate and chamber size affect the dosage and multiple
contact chambers may be used for larger flows. Depending upon the design,
flow may be sent to a small reservoir before being returned to the pipe. A gas or
liquid feeder works under the same principle with the disinfectant typically fed
directly to the flow with a device to insure proper mixing.

4.2.1.2.1 Source Concentration

In most water quality models, the concentration for all external flow entering a
node can be specified. The flow is typically a negative demand at a junction
node or a flow from a reservoir or water treatment plant. The input water
concentration, Cin in Eq. 4-3, is described as the source concentration.
4-6 CHAPTER FOUR

Figure 4-2: Tablet feeder chlorinator system. Flow is drawn into the
system by the pump in the lower left. Tablets are added to the cylinder on
the top of the unit.

4.2.1.2.2 Mass Booster Injection

A mass booster injects a fixed mass rate ( m& in ) of constituent to the junction
inflow. This option is useful when analyzing a tracer study or when modeling
the possible impacts of an unwanted intrusion due to a backflow event or
intentional contamination. The inflow can represent the mass of tracer injected
or contamination entering the system over time. In Eq. 4-1, the mass rate of
injection is:

dmc
m& in =
dt
= C ininj ∑Q
l ∈ J in
l (4-4)

where C ininj is the effective concentration resulting from injecting the defined
constituent mass. Substituting this term in Eq. 4-1 and solving results in:
 WATER QUALITY FUNDAMENTALS 4-7

∑C
l ∈ J in
l Ql + C in q in + m& in ∑C
l ∈ J in
l Ql + C in q in + C ininj ∑Q
l ∈ J in
l

C out = =
q out + ∑Q
l ∈ J out
l q out + ∑Q
l ∈ J out
l

(4-5)

Example 4.2

Problem: A 2.5 lb (1.1 kg) tablet that is 16% Cl2 dissolves in one hour in a
tablet feeder chlorinator. Three percent of the 800 gpm (50 lps) supply pipe
flow is passed through the unit. Determine the increase in concentration in the
water being returned to the pipe and in the water in the pipe downstream of the
chlorinator return.

Solution: The 1.1 kg provides 0.176 kg of Cl2 (16%*1.1) to the flow. In the
main pipeline, the mass rate of 0.176 kg/hr is dissolved in the flow of 50 lps.
Thus,

m& c = Q ∆C = 0.176 ( kg / hr ) 10 6 ( mg / kg ) / 3600 ( s / hr ) = 50 (l / s ) * ∆C pipe

⇒ ∆C pipe = 0.98 mg / l

The concentration in the feeder unit has the same mass added but the flow is
only 3% of the 50 l/s or 1.5 l/s. Thus, the concentration is:

m& c = Q ∆C = 0.176 ( kg / hr ) / 3600 ( s / hr ) = 1.5 (l / s ) * ∆C feeder

⇒ ∆C feeder = 32.6 mg / l

Example 4.3

Problem: A mass loading rate of 10000 units/hr of the constituent modeled is

added to the node shown in Figure 4-1. Determine the effective injection
concentration and the resulting concentration in flow leaving the node.

Solution: The effective injection concentration, Cininj , can be computed from Eq.
4-4.

m& in = C ininj ∑Q
l ∈ J in
l = 10000 / 3600 (units / s ) = C ininj (Q1 + Q2 + Q3 )
4-8 CHAPTER FOUR

= C ininj unit / L3 (1.5 + 2.5 + 2) L3 / s ⇒ C ininj = 0.46 units / L3

The concentration of flow leaving the node is determined by Eq. 4-5.

∑C l Ql + C in q in + m& in (4 ⋅ 1.5 + 3 ⋅ 2.5 + 5 ⋅ 2) + 0 +

10000
C out =
l ∈ J in
= 3600
q out + ∑Q
l ∈ J out
l
1 + (2 + 3)

23.5 + 2.8
= = 4.38 units / L3
6

The injected mass increased the outflow concentration by 0.46 units/L3 from
3.92 to 4.38 units/L3.

4.2.1.2.3 Setpoint and Flow Paced Boosters

The last two injector types supply constituent on the outlet side of the node to
increase the concentration of the nodal withdrawal and the outlet pipe flows.
Based on that definition, the added constituent mass rate is:

dmc ⎛ out ⎞
dt
inj
= C out ⎜q +
⎜ ∑ Ql ⎟
⎟
(4-6)
⎝ l ∈ J out ⎠

Substituting this term in Eq. 4-1 and assuming no nodal storage gives:

dmc
∑C
in flows
in Qin − ∑C
outflows
out Qout +
dt
=0

⎛ ⎞ ⎛ out ⎞
= ∑C l Ql + C in q in − C out ⎜ q out +
⎜ ∑ Q ⎟⎟ + C l
inj
out
⎜q +
⎜ ∑ Q ⎟⎟ l
l ∈ J out ⎝ l ∈ J out ⎠ ⎝ l ∈ J out ⎠

that can be solved to show:

∑C
l ∈ J out
l Ql + C in q in
inj
C out = + C out (4-7)
q out
+ ∑Q
l ∈ J out
l
 WATER QUALITY FUNDAMENTALS 4-9

inj
A flow paced booster adds a user defined fixed concentration of C out to all
inj
outflows. A setpoint booster fixes Cout and determines the required C out to meet
the setpoint. Using different logic, both boosters can be modeled in a water
quality computer model with Eq. 4-7. If the setpoint concentration is less than
the concentration without injection, i.e., the first term in Eq. 4-7, the
inj
concentration is not reduced. Rather, C out is set to zero and the Cout is set to the
available concentration.

Example 4.4

Problem: Determine the constituent concentration for the node in Figure 4-1 if
a flow paced booster injects 0.5 units/L3 to all flows leaving the node.

Solution: The concentration without any constituent injected at the node was
determined in the text to be 3.92 units/L3 using Eq. 4-3 which is equivalent to
inj
the first term on the left hand side of Eq. 4.7. The injected concentration, C out ,
3
is given as 0.5 units/L . Eq. 4-7 is then applied to determine the outlet
concentration, Cout.

∑C
l ∈ J out
l Ql + C in q in
inj
C out = + C out = 3.92 + 0.5 = 4.42 units / L3
q out + ∑ Ql
l ∈ J out

Example 4.5

Problem: A set point booster is used to increase the constituent concentration

of the flow leaving the node in Figure 4-1 to 4.25 units/L3. What is the injection
concentration and loading rate of constituent injected?

Solution: A setpoint booster defines the outlet concentration at the node, Cout in
Eq. 4-7. As noted, the concentration without the addition of injected constituent
is 3.92 units/L3 which is the first LHS term in Eq. 4-7. The required injection
inj
concentration, C out , can be determined by substituting the known values in Eq.
4-7 giving:
∑
C l Ql + C in q in
l ∈ J out inj inj
C out = 4.25 = + C out = 3.92 + C out
q out + ∑ Ql
l ∈ J out
4-10 CHAPTER FOUR

inj
⇒ C out = 0.33 units / L3

As defined in Eq. 4-6, the loading rate is the flow rate leaving the node times
the injection concentration or:

⎛ ⎞
inj ⎜ out
m& c = C out
⎜
q + ∑ Ql ⎟
⎟
⎝ l ∈ J out ⎠
[ ] [ ]
= 0.33 unit / L3 (1 + (2 + 3)) L3 / s = 2 unit / s

4.2.2 Advective Transport in Pipes

Transport of a general fluid property can occur by five mechanisms: advection,

molecular diffusion, turbulent diffusion, dispersion and radiation. Radiation is
restricted to energy transport by electromagnetic waves and is not considered
here. Under most conditions, the dominant mechanism for transport in the pipe
network is advection. Molecular diffusion and turbulent diffusion are normally
neglected in water distribution networks since the flow is generally turbulent
with a relatively high velocity. Most water quality models represent advection
only. Even if multiple mechanisms are modeled under conditions of laminar
flow, advection must be included. So we begin with advection and develop
relationships for advective transport. Extensions to other transport mechanisms
are then discussed.
Advection is the movement of the constituent with the water in the
direction of flow with the magnitude of the main velocity component. In other
words, transport by carrying a constituent along with the flow of water. An
example of advection is the movement of a cleaning “pig” in a pipe. To remove
encrusted material from a pipe wall, one practice is to insert a “pig” into the
line. The pig is a bullet-shaped object that is covered with rough material, often
a metal mesh, and acts like a scouring pad (Figure 4-3a). It is inserted at a
hydrant and moves with the water’s velocity to a withdrawal point downstream
(Figure 4-3b). This movement is advective transport. In Eq. 4-1, advection is
represented by the first two terms on the left hand side. Each term is related to
the mean flow velocity through the discharge rate.
In pure advective transport, a mass of some constituent injected into a pipe
will move in a similar manner to the pig and a pipe will act as a plug flow
reactor (PFR). Flow passes through a PFR in the sequence that it enters. In
other words, the pipe is first in-first out reactor. Consider a pipeline with a
fluoride injector. To begin the injector is off, flow is steady and no fluoride is in
the pipeline (Figure 4-4). At time t, the injector is instantaneously turned on. At
time t + ∆t, the injector is turned off. The fluoride injected in the ∆t time step is
 WATER QUALITY FUNDAMENTALS 4-11

carried downstream in the water in a pulse (like the scouring pig). Assuming
other transport mechanisms are negligible, the pulse length, Lseg, remains
constant and the time required for the front of the pulse to move from the
injector to the end of the pipe can be computed given the flow velocity as the
distance divided by the velocity or:
L
τ= (4-8)
V

Figure 4-3a: Polyester foam pipeline pigs can be bare foam or coated with
a polyurethane material. Coated pigs may have a spiral coating of
polyurethane, various brush materials or silicon carbide coating to
improve wall scrubbing. The pigs above are medium density (5-8 lb/ft3)
open cell polyurethane foam with a polyurethane coating. (Courtesy of Girard
Industries Incorporated (http://www.girardind.com/redpolly.htm). See also Pigging
Products and Services Association at http://www.piggingassnppsa.com/).

Figure 4-3b: Movement of pig with mean flow velocity through pipeline.
4-12 CHAPTER FOUR

where L is the pipe length and τ is the travel time. For example, if the pipe
length is 1000 ft and the velocity is 1.25 ft/s the travel time is 1000 ft/1.25 ft/s =
800 seconds. The entire pulse will move with this velocity through the pipe.
Note that travel times through pumps, valves and other appurtenances are very
small so they are not considered as components in a water quality analysis.
Following or tracking the pulse of water with fluoride and identifying its
location over time is a Lagrangian analysis and is one approach to modeling
water quality in networks. The alternative Eulerian approach is to partition the
pipe into discrete volume elements (i.e., control volumes) and monitor the
concentration within each element as the pulses of constituent move through
the system. The series of elements in an Eulerian approach corresponds to a
cascade of PFR’s. Both approaches can provide identical results and are
discussed further in this chapter and in Chapter 6.

Figure 4-4: Advective transport of pulse of constituent injected at left

beginning at time t. The input pulse duration is ∆t hrs and results in the
gray block. The fluid mass moves with the same length through the entire
length of the pipe. The front of the pulse reaches the downstream end of
the pipe in τ hrs where τ is the travel time in the pipe.

4.2.2.1 Advection Equation

The first governing constituent mass balance for a pipe describes advective
transport in a pipe. Eq. 4-1 can be written for a pipe filled with water (V is
constant) with no external withdrawal or supply under steady flow conditions
as:
 WATER QUALITY FUNDAMENTALS 4-13

∂C dmc
V = (C Q) in − (C Q ) out + (4-9)
∂t dt

If we write the inflow-outflow terms in a single differential form for a pipe

segment of length ∆x and divide both sides by the pipe volume. The inflow-
outflow terms are:

(C Q) in − (C Q) out Q (− ∆C ) ⎛ A ∆x ⎞ ⎛ − ∆C ⎞ ∆x (− ∆C ) ∂C
= =⎜ ⎟ ⎜⎜ ⎟⎟ = = −V
V V ⎝ ∆t ⎠ ⎝ A ∆x ⎠ ∆t ∆x ∂x
(4-10)

1 dmc
Substituting this term in Eq. 4-9 and defining = r (C ) results in the final
V dt
differential form of conservation of constituent mass for a pipe element:

∂C ∂C
+V = r (C ) (4-11)
∂t ∂x

This equation represents advective transport in a plug flow reactor with

reactions. The terms represent changes in concentration over time, longitudinal
transport along the pipe, and reactions, respectively. The units are concentration
per time (e.g., mg/l/t). Eq. 4-11 can be applied to an entire pipe or a pipe
element. The reaction relationships and their parameters are described later in
this chapter.

Example 4.6

Problem: Water flows at a rate of 2.0 ft3/s through a 900 foot long 8-inch
diameter pipe. Determine the velocity in the pipe and the travel time.

Solution: For a flow rate of Q = 2 ft3/s, the flow velocity is:

Q 2.0 2.0
V= = =
A πD 4(
2
) ((
π (8 / 12) 2 ) 4) = 5.73 m/s
The travel time is:

L 900
τ= = = 157 s = 2.6 minutes
V 5.73
4-14 CHAPTER FOUR

Example 4.7

Problem: Three grams of fluoride are injected at a rate of 0.1 g/s into a pipe
that carries water at a flow rate of 0.3 m3/s beginning at time 0 s. The pipe has a
length of 100 m and diameter of 800 mm.
Determine the concentration, the length of the pulse, and the time that the
pulse reaches and leaves the pipe outlet.

Solution: The 3 g are injected at a rate of 0.1 g/s. The duration of the pulse is:

tinj = 3 (g) / 0.1 (g/s) = 30 s = 0.5 min

The concentration of fluoride in the water is:

C = m& c / Q = 0.1( g / s ) / 0.3 ( m3 / s ) = 0.33 g / m 3 = 0.33 mg / l

The velocity is:

Q 0.3 0.3
V= = = = 0.60 m/s
(
A πD 42
) ((
π (0.8) 2 4 ) )
Since the fluoride is injected over a 30 s period, the length of the pulse is:

Lseg = t inj V = 30 s ⋅ 0.60 m / s = 18 m

The front of the segment begins at time 0. The travel time through the reach is:

L 100
τ= = = 167 s = 2.78 minutes
V 0.60

where L is the length of the pipe. Thus, the front edge of the segment will reach
the end of the pipe at time 2.78 minutes. The 18 m segment takes 30 s to
develop with the injected fluoride. Thus the back edge of the segment will
reach the outlet at time 2.78 minutes + 0.5 minutes = 3.28 minutes.

Example 4.8

Problem: For the pipe conditions in Example 4.7, track the segment of fluoride
through the pipe. Specifically show the location of the segment at times 0 s, 30
s, 90 s, 2.78 minutes, and 3.28 minutes.
 WATER QUALITY FUNDAMENTALS 4-15

Figure E4-8 (a-e): Time history of segment affected by fluoride injection at

the left pipe inlet beginning at time 0 s. in the 100 m long pipe in Example
4.8.

Solution:

a) Time 0 s. – The fluoride has just begun to be injected so the water has a
zero concentration for the entire length of the pipe (Figure E4.8a).

b) Time 30 s. – The fluoride has been injected for 30 s and, as computed

in the previous example, the distance the water at the injector at time 0
has traveled 18 m. which is the length of the segment (Figure E4.8b).

c) Time 90 s. – During the time period of 30 to 90 s, the water will move

36 m = 0.60 m/s * 60 s. Therefore the front of the segment at time 90 s
that was at 18 m into the pipe travels to a location that is 54 m (= 18 +
4-16 CHAPTER FOUR

36) from the inlet. The back end of the segment was at the pipe
entrance so it travels to a location 36 m into the pipe (Figure E4.8c).

d) Time 2.78 min (167 s) – The travel time for the pipe is 2.78 minutes.
Therefore, water at the entrance at time 0 s traversed the entire pipe
length. This water corresponds to the front of the segment. The back of
the segment is 18 m to the left of the front. The back of the segment
entered the pipe at time 30 s. so it has traveled through the pipe for 137
s (=167 s – 30 s) and a distance of 82 m (=0.60 m/s * 137 s) (Figure
E4.8d).

e) Time 3.28 min (197 s) – The front of the segment reached the outlet of
the pipe at time 167 s. After 30 s (=197 - 167s), the remainder of
segment reaches the downstream end of the pipe so the back end of the
segment is just leaving the pipe at time 197 s. (Figure E4.8e)

4.2.2.2 System of Equations for Advective Transport

In summary, the primary mechanisms governing water quality in a water

distribution system are advective transport in a pipe and complete turbulent
mixing at a node. Mixing at a node without injection is represented by Eq. 4-3:

∑C
l ∈ J in
l Ql + C in q in
C out = (4-3)
q out + ∑Q
l ∈ J in
l

One equation of this form can be written for each node. Pipe transport is
described by Eq. 4-11 or:

∂C ∂C
+V = r (C ) (4-11)
∂t ∂x

One equation of this form can be written for each pipe. Example 4.9
demonstrates how the advection and node balance equations can be combined
to determine downstream concentrations. The approach shown is the basis for
steady state and dynamic water quality analyses.
Since flow is unaffected by water quality, the system hydraulics including
tank flows can be determined by a standard hydraulic analysis prior to
considering water quality. Given the flow distribution, these equations can be
solved to determine the constituent concentrations throughout the distribution
 WATER QUALITY FUNDAMENTALS 4-17

system for steady conditions or over time. Tanks are modeled with the
relationships described in the next chapter.
Water quality in a water distribution system can vary over time (described
as dynamic or unsteady) or reach a constant time invariant condition (steady
state). Steady conditions are not typical for most systems as nodal demands will
change faster than the time needed to reach constant conditions. However, a
steady state solution may provide an initial assessment of problem areas in a
system, requires less information regarding demands, and can be solved more
quickly than a dynamic model. Chapter 5 presents a formulation and solution
for a steady state modeling of a general constituent.
Dynamic simulation is more detailed and will track how the network
conditions will change over time with variations in demands and pump (on/off)
and tank (filling/draining) operations. More information is needed than a steady
state simulation but the majority of that information is demand related. A tank
water quality model is also necessary (Chapter 7). Several methods (Eulerian
and Lagrangian) for dynamic water quality modeling are discussed in Chapter
6. These methods have been successfully applied to model water quality
(conservative and reactive species) in simple as well as very large and complex
water distribution systems.

