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CHLORINATION AND OPTIMAL CHLORINE DOSAGE FOR NILE WATER

Conference Paper · April 2005

DOI: 10.13140/2.1.3713.6962

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 CHLORINATION AND OPTIMAL CHLORINE
DOSAGE FOR NILE WATER
Mohamed Shamrukh *
Department of Civil Engineering, Faculty of Engineering,
ElMinia University, EGYPT
E-mail: mshamrukh@hotmail.com

Yahia Hassan
Department of Chemical Engineering, Faculty of Engineering,
ElMinia University, EGYPT

Abstract
Chlorine is the most widely used disinfectant in Egyptian drinking water
because it is effective at low concentration, is cheap, and forms a residual if
applied in sufficient dosage. Chlorine dosage is applied at the treatment plant
and is very much dependent upon raw water characteristics. With traveling
through the distribution system, chlorine decay Nevertheless, Egyptian water
suppliers attempt to maintain a detectable chlorine residual (0.1 to 0.2 mg/L free
Cl2) within the distribution system to minimize the potential for microbial
growth. In Upper Egypt, rural residents are supplied with treated Nile water
throughout a compact treatment plants. However, Egyptian drinking water
supplies recommend a primary and secondary dose of 6 and 4 mg/L,
respectively to be applied in the treatment plants. Samples were collected at the
intake of selected treatment plants located in AbuTisht, Upper Egypt. Different
chlorine dosages and residuals for these samples were measured and analyzed
laboratory in May 2004. The breakpoint curve of chlorine was delineated and
the obtained results are used to determine the suitable chlorine dosage that added
into Nile water. Furthermore, the coefficient of bulk chlorine decay was
determined. The obtained optimal chlorine dosage and decay coefficient could
be used to simulate chlorine concentration in the distribution systems in Upper
Egypt using any water quality code such as EPANET developed by USEPA.
From this study, the optimal primary dose and decay coefficient that might be
apply for Nile water treatment in Upper Egypt are 3.5mg/L and 0.034 /hour,
respectively.

Keywords: Chlorine, Disinfection, Drinking water, Water supply, Nile.

644
INTRODUCTION
A major objective of drinking water treatment is to provide microbiologically safe
drinking water. The combination of conventional drinking water treatment and disinfection
has proved to be one of the major public health advances in modern times. The most
important use of disinfectants in water treatment is to limit waterborne disease and inactivate
pathogenic organisms in water supplies. Chlorine is, by far, the most commonly used
disinfectant in the drinking water treatment industry (White 1992; Haested 2003). In Egypt,
chlorine is most often the primary and the only final disinfectant added to treated water for
microbiological protection before it is discharged into a drinking water distribution system.

However, disinfectants, especially chlorine, react with natural organic matter (NOM) to
form disinfection by-products (DBPs), which are considered to be of concern from a chronic
exposure point of view. These DBPs include halogenated organics, such as THMs, and
organic oxidation byproducts such as aldehydes, and inorganics such as chlorate and chlorite.
A high NOM concentration, exceeds 2.0 mg/L, indicates a high potential for DBPs formation.
Therefore, the applied disinfectant dose must be sufficient to meet the inherent demand in the
treated water, to provide sufficient protection against microbial infection, and at the same
time minimize DBPs. Drinking water disinfection, therefore, poses the dilemma of a risk
tradeoff. Chemical disinfection reduces risk of infectious disease, but the interaction between
chemical disinfectants and precursor materials in source water results in the formation of
DBPs. In fact, disinfection of drinking water has dramatically reduced outbreaks of diseases
attributable to waterborne pathogens. However, the identification of DBP such as
trihalomethanes (THM), in drinking water (USEPA 1990, 1999) raised questions about
possible health risks posed by these DBPs. Trihalomethanes and other DBPs have been shown
to be carcinogenic, mutagenic, etc. Since 1974, additional DBPs have been identified, and
concerns have intensified about health risks resulting from exposures to DBPs.

The most common disinfection method used by water systems in Egypt is chlorination.
Chlorine may be added to drinking water as a gas or liquid. The advantages of gas chlorine
are the realtive cost of the gas chlorine and the minimal effect that gas chlorine has on pH.
The safety issues are considered the negative aspects of its useThe gas form or chlorination
system is most common for water systems in Egypt and therefore is the focus of this work. In
addition to chlorine gas, chlorine is also available in hypochlorite form as both aqueous
solutions and dry solids. The most common forms are sodium hypochlorite as aqueous and
calcium hypochlorite (White, 1992). Sodium hypochlorite solution typically contains 12.5%
available chlorine. Granular calcium hypochlorite commercially available typically contains
65% available chlorine. The powder is mixed with water and fed with the chemical feed pump
used for the calcium or sodium hypochlorite.

