Chemosphere 164 (2016) 649e656

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Chemosphere
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Disinfection by-products of chlorine dioxide (chlorite, chlorate, and

trihalomethanes): Occurrence in drinking water in Qatar
Fatima Al-Otoum a, Mohammad A. Al-Ghouti b, *, Talaat A. Ahmed b,
Mohammed Abu-Dieyeh b, Mohammed Ali a
a
Supreme Council of Health, Public Health Department, P.O. Box: 42, Doha, Qatar
b
Department of Biological and Environmental Sciences, College of Arts and Sciences, Qatar University, State of Qatar, Doha, P.O. Box: 2713, Qatar

h i g h l i g h t s

ClO2 level varied from 0.38 to 0.02 mg L1 as a result of auto-decomposition.

The chlorite concentrations varied from 12.78 to 436.4 mg L1.

The chlorate concentrations varied from 10.66 to 282.7 mg L1.

All species of THMs (CHBr3, CHCl3, CHCl2Br, and CHClBr2) were detected.

The CHBr3 was the most abundant compound.

a r t i c l e i n f o a b s t r a c t

Article history: The occurrence of chlorine dioxide (ClO2) disinfection by-products (DBPs) in drinking water, namely,
Received 11 June 2016 chlorite, chlorate, and trihalomethanes (THMs), was investigated. Two-hundred-ninety-four drinking
Received in revised form water samples were collected from seven desalination plants (DPs), four reservoirs (R), and eight mos-
28 August 2016
ques (M) distributed within various locations in southern and northern Qatar. The ClO2 concentration
Accepted 2 September 2016
levels ranged from 0.38 to <0.02 mg L1, with mean values of 0.17, 0.12, and 0.04 mg L1 for the DPs, Rs,
and Ms, respectively. The chlorite levels varied from 13 mg L1 to 440 mg L1, with median values varying
Handling Editor: Xiangru Zhang from 13 to 230 mg L1, 77e320 mg L1, and 85e440 mg L1 for the DPs, Rs, and Ms, respectively. The
chlorate levels varied from 11 mg L1 to 280 mg L1, with mean values varying from 36 to 280 mg L1, 11
Keywords: e200 mg L1, and 11e150 mg L1 in the DPs, Rs, and Ms, respectively. The average concentration of THMs
Disinfection by-products was 5 mg L1, and the maximum value reached 77 mg L1 However, all of the DBP concentrations fell
Chlorine dioxide within the range of the regulatory limits set by GSO 149/2009, the World Health Organization (WHO),
Chlorite and Kahramaa (KM).
Chlorate
2016 Elsevier Ltd. All rights reserved.
Trihalomethanes
Drinking water

1. Introduction
Drinking water is essential to human life; therefore, water safety
is one of the most important public health issues (Ohanian et al.,
1989). Qatar is located in the Arabian Gulf, which is an arid re-
gion that suffers from water scarcity and limited surface and fresh
water resources. As a result, the main source of drinking water
(DW) in Qatar comes from the desalination of seawater (Kahramaa,
KM, Statistical Report, 2012). The water demand has increased in
* Corresponding author.
E-mail address: mohammad.alghouti@qu.edu.qa (M.A. Al-Ghouti).
the last few decades because of the expanding population and
increasing infrastructure required to sustain the socio-economic
development since the 1970s. Moreover, in 2012, Kahramaa (KM)
reported that the water demand increased from 312.4 million
m3 d1 in 2008 to 437.1 million m3 d1.
The process of providing the public with safe water requires the
addition of some chemical disinfectants, and this is a critical step to
reduce the incidence of water-borne diseases and to inhibit biolm
formation. This is important for public health (Agusa et al., 2009).
The most common disinfectants are chlorine, chloramines, ozone,
and ClO2 (WHO, 2004). However, each of the common disinfectants
can produce disinfection by-products (DBPs) that can pose a threat
to human health. ClO2 has recently been used as an alternative to