Example 4.9

Problem: A conservative constituent is injected at time 0 at the source nodes 1

and 2 with concentrations of 2 and 5 mg/l, respectively (Figure E4-9a). The
injection remains on and the flow rates do not change. The water initially in the
pipe contains no constituent (i.e., C = 0)

a) Calculate the outflow from node 3 (q3)

b) Compute the flow velocities and the travel times for each pipe.
c) Calculate node 3’s constituent concentration, C3, at times t= 0, 12,
30, and 45 minutes.

Solution:

a) Based on the steady flows, the outflow from node 3 is the sum of the flows
from the two pipes (Eq. 3-7) or:

Q1 + Q2 = q 3 ⇒ q 3 = 0.7 + 0.2 = 0.9 m 3 / s

b) Given the flow rates, the velocities are computed by V = Q/A and travel
times are found using τ = L/V.
4-18 CHAPTER FOUR

Figure E4-9a: Two-pipe system with fluoride injection.

5
Concentration (mg/l)

4
Pipe 1
3 Pipe 2
Node 3
2

0
0 10 20 30 40 50 60
Time (minutes)

Figure E4-9b: Concentration versus time for Example 4-9. Concentrations

are shown for flows at the downstream end of pipes 1 and 2 as they enter
node 3 (Pipe 1 and Pipe 2) and the resulting weighted concentration
leaving node 3. Although pipe 2’s concentration is 5 mg/l, the pipe only
contributes 2/9 of the nodal flow. So the node 3 concentration does not
increase dramatically when the constituent arrives in that pipe.

Pipe 1:
Q1 0.70 m 3 /s 0.70
V1 = = 2 2
= = 2.48 m/s
A1 π D1 4 m π ( 0.6 2 ) 4
 WATER QUALITY FUNDAMENTALS 4-19

L1 2340 m
τ1 = = = 943 s = 15.7 min
V1 2.48 m/s
Pipe 2:
Q2 0.20 0.20
V2 = = = = 1.59 m/s
A2 π D2 4 π ( 0.4 2 ) 4
2

L2 3200
τ2 = = = 2010 s = 33.5 min
V2 1.59

c) To determine the concentrations at the node 3, the movement of constituent

laden water is tracked over time. Since the initial constituent concentration is
zero, the concentration at the node 3 is equal to zero. It is calculated by
applying the nodal concentration equation (Eq. 4-3) or:

(C1 Q1 + C 2 Q2 ) ((0) (0.7) + (0) (0.2) )

C 3,t = 0 = = =0
Q3 0.9

The concentration remains equal to zero until the first constituent reaches
node 3. This holds until flow from pipe 2 that contains constituent reaches the
node. Since the travel time in pipe 1 is 15.7 minutes, node 3’s concentration at
time 12 minutes is equal to 0 mg/l.
This concentration will change when water that contains constituent from
the upstream nodes reaches node 3. This occurs at time 15.7 minutes due to the
inflow from pipe 1. A second change in concentration at node 3 does not occur
until time 33.5 minutes (= τ2). Therefore, the concentration at node 3 at time 30
minutes will only be affected by node 1 injection. The outflow concentration at
node 3 at time 30 minutes is computed using equation 4-3 or:

(C1 Q1 + C 2 Q2 ) (( 2) (0.7) + (0) (0.2))

C 3 , t =30 min = = = 1.56 mg / l
Q3 0.9

Finally, after water containing constituent in pipe 2 reaches node 3 the

concentration changes and is computed by Eq. 4-3 for all times greater than
33.5 minutes. Therefore, the concentration at time 45 minutes is:

(C1 Q1 + C 2 Q2 ) (( 2) (0.7) + (5) (0.2))

C 3 ,t = 45 min = = = 2.67 mg / l
Q3 0.9

Figure E4-9b is a plot of the concentrations at the outlet of each pipe and
the flow-weighted nodal concentration as a function of time. The steps occur
when constituent-laden waters reach node 3.
4-20 CHAPTER FOUR

4.2.3 Other Transport Mechanisms

Advective transport is the dominant transport mechanism in most distribution

system pipes. However, other transport mechanisms may be important in
conditions that are not fully turbulent. The non-uniform velocity distribution
occurring in laminar flow causes longitudinal mixing or dispersion that does
not take place in turbulent flow. In addition, radial mixing must be understood
to correctly account for reactions between waterborne constituents and the pipe
wall. Mixing decreases with the level of turbulence. Research has progressed to
model radial and longitudinal mixing to represent and characterize the other
transport mechanisms that are described in the following paragraphs.
In 1883, Reynolds reported on experiments that led to development of the
first laws describing laminar and turbulent flow. The experiments also provide
a visual picture of transport in a pipe. Reynolds’ apparatus was a tank
connected to a glass pipe that contained a valve (Figure 4-5). The tank included
a thin tube to inject dye into the pipe. By manipulating the valve, he created
different flow regimes that were visually apparent in the motion of the dye.
With low flow rates and laminar conditions, the dye continued in a near straight
line (Figure 4-5a). When the valve was opened slightly further, the dye began
waving as it moved through the pipe and may have completely colored the
downstream water (Figure 4-5b). If the valve was opened further causing higher
velocities, turbulent flow resulted and the dye was rapidly spread across the full
pipe section (Figure 4-5c).

Figure 4-5: Reynolds’ experimental setup (left) and spread of dye for (a)
laminar, (b) transition and (c) fully turbulent flow (right).

4.2.3.1 Molecular Diffusion

The spread of dye across Reynolds’ pipe was caused by random motion of
molecules and parcels of fluid. Movement due to random motion is described
as diffusion. Molecular diffusion, also termed conduction, is mass transport
caused by the movement of molecules (Figure 4-6a) known as Brownian
 WATER QUALITY FUNDAMENTALS 4-21

motion. Molecular diffusion can be very small. In Figure 4-5 (a), no diffusion is
shown in the short pipe.

Figure 4-6: Flow in a pipe showing (a) molecular diffusion as demonstrated

by a droplet of dye at three different times. The droplet expands as it
travels with flow (advection). (b) Pipe flow at an instant in time with eddies
in flow resulting in turbulent diffusion.

An example of molecular diffusion is a cup of hot water. A tea bag is

slowly placed in the cup causing little motion. The water will slowly turn
brown as the tea is mixed with the water by the random motion of molecules in
the fluid. This molecular effect occurs very slowly. Redistribution of a
constituent in a tank or in a pipe with still or very slow moving water is also
caused by conduction. Since this mechanism can occur when the water is not
moving, it is accounted for in the last term on the left hand side of Eq. 4-1.
Molecular diffusion occurs as a result of the nonuniformity of constituent
concentration throughout the fluid. The rate of conduction is related to the
magnitude of the concentration imbalance by Fick’s First Law. Fick’s law
states that the rate of mass transfer is related to the mass concentration gradient
(Chapra, 1997) or:

∂C ∂2 C
= Dm (4-12)
∂t ∂ y2

where Dm is the molecular diffusion coefficient [L2/T], which is on the order of

10-5 cm2/s. The direction y is arbitrary since conduction occurs in all directions.
The velocity of water in a pipe is on the order of feet or meters per second
while molecular diffusion is on the order of feet/day. Thus under most
conditions, the additional spreading in the direction of flow (longitudinal
spreading) due to molecular diffusion is not detectable unless flow is very slow.
4-22 CHAPTER FOUR

It may become important in low velocity conditions that occur in dead-end

pipes under constant or intermittent conditions.

4.2.3.2 Turbulent Diffusion

Turbulent diffusion is transport caused by the random movement of fluid

parcels due to turbulence versus fluid molecules in molecular diffusion. Again
consider the cup of hot water. Instead of placing the tea bag in and leaving the
cup, now the tea bag is lifted in and out of the water. This action will cause
eddies (turbulence) in the water and increase the rate of mixing and coloration.
Parcels of water with high tea concentrations mix in parts of the cup that have
low concentrations until the tea is uniformly distributed throughout the cup. In
tanks like the tea cup, mixing is critical to understanding constituent
distribution. A jet of water entering a tank may cause turbulence and mixing.
Turbulent diffusion also occurs in a pipe during turbulent flow. At the pipe
wall under laminar flow with low velocities, water will pass over and around
the imperfections on the pipe wall. As velocities increase, water essentially runs
into the bumps and bounces away from the pipe wall forming eddies. This
process distributes a constituent through the water across the pipe section more
rapidly than molecular diffusion since the fluid is mixing (Figure 4-6b). The
momentum and velocity are mixed in the same way resulting in a relatively
uniform velocity distribution across a pipe as shown in Figure 3-4. In
Reynolds’ experiments, as the level of turbulence increased with the flow
velocity, the dye mixing was more rapid (Figures 4-5b and c).
The formation and size of eddies is a random process so the transport can
be modeled as a Fickian diffusion process. Thus mathematically, turbulent
diffusion is also described by Eq. 4-12 but with a turbulent diffusion
coefficient, Dt [L2/T]:

∂C ∂2 C
= Dt (4-13)
∂t ∂ y2

where Dt is typically in the range of 100-105 cm2/s.

4.2.3.3 Dispersion

Advection is the transport at the mean fluid velocity. In turbulent flow, the
velocity is nearly uniform across a section and nearly equal to the mean value
(Figure 3-4) so spreading of a constituent laden mass in the axial direction is
small. At low flow rates and laminar flow, the non-uniform velocity
distribution (Figure 3-3) causes variations in axial transport across the pipe. As
shown in Figure 4-7, the center of the pipe has a velocity greater than the mean.
 WATER QUALITY FUNDAMENTALS 4-23

If only advection is considered, the additional transport above the mean

velocity would not be considered.
Axial (also termed longitudinal) spreading of a constituent mass due to
non-uniform velocities is known as dispersion. It has been shown that
dispersion can also be represented by a Fickian diffusion process (Eq. 4-12) or:

∂C ∂2 C
= Ddisp (4-14)
∂t ∂ y2

where Ddisp is a dispersion coefficient that is usually in the range of 106 cm2/s.

Figure 4-7: Laminar velocity distribution showing average velocity. The

higher velocities at the center of the pipe will cause constituents in those
waters to arrive at downstream locations before constituent reaches the
locations near the pipe wall.

4.2.3.4 Impacts of Diffusion and Dispersion

To summarize the effect of the transport mechanisms introduced in this section,

diffusion affects mass transport in the radial (across pipe) and axial (along pipe)
directions. Dispersion is a laminar flow transport mechanism that only affects
axial transport. Table 4-1 lists conditions in which each transport mechanism is
applied and its associated parameter.
Molecular diffusion occurs under all flow conditions although it is
generally negligible if the fluid is moving. Turbulent diffusion only occurs in
turbulent flow but as the level of turbulence increase its impact in the
longitudinal direction diminishes since momentum and the constituent is
uniformly distributed across the pipe.
The advective transport equation (Eq. 4-11) can be extended to account for
diffusion and dispersion to the two-dimensional advection-dispersion equation
for turbulent conditions as:
4-24 CHAPTER FOUR

∂C ∂C ∂ 2C ∂ 2C
+V − ( D m + Dt ) − ( D m + D t ) = r (C ) (4-15)
∂t ∂x ∂r2 ∂ x2

where x is the distance along the pipe and r is the radial distance from the
center of the pipe. The first term on the LHS is the unsteady concentration, the
second term represents advective transport in the axial direction, the third term
is radial transport due to molecular and turbulent diffusion, and the final LHS
term is longitudinal diffusion. As noted, for laminar conditions Dt is dropped
and dispersion is added so the resulting advective–dispersion equation for
laminar flow is:

∂C ∂C ∂ 2C ∂ 2C
+V − Dm − ( Dm + Ddisp ) = r (C ) (4-16)
∂t ∂x ∂ r2 ∂ x2

Alternative formulations of Eqs. 4-15 and 4-16 are discussed below and
solution methods and results are presented in Chapter 6 for longitudinal
transport and Section 4.3.4.3.2 for radial transport.

Table 4-1: Impact of alternative transport mechanisms in radial and

longitudinal directions.
Molecular Turbulent diffusion Dispersion
diffusion
Cause Movement of Eddy transport in Variation of velocity
molecules within turbulent flow across a pipe section
fluid.
Longitudinal Little impact in No impact since Significant in laminar
transport moving fluid. turbulence causes flow ( ℜ < 2300 )*
May be important uniform velocity No impact in fully
in static water. profile ( ℜ > 10000 )* turbulent flow
Radial Little impact in Significant impact No impact
transport moving fluid. causing complete
May be important mixing across section
in static waters
Parameter Molecular Eddy diffusivity, Dt Dispersion
diffusivity, Dm coefficient, Ddisp
Coefficient
magnitude 10-4 100 – 105 106
(cm2/s)
*
The range in which turbulent diffusion and dispersion fully occur is shown in the Table. With
2300 < ℜ < 10000 mixed flow will occur that is not fully laminar or turbulent. Clear
distinctions of transport in this range are difficult to define since flow conditions vary in time and
space. Radial transport has been modeled more accurately for these conditions and discussed in
Section 4.3.2.4.2.
 WATER QUALITY FUNDAMENTALS 4-25

4.2.3.4.1 Dispersion Effect on Axial Transport

Axial transport above advection is caused by molecular diffusion and

dispersion and for laminar flow regimes can be modeled by:

∂C ∂C ∂ 2C
+V − ( Dm + Ddisp ) 2 = r (C ) (4-17)
∂t ∂x ∂x

Eq. 4-17 can be solved step-wise. First, only the first two LHS terms are
considered and advective transport is resolved. Then, the impact of diffusion
and dispersion are modeled by an equation including the first and third LHS
terms. Finally, constituent decay is represented using the concentrations
resulting after transport.
If the magnitude of the advective term is large compared to the
diffusion/dispersion term, the latter term can be dropped. The dimensionless
Peclet number can provide an indication under what conditions dispersion will
be important. Axworthy and Karney (1996) and Lee and Buchberger (2001)
developed relationships between the mean velocity and the dispersion
coefficient to identify when the dispersion effects would be negligible and
advection dominates. In most water distribution system pipes this condition
holds. Dead end or slow moving laterals pipes may be the exception (Lee and
Buchberger, 2001). Based on experimental and computational studies, Lee and
Buchberger found that dispersion can be a significant portion of the lateral
transport at low Reynolds numbers. These modeling approaches are not
available in first generation water quality models but research work is discussed
in Chapter 6.

4.2.3.4.2 Diffusion Effects on Radial Transport

Radial transport is important when examining the reaction of water-borne

constituent with material on the pipe wall. The radial advection-diffusion
equation for general flow conditions is:

∂C ∂C ∂ 2C
+V − ( Dm + Dt ) 2 = r (C ) (4-18)
∂t ∂x ∂r

One example where radial transport is important is the effect of the

interaction of chlorine with biological material (biofilm) on the pipe wall.
Biswas et al (1993) and Ozdemir and Ger (1998 and 1999) evaluated the effect
of radial diffusion on chlorine decay through two-dimensional modeling.
Biswas et al examined fully turbulent conditions while Ozdemir and Ger
focused on conditions with less turbulence. Rossman et al (1994) developed a
4-26 CHAPTER FOUR

mass transfer relationship for modeling the wall-bulk fluid interaction. For fully
turbulent flow all three methods gave similar results. These methods and results
are described in detail in Section 4.3.2.4.2.

4.3 REACTION KINETICS

As discussed in Chapter 1, constituents in the distribution system react with

materials in the water and on the pipe and tank walls. These reactions must be
represented in the conservation of constituent mass relationship (Eq. 4-1).
Substances react according to different relationships and rates. Reaction
kinetics are used to describe these relationships and include parameters that
relate the reaction rate to system conditions (Connors, 1990).
The net change of constituent in the distribution system is dependent on the
time spent in the system. Longer detention times can cause or worsen water
quality problems for a number of constituents (Table 4-2). As such, water age is
often used as a water quality surrogate indicator. Beyond water age, efforts to
date have primarily focused on modeling disinfection decay and disinfection
by-product. Microbial transport has been studied to a lesser degree. This section
provides background on reaction kinetics, their mathematical description and
determining reaction coefficients.