To maintain biological stability in the distribution system, the standards requires that
treated water have a residual disinfectant of 0.2 mg/L when entering the distribution system.
A measurable disinfectant residual (0.1 to 0.2 mg/L) must be maintained in the distribution
system, or the utility must show through monitoring that the heterotrophic plate count (HPC)
remains less than 500/100mL. Several environmental factors influence the inactivation
efficiency of chlorine, including water temperature, pH, contact time, mixing, turbidity,
interfering substances, and the concentration of available chlorine. In general, the highest
levels of pathogen inactivation are achieved with high chlorine residuals, long contact times,
high water temperature, and good mixing, combined with a low pH, low turbidity, and the
absence of interfering substances. One aspect of this research is the assessment of
chlorination of Nile water in Upper Egypt areas. The results of this study will assist utilities in

645
selecting optimal chlorine dose for microbial inactivation which ensures protection against
pathogens while minimizing the formation of chlorine dioxide-related DBPs. Chemical
kinetics of chlorine to define the bulk decay coefficient is presented which could be used in
chlorine simulation in water distribution systems in Egypt.

CHLORINATION PROCESS
Chlorination is used in water treatment facilities primarily for disinfection. Because of
chlorine’s oxidizing powers, it has been found to serve other useful purposes in water
treatment, such as iron and manganese oxidation. In Egyptian treatment plants, liquefied
chlorine gas is typically evaporated to gaseous chlorine prior to metering. Once the
compressed liquid chlorine is evaporated, chlorine gas is typically fed under vacuum
conditions. Either an injector or a vacuum induction mixer usually creates the required
vacuum. The injector uses water flowing through a venturi to draw the chlorine gas into a
side stream of carrier water to form a concentrated chlorine solution. This solution is then
introduced into the process water through a diffuser or mixed with a mechanical mixer. A
vacuum induction mixer uses the motive forces of the mixer to create a vacuum and draws the
chlorine gas directly into the process water at the mixer (USEPA 1990).

Chlorine Dosage & Residual

The total amount of chlorine fed into a volume of water by the chlorine feed equipment is
referred to as dosage and is calculated in mg/L. Chlorine is a very active chemical oxidizing
agent. When injected into water, it combines readily with certain inorganic substances that are
oxidizable (e.g., hydrogen sulfide, ferrous iron, etc.) and with organic impurities including
microorganisms and nitrogen compounds (e.g. animal wastes, ammonia from fertilizers, etc.).
These reactions consume some of the chlorine. The amount of chlorine added is called the
chlorine dose and the amount of chlorine consumed is called chlorine demand. Then chlorine
residual is estimated from the following equation:
Chlorine Residual = Chlorine Dose - Chlorine Demand (1)

Chlorine Reaction in Water

Regardless of the form of chlorine used, the reaction in water is basically the same. The
chlorine mixed with water will produce hypochlorous acid (HOCl). The following equation
presents the hydrolysis reaction (USEPA 1999; White 1992):
Cl2(g) + H2O ⇒ HOCl + H+ Cl − (2)
The addition of chlorine gas to water reduces the pH of the water due to the production of
hydrogen ion. Hypochlorous acid is a weak acid, meaning it dissociates slightly into hydrogen
and hypochlorite ions as noted in Equation 3:
HOCl ⇔ H+ + OCl − (3)
The measurement of hypochlorous acid (HOCl) and hypochlorite ion ( OCl − ) is called free
chlorine residual (Figure 1). Between a pH of 6.5 and 8.5 this dissociation is incomplete and
both HOCl and OCl- species are present to some extent (White, 1992). Below a pH of 6.5, no
dissociation of HOCl occurs, while above a pH of 8.5, complete dissociation to OCl- occurs.
As the germicidal effects of HOCl is much higher than that of OCl-, chlorination at a lower
pH is preferred. This is due to the more facile movement of the uncharged acid through the
bacterial cell wall compared to OCl-. For this reason, careful regulation of pH is necessary to
assure maximum disinfection with minimum chlorine dose. In the case of potable water,

646
however, it is also necessary that waters with relatively low pH (below 7.5) tend to be
corrosive.