http://dx.doi.org/10.1016/j.chemosphere.2016.09.008
0045-6535/ 2016 Elsevier Ltd. All rights reserved.
650 F. Al-Otoum et al. / Chemosphere 164 (2016) 649e656
chlorine as it does not typically lead to the formation of toxic DBPs
(Pereira et al., 2008), but it still kills bacteria efciently and is more
powerful than chlorine over a wide pH range (Pereira et al., 2008;
Haas, 1990). ClO2 does not produce signicant amounts of haloge-
nated organic DBPs. Chlorite and chlorate are the primary by-
products (Korn et al., 2002). DBP formation during ClO2 pre-
treatment has been studied (Linder et al., 2006; Lee et al., 2007;
Yang et al., 2013). ClO2 oxidation prior to chlorination can reduce
the formation of THMs and total organic halogens (TOX) (Linder
et al., 2006). A recent study reported that ClO2 pre-oxidation
reduced THMs and other by-products (Yang et al., 2013). In addi-
tion, ClO2 is a more powerful bactericide than chlorine (Cl2) for
water treatment because of its higher oxidation capacity (Pereira
et al., 2008).
ClO2 produces low levels of organic by-products compared to
chlorine (Gordon et al., 1990). Chlorite (ClO 
2 ) and chlorate (ClO3 )
are the disinfection by-products that result from the use of ClO2 as a
disinfectant. The production of chlorite and chlorate varies and
depends on the natural organic matter (NOM) source in the raw
water. Typically, up to 60% of the applied ClO2 dose is reduced into
chlorite ions and up to 10% is converted into chlorate ions. ClO2
does not typically react with NOM or humic substances (Lykins and
Griese, 1986; Werdehoff and Singer, 1987; Lafrance et al., 1992;
Muttamara et al., 1995), but it rapidly decomposes into inorganic
DBPs, namely chlorite and chlorate (Plewa et al., 2004a,b). There-
fore, the chief disadvantage of ClO2 is the production of potentially
risky inorganic by-products: chlorate and chlorite ions. Despite its
numerous advantages, ClO2 may signify a potential risk to human
health because of the production of these inorganic by-products.
Chlorite and chlorate ions induce hematological responses in sub-
chronic and acute exposures, which result in oxidative damage to
erythrocytes, leading to methemoglobinemia and hemolytic ane-
mia (WHO, 2011). The reproductive, neurodevelopmental, and
endocrine toxicities of sodium chlorite have been reported in lab-
oratory animals (Gill et al., 1989). Oxidative stress causing changes
in red blood cells is the main and consistent nding arising from
exposure to chlorite and chlorate (WHO, 2011). In the United States,
the USEPA established a federal drinking water threshold level of
0.8 mg L1 for ClO2 and 1.0 mg L1 for chlorite ions (USEPA, 1998).
Parts of the EU and North America have more stringent regulations
for chlorite ions. For example, the maximum allowed concentration
in drinking water in Italy was 200 mg L1 in 2006 (Linder et al.,
2006; Chu et al., 2011). Despite the intensive work conducted on
DBP formation in disinfected water around the world, the potential
hazards of DBPs and the scarcity of this type of data in Qatar make
this type of research essential.
However, various factors may affect the formation of DBPs.
These include the pH, disinfectant concentration, temperature,
natural organic matter (NOM), and precursor properties (Yang
et al., 2013). The chemical and physical properties of disinfectants
and DBPs can affect their behavior in drinking water (Yang et al.,
2013; Richardson et al., 2000; Korn et al., 2002; Schmidt, 2004).
However, when ClO2 is used, it can react with both organic and
inorganic compounds to form chlorite and chlorate, which can have
adverse effects on human health.
Studies have been conducted to establish the effect of pH,
temperature, and suspended matter on the disinfection efciency
of ClO2. Several investigations have shown that the pH has less of an
inuence on pathogen inactivation for viruses and cysts with ClO2
than with chlorine in the pH range of 6.0e8.5 (Liyanage et al., 1997).