Table 4-2: Water quality problems associated with water age (from
EPA/AWWA white paper
(http://www.epa.gov/safewater/tcr/pdf/waterage.pdf)).
Chemical issues Biological issues Physical issues
Disinfection by-product Disinfection by-product Temperature
formation biodegration increases
Disinfectant decay Nitrification Sediment
deposition
Corrosion control Microbial Color
effectiveness regrowth/recovery/shielding
Taste and odor Taste and odor

Conservative (inert) constituents, like fluoride, are not reactive. Others, like
chlorine, react with other constituents in the water and are reduced in the
system. Most system models assume that, within the pipe network, the rate of
reaction for chlorine decreases exponentially with time and is not related to the
amount of chlorine present. This relationship is described as a first-order
reaction. Trihalomethanes (THMs) and other constituents may increase in water
during travel through the pipe network. The reactions are also usually described
 WATER QUALITY FUNDAMENTALS 4-27

by first order kinetics. In some cases, due to the availability of a co-constituent,

the amount of a constituent may be bounded. If the reaction rate is dependent
upon the amount of the constituent, the relationship is described as second
order. Finally, kinetic models representing the interactions between multiple
species have been recently developed.
Reactive constituents are affected by the other chemicals in the water in so-
called bulk flow reactions and by materials on pipe surface in wall reactions.
Bulk reaction relationships occur in pipes and tanks and their rate constants can
be estimated by laboratory jar tests. Wall reactions only occur in pipes and are
more difficult to quantify.

4.3.1 Reaction Relationships

The kinetics or rate of reactions is assumed to be a function of the time and/or

the reactants concentration. The reaction term is introduced in conservation of a
constituent mass through the term, dmc dt . In developing conservation of a
constituent mass for an unsteady system with only advective transport and
constituent reactions, dmc dt was defined as V r (C ) . With this assumption the
resulting relationship is Eq. 4-11 or:

∂C ∂C
+V = r (C ) (4-11)
∂t ∂x

A simple reaction relationship is a first order relationship in which the

reaction is linearly related to the concentration or:

r (C ) = k C (4-19)

where k is the reaction constant.

This section focuses on conditions within pipes that act as plug flow
reactors. As will be shown, the reactions are time dependent and are related to
the flow velocity and length of the pipe. Before moving to pipes for a clearer
understanding of reaction relationships, a closed tank will be studied first.
Consider chlorine in a tank that acts as a continuously stirred reactor (CSTR),
i.e., the tank is completely mixed and C is uniform through the tank. The pipe
to the tank is closed so no flow enters or leaves. In this case, the second term on
the LHS of Eq. 4-11 is zero and assuming chlorine decays following a first
order relationship the equation becomes:

∂C
= r (C ) = k C (4-20)
∂t
4-28 CHAPTER FOUR

where k will be negative since chlorine is a decaying substance. Eq. 4-20 is

solved by separating variables and integrating:

dC
∫ C ∫
= k dt ⇒ C = C 0 e kt (4-21)

where C0 is the initial concentration in the tank. Thus, the chlorine

concentration decreases exponentially from C0 at time t = 0. The rate of decay
is defined by the rate constant, k [1/T]. If the initial tank chlorine concentration
is 3 mg/l and the decay constant is -0.125/hr, the concentration after 3 hours
will be 2.06 mg/l (= Co ekt = 3 e(-0.125*3) = 3 * 0.687 = 2.06 mg/l).
An interesting interpretation of k is that if the absolute value of k is less
than 0.5, k * 100% is approximately equal to the percentage of constituent lost
in each time increment defined by the time units. For example, if k = -3 1/day
we can convert k to hr-1 to reduce k less than 0.5 or k = -3 (1/day) * 1/24
(day/hr) = -0.125 (1/hr). Since k is less than 0.5, this implies that 12.5% of the
remaining constituent is lost each hour regardless of the remaining
concentration. This interpretation for k is only valid for a first order reaction.
The general form for r (C ) for decay and growth processes are:

r (C ) = k (C − C* ) C nc −1 (4-22)

r (C ) = k (C * − C ) C nc −1 (4-23)

respectively, where C* is the limiting concentration or non-reactive portion of

the constituent, k is the reaction constant, and nc is the reaction order (e.g., nc =
1 defines a first order reaction). Common mathematical forms for alternative
reaction types are listed in Table 4-3. In the previous chlorine decay example,
the final chlorine concentration, C*, was 0 and nc equaled 1 so Eq. 4-22 became
kC.
The future direction of distribution system water quality modeling is to
account for and simultaneously represent multiple components since the growth
or decay of a substance may be related to the reactions with other constituents
in the system. For example, THM production is linked to the reaction of
chlorine with organics. A joint relationship has been proposed by Clark (1998)
and extended by others. Others have (e.g., Lu et al, 1995; Munavalli and
Kumar, 2004) developed a multi-constituent reaction/transport model for
distribution systems and linked the changes in chlorine, organic substrate and
bacterial growth. Research has progressed in this area in the past decade and it
is expected that practical models will soon introduce these higher-level
representations.
 WATER QUALITY FUNDAMENTALS 4-29

Table 4-3: Reaction types and mathematical forms.

Reaction type nc C* k Rate units r(C) Example constituent
Conservative - - 0 - 0 Fluoride
Zero order growth 0 0 1 Mc/(L3 T) k Water age
First order decay 1 0 <0 1/T kC Chlorine
First order 1 C* >0 1/T k(C* - C) Trialomethanes (THM)
saturation growth
Second order 2 0 <0 L3/(Mc T) kC 2 Initial chlorine
decay reactions
Second order 2 0 L3/(Mc T) kCACB Chlorine-THM (where
reactions for CA and CB are the
dependent concentration of the
constituents two constituents)

The focus of the remainder of this chapter will be on pipe transport and
reactions. For a pipe, Eq. 4-11 can be solved analytically for different cases of
r (C ) for steady conditions. Recall that ∂ C ∂ t in Eq. 4-11 is related to the rate
of change of constituent concentration within the differential element. Steady
hydraulic and water quality conditions imply that this term equals zero. This
assumption states that the difference of concentration over time is zero. It does
not require that the inflow and outflow concentrations are the same; only that
each value is constant over time.

4.3.1.1 Conservative Constituents

Conservative substances do not react. Salt, possibly measured as dissolved

solids, and fluoride are examples of non-reactive or conservative species.
Unless additional conservative substance is added or dilution occurs,
conservative constituent concentrations remain constant. As seen in Table 4-3,
r (C ) for conservative constituents equals zero since k = 0. So Eq. 4-11
becomes:

∂C ∂C
+V =0 (4-24)
∂t ∂x

⎛ ∂C ⎞
Under steady conditions, ⎜⎜ = 0 ⎟⎟ ,
⎝ ∂t ⎠

∂C
V =0 (4-25)
∂x
4-30 CHAPTER FOUR

Considering a pipe segment (Figure 4-8), if we separate variables and

integrate Eq. 4-25, the left hand side equals zero or:

C2 x2
∫ ∫
C2
dC = 0 dx ⇒ C1 C = 0 ⇒ C 2 − C1 = 0 ⇒ C 2 = C1 (4-26)
C1 x1

where C1 and C2 are the pipe segments’ inflow and outflow concentrations. Eq.
4-26 states that, under steady conditions, a conservative substance will not
change in the direction of flow and have the same inflow and outflow
concentrations.

Figure 4-8: Pipe section with inflow and outflow concentrations.

4.3.1.2 Zero Order Decay/Growth Kinetics

For zero-order decay, nc=0 and r (C ) is then:

r (C ) = k (C − C*) C nc −1 = k (C − 0) C ( 0−1) = k (4-27)

Note the dimensions of k for a zero order reaction are (Mc/L3)/T. Thus, the
constituent mass decreases/increases by k units per unit mass per unit time.
Under steady state conditions, Eq. 4-11 reduces to:

∂C
V =k (4-28)
∂x

Separating variable and integrating Eq. 4-28 yields:

x2 − x1
C2 − C1 = k = k τ 1− 2 (4-29)
V
 WATER QUALITY FUNDAMENTALS 4-31

The fraction on the right hand side is the travel time, τ1-2, for flow to move from
section 1 to 2. Thus, the final right hand side is the rate of addition of
constituent times the time step or the total constituent addition.
A useful special case of zero order kinetics is for a constituent representing
water age (i.e., Mc = T). Water age can act as a surrogate for first order reaction
constituents since their concentrations are directly related to the retention time
in the network.
For water age k equals 1 [T/L3/T] representing an increase of one unit of
time per unit time. With this definition in Eq. 4-29, the difference in
concentrations (water age) is the travel time. Thus, the difference in water age,
C2 – C1, in Eq. 4-29 is equal to the travel time in the pipe.
Water age can identify regions of long travel times that may indicate
potential poor disinfectant levels. An advantage of using water age as a first
level indicator of water quality over other parameters is that no water quality
calibration is necessary. Water age is only based upon the flow distribution in
the pipe network and the resulting pipe travel times. This clearly demonstrates
the relationship between the flow distribution and water quality and reinforces
the need for a well calibrated hydraulic model.

4.3.1.3 First Order Growth/Decay Kinetics

As noted earlier, decaying constituents often approximately follow first order

reactions with nc equal to 1 and C* equal to 0. Chlorine and other disinfectants
in the distribution network fall in this category. Substituting these values for
r (C ) in Eq. 4-22 gives:

r (C ) = k (C − C* ) C nc −1 = k (C − 0) C (1−1) = kC (4-30)

For steady state conditions,

∂C
V =kC (4-31)
∂x

where a k value less than zero denotes a decaying constituent. For a pipe, Eq. 4-
31 can be solved by separating variables and integrating along the pipe length
or:

dC 1 C2 dC x2 1 x
= dx ⇒ ∫ = ∫ dx ⇒ C2
C1 ln(k C ) = x2
x1 (4-32)
kC V C1 kC x1 V V

After substituting,
4-32 CHAPTER FOUR

ln (k C 2 ) − ln (k C1 ) =
(x2 − x1 ) = τ (4-33)
V

Note that the pipe segment length (x2 – x1) divided by the flow velocity is
equal to the travel time in the pipe segment, τ. The ln denotes log base e.
Rearranging and raising both sides to the power of e gives:

C 2 = C1 e k τ (4-34)

With k < 0, this relationship states that the downstream constituent

concentration decreases exponentially with the length of the pipe and the travel
time. This equation is very similar to Eq. 4-21 for the decay in concentration in
a closed system over time. Eq. 4-34 makes an important extension showing that
the change can occur in a moving fluid. In steady state, the downstream
concentration has decreased relative to the inlet concentration.
This relationship can be used to estimate the concentration at the end of the
pipe given the inlet concentration. In addition, the profile within the pipe can be
computed for steady condition by recognizing the travel time to different
locations in the pipe. Finally, the concentration in a pulse of water moving
through the network can be computed given the travel time between points
under steady or unsteady conditions.

4.3.1.4 First Order Saturation Growth Kinetics

First order saturation growth is an exponential growth model similar to first

order decay except that the sign of k is positive rather than negative and we
assume that the amount of constituent that can be produced is limited. The
concentration is bounded by a maximum of C* due to the inability of the
system to sustain a larger concentration or that the precursors that form the
constituent are limited. An example is the formation of trihalomethanes that is
constrained by the initial chlorine concentration. As demonstrated by
Elshorbagy (2000), the bounding concentrations can be estimated from
empirical equations and field data, lab studies and/or from stoichiometry for
multiple species of THM’s.
For steady conditions in a pipe segment, substituting the growth
relationship from Table 4-3 results in:

∂C
V = k (C * − C ) (4-35)
∂x

where k is a positive growth coefficient. Eq. 4-35 has the same form as Eq. 4-31
and can be solved in a similar manner. The result is:
 WATER QUALITY FUNDAMENTALS 4-33

C 2 = C * − (C * − C1 ) e − k τ (4-36)

Since k is positive, the second term on the left hand side goes to zero as t
increases and the concentration at the pipe outlet approaches the maximum
concentration. Similarly for a very short travel time (t ~ 0), the exponential term
equals one and the concentration at the downstream section is close to C1.

4.3.1.5 Second Order Reaction Kinetics

4.3.1.5.1 Special Case: Single Reactant Species

Second order reactions (nc=2) relate the reaction rate to the present level of the
constituent. Thus, at higher constituent levels reactions are more likely and the
rate of change in the constituent level will be higher. During disinfection in the
water treatment plant, a rapid initial loss occurs corresponding to high
disinfection levels. It may be more appropriate to model initial disinfection
using a second order model. After some time disinfected waters are released in
to the pipe system, the decay rates are reduced and a first order reaction rate fits
in many cases or the second order may remain appropriate.
For the special case of a single constituent with second-order kinetics, nc is
2. With C* equal to 0, Eq. 4-22 reduces to:

r (C ) = k C 2 (4-37)

For a decaying substance k will be negative. Substituting r (C ) in the steady

state form of Eq. 4-11 yields:

∂C
V = kC2 (4-38)
∂x

This equation can also be solved by separating variables and integrating

along the pipe length.

dC 1 C2 dC x2 1 1 1 x − x1
kC 2
=
V
dx ⇒ ∫ C1 kC 2
= ∫ x1 V
dx ⇒ −
C1 C 2
=k 2
V
=kτ

C 2 − C1 ⎛ 1 ⎞
⇒ = τ ⇒ C 2 = C1 ⎜⎜ ⎟⎟ (4-39)
kC1C 2 ⎝ 1 − k C1 τ ⎠
4-34 CHAPTER FOUR

For the second-order decay kinetics with C* not equal to zero, Eq. 4-22
reduces to:

r (C ) = k (C − C* ) C (4-40)

Substituting r (C ) in the steady state form of Eq. 4-11 yields:

∂C
V = k (C − C*) C (4-41)
∂x

The above equation can be solved for the general form for the downstream
constituent concentration:

(C1 − C * )
C2 = C * + (4-42)
1 + k ( C1 − C* ) τ

Note that Equation 4-39 is a special case of this equation with C* equal to 0.

4.3.1.5.2 General Case: Multiple Competing Species

A general second order model for two constituents can be developed based on
the chemical reaction:

aAr + bBr ⇒ pP (4-43)

where Ar and Br are the two reactive constituents with concentrations in mg/l of
CA and CB, respectively. Their reaction constants are kA and kB, respectively. P
is the resulting product. This model has been applied in distribution system
modeling with chlorine and natural organic matter as the reactive constituents
and trihalomethanes as the resulting product (Clark, 1998). However, most
water quality models to date have not included this level of reaction kinetics
complexity. The reaction rates of the two constituents are the same and can be
written as:

dC A
r (C A ) = - = k A C A CB
dt
dC
r (C B ) = - B = k B C A C B
dt

where kB = (b/a) kA. Following Clark and Sivaganesan (1998), the general
solution for this formulation is:
 WATER QUALITY FUNDAMENTALS 4-35

C A ,0 − (a CB ,0 / b)
C A (τ ) = − (( b C A ,0 / a C B ,0 − 1) k A C B ,0 τ )
(4-44)
1 − (a CB ,0 / b C A ,0 ) e

Defining u = N (1-KAB), KAB = a CB,0/b CA,0, and N = kA b CA,0/a this form can
be rearranged to:

C A ,0 (1 − K AB )
C A (τ ) = (4-45)
1 − K AB e −u τ

The two parameters, N and KAB provide flexibility in the shape of the resulting
relationship and result in better fits to field data. Two special cases of this
model for chlorine reactions are presented in Section 4.3.2.2.

4.3.1.6 Michaelis-Menton Reaction Kinetics

A special reaction relationship outside the forms described thus far is the
Michaelis-Menton (M-M) rate equation. The M-M kinetics equation was
derived from rates of chemical reactions of enzymes and is given by:

kC
r (C ) = M
(4-46)
(C − C)

where CM is the Michaelis constant. The denominator becomes CM + C for

growing constituents. The additional parameters and alternative mathematical
form provides flexibility in the shape of the function (Figure 4-9). As discussed
in the next section, CM and k can be determined from a Lineweaver-Burk plot.
Microbial activity and bacterial growth is often modeled by Monod
equation that has the same functional form as M-M kinetics. In biological
applications, the Monod equation is strictly empirical for microbial growth.
As shown for the previous reactions, the concentration of a constituent
following MM kinetics in the pipeline example can be determined by
integrating Eq. 4-46. The result is:

C M ln C2 − C2 − (C M ln C1 − C1 ) = k τ (4-47)

A direct solution for C at a given location/time is not available and must be

solved iteratively by successive substitution or a Newton-Raphson type scheme.
At concentration extremes, simplifying approximations result in more
easily solved conditions. Examination of Equation 4-46 shows that when C is
large (C >> CM), CM can be neglected and the reaction rate approaches a
constant value. The constant value implies that the growth/decay follows a zero
4-36 CHAPTER FOUR

order relationship. When C is small the denominator equals CM and the reaction
relationship approaches kC/CM or k’ C. This relationship has the same form as a
first order relationship.

Figure 4-9: Schematic of Michaelis-Menton rate of growth as function of

concentration.