Figure 1. Chlorine reactions with water

If organic or inorganic compounds are available in the water, particularly nitrogen

compounds, the hypochlorous acid will combine with these compounds to produce
chloramines and/or chloro-organic compounds. The measurement of the presence of these
compounds is called combined chlorine residual. Free chlorine has proven to be a more
effective disinfectant than combined chlorine compounds. The measurement of both the free
and combined chlorine residuals is called total residual as following:
Free Residual Chlorine + Combined Residual Chlorine = Total Chlorine Residual (4)
If there are organic and inorganic compounds in the water, then enough chlorine has to be
added to complete the reactions with these compounds before an adequate free residual can be
produced. This process is called breakpoint chlorination which represented from plotting of
applied chlorine dose versus total chlorine. This curve evolves four distinct areas as shown in
Figure 2. The first area represents the oxidation of more reactive compounds than NH3 by
chlorine and is an inorganic demand phase. The second area represents an increase in
combined chlorine residual (chloramines). The residual begins to drop because of destruction
of the combined chloramines. At this point the nitrogen is given off as a gas and is lost to the
atmosphere. Phase three continues until breakpoint. After breakpoint, all NH3 products have
been fully oxidized and free chlorine residual begins to form phase four. As a rule of thumb,
the free residual should be at least 85% of the total residual in order to prevent chlorine taste
and odor problems and insure an adequate free residual for effective disinfection (USEPA
1990).

Disinfection with chlorine is not instantaneous. Time is required in order that any
pathogens present in the water are inactivated. The time taken for different types of microbes
to be killed varies widely, therefore need an adequate contact time; this is usually 30 minutes.
One of the most important factors for determining or predicting the germicidal efficiency of
any disinfectant is the CT factor. The CT factor is defined as the product of the residual
disinfectant concentration, C, in mg/L, and the contact time, T, in minutes that residual
disinfectant is in contact with the water.

647
 Chlorine
Reducing
Compounds

Figure 2. Breakpoint chlorination curve, (EPA, 1990)

MATERIALS AND METHODS

Study Area
As concern over disinfection by products and disinfectant decay within the distribution
systems has increased, more attention has been paid to the chlorination. To provide water
suppliers in Upper Egypt, raw water at three water treatment's intakes located at AbuTisht
County in Qena Governorate were chosen to carry out this investigation. The locations of the
sampling points could represent the area from Aswan to Assiut which is 500 Km long of
River Nile. The treatment plants serve a population of 20 thousands (Figure 1). River Nile and
its main streams in the study area were the source of raw water that has been studied. The
treatment processes used are the conventional method which consists of screening,
coagulation/flocculation by alum, sedimentation, and sand filtration.

There are a primary and secondary disinfection in treatment plants which are applied
before coagulation and before reservoir, respectively. The detention time in the plant reservoir
before distribution is 30 min. Disinfection in the plants is applied using chlorine gas contained
in pressurized cylinders. The primary and secondary chlorine dosage is 5.0 to 3.0 mg/L,
respectively. These doses are constants all year seasons no matter is the quality of raw water.
Egyptian regulations of drinking water specify that residual chlorine must be in range of 0.1
to0.2 mg/l to prevent microbial growth in the water distribution system.

Sampling and Analytical Program

During the period from April to May 2004, many water samples of raw water from River
Nile and its main streams were collected at the three water treatment plants. Samples of Nile
water were collected from the depth of 1.5m from surface near the plants' water intake points.
Collected samples were analyzed using a Hach DR2000 Spectrophotometer for most of water
measurements. Meters for pH and TDS measurements were used for other water quality.

648
Instrument startup and analysis were carried out as detailed in the operating manual. Each
measurement was made in duplicate and the absorbance due to background was subtracted
from the mean of the two values. DPD indicator (N, N, diethyl-p-phenylenediamine) was
used as chemical reagent for chlorine measurements. Free available chlorine (Cl2, HOCl,
OCl) oxidizes DPD to produce a red color. This color is then measured using DR2000.
Quality characteristics of Nile water at the sampled locations were analyzed and given in
Table 1.

Chlorine dosages were created using a granular calcium hypochlorite which contains 65%
available chlorine was used to prepare the different values of chlorine dosages .About 12
flasks have been prepared for each sampling site of the three plant intakes. The chlorine
dosage were as following: 0.5, 1.0, 1.5, 2.0, 3.0, 4.0, 6.0, 8.0, 10, 12, 14, 16 mg/L.
Measurements of free chlorine and combined chlorine were taken 30 minutes after dosing.
Three flasks were continued in measurements of free and combined chlorine for a period of
24 hours along to estimate the coefficient of chlorine bulk reaction.