The disinfection effectiveness of ClO2 decreases as the temperature
decreases (Chen et al., 1984). LeChevallier (1997) showed that
decreasing the temperature from 20  C to 10  C led to a reduction in
the disinfection efciency of ClO2 on Cryptosporidium by 40
percent, which is the same as previous results for Giardia and
viruses. The chief DBPs of ClO2 are chlorite and chlorate ions (WHO,
2004). The main features affecting the formation of chlorite and
chlorate ion in drinking water include (Aieta et al., 1984) the
applied dose, water temperature, pH, exposure to sunlight, and
distribution system for residual maintenance.
Thus, the main goal of this study was to investigate the occur-
rence of DBPs (chlorite, chlorate, and trihalomethanes) in drinking
water from different drinking water and distribution locations as a
result of using ClO2 as a disinfectant. The concentration of residual
ClO2 in the collected water samples was also investigated. The re-
sults were compared with international and local guidelines. To
achieve these aims, the following specic objectives were studied:
the concentration of chlorite, chlorate, and trihalomethanes in the
collected water samples, the residual ClO2 concentration in the
collected samples, and correlations between the two using a sta-
tistical package for the social sciences (SPSS).
2. Materials and methods
2.1. Sample collection
The water samples were collected from seven DPs, four Rs, and
eight Ms. The sampling regime covered three major categories:
drinking water production facilities, reservoirs, and customer
points of use. The rst category of the water samples was collected
from seven desalination plant outlets either at the northern (RLC,
Q-power and Ras-Girtas) or southern (RAF A, RAF A1, RAF B and RAF
B2) side of Qatar. These samples represented the feed water (water
source) for the distribution system, and the measured DBP levels
represented the inuence of the desalination and treatment pro-
cesses on DBP formation. The second category of water samples
was collected from the KM reservoirs (New Salwa (NS), Airport,
Duhail (D), and West Bay (WB)). These reservoirs represent key
points within the distribution system as they supply DW to the bulk
of customers, and the aging water inside the reservoir may inu-
ence DBP formation. These reservoirs are located in the Abu-
Hammor, Um-Goulina, Al-Kheesa and Al-Markhiya areas, respec-
tively. The third category of samples was collected from the
customer point of use. These samples represent drinking water, and
ablution areas at mosques were selected for sampling purposes to
reect high use areas. For each of the aforementioned reservoirs,
two mosques were selected. The water samples were collected
from eight mosques (mosque numbers: 82, 266, 141, 600, 1077,
1146, 1164, and 1066). All of the water samples were collected ac-
cording to the international protocol and practices for collection
and handling of drinking water samples (Quick Guide to Drinking
Water Sample Collection U.S EPA, 2005). Two types of vials were
used for collection. Sodium thiosulfate was added to the rst vial,
and ethylene diamine (EDA) was added to the second vial, which
was used to analyze chlorite and chlorate. The second water sample
was sparged with nitrogen gas for 5 min. After collection, all the
vials were labeled, stored in an icebox with an ice package, main-
tained at 10e12  C, and kept away from light until they were
delivered to the Central Food Laboratory (CFL) in Qatar for analysis.
Onsite measurements were used to measure some of the physical
and chemical parameters, such as the temperature, pH, conduc-
tivity, turbidity, and ClO2. These parameters were measured using
calibrated portable devices.
2.2. Sample analysis
2.2.1. Physical parameters
The water temperature, conductivity, turbidity and pH were
measured for all the water samples at the time of collection, and the
results are shown in Table 1.
 F. Al-Otoum et al. / Chemosphere 164 (2016) 649e656 651