4.3.1.7 Multi-Species Models

Multiple dependent constituent models have also been proposed (Lu et al, 1995;
Dukan et al, 1996; Bois et al, 1997; and Munavalli and Kumar, 2004). The
constituents in these models include terms representing chlorine, organic
matter, and biomass/biofilm growth. Reactions are caused by interactions
between constituents. Thus, reaction equations describing growth/decay and
constituent concentrations are functions of the concentrations of the other
constituents. As a result, a set of coupled equations must be formulated and
solved. For example, Monod kinetics are commonly assumed for biofilm
growth. This assumption is common for bacterial growth models and results in
a model the growth constant will vary with an available substrate or:

dX b
= ( µ b + k d) X b (4-48)
dt

where Xb is the bacterial concentration and µb and kd are the bacterial growth
and death rates (T-1). µb is often modeled with M-M kinetics using Eq. 4-46
with the C being the concentration of a supporting constituent (substrate). This
approach is similar to the competing model described in Section 4.3.1.5.
However, rather than relating production of one constituent to the decay in a
 WATER QUALITY FUNDAMENTALS 4-37

second through a stoichiometric relationship, here the growth and decay

constants are linked and form a set of differential equations.
The formulation presented by Zhang et al (2004) is representative of linked
multi-species models. Munavilli and Kumar (2004) developed a similar but
somewhat more complex formulation. Zhang et al defined the substrate as
biodegradable dissolved organic carbon (BDOC) and considered a balance of
the terms in the four solid boxes in Figure 4-10. The following relationships
were applied in their model:

∂ Xb
= µ b X b + k det X a V / Rh − k d X b − k dep X b (4-49)
∂t
∂ Xa
= µ a X a − k det X a V − k d X a + k dep X b Rh (4-50)
∂t

⎛ 1 ⎞
∂S
∂t
= −⎜ ⎟
⎜ Yg χ ⎟
(µ a X a / Rh + µ b X b ) (4-51)
⎝ ⎠
∂ Cl
= − k b Cl − k w / Rh (4-52)
∂t

where Xb, Xa, S, and Cl are the concentrations of free bacteria in the bulk water,
bacteria attached to the pipe wall, substrate measured as BDOC, and chlorine,
respectively. Equation 4-49 is the reaction rate of free bacteria. Its first and
third terms correspond to the growth and death in the bulk water with growth
rate and mortality constants, µb and kd, respectively. The second RHS term
represents the rate of attached bacteria that detaches and enters the bulk water
while the fourth RHS term is the rate of free water bacteria that deposits on the
wall. The rates that these physical processes occur are defined by rate constants,
kdet and kdep, respectively. V and Rh (=R/2) are the flow velocity and hydraulic
radius, respectively. The reaction terms for the attached bacteria (Eq. 4-50) are
similar as the free bacteria but growth and death coefficients and signs on the
detachment and deposition are changed.
BDOC concentration is reduced as a function of the growth of bulk and
attached bacteria (Eq. 4-51) that are scaled by the growth yield coefficient of
bacteria, Yg, and the number of cells in the cell biomass produced per milligram
of organic carbon, χ. Finally, although recognizing that the rate of chlorine
disappearance is likely related to the substrate concentration, first order decay
for bulk water and zero order for wall reactions models are applied (Eq. 4-52).
µb is represented by a Monod reaction and, most importantly, is related to
the BDOC and chlorine concentrations by:
4-38 CHAPTER FOUR

⎛ S ⎞ ⎛ Cl − Cl t ⎞ ⎛ ⎛ T −T ⎞
2
⎞
µ b = µ max,b ⎜⎜ ⎟⎟ exp ⎜⎜ − ⎟⎟ exp ⎜ − ⎜ opt ⎟ ⎟
⎜⎜ ⎜ T − T ⎟ ⎟⎟ Cl > Cl t (4-53a)
⎝ S + Ks ⎠ ⎝ Cl c ⎠ ⎝ ⎝ opt i ⎠ ⎠

⎛ S ⎞ ⎛ ⎛ T − T ⎞2 ⎞
µ b = µ max,b ⎜⎜ ⎟⎟ exp ⎜ − ⎜ opt ⎟ ⎟ Cl ≤ Cl t (4-53b)
S + K ⎜⎜ ⎜ T − T ⎟ ⎟⎟
⎝ s ⎠
⎝ ⎝ opt i ⎠
⎠

where µmax,b is the maximum bacteria growth rate in the bulk water, Ks is the
half-saturation constant for substrate uptake, Clt and Clc are the threshold and
characteristic chlorine concentrations, respectively, and Topt and Ti are the
optimal temperature for bacterial activity and a temperature parameter,
respectively.

Figure 4-10: Schematic of processes and interactions between constituents.

Research models have represented the solid lines. DBPs have not been
included in formulations to date.

Since the constitute concentrations are dependent upon each other, these
reaction relationships form a system of differential equations. Given the
 WATER QUALITY FUNDAMENTALS 4-39

complexity and dependency of these relationships, general analytical solutions

are not available. Zhang et al and Munavilli and Kumar solved for the reaction
effect on constitute concentrations using a Runge-Kutta fourth order scheme.
Most numerical analysis texts present the Runge-Kutta method (Press et al,
2002 - http://lib-www.lanl.gov/numerical/index.html).

4.3.1.8 Summary of Reaction Relationships

Analytical solutions for the reaction relationships described in the previous

section are summarized in Table 4-4. A half-life column is introduced to
provide context on the rate of change of a constituent. The number of
parameters describing the reactions increases with reaction order and provides
more variability in the shape of the function.

Table 4-4: Summary of reaction relationship solutions.

Reaction type nc r(C) Half-Life* Concentration profile
Conservative - 0 - Constant

Zero order 0 k C0/(2k) C0 – kτ

growth/decay
First order decay 1 kC 1/(1.44k) C0 e-kτ

First order saturation 1 k(C* - C) 1/(1.44k) C* - (C*-C)e-kτ

growth/decay
Second order decay 2 kC2 1/(kC0) C0 /(1+k C0τ)

Second order 2 kCACB - Eq. 4-45

competing reaction
* Half-life relates to decaying substances. It is equal the doubling time required for growth
reactions. Note C0 is the initial concentration in time or at the beginning of the pipe (i.e., C1 in
the pipe results.)

The concentration profile can be related to the profile along a pipe where
the distance is related to the travel time to that location (see Example 4.10). It
can also describe the concentration over time for a closed well-mixed system
such as a tank. In this case, rather than defining travel time, τ is the time in the
tank.
From Table 4-4, it is seen that a zero or first order reaction is only a
function of time and system characteristics. In a second order reaction, the
concentration is multiplied by a term that includes the travel time but it also
contains the initial concentration. With a positive k, for a growing constituent, a
higher initial concentration will result in a larger downstream concentration for
the same travel time. The reverse holds for a decaying constituent. Thus, the
decay/growth of a constituent following a second order reaction will be more
4-40 CHAPTER FOUR

dramatic than a first order reaction. Higher order reactions will result in more
pronounce differences. Like the first order reaction for a decaying relationship,
it asymptotically approaches zero or a defined limiting concentration. Figure 4-
11 shows the shape of the decay functions for four different single species
models.

Figure 4-11: Illustration of various reaction kinetics orders.

A second order competing reactant model was also introduced in this

section. Its application to chlorine decay and TTHM development is presented
in the next section. Complementary work in this area has followed extending
the model for both chlorine and DBP subspecies of chlorine and developing
parameter relationships. Finally, microbial growth is often defined using the
Michaelis-Menton reaction kinetics. This relationship has a steep portion
followed by a flat region approaching a maximum rate.
The following two examples demonstrate reactions in pipes. The first
example shows a steady state system and examines the variation of
concentration along the pipe. In steady state, conditions within the pipe are
constant and mixing at a node is a function of concentration at the pipe outlet.
In the next chapter, the relationship for the pipe outlet concentration is linked
with nodal mixing (Eq. 4-3) for computing steady state concentrations
throughout a network. The second example extends Example 4.4. In this
example, the variation of constituent concentration in the water is shown.
Tracking the movement of water parcels in a pipe is the basis for a class of
dynamic simulation methods (Chapter 6).
The third example returns to Example 4.9 and shows the variation of a
concentration at the junction of two pipes but in this example constituent decay
during travel in the pipe is included.
 WATER QUALITY FUNDAMENTALS 4-41

Example 4.10

Problem: An 18,000-foot long pipeline transports water with a velocity of 1

ft/s. Compute the concentration at 1,800 ft increments for a constituent in a
water that: (a) is conservative (k = 0), (b) follows a first-order decay reaction
with k = -0.5/hr, (c) follows a zero-order growth reaction, and (d) follows a
first-order saturation growth reaction with k = 0.5/hr and C* = 10. Assume that
the concentration at the source is 10 except for first order growth where C0=0.

Figure E4-10a: Pipe segment for constituent transport Example 4.10.

Solution: The concentration at 1800 ft corresponds to a travel time of 0.5 hours

(= L/V = 1800 ft/1 ft/s) and is computed for each reaction below. All results at
1800 ft (0.5 hr) intervals are listed in Table E4-10 and plotted in Figure E4-10b.

a) Conservative constituent:
Since k=0, the concentration is constant for all time, Ct = C0 by Eq. 4-26.
So Ct = 0.5 hr = C0 = 10.
b) First-order decay:
The first-order reaction results in an exponential decay relationship that is
represented by Eq. 4-34. With k = -0.5/hr, the relationship is:

C t =τ = C 0 e k τ = 10 e −0.5τ

For L = 1800 ft, τ = L/V = 0.5 hrs, the resulting concentration is 7.8.
c) Zero-order growth model:
The zero-order growth is equivalent to the time spent in the pipeline. So by
Eq. 4-29, the concentration at t = 0.5 hrs equals 0.5.

C L =1800' = C 0 + τ L =1800' = 0 + 0.5 = 0.5 hr

d) First-order saturation growth:

First-order saturation growth is described by Eq. 4-36 or:

C t =τ = C * − (C * − C 0 ) e − k τ
4-42 CHAPTER FOUR

where C0 is the initial concentration (=0).

With k = 0.5/hr and C* = 10, the concentration at a location 1800 feet from the
source or 0.5 hours travel time in the pipeline is:

Cτ = C * − (C * − 0 ) e −0.5τ = 10 − (10 − 0) e −0.5 ( 0.5) = 10 − 7.8 = 2.2

Results for all locations are shown in Table E4-10 and in Figure E4-10b.

Table E4-10: Results for concentration as a function of pipe location for

different reaction relationships for Example 4.10.
Distance Time Conservative First order Zero order First order
(feet) (hrs) constituent decay growth growth
0 0.0 10 10 0.0 0
1800 0.5 10 7.8 0.5 2.2
3600 1.0 10 6.1 1.0 3.9
5400 1.5 10 4.7 1.5 5.3
7200 2.0 10 3.7 2.0 6.3
9000 2.5 10 2.9 2.5 7.1
10800 3.0 10 2.2 3.0 7.8
12600 3.5 10 1.7 3.5 8.3
14400 4.0 10 1.4 4.0 8.6
16200 4.5 10 1.1 4.5 8.9
18000 5.0 10 0.8 5.0 9.2

12
10
Concentration

8
6
4
2
0
0 5000 10000 15000 20000
Distance along pipe (ft)

Conservative First order decay Zero order growth First order growth

Figure E4-10b: Plot of constituent concentrations versus pipe distance for

different reaction kinetics for Example 4.10.
 WATER QUALITY FUNDAMENTALS 4-43

Example 4.11

Problem: For the pipe conditions presented in Example 4.10, consider four
conditions of constituent tracking for a fluid mass that is moving through the
pipe. First, water age is to be monitored as a flow moves through the pipe.
Next, a conservative substance is to be evaluated. Finally, first and second
order decaying substances are to be modeled.
Assume that the constituent is continuously injected into the 18000 foot
long pipe for 1000 seconds. The pipe flow velocity is 1 ft/s. The initial
concentration of all substances except water age is 10 units. The decay
coefficient is -0.5 in all cases. Determine the pulse location and constituent
concentrations of the pulse at 1, 2 and 5 hrs.

Solution: Conservative constituent - A conservative substance is identical to

Example 4.4. The injected mass begins at time zero and moves into the pipe.
After one hour the material that was injected at time zero has moved 3600 ft
(=1 ft/s * 3600s). This material is at the front of the segment and is called the
front. The back end of the segment was injected at time 1000s. The segment
length is 1000 ft. Locations of the segment for all three periods are shown in
Figure E4-11. Note that the location of the segment is the same for all
constituents since it is driven by advective transport.

Figure E4-11(a-c): Time history of segment affected by constituent

injection at the pipe inlet (left side) beginning at time 0 s. Pipe is 18000 ft
long.
4-44 CHAPTER FOUR

Time 1 hour – At 3600 s, the front of the segment has traveled 3600 ft while the
back of the segment, which entered the pipe at 1000 s has traveled for 2600 s to
a location 2600 ft into the pipe. Since the constituent is conservative the
concentration for its entire length is 10 units.

Time 2 hours – The front of the segment has moved another 3600 ft from hour
1 to 2. The new location is 7200 ft into the pipe. The back of the segment is
now at location 6200 ft. (=2600 ft + 3600 ft). As before the concentration at all
locations within the segment is 10 units. The concentration at all other locations
is 0 units.

Time 5 hours – The total travel distance for a point beginning at the pipe inlet at
time zero is 18000 ft (=5 hrs * 3600 s/hr * 1 ft/s). This location is the pipe
outlet and the location of the front. The back of the segment is at location
17000 ft. Locations within the segment have a concentration of 10 units and
elsewhere the concentration is 0 units.

Water age – Time 1 hour - The water age is the time parameter necessary for
evaluating temporal variations in concentrations. After one hour the front of the
parcel has moved from the entrance to a distance 3600 feet into the pipe. This
water had a water age of zero at time 0 s. Thus, its water age at 1 hour is 3600 s
(= 0s + 3600s). The back of the segment entered the pipe at time 1000 s. At
time 1000 s, its water age was zero. Thus at time 3600 s, its age is 2600 s (=
3600 s – 1000 s).

Time 2 and 5 hrs – After the segment is fully within the pipe, it ages with the
clock time. So the water ages for the front at 2 and 5 hours are 7200 s and
18000 s, respectively. The water ages at the back of the segment are 6200 s and
17000 s for times 2 and 5 hrs., respectively, since they did not enter the pipe
until time 1000 s. Water age varies linearly in the segment with the oldest water
at the front and youngest at the back of the segment.

First order decaying constituent – Time 1 hour – First order decay is a function
of time and the decay constant. Thus, at time 1 hour, the water at the front is 1
hour old and its concentration decreased from 10 units to:

C = C 0 e − kt = 10 e −0.5(1) = 10 ( 0.61) = 6.1 units

The water at the back of the front had a concentration of 10 units when it
entered the pipe at time 1000 s. It has spent 2600 s in the pipe and its
concentration only decreased to:
 WATER QUALITY FUNDAMENTALS 4-45

C = C 0 e − kt = 10 e −0.5( 2600 / 3600) = 10 ( 0.70) = 7.0 units

Times 2 and 5 hours – At these times, the water age can again be substituted in
the first order relationship for constituent concentrations of 3.7 and 0.8 units for
hours 2 and 5, respectively, for the front and 4.2 and 0.94 units, respectively,
for the back of the segment.
The concentration varies in the segment following the shape of the
exponential decay function with higher concentrations in the back of the
segment with the lowest values at front.

Second order decaying constituent – Time 1 hour – To model second order

decay we apply Eq. 4-39 with τ equal to the water ages. For the front at time 1
hour, C1 hr (front) = C0 /(1+k C0 τ) = 10/(1+0.5*10*1) = 1.7 units. The back of the
segment is slightly younger with τ = 2600/3600 = 0.72 hrs and the
concentration is C1 hr (back) = C0 /(1+k C0 τ) = 10/(1+0.5*10*0.72) = 2.2 units.

Times 2 and 5 hours – Similar calculations as for 1 hour are made using the
water age at these times. The concentrations at times 2 and 5 hrs for the front
are 0.91 and 0.38 units, respectively. The segment back concentrations are 1.04
and 0.41 units for times 2 and 5 hours, respectively. As seen in Figure 4-11,
concentrations for constituents following this higher order relationship are
lower than those for first order decay.

Example 4.12

Problem: (a) A fast reacting constituent that follows a first order reaction is
injected in the Example 4.9 pipe system at the same times as that example.
Calculate the node 3 concentrations at time 0, 12, 30, and 45 minutes if the
decay coefficient is -0.5/hr.

(b) If the injection in pipe 1 is stopped after 45 minutes and the pipe 2 injection
is ended at time 1 hour. Determine the concentration at node 3 at 60, 75, and
120 minutes.

Solution: a) Here the mixing relationships will be the same as in the previous
examples. The node 3 inflow concentrations will be decreased by decay during
travel in the pipe. The concentrations at the pipe outlets are found by:

C pipe 1 outlet = C pipe 1 in e − k τ 1 = 2 e − ( 0.5) (15.7 / 60) = 1.75 mg / l

and
4-46 CHAPTER FOUR

C pipe 2 outlet = C pipe 2 in e − k τ 1 = 5 e − ( 0.5) (33.5 / 60) = 3.78 mg / l

As in Example 4.9, node 3’s concentrations at times 0 and 12 minutes are 0

mg/l since no constituent has reached that node. At time 30 minutes, the
concentration is altered due to the input from pipe 1. As in Example 4.9, the
outflow concentration is computed using Eq. 4-3 with the pipe 1 concentration
after decay or:

(C1 Q1 + C 2 Q2 ) ((1.75) (0.7) + (0) (0.2))

C 3 , t =30 min = = = 1.36 mg / l
Q3 0.9

The concentration at time 45 minutes the outflow concentration is again altered

with inflow from pipe 2 (Figure E4-12) or:

C3 ,t = 45 min =
(C1 Q1 + C2 Q2 ) = ((1.75) (0.7) + (3.78) (0.2)) = 2.20 mg / l
Q3 0.9

b) Since the injector is shut off, the constituents now move as pulses through
the system as in the previous example. Schematics of the pulse movement can
be drawn for each pipe as in Figure E4-11a-e.
The pulse injected into pipe 1 reaches node 3 at time 60.7 minutes (tend + τ1
= 45 + 15.7). Water without constituent in pipe 2 reaches node 3 at time 93.5
min. (tend + τ 2 = 60 + 33.5).