Mediterranean Sea

Cairo Sinai
Valley

EGYPT
Nile
Qena
Red Sea

Aswan Aswan
High Dam

Study site

Figure 3. Study site location and sampled area

RESULTS AND DISCUSSION

Nile Water Quality
Important water quality parameters of raw Nile water at the study area in Qena
governorate are listed in Table 1. Most of quality parameters are under the allowable limits
for drinking purposes. There was a relatively high concentration of organic matter (4.50
mg/L) that may cause a problem for forming DBP in the distribution systems upon using
excess chlorine dosage. In addition there nil concentration of ammonia and very small
amounts of reduced iron and manganese that will consume chlorine for oxidation. Actually it

649
is anticipated that the DBP especially THM will be formed due to high concentration of
organic matter 3.0 to 4.0 mg/L which exceeds 2.0 mg/L. It is recommended to carry out an
investigation to measure these DBP in the study site to confirm this anticipation.

Table 1. General characteristics of raw River Nile water at the study site

Parameter pH TDS DO NOM Fe Mn NO3 SO4 alkalinity hardness

Value 7.5 135 5.5 3.0 0.1 0.05 0.7 35 105 100
mg/L 7.7 150 6.5 4.0 0.2 0.15 1.5 40 115 110
-NOM: natural organic matter
-alkalinity and hardness given as CaCO3

Breakpoint Chlorination Curve

In the study area, Egyptian drinking water supplies recommend a primary and secondary
dose of 6 and 4 mg/L, respectively to be applied in the treatment plants. In fact these values
are constant for all the treatment plants in the study area all times without change. Up to
knowledge of the authors, there is no breakpoint curves are carried out experimentally for the
chlorination of the treatment pants in Upper Egypt. In order to effectively treat drinking water
with chlorine, the chlorine demand and breakpoint of the water to be treated needs to be
calculated. Results of the bottle analysis for chlorine doses and residuals are presented in
Table 2. Free residuals were measured at some points of chlorine doses. Chlorine demands
have been calculated according to Equations 1. It is clear from Table 1 that the total residuals
(combined and free), free, and demand are increasing with the increasing of chlorine added to
the water samples.

Table 1. Chlorine doses and residuals measurements

Chlorine dose (mg/L) 0.5 1.0 2.0 3.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
Chlorine residual (mg/L) 0.20 0.35 0.61 1.07 1.30 2.10 2.80 3.51 4.42 5.11 6.60
Free chlorine (mg/L) - - 0.33 0.45 0.56 0.72 1.21 - 2.1 - 2.95
Chlorine demand (mg/L) 0.3 0.65 1.39 1.93 2.7 3.9 5.2 6.5 7.6 8.9 9.4

The results of chlorine measurements were taken to graph the breakpoint chlorination as
shown in Figure 4. Dash lines represent the trendlines of total available chlorine and free
available chlorine for the sampling water. At the beginning of graph there is zone one in
which added chlorine start to oxidize the reduced compounds in sampled Nile water such as
iron, manganese, and nitrate. As listed in Table 1, these reduced constituents are found in
small amounts in Nile water in the study area. Therefore, the amount of chlorine consumed in
this process is about 0.2mg/L. The important notice from Figure 4, is the breakpoint of
chlorine. Figure 4 shows that there is no clear breakpoint in this graph where the chlorine
residual s the least. This is may be due to the nil existence of ammonia-nitrogen in sampled
Nile water. Therefore, no show up for zones two and three of the typical breakpoint curve
(zones just before breakpoint, Figure 2). Chloro-organic compounds and chloramines
formation in zone two and its destruction in zone three did not clearly formed for Nile water
in the sampled area. However, zones from one to three shown in Figure 2 of breakpoint curve

650
need more investigations with more small amounts of chlorine doses in order to highlight its
details.

Thus, in Nile raw waters that do not contain ammonia, the chlorination curve begins at
the point where chlorine additions provide “free and available” chlorine in the system (at
0.2mg/L chlorine dose). Chlorine dose added to drinking water must satisfy demand, give a
free residual at customers tape equal to 0.1~0.2mg/L, and minimize the cost and DBP
formation (Rodriguez, 1995).. Hence, the most suitable chlorine dose could be obtained from
Figure 4 which gives free chlorine of 0.5 mg/l at entrance of the distribution systems is
3.5mg/L. This dose might be divided to two parts for primary and to secondary disinfection in
the treatment plants in Upper Egypt. This chlorine dose which operators need to add order to
maintain 0.20mg/L free chlorine residual in their systems.