Table 1
Water temperature, conductivity, turbidity and pH for the water samples.

Parameter Minimum value Maximum value Median value KM/WHO acceptable value

Water temperature 18.7  C 46.0  C 38.5  C KM (45  C)

WHO (e)
pH 7.2 8.5 7.9 KM and WHO (6.5e8.5)
Turbidity 0.01 NFU 2.7 NFU 0.18 NFU KM (<4 NFU)
WHO (<5 NFU)
Conductivity 95.3 ms cm1 384 ms cm1 170 ms cm1 KM and WHO (<500 ms cm1)

2.2.2. Chemical analysis
All samples were fully analyzed for chlorate and chlorite ions
with ion chromatography using the EPA Method 300.1: Determi-
nation of inorganic anions in drinking water by ion chromatog-
raphy. The instrument used for chlorite and chlorate ion analysis
was a Dionex ICS 5000. Method 8260B is approved by the EPA for
the quantitation of volatile organic compounds with boiling points
lower than 200  C using gas chromatography/mass spectrometry
(GC/MS). This method was used to measure the THMs using
headspace sampling. The Perkin Elmer GC-MS Clarus 600 was used
to measure the THMs. The Orion Star and Star Plus Meter from
Thermo Scientic was used to measure the temperature, pH, and
conductivity. A 2020wi Tc- 300wi LTC-3000wi, Turbidimeter
(LaMotte) portable device was used to measure the turbidity. It was
calibrated using three turbidity standards of 0.0, 1.0, and 10 FNU.
The Thermo Scientic ChlordioXense Palin test was used to mea-
sure the ClO2 concentration. It is a precise instrument with unique
pre-calibrated disposable sensors. It offers a simple and rapid
technique with a reagent-free method for the analysis of ClO2 in
water. The sensor is designed for a single use only. The surface of
the sensor is highly sensitive and must be handled with care in the
foil packaging. The sensor response compensates for the sample
temperature in the range from 2 to 25  C. However, the tempera-
ture at some locations exceeded this range, and all the water
samples were pre-cooled before measuring the ClO2 levels. A ni-
trogen gas cylinder with a capacity of 50 L and pressure of 5 psi was
used to purge all the water samples for 4 min to prepare them for
reservoirs, the highest value (0.24 mg L1) was recorded in West
Bay, and the lowest value (0.02 mg L1) was recorded in New Salwa.
In the mosques, the highest value (0.13 mg L1) was recorded in
mosque number 1066 WB.
The average concentration at the desalination plants was
0.17 mg L1, and the concentration decreased by 30% to 0.12 mg L1
at the reservoir outlets. An additional 46% decrease was observed
from the reservoir outlets to the customer point of use (mosques) to
a concentration of 0.04 mg L1. Overall, a 76% decrease in the ClO2
levels was observed over the entire distribution system (Fig. 1B).
While the ClO2 levels at a few customer points of use are compliant
with the KM requirements, it would be benecial to slightly in-
crease the average ClO2 dosage at the desalination plants. A slight
increase (approximately 0.2 mg L1) would provide a safer margin
at the customer points of use in case of any microbial activity.
Volk et al. (2002) found that the total disinfectant residual
average was 0.27 mg L1 in the distribution network (when ClO2
was used as a disinfectant) and 0.20 mg L1 at the end of the sys-
tem. The ClO2 average consumption in the same study was 50% (for
a water temperature of 16.1  C). As a comparison with other studies,
a lower ClO2 concentration was measured at the point of entry for
0.18 0.17 A
0.16
0.14
Chlorine dioxide mg L-1

0.12
the chlorite and chlorate test. 0.12 0.11

0.10
2.3. Statistical analysis 0.08

0.06
Excel Microsoft Ofce and SPSS version 22 (IBM, Armonk, NY) 0.04
were used for the data analysis. Basic descriptive statistics were 0.04
calculated for each variable. A bivariate regression was run between 0.02
the ClO2 concentration and other parameters. Pearson's correlation
0.00
coefcients were calculated to assess the relationship between the Desalinaon Plant Reservoir Distribuon System Overall Water
ClO2 concentration and chlorite formation and other applicable
0.90
associations. B
0.80 76%
3. Results and discussion 0.70
chlorine dioxide mg L-1

0.60
3.1. Occurrences of DBPs (chlorite, chlorate, and trihalomethanes)
0.50
and residual ClO2
0.40 30%
3.1.1. Residual ClO2 0.30
The median, maximum, and minimum residual ClO2 concen-
0.20
trations in the water showed that the concentration of ClO2
decayed by one order of magnitude and was smaller in the mosques 0.10
compared to the concentration in the reservoirs and desalinated 0.00
plants, as shown in Fig. 1A. The median levels of ClO2 were 0.17, Desalina on Plant Reservoir Distribu on System
0.12, and 0.04 mg L1 in the desalination plants, reservoirs, and percentage of decay

mosques, respectively. The highest concentration of ClO2, which

was 0.38 mg L1, was recorded at the Ras-Girtas DP, and the lowest Fig. 1. A. The overall decay of ClO2 (mg L1) and B. The percentage of ClO2 decay over
value, which was 0.02 mg L1, was recorded at RAF B and B2. In the the entire system.
652 F. Al-Otoum et al. / Chemosphere 164 (2016) 649e656

two different distribution systems (Gatel et al., 1995). However, 800 A

ClO2 was had completely dissipated by the end of the system. The 700.0
disappearance of ClO2 was greater at higher temperatures and with 700
higher organic matter concentrations. In another distribution 600
network (Laval, Italy), the plant efuent ClO2 residual varied with