Time 60 min. - As shown in Figure E4-12, the concentration at time 60 minutes

is the same as at time 45 min. or 2.20 mg/l.

Time 75 min. - At this time, the concentration has dropped since constituent is
only supplied from pipe 2 until time 60.7 min. The node 3 concentration from
time 60.7 to 93.5 minutes is found by substituting a concentration of zero for
pipe 1 and 3.78 for pipe 2 in Eq. 4-3 or:

C3,t = 75 min =
(C1 Q1 + C2 Q2 ) = ((0.0) (0.7) + (3.78) (0.2) ) = 0.84 mg / l
Q3 0.9

Time 120 min. – After time 93.5 min., all constituent has passed through the
system from both pipes. Thus, the concentration at node 3 after this time is
equal to zero (Figure E4-12).
 WATER QUALITY FUNDAMENTALS 4-47

Concentration (mg/l) 3.5

3
2.5 Pipe 1

2 Pipe 2
Node 3
1.5
1
0.5
0
0 20 40 60 80 100 120
Time (minutes)
Figure E4-12: Concentration versus time at node 3 for Example 4-12.
Concentrations are shown for flows in pipes 1 and 2 as they enter node 3
(Pipes 1 and 2) and the resulting weighted concentration leaving node 3.

4.3.2 Estimating Reaction Order and Coefficients

Given an understanding of some reaction relationships, the next issues are

estimating the reaction order for a specific constituent and the coefficients in
that relationship for a specific constituent in a particular system. Reaction
coefficients and, possibly the reaction order, can be different for the same
constituent in different waters.
Reactions are impacted by the surrounding conditions due to the
availability of reacting substances. Reactants are present in the bulk water and
may also occur at high concentrations on surfaces of pipes or tank walls. For
example, chlorine reacts with organic carbon in the moving water or material
held to the pipe wall in a biofilm or as corrosion products as illustrated in
Figure 4-12. Here, free chlorine (HOCl) is shown reacting with natural organic
matter (NOM) in the bulk phase and free chlorine is also transported through a
boundary layer at the pipe wall to oxidize iron (Fe) released from pipe wall
corrosion.
In tanks, the wall mixing zone is small relative to the tank size as a whole
and this effect is not considered separately from the bulk reaction. In pipes,
however, these so-called wall reactions can be significant and theory to model
those reactions has been developed. Due to their complexity and variability
4-48 CHAPTER FOUR

between pipes, wall reactions are typically represented by first or zero-order

reaction kinetics.

Bulk Fluid
kb
HOCl NOM DBP

kw
Fe+2 Fe+3 Boundary Layer

Figure 4-12: Reaction zones within a pipe (adapted from EPANET, 2000).

In most models to account for both bulk and wall reactions, a total reaction
constant is used:

k = k b + k wall (4-54)

where kb and kwall are the bulk and wall decay coefficients, respectively.
Bulk decay coefficients can be estimated from jar tests. Procedures for
conducting and analyzing jar test results are described in the next section. To
generalize jar test results, several researchers have taken data describing water
quality from a range of locations and developed equations for estimating bulk
reaction coefficients. These equations are presented in the next section.
Wall reactions are more difficult to estimate since they can vary with flow
conditions and the availability of reacting material. Biofilm and pipe
conditions, however, are rarely, if ever available at the individual pipe level. As
a result, a single coefficient describing reaction efficiency is usually defined for
the entire distribution system. A general mixing theory based on the level of
mass transport is applied to account for waters contact with the wall in
individual pipes. This theory is also presented below.

4.3.2.1 Methods for Estimating Reaction Order and Coefficients

Reactions of the constituent of concern with other substances in the moving

water are described as bulk reactions and the corresponding reaction order and
coefficients can be estimated from laboratory jar (bottle) tests. These
coefficients vary by constituent and possibly other factors for the given
substance. For example, chlorine bulk reaction coefficients depend on the
 WATER QUALITY FUNDAMENTALS 4-49

amount and type of organic matter in the water and on the temperature. Ground
waters will typically be less reactive than surface waters (unless there are
significant amounts of inorganic reductants, such as iron). The coefficients
usually increase with increasing temperature. Running multiple jar tests at
different temperatures will provide more accurate assessment of how the rate
coefficient varies with temperature.

4.3.2.1.1 Jar Tests

Jar tests consist of taking a sample volume of water in a series of non-reacting

glass bottles and analyzing the contents of each bottle at different times. It is
best to obtain the water samples at the distribution system inlet, such as from
the treatment plant clearwell or from the pump station feeding the pressure
zone. This water should be stored at the temperature that is expected to be
experienced in the pipe network. An adequate sample volume should be taken
since analysis for some constituents may require removal of a portion of the
sample water. The sample volume should also be taken to ensure adequate
water is available for the experiment duration. The experiment should last at
least as long as the expected maximum travel time in the network or until the
initial concentration has been reduced by more than half.
Samples are periodically tested for the constituent of concern and the
measured values are recorded with their measurement time. After the
experiment duration is completed, constituent concentration, Ct, or a
permutation of it, are used to estimate the proper reaction order and coefficients
as described below. Vasconcelos et al (1997) describe this procedure in more
detail for chlorine analysis.

4.3.2.1.2 Analysis of Data

Several approaches can be applied to estimate the reaction relationship order

and determine the rate coefficients (Chapra, 1997). Through plotting, the
Integral Method graphically examines the data fit to various relationships. To
test for a reaction order, the constituent concentrations to the nc-1 power are
plotted versus time. For a first order relationship, ln Ct is plotted. If the correct
order is chosen the data will plot as a straight line. Figure 4-13 shows plots for
zero, first and second order relationships. The reaction coefficients can then be
estimated as listed in Table 4-5 and are sufficient to apply the equations
discussed in Section 4.3.1. For example, the resulting linear relationship for a
first order reaction is:

ln C = k b t + ln C 0 (4-55)
4-50 CHAPTER FOUR

Table 4-5: Parameters determined from plots of concentration data for

various reaction orders.

Order Dependent value Intercept Slope

Zero C C0 -kb
First ln C ln C0 -kb
Second 1/C 1/C0 kb
Second order ln (CA/CB) ln (CA,0/CB, 0) (CA, 0-CB, 0) kb
competitive
ncth C 1− n c
C01− nc (nc -1)kb
Note: If a portion of the constituent, C*, is non-reactive or the constituent is growth limited, the
term in dependent value is (C - C*) rather than C and the intercept term will be (C0 – C*).

As shown in Figure 4-13b, if the reaction is first-order, plotting log(Ct)

against time should result in a straight line, where Ct is concentration at time t
and C0 is concentration at time zero.
In all reactions, the linear fit can only provide three parameters for the
model, k, C0 and nc. The reaction order is determined by confirming the data
follow a line on the appropriate plot and the equation of the line gives two other
equations that are used to compute k and C0. Zero order relationships (Eq. 4-29)
and the equations for constituents that decay completely only use these three
parameters (Eq. 4-34 and 4-39).
However, when a constituent is either growth limited or has a recalcitrant
component that does not decay completely, C* is not equal to zero in Eq. 4-36
and Eq. 4-40. Therefore, a fourth unknown, C*, must be determined by plotting
concentration, C, versus time. C* is then the estimated limiting concentration
that is asymptotically approached over time. For example, assume that the data
for the first order decay and growth constituents in Example 4.10 (Table E4.10)
was measured and provided to a modeler. By plotting the C vs. t data, as shown
in Figure E4.10b, the modeler could assume that the decaying constituent
*
would decay completely ( C decay = 0) and the relationships above would be
applied directly. The growth saturated constituent, on the other hand, would be
*
limited at about 10 ( C growth = 10). Given that estimate, the dependent variable
in the plots defined in Table 4-5 would be modified to be C – C* = C - 10. With
this change, the appropriate plotting relationship would be linear and provide k
and C0.
A second approach, the Differential Method, provides the reaction order
and reaction coefficients directly but requires plotting the derivative of the
concentration with respect to time rather than the concentration directly. An
equation of the form:
 WATER QUALITY FUNDAMENTALS 4-51

⎛ dC ⎞
ln ⎜ − ⎟ = ln k b + nc ln C (4-56)
⎝ dt ⎠

The derivative terms are numerically estimated by (Ci+1-Ci-1)/(ti+1-ti-1)

where the i+1 and i-1 subscripts correspond to non-consecutive data points.
Numerical derivatives may introduce errors so an approximate dC/dt versus
time curve may be fit to the discrete points (Figure 4-14a). Data points from the
approximate curve for log (-dC/dt) and log C are then plotted (Figure 4-14b). A
best fit line of the form of Eq. 4-56 is made to the approximate points to
estimate nc and kb where nc is the slope and kb is found from the y-intercept. As
in the Integral method, the procedure is slightly modified for constituents that
are saturated growth limited or do not decay completely. C* is again estimated
by plotting C vs. t. Then to determine kb and nc, ln (C – C*) is plotted on the x-
axis in Figure 4-14b.

Figure 4-13(a-c): Plots to test if reaction follow (a) zero order, (b) first
order, or (c) second order relationships.

A differential type method can also assist in identifying reactions that

follow Michaelis-Menton kinetics. A Lineweaver-Burk plot is used to confirm
the model and determine the reaction coefficients (Figure 4-15). In this case,
1/(-dC/dt) is plotted versus 1/C. If a straight line is obtained, the slope is equal
to kb/CM and the y-intercept is equal to -1/CM.
4-52 CHAPTER FOUR

Figure 4-14(a-b): Graphical representation of differential method for

reaction order and coefficient determination. Computed numerical
derivatives are plotted versus time as a histogram (a). A curve is drawn to
the data to smooth the results while ensuring that the areas under the
drawn curve and the histogram are the same. The log transforms of the fit
gradients and the concentration are plotted in (b). A best fit line is
determined via regression.

Figure 4-15: Lineweaver-Burk plot for verifying Michaelis-Menton

reaction and determining reaction coefficients.
 WATER QUALITY FUNDAMENTALS 4-53

Numerical Curve Fitting is the third method for determining reaction order
and coefficients. In most cases, a reaction form must be selected and the
analysis scheme solved several times. Most spreadsheets can minimize the least
squares errors between data and a general function form. Full exposition of this
method is beyond the scope of this text. Several texts cover data analysis
methods and using spreadsheets for data analysis.

Example 4.13

Problem: The data below (Table E4-13) is chlorine data taken from a jar test.
Apply the Integral method to determine the reaction function and its rate
constants.

Table E4-13: Chlorine concentrations over time from a jar test.

Time (hrs) Concentration (mg/L)
0 9.79
12 8.13
24 6.53
36 4.26
48 3.34
60 2.94
72 2.14
84 1.26
96 1.04
108 1.45
120 1.28
132 0.57
144 0.99
156 0.42
168 0.17
180 0.28

Solution: To determine the reaction order, the concentration and inverse

concentrations are plotted in Figure E4-13a and b. Neither set of data can be
represented by a straight line suggesting that the reaction is neither zero nor
second order. From Figure E4-13a, it appears that the substance does decay
completely (C*=0) so no adjustment is needed in plotting concentrations.
Figure E4-13c shows a plot of the log base 10 of concentration versus time.
This data appears reasonably well fit by a straight line and the data likely
follows first order kinetics. This fit is consistent with the concentration plot
(Figure E4-13a) that appears to be an exponential decay function. The
functional equation is then:
4-54 CHAPTER FOUR

C = C 0 e kt ⇒ ln C = ln C 0 + k b t

From the semi-log plot, the y-intercept is near or slightly below 9.79 (the
value at t = 0) and the slope can be roughly estimated by the first and last data
points or:

kb = (ln 0.28 – ln 9.79)/(180-0) = (-1.28 -2.28)/180 = -0.0198

By this approximation, the resulting equation is:

C = 9.79 e-0.0198 t

The equation can also be computed using linear regression analysis that is
available in most spreadsheets. Using the Excel trendline option, the best-fit kb
is -0.020 hr-1 and the intercept (C0) is 9.63 or:

C = 9.63 e −0.020 t (r2 = 0.9376)

where t is in hours. These coefficients provide a better fit to the data and would
be used in the model. Note that this data was generated from C = 10 e −0.0208 t
with randomly introduced errors.

12
Measured concentration (mg/l)

10
-0.0202x
8 y = 9.6281e
2
R = 0.9376
6

0
0 50 100 150 200
Time (hrs)

Figure E4-13a: Plot of jar chlorine concentration versus time for Example
4.13 data.
 WATER QUALITY FUNDAMENTALS 4-55

7
6
5
1/C (1/(mg/l))

4
3
2
1
0
0 50 100 150 200
Time (hrs)

Figure E4-13b: Plot of jar inverse chlorine concentration versus time for
Example 4.13 data.

2.5
2
ln (Measured concentration)

1.5
1
0.5
0
-0.5 0 50 100 150 200
-1
-1.5
-2
Time (hrs)

Figure E4-13c: Semi-log plot of jar chlorine concentration data for

Example 4.13.

4.3.2.2 Empirical Bulk Chlorine Decay Coefficient Relationships

Chlorine modeling was the primary impetus for analyzing distribution system
water quality. As such, a large amount of work has been completed to develop
4-56 CHAPTER FOUR

reaction relationships and decay coefficients. The observed trend for chlorine
decay is that a large drop in concentration occurs just after chlorination (for
about four hours) then decay continues but at a slower rate.
Powell et al (2000) compared six kinetic models for the decay of free
chlorine in bulk waters using two in-situ pipes. They found that for network
modeling purposes a first-order decay model for bulk and overall decay was
appropriate, particularly after the initial steep post-chlorination drop.
Vasconcelos et al (1997) reached a similar conclusion with respect to bulk
decay based upon actual distribution system data. They also recommended that
reactions at the pipe wall be characterized by first or zero-order mass transfer
limited reactions. A wide range of bulk decay coefficients for first-order
reaction kinetics has been reported in the literature (Table 4-6).
Bulk chlorine decay has been shown to be related to temperature, initial
chlorine concentration, the number of times the water has been chlorinated and
the water’s total organic carbon. The relationships are usually shown as linear
equations or power functions. For example, using data from a treatment plant in
the UK, Hallam et al (2003) fit:

k b = 5.9 x 10 6 C 0−1 TOC 2.06 N Cl−1.14 e −[E A RI (Tw + 273 )]

(4-57)

where the bulk decay coefficient is in (1/hr), C0 is the initial chlorine

concentration, TOC is the total organic carbon (mg/l), NCl is the number of
times that the water has been chlorinated, EA is the activation energy (J/Mol), RI
is the ideal gas constant (8.31 J/Mol οC), and Tw is the water temperature in οC.
Hua et al (1999) varied a number of these parameters for two waters and fit
linear equations for kb as functions of TOC, 1/ C0, and T. Kiene et al (1998) also
fit a relationship for first order chlorine decay:

kb = 1.8 × 106 TOC e ( −6050 / (Tw + 273)) (4-58)

where kb is in 1/hr, TOC is in mg/l and Tw is the temperature in oC.

Chlorine decay has been modeled using Michaelis-Menton kinetics (Eq. 4-
46) and Koechling (1998) found that kb and CM could be related to the water’s
total organic content and ultraviolet absorbance for this reaction model as
follows:
(100 UVA)
kb = 0.32 UVA1.365 (4-59a)
DOC

C M = 4.98 UVA − 1.91 DOC (4-59b)

where DOC is the dissolved organic carbon concentration in mg/l.

 WATER QUALITY FUNDAMENTALS 4-57

Table 4-6: Reported bulk chlorine decay coefficients.

