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Environ Monit Assess


DOI 10.1007/s10661-012-3032-z

Quality assessment of various bottled waters marketed


in Saudi Arabia
Abdulrasoul M. Al-Omran &
Salem E. El-Maghraby & Anwar A. Aly &
Mohammed I. Al-Wabel & Zafer A. Al-Asmari &
Mahmoud E. Nadeem

Received: 5 June 2012 / Accepted: 27 November 2012


# Springer Science+Business Media Dordrecht 2012

Abstract This study focuses on the chemical analysis


of the available brands of domestic bottled water in
Riyadh City, Saudi Arabia. The distribution of the
chemical constituents (major, minor, and trace elements)
is determined and compared with the chemical content
labeled on the bottles and with drinking water standards
of Saudi Arabian, World Health Organization, and U.S.
Environmental Protection Agency. The obtained results
indicated that except for fluoride and bromate, the concentrations of dissolved salts, soluble cations and
anions, nitrate, and trace elements of most bottled waters
on sale were within the permissible limits set by standards used. On the other hand, the comparison between
determined and reported label values recorded a substantial variation in some parameter values. Results
indicated that more than 18 % of the sampled bottled
waters exceeded the allowable limits for drinking water.
Generated Piper diagrams revealed that the majority of
investigated waters were sodium chloridesulfate type;
however, the hydrochemical modeling indicated that all
A. M. Al-Omran (*) : S. E. El-Maghraby : A. A. Aly :
M. I. Al-Wabel : Z. A. Al-Asmari : M. E. Nadeem
Soil Science Department, King Saud University,
Riyadh, Saudi Arabia
e-mail: rasoul@ksu.edu.sa
A. M. Al-Omran
e-mail: anwarsiwa@yahoo.com
A. A. Aly
Soil and Water Science Department, Alexandria University,
Alexandria, Egypt

water samples were undersaturated for anhydrite, gypsum, and halite.


Keywords Bottled waters . Chemical composition .
Bromate . Hydrochemical modeling . Saudi Arabia

Introduction
Water has always been essential to survival of all organisms. Water makes up 62 to 70 % of an adult's total body
weight; without it in a regular range, the body's survival
time is limited to a matter of days (Ogbonmwan 2011).
Drinking water is water pure enough to be consumed
with low immediate or long-term risks. In many parts of
the world, humans have inadequate access to drinking
water and use sources contaminated with disease vectors, pathogens, or unacceptable levels of toxins or
suspended solids (William and Frank 2000). Using such
water leads to widespread acute and chronic illnesses
and is a major cause of death and misery in many
countries. For these reasons, the reduction of waterborne
diseases is considered as a main public health goal in
developing countries. Drinking water with different
qualities is now bottled and sold for public consumption
throughout the world. The periodical analysis of the
drinking bottled water is essential to ensure its safety
(U.S. Environmental Protection Agency (USEPA)
2007). In this respect, Guler (2007) found that a significant number of bottled water brands in Turkey contain
Na, Cl, SO4, F, polycyclic aromatic hydrocarbons, and

Environ Monit Assess

several heavy metals above the maximum concentration


allowed for bottled waters under Turkish legislation and
other international organizations. Also, Baba et al.
(2008) concluded that the Turkish bottled water varied
in chemical composition and the majority of bottled
waters exceeded the pH limit under Turkish drinking
water standards. Guler and Alpaslan (2009) revealed that
the analysis of 70 samples of bottled water collected
from Turkish market showed that the concentration of
arsenic (As) in one brand was three times more than the
standard value set by European Community Council (EC
1998) and the guideline values recommended by World
Health Organization (WHO 2006). On the other hand,
Batarseh (2006) concluded that the concentration levels
of various physiochemical parameters in potable water
on sale in Jordan did not exceed the international guidelines for drinking water. In Saudi Arabia, Khan and
Chohan (2010) pointed out that the mean level of F,
Ca, and pH in bottled water was significantly higher than
the reported on the labels. Since bromate is classified as a
potential carcinogen, various studies have focused on
studying its origin, formation, and control in drinking
water. Von Gunten (2003) concluded that the main byproduct formation in the presence of bromide during the
ozonation of drinking water is bromate. Moreover, Von
Gunten et al. (2006) summarized a procedure for evaluating the use of reduced ozone doses while implementing
an additional UV disinfection step for an actual drinking
water treatment plant in Paris area (France) and concluded that at low ozone dose of 0.5 mgL1, bromate formation could be kept below 0.4 gL1. Saudi Arabian
groundwater is coincidentally high in bromide content,
and the potential of forming bromate during the
treatment of such water is relatively high. Bassam
and Abdulrazaq (2011) mentioned that the formation of bromate is of a great concern whenever
ozone-based technologies are used for treating high
bromide-containing water. Othman et al. (2010)
studied bromate on 50 marketed bottled drinking
waters in Saudi Arabia and concluded that 30 % of the
studied samples were acceptable as USEPA standard
(10 gL1), and 40 % of the samples were acceptable
as Saudi Arabia standard (25 gL1).
The objectives of this study were to: compare the
accuracy of the chemical contents and concentrations
mentioned on the manufacturer labels of different
bottled drinking water in the Kingdom of Saudi Arabia
(KSA) with laboratory-measured values; compare
these measured values with drinking water standards