Chlorate g L-1
temperature and TOC levels and ranged between 0.02 and 500
0.41 mg L1 (Gordon, 1990). As observed in the study by Gatel et al. 400
(1995), the disinfectant residual disappeared within the network.
In the current study, the consumption of ClO2 in the distribution 300
system was 76% (Fig. 1B). The measured disinfectant residual at the 200
end of the distribution system (mosques) was less than 0.02 mg L1, 118.03
84.31
which is acceptable especially if the effect of high temperature is 100 49.47

taken into consideration (Ammar et al., 2014). This could also be 0

attributed to a normal decay process from auto-decomposition Desalinaon Plant Reservoir Distribuon System
reactions and reactions with organic and inorganic compounds, Median Max. Min. Limit
including biolms, pipe materials, corrosion products, and slime
produced by living cells and their metabolic by-products and scales.
ClO2 is also subject to photolytic decomposition (USEPA, 1983). 800 B
In addition, the decrease in the ClO2 levels in the distribution 700.0
700
system (mosques) may be due to water aging and mixing problems.
The latter can lead to stratication or large stagnant zones within 600
the water volume that cause a deterioration in water quality. The
500

Chlorite g L-1
pipe systems that carry water from the source for a long period of
time have biolms attached to the pipe walls, which can result in a 400
signicant loss of the disinfectant residual and adversely affect the
water quality (Geter et al., 2004). These unwanted changes may 300
occur because of failures at the treatment barrier, transformations
200
in the bulk phase, corrosion and leaching of pipe material, biolm
formation, and mixing between different sources of water. Few 100
researchers have investigated the factors that inuence water
quality deterioration in the distribution system (Geter et al., 2004; 0
Desalinaon Plant Reservoir Distribuon System
Chu et al., 2011). Maintaining adequate levels of disinfectant re-
sidual may require routine cleaning/replacement of pipes and Median Max. Min. Limit

intensive treatment. Volk et al. (2002) showed that the ClO2 re-
siduals could be maintained throughout specic distribution sys- Fig. 2. Maximum, minimum, median and accepted limits of: A. chlorate, B. chlorite in
tems without booster stations. Other studies have shown that the mg L1 at different water sources. Chlorine dioxide concentration: 0.17 mg L1.
residuals disappear in the systems without a booster addition; this
is in good agreement with the current study nding, where the
reservoirs, and mosques, respectively. However, the chlorite con-
ClO2 level was less than 0.02 mg L1 at the distribution end points
centrations in the water samples from the mosques were higher
(Gates, 1998).
than the chlorite concentrations at the desalination plants and
reservoirs, as shown in Fig. 2B. Our ndings are in good agreement
3.1.2. Chlorate
with other studies on chlorite, including a study on full-scale
The median, maximum, minimum and standard deviations for
treatment plants where the chlorite concentration was
chlorate in the collected drinking water are given in Fig. 2A. Fig. 3C
0.58 mg L1 (average chlorine dioxide concentration was
displays the overall median for chlorate. The concentrations of
0.88 mg L1) (Richardson, 2003) and another study in Virginia
chlorate in the collected water samples varied from 11 mg L1 to
where the median level of chlorite was 0.29 mg L1 (average
280 mg L1 with mean values from 36 to 280 mg L1, 11e200 mg L1,
chlorine dioxide concentration was 0.40 mg L1) (Hoehn et al.,
and 11e150 mg L1 in the desalination plants, reservoirs, and
2003). However, in Quebec, the maximum level of chlorite was
mosques, respectively. The concentrations of chlorate in the mos-
1.1 mg L1 (Korn et al., 2002), which is high compared to the
que samples were lower than the concentrations of chlorate in the
ndings from this study. The chlorite concentrations in all the
desalinated plant and reservoir samples, as shown in Fig. 2A. This
samples were less than 1000 and 700 mg L1, which are the
could be attributed to the reaction of chlorate with organic matter
maximum values regulated by the USEPA (1998 and updated in
that can occur with water from the DPs before distribution to the
2006) and WHO (WHO, 2004, GSO 149/2009 and KM (KM, 2012),
network, and this type of reaction can lead to decreasing chlorate
respectively. The EU guidelines are more stringent than guidelines
concentrations. The chlorate concentrations in all the water sam-
for the KM and WHO since the maximum allowable chlorite ion
ples were less than 700 mg L1, which is the maximum value
concentration in drinking water in Italy is 200 mg L1 (Linder et al.,
regulated by the US-EPA (USEPA, 1998), WHO (WHO, 2004), and
2006).
KM (KM, 2012).
When ClO2 reacts and decays, chlorite and chlorate are formed
(Yang et al., 2013). Previous studies have shown that approximately
3.1.3. Chlorite
60% of the applied ClO2 will eventually form chlorite and approx-
Fig. 2 shows the median, maximum and minimum values of
imately 8% will form chlorate (Yang et al., 2013). Volk et al. (2002)
chlorite and chlorate. Fig. 3B displays the overall median value for
showed that the median chlorite levels were 0.68 and 0.69 mg L1
chlorite. The chlorite concentrations in the samples varied from 13
in the plant efuent and distribution system, respectively. The
to 440 mg L1 with mean values varying from 13 to 230 mg L1,
chlorite levels were below the recommended level of 1.0 mg L1 in
78e320 mg L1, and 85e440 mg L1 in the desalination plants,
 F. Al-Otoum et al. / Chemosphere 164 (2016) 649e656 653