Reference/water source Bulk decay coefficient, kb (1/day)
Vasconcelos et al (1997)
Bellingham water treatment plant 0.833
Fairfield treatment plant 1.16
Harrisburg Oberlin pump station 0.232
North Marin Russian R. aqueduct 1.32
N. Marin Stafford L. treatment plant 17.7
N. Marin 50/50 blend of 10.8
aqueduct/treatment plant water
N. Penn Keystone tie-in 0.082
N. Penn Forest Park treatment plant 0.767
N. Penn 50/50 blend of tie-in/treatment 0.264
plant
N. Penn well W17 0.355
N. Penn well W12 0.102
Rossman et al (1994)/Cherry Hill & 0.55
Brushy Plains
Boulos et al (1996)/Azusa, CA 0.301 (full test), 0.82 (1st 4 hours after
chlorination)
Kennedy et al (1993)/Akron, OH 0.26 – 0.39
El-Shorbagy (2000)/Abu-Dhabi, UAE 1.68
Powell et al (2000)/32 locations in 0.24 – 7.7 with ~90% less than 3.6 and
Severn Trent region of the UK ~50% less than 1
Zhang et al (1992)/Macao 1.15 - 2.3
Hua et al (1999)/UK final treated and 0.48 – 5.4
tap

Using the second order competing reaction formulation (Eq. 4-45) in

Section 4.3.1.5.2, Clark (1998) proposed a joint chlorine decay-THM
production model with CA being the chlorine concentration. Later, Clark and
Sivaganesean (1998) developed the following regression relationships to
determine the equation parameters.
−0.44
K AB = e 0.32 Cl 0 TOC 0.63 pH −0.29 Tw0.14 (4-60a)

ln N = − 2.46 − 0.19 TOC − 0.14 pH − 0.07 Tw + 0.01 Tw pH (4-60b)

4-58 CHAPTER FOUR

where TOC and Tw are the total organic carbon (mg/l) and water temperature
(Co), respectively, and Cl0 is the initial chlorine concentration (mg/l).
Boccelli noted that these regression equations are inconsistent with the
parameter definitions (i.e., K should be linear with the 1/ Cl0 and M should not
be independent of Cl0). As a result, Boccelli et al (2003) considered a slightly
different form of Eq. 4-45 with parameters independent of Cl0:

Cl0 − K *AB
Cl (τ ) = * *
τ)
(4-61)
1 − ( K *AB / Cl0 ) e − (Cl 0 / K AB − 1) u

where K *AB = a CB,0/b and u* = kA CB,0 where CB,,0 is the initial reactant
concentration which, in this case, is the organic matter concentration. This
model could be evaluated over a larger range of initial chlorine concentrations
and applied to rechlorination conditions.
To better represent the observed chlorine decay, that is, initially rapid and
later gradual decay, Clark and Sivaganesan (2002) extended their second order
model for competing reacting constituents to account for the two types of
organic materials that react with chlorine. Rapidly reacting organic materials
were associated with part of the free chlorine (component 1) and the remainder
of the free chlorine (component 2) was associated with slow reacting organic
components. The resulting derived relationship for the change in overall
chlorine residual was:

Cl0 Z (1 − R1 ) Cl0 (1 − Z ) (1 − R2 )
Cl (τ ) = + (4-62)
1 − R1 e (1− R1 ) k1τ 1 − R2 e (1− R2 ) k 2τ

where the subscripts 1 and 2 refer to the chlorine component and k1, k2, R1, and
R2 are positive fit parameters. Z is the proportion of total chlorine that is
associated with component 1, i.e., Z = Cl1/Cl0 where Cl0 is the total initial
chlorine concentration. Note that if Z = 1, Eq. 4-62 reverts to a single chlorine
species second order decay model (Eq. 4-45). Regression equations based on 36
data sets were developed for the five equation parameters.

k1 = e 6.58 (TOC + 1) 2.66 (UV254 + 1) 7.63 (Cl0 + 1) −3.25 pH −1.45 ( Br + 1) 0.06

R1 = e −3.56 (TOC + 1)1.68 (UV254 + 1)3.94 (Cl0 + 1) −1.68 pH 1.05 Tw0.69
k 2 = e −4.83 (TOC + 1) (UV254 + 1)−7.71 (Cl0 + 1)3.63 pH −0.31 (Br + 1)−0.32 alk 0.14
−2.43

R2 = e 0.48 (TOC + 1)1.81 (Cl0 + 1) −1.82 e 0.03 Tw

Z / (1 − Z ) = e 4.94 (UV254 + 1) 2.89 (Cl0 + 1) −0.57 pH −1.16 Tw−0.79
(4-63a-e)
 WATER QUALITY FUNDAMENTALS 4-59

where UV254, Br and alk are the initial ultraviolet spectral absorbance (cm-1),
bromide ion concentration (mg/l) and alkalinity (mg/l), respectively.

4.3.2.3 Bulk Reaction Relationships for Disinfection By-Products

Within a pipe network, chlorine reacts with organic materials, such as humic
and fulvic acids, and forms disinfection byproducts (DBP) including
trihalomethanes (THM) and haloacetic acids (HAA). Either the amount of free
chlorine or organic precursors may limit DBP formation.
Empirical regression type models have been developed to estimate total
THM (TTHM) and its individual compound formation within a distribution
system (e.g., Amy et al, 1987). These equations tend to be site specific and
include factors such as total organic carbon, temperature, chlorine dosage,
bromide concentration, reaction time, and chlorination pH (Vasconcelos et al,
1996). Sung et al (2000) fit the following equation to data from the
Massachusetts Water Authority’s surface water systems:

[
TTHM = 2.2 ×10 6 O H − ] (C (1 − e ))
0.53
o
−k τ 0.52
(UV254 )0.47 (algae )−0.087
(4-64)

where TTHM concentrations are in µg/L, O H − is the hydroxide concentration

that incorporates temperature and pH, UV254 is the ultraviolet absorbance at a
wavelength of 254 nm (1/cm), algae is the algae concentration in ASU/mL, and
C0(1-e-k τ) is the amount of chlorine reacted from the point of chlorine addition
with concentration C0 to the point of concern during its travel time, τ. To
predict TTHM using models of this form or with a direct time in the
distribution system term, a water quality model would be run for the chlorine
concentrations or travel times and the results substituted in Eq. 4-64.
To model the spatial distribution of TTHM generation in a system, a first
order saturation growth model may be appropriate with the saturation level
being based on the limiting chlorine or precursor concentrations. Alternatively,
using the second order competing reaction formulation (Sect. 4.3.1.5.2), Clark
(1998) proposed a second order TTHM formation model that linked DBP
precursors with chlorine demand and availability. Based on a balanced reaction
(Eq. 4-43), TTHM production, P, is a linear function of the chlorine demand as
such he proposed:
⎧⎪ ⎡ Cl0 (1 − K AB ) ⎤ ⎫⎪
TTHM ( t ) = TTTHM ⎨Cl0 − ⎢ − (1 − K AB ) u t ⎥ ⎬
+ TTHM 0 (4-65)
⎪⎩ ⎣1 − K AB e ⎦ ⎪⎭

where TTTHM is a calibrated parameter and TTHM0 is the initial TTHM

concentration. Clark and Sivaganesean (1998) fit a regression equation to
identify TTTHM from water characteristics and field conditions.
4-60 CHAPTER FOUR

−0.48
TTTHM = e1.49 Cl 0 TOC 0.18 pH 0.96 Tw0.28 (4-66)

where KAB and u (= N (1-KAB)) are estimated using Eqs. 4-60a and b.
Boccelli et al (2003) computed TTHM production with a similar
relationship with their modified parameters. Both Clark’s and Boccelli’s groups
demonstrated that the second order model outperformed a first order kinetic
reaction model but at the expense of more model parameters. Boccelli’s work
further examined rechlorination conditions but did not evaluate sufficient sites
to provide guidance for the general model application. Clark et al (2001) further
extended their disinfection by-product relationship to multiple species of
chlorinated and brominated compounds. They also produced a set of regression
equations for estimating model parameters.
A difficulty in multiple source systems is that the THM formation is not a
simple additive response during mixing. El-Shorbagy (2000) developed a
general stoichiometric-based approach for modeling TTHM and the four
primary THM compounds: trichloromethane (chloroform), bromodichloro-
methane, dibromochloromethane, and tribromomethane (bromoform). The
model is based on first order kinetics for chlorine decay and DBP growth. It
requires chlorine levels, several calibrated parameters and the solution of a
small optimization problem at each modeling time step.

4.3.2.4 Pipe Wall Reactions for Chlorine Decay

To estimate constituent reactions with the pipe material or material on the pipe
wall, two issues must be addressed. First, the actual decay coefficient must be
identified. Some recent studies provide general guidance in this regard and they
are described in the next section. The second issue is radial mixing in the pipe
to determine the amount of contact that the waterborne constituent will have
with the wall material. The level of mixing depends on the flow regime. Several
models for radial mixing have been developed. The second subsection presents
those models and their parameters.

4.3.2.4.1 Reaction Coefficients

The range of impacts of wall reactions is quite large for chlorine decay. Hua et
al (1999) examined three test pipes and found the kwall was only 10% of kb
resulting in a minor change in chlorine demand. Clark et al (1993), however,
found that kwall could exceed kb. Clearly, conditions vary between networks and
field calibration is necessary.
Based on several published studies, Rossman et al (2001) reported that a
kwall value on the order of 3 day-1 (0.125 hr-1) was reasonable for cast and
ductile iron pipes. Hallam et al (2002) completed field and laboratory studies
and determined wall decay constants for a range of pipe materials. From tracer
 WATER QUALITY FUNDAMENTALS 4-61

tests, wall decay constants ranged from 0 to 1.64 hr-1 with 70% of the values
being less than 0.4 hr-1. Cast iron mains had the highest values and the most
variability. Cement lined iron (CICL), polyvinyl chloride (PVC) and medium
density polyethylene (MDPE) pipes were examined in the laboratory and found
to have decay constants of 0.01 to 0.78 hr-1. Based on these results they
classified, cast and iron (CI – k wall = 0.67 hr-1) and spun iron (SI – 0.33) pipes
as reactive and CICL (0.13), PVC (0.09) and MDPE (0.05) as non-reactive. The
value in parentheses for each type is the average in-situ wall coefficient. From
laboratory data, the coefficients were the same except the CICL was 0.12 hr-1.
Studies also indicated that kwall increased linearly with velocity in iron pipes but
a clear relationship was not apparent for the non-reactive pipes. Finally, kwall
was inversely related to the initial chlorine level. No other definitive
relationships could be discerned.

4.3.2.4.2 Radial Flow Transport

Pipe wall reaction coefficients are affected by three factors; (1) the reactive
ability of the bioflim layer, (2) the wall area available for reactions, and (3) the
movement of water to the wall. Rossman et al (1994) developed a theoretical
mass transfer approach for estimating kwall that accounted for these factors. The
reactive nature of the wall material is measured by a wall reaction rate constant,
kw [L/T]. The surface area per unit volume of pipe section accounts for the wall
area available to interact with water. For a circular pipe, this term equals 2/R
( )
= 2 π R L π R 2 L where R is the pipe radius and L is the pipe length.
Water mixing is more complex. Mass transfer between the bulk water and
the pipe wall is represented by the Sherwood number (Sh) in a mass transfer
coefficient, kf, as:

⎛D ⎞
k f = Sh ⎜ m ⎟ (4-67)
⎝ D ⎠

where Dm is the molecular diffusivity of the transported constituent and D is the

pipe diameter. The dimensionless Sherwood number differs with the flow
regime. In laminar flow ( ℜ <2300), molecular (conductive) scale mixing
dominates:
0.0668 (D L ) ℜ Sc
Sh = 3.65 + (4-68)
1 + 0.04 [(D / L )ℜ Sc ]
2
3

where Sc is the dimensionless Schmidt number (ν D m ) (Edwards et al 1976).

4-62 CHAPTER FOUR

More mixing is expected in turbulent flow compared to laminar flow as

turbulent diffusion causes significant movement of water masses through the
fluid. For this condition, Notter and Sleicher (1971) proposed the following
empirical relationship for the Sherwood number:

Sh = 0.0149 ℜ 0.88 Sc1 3 (4-69)

For a first-order reaction, the terms that describe the three factors are
combined to form:

2 kw k f
k wall = (4-70)
(
R abs (k w ) + k f )
where abs is the absolute value operation. kwall is then substituted in Eq. 4-54 to
compute the overall decay coefficient for the reaction relationship r(C) = k C.
Note that the Sherwood number and the resulting kf and kwall can be different for
each network pipe accounting for variable flow conditions.
If the wall reaction is modeled as a zero-order reaction, nc equals 0 and r(C)
is a constant. The reaction rate cannot be higher than the rate of mass transfer
so r(C) equals the minimum of kw (2/R) or an apparent first-order reaction
coefficient kf C (2/R).
All terms in Eq. 4-70 are available from the physical data or hydraulic
analysis except the wall reaction rate coefficient (kw) and the constituent’s
molecular diffusivity (Dm). The only means to determine the reaction rate
constant is to calibrate the water quality model to measured field data. The
molecular diffusivity is a physical property of the constituent. For example, Dm
for hypochlorous acid (HOCl-), the dominant species of free chlorine, is 1.44 x
10-5 cm2/s (0.00112 ft2/day) while Dm for methyl ethyl ketone (a representative
trihalomethane precursor) is 9.8 x 10-6 cm2/s.
The wall reaction coefficient can depend on temperature and can also be
correlated to pipe age and material. As metal pipes age their roughness tends to
increase due to encrustation and tuberculation of corrosion products on the pipe
walls. This increase in roughness produces a lower Hazen-Williams C-factor or
a higher equivalent sand roughness coefficient (e), resulting in greater frictional
head loss in flow through the pipe.
Some evidence suggests that the same processes that increase a pipe's
roughness with age also tend to increase the reactivity of its wall with some
chemical species, particularly chlorine and other disinfectants (Vasconcelos et
al 1996, 1997). Based on their work, a pipe's kw can be expressed as a function
of the coefficient used to describe its roughness and a wall reaction correlation
coefficient F as listed in Table 4-7.
 WATER QUALITY FUNDAMENTALS 4-63

Table 4-7: Wall reaction coefficient relationships for different headloss

equations.
Headloss Equation Wall Reaction, kw
Hazen-Williams F / CHW
Darcy-Weisbach -F / log(e / D)
Chezy-Manning F nm

F has a different meaning depending on the head loss equation. The

advantage of using this approach is that it requires only a single parameter, F,
to allow the wall reaction coefficient to vary throughout the network. Both kw
and F are system specific. Vasconcelos et al (1996, 1997) reported values for kw
ranging from 0.1 to 5.0 ft/day and values for F ranging from 10 to 650 for the
four distribution systems that they studied.
Ozdemir and Ucak (1998) solved the radial flow relationship with an
effective diffusion coefficient that varied with the Reynolds’ number and was
available from the literature. For Reynolds numbers greater than 10000
(nominally fully turbulent) the results matched the Rossman and Biswas’
models. For lower ℜ ’s, a variable bulk decay coefficient and the modeled kw
improved the match between experimental and modeled results compared with
the other two models. For first order reactions a correction factor, FC, was then
developed based on two-dimensional flow modeling as:

⎛ 100 FC ν R ⎞ ℜ ⎞
log ⎜⎜ ⎟⎟ = − 0.9538 log ⎛⎜ ⎟ −1 (4-71)
⎝ kw L ⎠ ⎝ 1000 ⎠

FC is inversely related to ℜ and its effect is negligible with ℜ greater than

30000. FC can be used to adjust the total decay constant by:

⎛ Ct ⎞
Ctdiff = ⎜⎜ ⎟⎟ (4-72)
⎝ 1 + FC ⎠

where Ct is the chlorine concentration at time t using a first order decay

relationship and decay constant computed using the estimated bulk and wall
decay coefficients and Ctdiff is the chlorine concentration after correction for
diffusion.

Example 4.14

Problem: Determine the total reaction coefficient for water at 50o F with a bulk
decay coefficient of -0.15/day in a 10-inch diameter, 1000-ft long pipe that is
4-64 CHAPTER FOUR

carrying 0.5 cfs. The wall coefficient, kw, is -0.5 ft/day and the molecular
diffusivity of the chlorine species of concern is 0.00112 ft2/day. Assume that a
first-order decay model holds.

Solution: The total k value equals:

k = k b + k wall

where kb is given at -0.15/day. kwall must be computed for the pipe’s flow
condition using Eq. 4-70. R and kw are given as 5 inches (0.42 ft) and -0.5
ft/day, respectively. The mass transfer coefficient, kf, is based upon the
Sherwood number that varies with flow regime. The Reynolds’ number for this
pipe and velocity (V = Q/A = (0.5 cfs)/((π(10/12)2/4) ft2) = 0.92 ft/s) is:

VD (0.92) (10 / 12)

ℜ= = = 7.02 ×10 4 ⇒ flow is turbulent
ν 1.09 × 10 −5

The Sherwood number for turbulent conditions is estimated by Eq. 4-69

with the Schmidt number equals to 839 (Sc = ν/Dm = (0.94 ft2/d)/(0.00112
ft2/d)). Note that the kinematic viscosity is converted to ft2/d to be consistent
with the diffusivity so that Sc is dimensionless. The dimensionless Sherwood
number is then:

Sh = 0.0149 ℜ 0.88 Sc 1 3 = 0.0149 (7.02 × 10 4 ) 0.88 (839)1 / 3 = 2581

and the mass transfer coefficient is computed by:

⎛D ⎞ ⎛ 0.00112 ⎞
k f = Sh ⎜ m ⎟ = 2581 ⎜⎜ ⎟⎟ = 3.47 [1 / day ]
⎝ D ⎠ ⎝ (10 / 12) ⎠

Finally, kwall is:

2 kw k f 2 (−0.5) (3.47)
k wall = = = − 2.1 / day
(
R kw + k f ) (5 / 12) (abs (−0.5) + 3.47 )

Interestingly, the wall reaction constant is quite large compared to the bulk
reaction term of –0.15 due to the high level of turbulence. Finally, the overall
decay constant is:

k = kb + k wall = (−0.15) + (−2.10) = − 2.25 / day

 WATER QUALITY FUNDAMENTALS 4-65

The sign on the term is negative since it is a decay reaction. If the chlorine
concentration entering the pipe is 10 mg/l, the outlet concentration under steady
conditions is:
Coutlet = Cin e k τ = 10 e −2.25 ( 0.30 / 24) ⇒ Coutlet = 9.72mg / l

where τ is the travel time in the pipe (τ = L/V = 1000 ft/(0.92 ft/s * 3600 s/hr *
24 hr/day) = 0.0126 day = 0.3 hr).
Table E4-14 lists k, the travel time and steady state outlet concentration for
different flow rates for an inlet concentration of 10 mg/L for the 1000 ft long
pipe. In this example, the outlet concentration decreases with decreasing flow
rate. Although the level of turbulence decreases causing less reaction at the
wall, the travel time in the pipe increases faster than the reaction coefficient
reduction.