6
Chlorine residual mg/L

1 total residual
free residual
0
0 2 4 6 8 10 12 14 16 18
Chlorine dose mg/L

Figure 4. Breakpoint chlorination curve for Nile water in Upper Egypt

Bulk Reaction Coefficient

For water distribution systems, chlorine is shown reacting in the bulk fluid with natural
organic matter (NOM), and at the pipe wall, where oxidation reactions with biofilms and the
pipe material can occur (Clark 1994). For chlorine decay analysis, reaction dynamics can be
specified using bulk and wall reaction coefficients. Bulk reaction coefficients associated with
individual pipes and storage tanks. Wall reaction coefficients only associated with individual
pipes, applied globally, or assigned to groups of pipes with similar characteristics. Bulk
reaction coefficients can be determined through laboratory testing. Wall reaction coefficients
must be measured using field tests or determined as part of the calibration process of
distribution systems. The most commonly used reaction model is the first order decay model

651
(Haested, 2003). This has been applied to chlorine decay, and other decay processes. A first
order decay is equivalent to an exponential decay, represented by Equation 5:

C t = C o e − kt or ln C o − ln C t = kt (5)

where Ct is chlorine concentration at time t, Co is the initial concentration (at time zero), and k
is reaction rate. The values of bulk decay, k, generally expressed 1/hr or 1/day.

Two bottles of chlorine measurements were kept for 24 hours to measure chlorine
concentrations along time. 24 hours represent the longest residence time in most of the water
distribution systems in the studied area. Figure 5 show the graphing of the first order decay of
chorine. The chlorine concentrations are charted along the y-axis logarithmic(the dependent
variable), and the time is charted along the x-axis. Reaction rate coefficient, k, can be found
using linear regression techniques. A best-fit straight line is drawn through the data collected
from the two bottles test as illustrated in Figure 5. The slope of the line for the drawn data in
Figure 5, 0.034 hr-1, becomes the bulk reaction coefficient. Note that the reaction coefficient
is negative since the chlorine concentration decays over time.

Bulk reaction coefficients are associated with pipes for purposes of a simulation, and are
assumed to remain constant throughout the simulation for a particular pipe. Since the bulk
reaction coefficient is, in reality, associated with the fluid itself, the bulk reaction rate can
change throughout the actual system as water from different sources (Nile and groundwater)
becomes mixed at nodes. When assigning bulk reaction coefficients for pipes, the mixing can
be considered by designing and conducting bottle tests with representative source mixtures. A
source tracing analysis can assist in determining the degree of mixing in a system. Source
blending can change over the course of the day for a particular pipe, thus the predominant
source or mix of sources should be used in assigning the bulk reaction coefficient.

10
Chlorine concentration, mg/l

-0.034t
Ct/Co = 3.64e

0.1
0 5 10 15 20 25
Time, hr
Figure 5. First order equation of chlorine bulk decay

652
CONCLUSIONS
Egyptian drinking water supplies recommend a chlorine dose for drinking water to be
10mg/L which applied in the treatment plants. Samples were collected at the intake of
selected treatment plants located in AbuTisht, Upper Egypt in April and May 2004.
Experimental work has been carried out to determine the suitable dose and reaction
coefficient of chlorine applied in the treatment plants in Upper Egypt. The suitable chlorine
dose that could be added to drinking water in Upper Egypt is 3.5mg/L. This chlorine dose will
satisfy demand, give a free residual at customers tape equal to 0.1~0.2mg/L, and minimize
both chlorine cost and DBP formation. This dose could be divided to two parts, primary and
secondary disinfections. Chlorination breakpoint curve has been delineated for Nile water in
the studied area. Results show that there is no breakpoint where the chlorine residual is the
least. This may be due to the nil content of ammonia-N in Nile water in the site. In fact more
investigation is needed to carry out to give more details for small chlorine doses. In addition,
the coefficient of bulk chlorine decay was determined. The obtained bulk decay coefficient
could be used to simulate chlorine concentration in the distribution systems in Upper Egypt
using any water quality code such as EPANET. From this study, the coefficient of chlorine
bulk decay for Nile water in the study area in Upper Egypt is 0.034 /hour.

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