Fig. 3. The overall median of A. ClO2, B. chlorite, and C. chlorate at the desalination plants, reservoirs, and mosques. N 294, where N is the total number of samples.
654 F. Al-Otoum et al. / Chemosphere 164 (2016) 649e656

Table 2 are not related to ClO2 reactions and decay but to inefcient ClO2
Maximum, minimum, and average values for THMs (mg L1) from different water production.
sources.
Fig. 3B illustrates the increase in the chlorite levels within the
THMs Source Average Max. Min. distribution system compared to other sources as a result of ClO2
Bromoform DPs 21 73 4 decay. The median level detected at the desalination plant was
R 15 73 2 approximately 79 mg L1, and it increased to 160 mg L1 at the
M 15 56 1 reservoir outlets. Another increase in the chlorite level was
Chloroform DPs 0 5 0
observed at the customer points of use (mosques) to give levels
R 1 5 0
M 1 5 0 closer to 250 mg L1. A 218% increase in the chlorite level was
Bromodichloromethane DPs 0 3 0 observed over the entire distribution system. The levels detected at
R 1 5 0 the customer points of use were less than the maximum value
M 3 26 0
required by both WHO and the KM (700 mg L1). If the ClO2 dosage
Dichlorobromomethane DPs 1 3 0
R 1 2 0
was increased at the desalination plants to 0.20 mg L1 (as rec-
M 1 2 0 ommended in the ClO2 charts), the chlorite levels would still be
Overall 5 73 0 compliant.
N 294, where N is the total number of samples.

the United States (USEPA, 1998). Volk's study showed that the
maximum daily average chlorite concentration measured in the
distribution system was approximately 0.9 mg L1, and the highest
overall measurement of 1.0 mg L1 was taken at the water treat-
ment plant. That level is not compliant with the regulations set by
WHO and KM. During the study period, the highest ClO2 residual
concentration was 0.38 mg L1 at the Ras Girtas DP. This value could
be reduced over time, and the associated chlorite concentration
could also be lowered. This observation could be related to the fact
that the distribution system was too large, which can lead to drastic
changes in the disinfectant residual. The same trend was observed
for a larger system in Laval (city in North Italy) (Lafrance et al., 1992)
where ClO2 disappeared rapidly in the distribution network. This is
in good agreement with the ndings in the current study, and only
residual chlorite was found in the extremities of the systems. In that
study, the chlorite disappeared entirely at the dead end points
(small pipes with low ow) (Lafrance et al., 1992), but in our study,
the average chlorite level at the end points was 250 mg L1. Past
surveys of water treated with ClO2 have often showed high chlorate
concentrations (Gordon et al., 1995). High chlorate concentrations
3.1.4. THMs
Table 2 shows the formation potentials for the 294 water sam-
ples from all sampling points. The average value was 5 mg L1, and
the maximum and minimum measured values were 77 and
0 mg L1, respectively. All THM species (CHBr3, CHCl3, CHCl2Br, and
CHClBr2) were detected in the current study; however, CHBr3 was
the most abundant compound. This result can be explained using
the ndings. They revealed that CHBr3 formed in water containing
bromide ions because ClO2 can oxidize bromide ions to hypobro-
mous acid, which subsequently reacts with humic acid. Bromide
ions are good precursors for the formation of brominated THMs.
Under certain conditions and because of the presence of bromide in
raw materials, bromate may also form in concentrated hypochlorite
solutions used to disinfect drinking water. The application of
ozonation and UV light can increase the formation of bromoform.
The formation of bromomethanes is linked to the oxidation of
bromine into hypobromous acid.
In the current study, all the water samples showed values within
the acceptable range for THMs. The replacement of chlorine with
ClO2 in the distribution systems corresponded to an 81% reduction
in the THM concentrations (Volk et al., 2002).