Table E4-14: Decay coefficients, travel times and outlet concentrations for
various flow rates in the 1000 ft long pipe described in Example 4.10.
Travel time
Q (cfs) k (1/T) Coutlet (mg/L)
(days)
3 -2.48 0.0021 9.948
2 -2.45 0.0032 9.923
1 -2.38 0.0063 9.851
0.5 -2.25 0.0126 9.720
0.25 -2.05 0.025 9.496
0.125 -1.76 0.051 9.148
0.05 -1.30 0.126 8.490
0.025 -0.95 0.253 7.874
0.02 -0.85 0.316 7.657
0.015 -0.27 0.420 8.926
0.010 -0.25 0.631 8.517

Flow rates less than 0.016 cfs result in laminar flow. In these instances, the
Sherwood number was computed using Eq. 4-68 while Eq. 4-69 was used in
flows greater than 0.016 cfs. The transition between laminar and turbulent
regimes is not smooth. Although the travel time increases, Coutlet actually
increases because k drops dramatically when switching equations from Eq. 4-69
to Eq. 4-68. The magnitude of the jump to laminar flow conditions is related to
the flow conditions and the pipe length. Note that the turbulent flow equation
does not consider pipe length. So as L decreases, the time and the contact area
both decrease.

4.3.3 Water Age and Source Tracing

The initial driving concern that led to water quality modeling was chlorine
residuals. If decay coefficients are not known, a surrogate measure for chlorine
4-66 CHAPTER FOUR

decay is water age. As noted earlier, a zero-order growth model can be used to
represent water age. A water age analysis may suggest useful more detailed
studies.
Water age is a function of the pipes’ volumes and flow rates. Pipes are plug
flow reactors and, in effect, act as tanks in transmitting flow from one node to
the next. The pipe flow rate and velocity is directly related to its travel time and
water age. A pipe that was designed with a large diameter to reduce energy
losses or was oversized in expectation of future growth can adversely affect
quality as water may remain in the pipe for long periods of time. A tank can
have a similar effect. Since it is purely hydraulically dependent, a hydraulic
analysis provides all of the information necessary to compute the average age
of water withdrawn at all nodes.
A second useful analysis can identify the source of water for a particular
withdrawal point. If multiple supplies of varying quality provide water to a
network, the final mixed water may be of concern with respect to taste, odor
and, possibly, water quality. The utility of source tracking is also helpful in
identifying vulnerabilities and contamination sources. For example, if a field
meter detected a change in water quality, one could identify possible
contributing locations and other nodes that those locations are impacting.
To identify the contributions of the Ns sources under dynamic conditions,
(Ns – 1) water quality forward simulations must be run. The individual runs are
made with a fictitious conservative substance supplied from one source node
(ns) with concentration of 100. This water is distributed through the network
and a node’s withdrawal concentration is its percentage contribution from
source node ns or p(ns). Under unsteady demands, this percentage will change
over time. The conservative tracer analysis is completed for all but one of the
other source nodes. The percentage contribution for the last source node (source
node Ns) is the unaccounted withdrawn water and computed by:

N s −1
p ( N s ) = 100 - ∑ p(n )
ns = 1
s (4-73)

Backtracking algorithms can be more efficient in determining source

locations, particularly for individual nodes, under dynamic conditions. These
approaches (Chapter 6) begin their analysis at the withdrawal points and work
back through the system using the hydraulic conditions to identify sources and
when water was supplied to contribute to the withdrawn flows.

Problems

Problem 1. Determine the concentration in pipe 1 in Figure P4-1 if the outflow

concentration in pipe 3 is 3.5 mg/l.
 WATER QUALITY FUNDAMENTALS 4-67

Figure P4-1: Junction node with two inputs and three withdrawals.

Problem 2. A 1.4 kg tablet that is 17% Cl2 dissolves in 1.5 hours in a tablet
feeder chlorinator. Four percent of the 62 lps supply pipe flow is passed
through the unit. Determine the increase in concentration in the water being
returned to the pipe and in the water in the pipe downstream of the chlorinator
return.

Problem 3. A mass loading rate of 50,000 g/hr of a constituent is added to the

node shown in Figure P4-3. Determine the effective injection concentration and
the resulting concentration in flow leaving the node.

Figure P4-3: Junction node with two inputs and three withdrawals.

Problem 4. Determine the constituent concentration for the node in Figure P4-3
if a flow paced booster injects 0.25 g/m3 to all flow leaving the node. Also
compute the mass injection rate.
4-68 CHAPTER FOUR

Problem 5. A set point booster is used to increase the constituent concentration

of the flow leaving the node in Figure P4-3 to 1.94 g/m3 (= 1.94 mg/l). What is
the mass injection rate?

Problem 6. A 300 m long, 150 mm diameter pipe carries 0.05 m3/s of water.
Determine the pipe’s velocity and the travel time.

Problem 7. Determine the velocity and travel time for a pipe flowing with 0.07
m3/s of water. The pipe has a diameter of 250 mm and is 250 m long.

Problem 8. A mass of 0.015 lbs of fluoride is injected at a rate of 3.0 lb/day

into an 8 inch diameter, 2500 ft long pipe. The pipe’s flow rate is 1.5 ft3/s.
Determine the concentration, the pulse length, and the time that the pulse
reaches and leaves the pipe outlet (starting at an arbitrary time zero).

Problem 9. For the pipe and injection defined in problem 8, track a segment of
a conservative constituent through the pipe. Specifically, show the location of
the segment at 0, 7.2, 8, 9.69, 12, and 16.89 minutes.

Problem 10. Water flows through a 6,000-meter long pipeline with a velocity
of 0.45 m/s (Figure P4-10a). Under steady state conditions, compute the
concentration at 600 m increments along the length of the pipe for the
following conditions. (A) A conservative constituent (k = 0), (B) Water age
(zero-order growth reaction), (C, D and E) A constituent following first-order
decay reaction, a first-order saturation growth reaction and a second-order
saturation growth reaction. Each has a reaction coefficient of 0.5/hr with
appropriate sign, (F) A constituent that follows a Michaelis-Menton reaction
(CM=15). The limiting concentration, C* , when applicable is 12 mg/l. Assume
that the concentration at the source is C0 = 12 for the decay reactions and 0 for
the growth reactions.

Figure P4-10a: Pipe segment for constituent transport Problem 4-10.

Problem 11. For the pipe in Problem 10, track a constituent pulse through the
pipe for the four reaction conditions listed below. Assume that constituents are
injected at the upstream end of the pipe for 1000 seconds. Determine the pulse
 WATER QUALITY FUNDAMENTALS 4-69

location and constituent concentrations at the front and back of the segment at
1, 2 and 3.7 hrs. Compute the water age and the concentrations for conservative
and first and second order decaying constituents. Use the same parameters as in
Problem 10.

Problem 12. Assume that a conservative constituent is injected into two pipes
beginning at time 0 sec. as shown in Figure P4-12.
a) Calculate the outflow q3
b) Calculate the outgoing fluoride concentration at t = 0 minutes.
c) Calculate the outgoing fluoride concentration at t = 15 minutes.
d) Calculate the outgoing fluoride concentration at t = 20 minutes.
e) Calculate the outgoing fluoride concentration at t = 30 minutes.

Repeat the analysis with a constituent that decays following a first order
relationship with decay constant of k = -3.0 /day.

Figure P4-12: Two pipe, three node configuration. Flow enters through
nodes 1 and 2 toward node 3.

Problem 13. The data in Table P4-13 is chlorine data taken from a jar test.
Determine the reaction function and its rate constants using the integral method.

Problem 14. Using the differential method determine the reaction order and its
decay constant for the constituent for the data in Table P4-14a.
4-70 CHAPTER FOUR

Table P4-13: Chlorine concentrations over time from jar test.

Time (hrs) Concentration (mg/l)
0 11.50
12 10.37
24 7.27
36 6.39
48 6.18
60 4.23
72 4.20
84 2.95
96 3.22
108 2.25
120 2.73
132 1.45
144 0.80
156 0.66
168 0.78
180 0.81

Table P4-14a: Measured concentration over time from jar test.

Time (days) Concentration (mg/l)
0.00 6.01
0.25 4.89
0.50 4.14
0.75 3.60
1.00 3.15
1.25 2.82
1.50 2.58
1.75 2.35
2.00 2.16
2.25 1.97
2.50 1.87
2.75 1.72
3.00 1.60
3.25 1.55
3.50 1.47
3.75 1.38
4.00 1.30
4.25 1.24
4.50 1.17
4.75 1.16
5.00 1.07
5.25 1.04
5.50 1.02
 WATER QUALITY FUNDAMENTALS 4-71

Problem 15. A 14-inch diameter, 2000-ft long pipe has a 0.1 cfs flow rate.
Determine the pipe’s total reaction coefficient for water if kb = -0.30/day. The
wall coefficient, kw, is -0.25/day and the molecular diffusivity of the chlorine
species of concern is 0.00112 ft2/day. Assume that a first-order decay model
holds. Use ν = 1.09 x 10-5 ft2/s.

Solutions

1. All outflows have the same concentration as pipe 3 so the constituent mass
balance for the node is:

C1 Q1 + C2 Q2 – Cout(Q3 + Q4 + qout) = 0

Substituting the known values gives:

C1 (4) + (1.5) (3 ) – 3.5(3 + 2.5 + 1.5) = 0 ⇒ C1 = 5 mg/l

2. The 1.4 kg tablet provides 0.238 kg of Cl2 (17%*1.4 kg) to the flow. In the
main pipeline, the mass rate of 0.159 kg/hr (=0.238 kg / 1.5 hr) is dissolved in
the flow of 62 lps. Thus,

m& c = Q ∆C = 0.238 (kg / hr ) / 1.5 hr / 3600 ( s / hr ) = 62 (l / s ) * ∆C pipe

⇒ ∆C pipe = 0.71 mg / l

The concentration in the feeder unit has the same mass added but the flow is
only 4% of the 62 l/s or 2.48 l/s. Thus the concentration in flow leaving the
feeder is:

m& c = Q ∆C = 0.238 (kg / hr ) / 1.5 hr / 3600 ( s / hr ) = 2.48 (l / s ) * ∆C feeder

⇒ ∆C feeder = 17.8 mg / l

3. Without the additional loading the outflow concentration is computed

assuming complete and instantaneous mixing occurs at the node. Thus, the
concentrations in pipes 3 and 4 and the nodal withdrawal are the same and Cout
can be computed from Eq. 4-3:

C1 Q1 + C 2 Q2 4 (2.0) + 3 (1.5)
C out = = ⇒ C out = 1.79 g/ m 3 = 1.79 mg/l
Q3 + Q4 + q out
3 + 2.5 + 1.5
4-72 CHAPTER FOUR

Based on the rate of mass injected (50 kg/hr), the effective injection
concentration, Cininj , is the incremental concentration increase or from Eq. 4-4:

m& in = C ininj ∑Q
l ∈ J in
l = 50000 g / hr / 3600 ( s / hr ) = C ininj (Q1 + Q2 )

= C ininj g / m 3 (4.0 + 3.0) m 3 / s ⇒ C ininj = 1.98 g / m 3 or mg / l

Thus the outflow concentrations will be increased by 1.98 mg/l. The

concentration of flow leaving the node can be confirmed by Eq. 4-5:

∑C l Ql + C in q in + m& in (4 ⋅ 2.0 + 3 ⋅ 1.5 ) + 0 +

50000
C out =
l ∈ J in
= 3600
q out + ∑Q
l ∈ J in
l
1.5 + (3.0 + 2.5)

12.5 + 13.9
= = 3.77 g / m 3 = 3.77 mg / l
7

Thus, the injected mass increased the outflow concentration by 1.98 mg/l from
1.79 to 3.77 g/m3(=mg/l).

4. A flow paced booster increases the concentration by a defined increment,

inj
C out (0.25 mg/l in this example). In the previous problem the concentration
without any constituent injection at the node was determined to be 1.79 g/m3.
The outlet concentration, Cout, is then (Eq. 4-7):

∑C
l ∈ J in
l Ql + C in q in
inj
C out = + C out = 1.79 + 0.25 = 2.04 g / m 3 = 2.04 mg / l
q out + ∑
l ∈ J in
Ql

The mass injection rate is:

⎛ ⎞
inj ⎜ out
m& in = C out
⎜
q + ∑ Q ⎟⎟ = 0.25 g / m (1.5 + 3 + 2.5) m
l
3 3
/s
⎝ ⎠
l ∈ J in

= 1.75 g / s = 6.3 kg / hr

Recall that a flow paced booster injects a constant injection rate and mass. So if
the inflow concentrations at this node were changed, the outflow concentration
would be changed but the injection increment would remain constant.
 WATER QUALITY FUNDAMENTALS 4-73

5. The setpoint booster sets the concentration for all flow leaving the node to
1.94 mg/l. The concentration without the addition of injected constituent is 1.79
g/m3 (1.79 mg/l) so the additional constituent is added at a rate of 0.15 mg/l or
by Eq. 4-7:

∑C
l ∈ J in
l Ql + C in q in
inj inj
C out = 1.94 = + C out = 1.79 + C out
q out + ∑ Ql
l ∈ J in
inj
⇒ C out = 0.15 g / m 3 = 0.15 mg / l

The mass loading rate is then:

⎛ ⎞
inj ⎜ out
m& c = C out
⎜
q + ∑ [ ] [ ]
Ql ⎟ = 0.15 g / m 3 (1.5 + (3 + 2.5)) m 3 / s = 1.05 g / s
⎟
⎝ l ∈ J in ⎠

With a setpoint booster if the flow rate or the inflow concentrations change the
injected concentration and mass rate would change to maintain the desired
outflow concentration.

6. By continuity, the flow velocity is:

Q 0.05 0.05
V= = = = 2.83 m/s
A π D 4 π 0.15 2 4
2
(( ) )
which results in a travel time of:

L 300
τ= = = 106 s = 1.77 minutes
V 2.83

7. The flow velocity and travel time are:

Q 0.07 0.07
V= = = = 1.43 m/s
A π D 4 π 0.25 2 4
2
(( ) )
and
L 250
τ= = = 175 s = 2.91 minutes
V 1.43

8. At an injection rate of 3 lbs/day, the 0.015 lb is supplied to the pipe over an

injection period of:
4-74 CHAPTER FOUR

tinj = 0.015 lb / 3.0 lb/day = 0.005 day = 7.2 min = 432 sec

The fluoride concentration in the water is:

Cinj = m& c / Q = 3.0 lb / day / (1.5 ft 3 / s * 86400 s / day )

= 2.31×10 − 5 lb / ft 3 = 3.7 ×10 − 7 lb Fluoride / lb water = 0.37 ppm

The flow velocity is:

Q 1.5 1.5
V= = = = 4.30 ft / s
A π D 4 ⎛ ⎛ 8 ⎞2
2
⎞
⎜π ⎜ ⎟ 4⎟
⎜ ⎝ 12 ⎠ ⎟
⎝ ⎠

The travel time through the reach then is:

L 2500
τ= = = 581 s = 9.69 minutes
V 4.30

where L is the length of the pipe. Since the fluoride is injected over a 432 s.
period the length of the pulse is:

Lseg = t inj V = 432 s ⋅ 4.3 ft / s = 1858 ft

The front edge of the segment will reach the end of the pipe 9.69 minutes after
the injection begins. The 1858 ft segment takes 432 s (7.2 min) to fully develop
and the back edge of the segment leaves the outlet at time 7.2 minutes. Since
the pipe travel time is 9.69 minutes, the back end of the segment will reach the
outlet at time 9.69 minutes + 7.2 minutes = 16.89 minutes.

9. The solution is presented for each time step below and on Figure P4-9.

a) Time 0 s. – The fluoride has just begun to be injected so the water has a
zero concentration for the entire length of the pipe (Not shown).

b) Time 7.2 min. – After injecting fluoride for 7.2 minutes, the complete
segment has developed in the pipe. As computed in the previous
problem, the segment front has traveled 1858 ft (Figure P4-9a).

c) Time 8 min. – In the next 0.8 minutes, the segment has traveled an
additional 206.4 ft. = 4.30 ft/s * 0.8 min. * 60 s/min. Since the segment
 WATER QUALITY FUNDAMENTALS 4-75

does not distort, the front of the segment has traveled to location 1858
+ 206.4 = 2064.4 ft from the injector. The back of the segment moved a
distance 206.4 ft from the injector. The water in the pipe from 0 to
206.4 ft does not contain any fluoride since the injector was turned off
(Figure P4-9b).

d) Time 9.69 min. – The travel time for the pipe is 9.69 minutes so the
water passing the injector at time 0 has just reached the pipe outlet.
This water contains fluoride and is at the front of the segment. The
back of the segment remains 1858 ft to the left of the front. The back of
the segment is now 642 ft (=2500 ft – 1858 ft) from the injector.
(Figure P4-9c).

e) Time 12 min. – A portion of the segment has now left the pipe. The
length of segment that has passed the outlet is 596 ft (= (12-9.69) min *
60 s/min * 4.3 ft/s). The length of the segment with fluoride is now
1269 ft (=1858 ft – 596 ft). The back of the segment is now 1231 ft
from the injector (= 2500 ft – 1269 ft) (Figure P4-9d).

Figure P4-9 (a-d): Time history of segment affected by fluoride injection at

the left pipe inlet beginning at time 0 s.
4-76 CHAPTER FOUR

At time 16.89 minutes the back of the segment has just passed the pipe outlet.
Thus, the pipe contains no fluoride (not shown).