Table 3
Different types of correlations between different variables.

Factors Water temp. C pH Br- mg L1 ClO2 mg L1 Chlorate mg L1 CHBr3 mg L1 THMs Chlorite mg L1

Water Temperature  C Pearson correlation 1.00 0.07 0.24** 0.25** 0.23** 0.10 0.11 0.26**
Sig. (2-tailed) e 0.21 0.00 0.00 0.00 0.08 0.07 0.00
N 294 294 293 294 294 294 294 294
pH Pearson Correlation 0.07 1.00 0.07 0.34** 0.16** 0.08 0.07 0.27**
Sig. (2-tailed) 0.21 e 0.21 0.00 0.01 0.18 0.23 0.00
N 294 294 293 294 294 294 294 294
Bromide mg L1 Pearson correlation 0.24** 0.07 1 0.37** 0.30** 0.25** 0.24** 0.51**
Sig. (2-tailed) 0.00 0.21 e 0.00 0.00 0.00 0.00 0.00
N 293 293 293 293 293 293 293 293
Chlorine dioxide mg L1 Pearson correlation 0.25** 0.34** 0.37** 1 0.22** 0.02 0.05 0.40**
Sig. (2-tailed) 0.00 0.00 0.00 e 0.01 0.678 0.40 0.00
N 294 294 293 294 294 294 294 294
Chlorate mg L1 Pearson correlation 0.23** 0.16** 0.30** 0.22** 1 0.13* 0.14* 0.56**
Sig. (2-tailed) 0.000 0.01 0.00 0.01 e 0.03 0.01 0.00
N 294 294 293 294 294 294 294 294
Bromoform CHBr3 mg L1 Pearson correlation 0.10 0.08 0.25** 0.02 0.13* 1 0.99** 0.35**
Sig. (2-tailed) 0.08 0.18 0.00 0.68 0.03 e 0.00 0.00
N 294 294 293 294 294 294 294 294
THMs mg L1 Pearson correlation 0.11 0.07 0.24** 0.05 0.14* 0.99** 1 0.35**
Sig. (2-tailed) 0.07 0.23 0.00 0.40 0.01 0.00 e 0.00
N 294 294 293 294 294 294 294 294
Chlorite mg L1 Pearson correlation 0.26** 0.273** 0.51** 0.40** 0.56** 0.35** 0.35** 1
Sig. (2-tailed) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 e
N 294 294 293 294 294 294 294 294

*Correlation is signicant at 0.01.

**
Correlation is signicant at the 0.01 level (2-tailed).
 F. Al-Otoum et al. / Chemosphere 164 (2016) 649e656 655

300 0.20 A 40%. (ii) A positive relationship was found between ClO2 and
0.17 chlorate ions, and the correlation coefcient was 0.165 with a p-
250
Chlorite concentarion g l-1

250

Chlorine dioxide in mg L-1

0.15 value of 0.005. The relationship is illustrated in Fig. 4. This can be
200 0.12
attributed to the normal decay process of chlorine dioxide, as re-
150 160 0.10
ported in the literature 10e20% of chlorine dioxide will be oxidized
100
79 0.05 to chlorate. (iii) A negative relationship was found between ClO2
50 0.04
and different water sources (DPs, reservoirs and mosques), and the
0 0.00
correlation coefcient was 0.26 with a p-value 0.00. (iv) A weak
Average concentra on mg L-1
positive correlation was observed between the pH and chlorite
Chlorite Chlorine Dioxide ions, and the correlation coefcient was 0.27 with a p-value of 0.00.
(v) Another positive relationship was found between ClO2 and
140 0.17 0.18 chlorate ions, and the correlation coefcient was 0.165 with a p-
B
value of 0.005. The relationship is illustrated in Fig. 4. (vi) There was
Chlorate concentarion g l-1

0.16

Chlorine dioxide in mg L-1

120
120 0.14 a positive correlation between ClO2 and water temperature, and the
100 0.12
0.12 correlation coefcient was 0.25 with a p-value of 0.00. This result
80 0.10
84 supports our nding that CHBr3 was the most prominent THM
60 0.08
49 0.06
species. (vii) A negative relationship was found between ClO2 and
40
0.04 0.04 pH, and the correlation coefcient was 0.34 and the p-value was
20 0.02 0.00. (viii) A positive relationship between chlorite and the water
0 0.00 source was found with a correlation coefcient of 0.39 and a p-
Average concentra on mg L-1 value of 0.00. The relationship among all the factors (water tem-
Chlorate Chlorine Dioxide
perature, pH, turbidity, conductivity, ClO2 concentration, chlorite,
chlorate, and bromoform concentration) was also determined using
Fig. 4. Chlorine dioxide versus (A) chlorite and (B) chlorate correlation. the ANOVA test (Table 4). A comparison of the various time in-
tervals had a meaningful difference (P < 0.05) for the ClO2 con-
centration, which indicated that the ClO2 concentration is an
3.2. Statistical analysis and correlation
inuential factor in the disinfection process.

In the present study, the Statistical Package for the Social Sci-
ences (SPSS) version 22 (IBM, Armonk, NY) was used for the data 4. Conclusion
analysis, and Excel was used for data illustration. The level of sta-
tistical signicance for all the statistical tests was set at p 0.01. Based on on-site measurements and lab analyses, the following
The one way Analysis of Variance (ANOVA) test presented in Table 3 conclusions can be drawn: (i) the ClO2 level ranged from 0.38 to less
shows that the water temperature, pH, chlorine dioxide, chlorate, than 0.02 mg L1 (the device detection limit), which indicated that
chlorite, and bromoform all have signicant differences with p- the concentration of ClO2 can decrease during its transportation
values < 0.01. However, the conductivity and turbidity did not show through the water distribution network. The median concentra-
signicant differences, and the p-values were 0.049 and 0.315, tions of ClO2 were 0.17, 0.12, and 0.04 mg L1 in the desalination
respectively. plants, reservoirs, and mosques, respectively. A few samples had a
The different types of applicable correlations were investigated lower ClO2 concentration than the recommended value set by the
using Pearson's correlation coefcients, and they are summarized KM, which is 0.05e0.70 mg L1. This can be attributed to the normal
in Table 3. Based on the obtained results, the following relation- decay processes of ClO2 as a result of auto-decomposition reactions
ships were determined: (i) A negative relationship was observed and reactions with organic and inorganic compounds, such as
between ClO2 and chlorite, this relationship was statistically sig- biolms, pipe materials, corrosion products, and slime formation.
nicant as the correlation coefcient was 0.360 with a p- The decrease in concentration can also be attributed to prolonged
value < 0.01. This can be attributed to the auto-decomposition of stagnation of water in the various stages of storage and distribution
chlorine dioxide to form chlorite. Decreasing chlorine dioxide in- through the network. (ii) The chlorite concentrations in the water
dicates the formation of chlorite because 76% of chlorine dioxide samples from the mosques were higher than the chlorite concen-
will form chlorite (Collivignarelli and Sorlini, 2004). This relation- trations at the desalination plants and reservoirs. (iii) The chlorate
ship is illustrated in Fig. 4, and it is in good agreement with other concentrations in the mosque water samples were lower than the
studies where the ClO2 consumed by an oxidation reaction was chlorate concentrations at the desalination plants and reservoirs.
converted to chlorite. In these studies, approximately 50%e70% of (iv) The THM median value was 5 mg L1, and the maximum and
the ClO2 concentration, depending on factors such as the oxidant minimum values reached 77 and 0 mg L1, respectively. All species
demand, temperature, competitive side reactions with other of THMs (CHBr3, CHCl3, CHCl2Br, and CHClBr2) were detected dur-
chemicals or processes, and generator efciency (Werdehoff and ing analysis, and CHBr3 was the most abundant compound. (v)
Singer, 1987; Gates, 1998) was converted to chlorite. Our study ANOVA was used to interpret the signicance between the pa-
showed that the percentage of chlorite formed was approximately rameters, and the results showed that the pH, ClO2, chlorate,

Table 4
Analysis of variance for the measured variables.

S.O.V. D.F. Means of squares

Water temperature pH Turbidity NFU Conductivity ms cm1 ClO2 mg L1 Chlorate mg L1 Chlorite mg L1 Bromoform mg L1
ns ns
Between groups 2 874** 1.49** 0.137 6990 0.416** 140,182** 658,224** 1450**
Within groups 291 21.0 0.060 0.118 2292 0.003 4202 5297 180
**
Signicant differences at 0.01; ns - not signicant.
656 F. Al-Otoum et al. / Chemosphere 164 (2016) 649e656

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