10. Under steady state conditions, the concentrations are time invariant for any
given location but vary along the pipe. The time needed for water to move 600
m is 0.37 hours (= L/V = 600 m/(0.45 m/s * 3600 s/hr)). The concentration for
location 600 m is computed for each reaction relationship and results for the
entire pipe are summarized in Table P4-10 and plotted in Figure P4-10b.

a) Conservative constituent: Since k=0, the concentration does not change as it

moves through the pipe or Ct = C0 by Eq. 4-26 for all times. Thus, Ct = 0.37 hr =
C0 = 12.

b) Zero-order growth model: Water age is the time spent in the pipe after
entering at the left inlet and is computed using Eq. 4-29 with k = 1 and
assuming that the age of water entering the pipe is zero. At 600 meters from the
pipe entrance, τ = L/V = 0.37 hrs so:

C L =600 m = C 0 + τ L = 600 m = 0 + 0.37 = 0.37 hr

c) First-order decay: The first-order decay follows the exponential relationship

(Eq. 4-34). With k = -0.5/hr, the general relationship is:

Ct =τ = C 0 e k τ = 12 e −0.5τ

At 600 feet with τ = L/V = 0.37 hrs, the concentration is 9.97.

Table P4-10: Results for Problem 4-10 for various decay/growth

relationships.
Distance Time Conservative Zero First First Second Michaelis-
(m) (hrs) constituent order order order order Menton
growth decay growth decay decay
0 0 12 0.00 12 0.00 12.00 12
600 0.37 12 0.37 9.97 2.03 3.73 11.35
1200 0.74 12 0.74 8.29 3.71 2.21 10.83
1800 1.11 12 1.11 6.89 5.11 1.57 10.38
2400 1.48 12 1.48 5.73 6.27 1.21 9.99
3000 1.85 12 1.85 4.76 7.24 0.99 9.64
3600 2.22 12 2.22 3.95 8.05 0.84 9.31
4200 2.59 12 2.59 3.29 8.71 0.73 9.02
4800 2.96 12 2.96 2.73 9.27 0.64 8.75
5400 3.33 12 3.33 2.27 9.73 0.57 8.5
6000 3.70 12 3.70 1.89 10.11 0.52 8.27
 WATER QUALITY FUNDAMENTALS 4-77

14

12
Concentration (mg/l or time)
10

0
0 1000 2000 3000 4000 5000 6000
Distance along pipe (m)

Conservative Water age First order decay

First order growth limited Second order decay M ichaelis-M enton

Figure P4-10b: Plot of constituent concentrations versus pipe distance for

different reaction kinetics for Problem 4-10.

d) First-order saturation growth: First-order saturation growth is described by

Eq. 4-36. The initial concentration, C0 , is 0. With k = 0.5/hr and C* = 12, the
concentration at a location 600 meter from the source or 0.37 hours travel time
in the pipeline is:

Cτ = C * − (C * − 0) e −0.5τ = 12 − (12 − 0) e −0.5 ( 0.37 ) = 12 − 9.97 = 2.03 mg / l

e) Second-order decay: Applying Eq. 4-42 with τ = 0.37 hr, k = -0.5/hr, C* = 0

and C0 = 12 , second-order reaction relationship is:
(C 0 − C *) (12 − 0)
C L =600 = C * + =0+ = 3.73 mg / l
1 + k (C 0 − C*) τ 1 + 0.5 (12 − 0) (0.37)

f) Michaelis-Menton decay: The Michaelis-Menton reaction is described by

Eq. 4-47. Substituting known values (CM =15, C0=12, k=-0.5) at τ = L/V = 0.37
hrs gives:
C M ln Cτ = 0.37 hr − Cτ = 0.37 hr − (C M ln C0 − C0 ) = k τ
⇒ 15 ln Cτ = 0.37 hr − Cτ = 0.37 hr = (15 ln 12 − 12) + − 0.5 (0.37) = 25.09
4-78 CHAPTER FOUR

Solving by trial and error or using a solver routine in a spreadsheet or calculator

gives Cτ=0.37 hrs = 11.35. Results for all locations are listed in Table P4-10 and
plotted in Figure P4-10b.

11. The injected mass begins entering the pipe at time zero. After one hour the
material that was injected at time zero has moved 1620 m (= 0.45 m/s * 3600s).
The back end of the segment was injected at time 1000s. The segment length is
450 m (=0.45 m/s*1000 s). After 1 hour, the back of the segment is at location
1170 m (= 0.45 m/s* 2600 s).
At time 2 hrs, the segment has traveled another 1620 m and the front is now
3240 m from the inlet. The segment length does not change and remains 450 m.
The back of the segment is at location 2790 m (=3240 – 450 or 1170 + 1620).
Finally, after 3.7 hrs the front of the segment has reached the pipe outlet.
The back of the segment is 450 m from the outlet or at 5550 m (=6000 m – 450
m). The segment location for all three times is shown in Figure P4-11.
Conservative constituent - Times 1, 2, and 3.7 hours – Since the constituent
is conservative, the concentration for the entire segment is 12 mg/l for all times.
Outside of the segment the concentrations are equal to zero since no constituent
is injected and advection is the only transport mechanism.
Water age – Time 1 hour - After one hour the front of the parcel has moved
from the entrance to a distance 1620 meter into the pipe. This water had a water
age of zero at time 0 s. Thus, its water age at 1 hour is 3600s (= 0s + 3600s).
Since the back of the segment entered the pipe at time 1000s, its water age was
zero at that time. After 3600 s, it had been in the pipe for 2600s (= 3600s –
1000s).
Time 2 and 3.7 hrs – After the segment is fully within the pipe, it ages with
the clock time. So the water ages at the segment front at 2 and 3.7 hours are
7200s and 13320s, respectively. The water ages at the back of the segment are
6200s and 12320s, respectively, since they did not enter the pipe until time
1000s. Water age varies linearly in the segment with the oldest water at the
front and youngest at the back of the segment.
First order decaying constituent – Time 1 hour – First order decay is a
function of time and the decay constant. Thus, at time 1 hour, the water at the
front is 1 hour old and its concentration is computed by:

C = C 0 e − kt = 12 e −0.5(1) = 12 (0.61) = 7.3 mg / l

The water at the back of the segment is 2600 s old so its concentration is:

C = C 0 e − kt = 12 e −0.5( 2600 / 3600 ) = 12 (0.70) = 8.4 mg / l

 WATER QUALITY FUNDAMENTALS 4-79

Times 2 and 3.7 hours – At these times, the water age is substituted in the
first order decay relationship. At the segment front, the values of the constituent
concentration are 4.4 and 1.9 mg/l for hours 2 and 3.7, respectively. At the back
of the segment the concentrations are slightly higher due to the lag time in
entering the pipe and are 5.1 and 2.2 mg/l for times 2 and 3.7 hrs, respectively.
The concentration decreases exponentially from the front to the back of the
segment.

Figure P4-11: Location of fluid segment containing constituent for

Problem 4-11 at three times.

Second order decaying constituent – Time 1 hour – Second order decay is

represented by Eq. 4-42 with τ equal to the water ages. At the segment front at
time 1 hour the travel time is one hour, the initial concentration is 12 units and
the limiting concentration is 0. Substituting those values gives:

(C0 − C *) (12 − 0)
C1 hr (front) = C * + =0+ = 1.71 mg/l
1 + k (C 0 − C*) τ 1 + 0.5 (12 − 0) 1

The back of the segment have spent τ = 2600/3600 = 0.72 hrs in the pipe so
the resulting concentration is:

(C0 − C *) (12 − 0)
C1 hr (back) = C * + =0+ = 2.26 mg/l
1 + k (C 0 − C*) τ 1 + 0.5 (12 − 0) 0.72
4-80 CHAPTER FOUR

Times 2 and 3.7 hours – The concentrations are determined using the above
equations with these water ages. The concentrations at times 2 and 3.7 hrs for
the front are 0.92 and 0.52 mg/l, respectively. The segment back concentrations
are 1.16 and 0.56 mg/l for times 2 and 3.7 hours, respectively. These values are
identical to those in Table P4-10 for the same locations. For example for second
order decay at the end of the pipe Table P4-10 and the value here are both 0.52
mg/l.

12. a) The flow leaving node 3 equals the inflow from pipes 1 and 2 or:

Q1 + Q2 = q3 ⇒ q3 = 20.0 + 9.0 = 29.0 ft3/s

b) The initial constituent concentration, C3, t=0, is equal to zero since it has just
been injected at the upstream nodes.
c) To determine the concentration at t = 15 minutes, we must determine the
travel times for each pipe. For pipe 1, with a flow rate of 20 cfs, the velocity is:

Q1 20 20
V1 = = = = 6.37 ft/s
A1 π D12 4 π 24
12
( ) 2
4

and the travel time is:

L1 7500
t1 = = = 1178 s = 19.6 min
V1 6.37

Similarly for pipe 2, the velocity and travel time are 5.09 ft/s and 21.3 minutes,
respectively. Since t = 15 minutes is less than t1 and t2, the constituent has not
reached the node and the concentration at the outlet is still equals to zero.
d) At 20 minutes, constituent is supplied from pipe 1 but the contribution from
pipe 2 has not yet reached the node.
The outflow concentration at 20 minutes is then:

C3t = 20 =
(C t = 20
1
=
)
Q1 + C2t = 20 Q2 (0.45 ⋅ 20 + 0 ⋅ 9)
= 0.31 mg / l
q3 29

e) After 30 minutes, both pipes are contributing constituent at the pipe outlet
since it occurs after both pipes’ travel times. So, the outflow concentration is:

C3t = 20 =
(C t = 20
1 )
Q1 + C2t = 20 Q2 (0.45 ⋅ 20 + 0.25 ⋅ 9)
= = 0.39 mg / l
q3 29
 WATER QUALITY FUNDAMENTALS 4-81

f) A decaying constituent will have the same travel times as the conservative
one. So the outflow concentrations for the decaying and conservative
constituents are zero until 19.6 minutes. Between times 19.6 and 21.3 minutes,
only pipe 1 contributes constituent.
The concentration at pipe’s 1 outlet is:

=19 .6 = 0 − kt
C1t,out = C1t,in e = 0.45 e −3(19.6 / ( 24* 60)) = 0.43 mg / l

The resulting concentration at node 3 is computed from Eq. 4-3:

C3t = 20 =
(C t = 20
1 )
Q1 + C2t = 20 Q2 (0.43 ⋅ 20 + 0 ⋅ 9 )
= = 0.30 mg / l
q3 29

At time 30 minutes, water in pipe 2 that contains constituent reaches node 3.

The concentration at the end of pipe 2 at that time is:

C2t =,out
21.3
= C2t =,in0 e − kt = 0.25 e −3( 21.3 / ( 24* 60)) = 0.239 mg / l

and the resulting node 3 concentration is:

C3t = 20 =
(Ct = 20
1 )
Q1 + C2t = 20 Q2 (0.43 ⋅ 20 + 0.239 ⋅ 9 )
= = 0.37 mg / l
q3 29

This problem combines reaction relationships, travel times, and nodal

mixing. Although only conservative and first order decay reaction relationships
were used the other relationships presented in this chapter can also be applied
(Problem 4-10).

13. Plotting the data suggests that the constituent exponentially decays to zero
(Figure P4-13a) or:

C = C0 e kt ⇒ ln C = ln C0 + kb t

For constituents that follow this reaction type, the concentrations will plot
as a straight line on a semi-log plot (Figure P4-13b). The line’s slope is kb and
can be determined by a linear regression analysis in most spreadsheets. Here,
the resulting kb is -0.163 hr-1 and the intercept (C0) is 12.25 or:

C = 12.25 e −0.0163 t (r2 = 0.9518)

4-82 CHAPTER FOUR

where t is in hours. Note that this data was generated from C = 12 e −0.015 t with
randomly introduced errors.

14
Measured concentration (mg/l)

-0.0163x
y = 12.234e
12 2
R = 0.9517
10

0
0 50 100 150 200
Time (hrs)

Figure P4-13a: Plot of concentration versus time.

100
Measured concentration (mg/l)

10

1
0 50 100 150 200

0.1
Time (hrs)

Figure P4-13b: Semi-log plot of jar concentration versus time.

14. The concentration data is plotted versus time in Figure P4-14a. Based on
this result, it is assumed that the concentration goes to zero over time (i.e., C* =
 WATER QUALITY FUNDAMENTALS 4-83

0). The differential method requires estimating the derivatives of the

concentration decay curve to determine the reaction order and decay
coefficient. They are computed numerically by -dC/dt = (Ci+1-Ci-1)/(ti+1-ti-1) and
are listed in Table P4-14b. No smoothing is performed on the numerical
derivatives. Figure P4-14b is a plot of log(-dC/dt) vs log C. Since no smoothing
was applied, the slope points scatter around the curve. Fitting a line to the data
gives:

log (-dC/dt) = log k + n log C = -0.845 + 2.059 log C

Thus, the relationship essentially follows a second order decay relationship (n =

2.059) and the decay constant is 0.143/day (= 10-0.845). The reaction equation for
this relationship is then:

r (C ) = k (C − C* ) C = − 0.0143 (C − 0) C = − 0.143 C 2

The data for this problem were developed assuming second order decay
with k equals to 0.15/day. Minor deviations were introduced representing
measurement errors. The impact of those deviations is small and the decay
curve (Figure P4-14a) is relatively smooth. However, they became important at
low concentrations and significantly affected the slope estimates resulting in the
scattered plotting points.

7.0
6.0
Concentration

5.0
4.0
3.0
2.0
1.0
0.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Time (days)

Figure P4-14a: Plot of concentration versus time for constituent in

Problem 4-14.

Recall that C* was assumed to be zero after examining Figure P4-14a. If it

is not equal to zero, C* must be subtracted from all concentrations prior to
4-84 CHAPTER FOUR

applying the differential method. Thus, the x-axis in Figure P4-14b becomes
log (C – C*) rather than log C. This approach can be verified by adding one
unit to all concentrations in Table P4-14a. This linear transformation does not
affect n and k but if Figure P4-14b is produced without subtracting C* (= 1) the
result is a nonlinear curve and the best fit values for n and k are incorrect.
A rigorous method for simultaneously determining the value of C* is not
presented here. If they are to be estimated, it would be necessary to perform a
regression analysis to simultaneously determine the best fit for the three
parameters, n, k and C*.

Table P4-14b: Calculations for slope of concentration versus time

relationship. Column 3 is plotted versus column 5 in Figure P4-14b.
Time (days) Concentration, C log C -dC/dt log (-dC/dt)
0.00 6.01
0.25 4.89 0.69 3.73 0.57
0.50 4.14 0.62 2.58 0.41
0.75 3.60 0.56 1.99 0.30
1.00 3.15 0.50 1.56 0.19
1.25 2.82 0.45 1.14 0.06
1.50 2.58 0.41 0.94 -0.03
1.75 2.35 0.37 0.84 -0.08
2.00 2.16 0.33 0.76 -0.12
2.25 1.97 0.30 0.58 -0.24
2.50 1.87 0.27 0.51 -0.29
2.75 1.72 0.24 0.54 -0.27
3.00 1.60 0.20 0.34 -0.47
3.25 1.55 0.19 0.26 -0.58
3.50 1.47 0.17 0.35 -0.46
3.75 1.38 0.14 0.33 -0.48
4.00 1.30 0.11 0.27 -0.58
4.25 1.24 0.09 0.27 -0.57
4.50 1.17 0.07 0.17 -0.76
4.75 1.16 0.06 0.19 -0.71
5.00 1.07 0.03 0.23 -0.64
5.25 1.04 0.02 0.09 -1.04
5.50 1.02 0.01 0.12 -0.92
 WATER QUALITY FUNDAMENTALS 4-85

0.80
y = 2.0589x - 0.8452
0.60 2
R = 0.9636
0.40
0.20
log (-dC/dt)

0.00
-0.200.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70
-0.40
-0.60
-0.80
-1.00
-1.20
log C

Figure P4-14b: Plot of log C versus log (-dC/dt) for the differential method
for determining the parameters k and n for the reaction relationship given
the data in Problem 4-14.

15. The total decay coefficient is equal to the bulk and wall decay coefficients
or:

k = k b + k wall

where kb is given as -0.30/day. kwall must be computed for the pipe’s flow
condition using Eq. 4-70:

2 kw k f
k wall =
R (abs (k w ) + k f )

R and kw are given at 7 inches (0.58 ft) and -0.25/day, respectively. The mass
transfer coefficient, kf, is (Eq. 4-67):

⎛D ⎞
k f = Sh ⎜ m ⎟
⎝ D ⎠

To determine the Sherwood number, we must know the flow regime that is
described by the Reynolds’ number or:
4-86 CHAPTER FOUR

VD (0.09) (14 / 12)

ℜ= = = 9630 ⇒ flow is mixed to turbulent
ν 1.09 × 10 −5

where V = Q/A = (0.1 cfs)/((π(14/12)2/4) ft2) = 0.09 ft/s. The Sherwood number
for turbulent conditions is estimated by Eq. 4-69 with the Schmidt number
equal to 839 (ν/Dm = (0.94 ft2/day)/(0.00112 ft2/day)). Note that the kinematic
viscosity is converted to ft2/day to be consistent with the diffusivity and Sc is
dimensionless. The dimensionless Sherwood number is then:

Sh = 0.0149 ℜ 0.88 Sc1 3 = 0.0149 (9630) 0.88 (839)1 / 3 = 450

and the mass transfer coefficient is (Eq. 4-67):

⎛D ⎞ ⎛ 0.00112 ⎞
k f = Sh ⎜ m ⎟ = 450 ⎜⎜ ⎟⎟ = 0.43
⎝ D ⎠ ⎝ (14 / 12) ⎠

Finally, kwall is:

2 kw k f 2 (−0.25) (0.43)
k wall = = = − 0.54 / day
R (kw + k f ) (7 / 12) (abs (−0.25) + 0.43)

and the total decay constant for this pipe is:

k = k b + k wall = (−0.30) + ( −0.54) = − 0.84 / day