of Kingdom of Saudi Arabian Standards Organization


(2003), WHO (2011), and USEPA (2007); and finally
classify the hydrochemical characterization of studied
waters.

Material and methods


Study area
The KSA is situated in southwest Asia between latitude
1632 North and longitude 3565 East. The total area
of the kingdom is about 2.25 million km2 which represents about 80 % of the area of the Arabian Peninsula
(Mohammed et al. 2011). Groundwater is considered
the most precious water sources for drinking and irrigation. Almost all groundwater resources are found in
eight large tectonic basins of sedimentary rocks bordering Arabian Shield (Vincent 2008). The Arabian shelf
includes deep sedimentary aquifers which are formed
mostly of limestone and sandstone that overlay the
basement rock formation known as Arabian Shield and
covers about two third of the KSA (Ministry of
Agriculture and Water 1984). Apart from shallow aquifers associated with the harraat and wadi fills of the
shield, all major aquifers are associated with the sedimentary cover rocks (Vincent 2008). Hydrogeological
investigations in the kingdom show that groundwater is
stored in more than 20 primary and secondary aquifers.
Edgell (1990) classifies the aquifers into two groups: (a)
primary aquifers, including quartz sandstones, conglomerates and some limestone, and quaternary alluvium; (b)
secondary aquifers, primarily in limestone where later
diagenetic changes and sometimes karstification have
increased the original porosity.
The most important aquifers in the kingdom summarized by Vincent (2008) were:

Wasia-Biyadh aquifer
The Wasia-Biyadh is a vast aquifer of lower
and middle Cretaceous sandstones located in the
northern interior Homocline and the Widyan Basin margin. The aquifer supplies water to Riyadh
with total dissolved solids (TDS) of 555 mgL1.
Saq Sandstone aquifer
The Saq sandstone is early Ordovician age and
forms the major aquifer in northern Saudi Arabia,
especially in the Tabuk Basin. Water from this
aquifer is generally of good quality.

Environ Monit Assess

Wajid Sandstone aquifer


The Wajid Sandstone aquifer is the lower Ordovician Wajid sandstone. Water quality is not ideal
for drinking, but is generally suitable for irrigation
and livestock.
Tabuk aquifers
The Tabuk aquifers are the lower, middle, and
upper Tabuk Ordovician quartz sandstone aquifers
of the Tabuk Basin and interior Homocline. There
has been considerable over-exploitation of this aquifer and a large cone of depression has developed.
Umm Er Radhuma aquifers
The Paleocene-Lower Eocene Umm Er Radhuma aquifer system is one of the most extensive
and important aquifers in the eastern region. It
extends almost all of the Rub' al Khali. Water quality declines towards the gulf due to the presence of
anhydrite in adjacent formations.
Minjur-Dhruma aquifer
The upper TriassicJurassic Minjur-Dhruma
sandstone aquifer is extended from Wadi Birk
south to the Rub' al Khali.
Neogene aquifer
The Neogene aquifer is the collective name for
aquifers developed in Mio-Pliocene formations in
the eastern region. The Neogene aquifer is an
important source of water near the gulf.

The groundwater in Saudi Arabia is classified into


six water types, the most dominant were Ca(HCO3)2
or NaHCO3 and NaCI water types. The Na2SO4 water
type is restricted to the basalt and paleovalley areas
(Alawi and Abdulrazzak 1993; Mohammed et al.
2011; Al-Omran et al. 2005).
Chemical analysis
Fifty-two different brands of bottled drinking water
locally produced from KSA well waters (Table 1 and
Fig. 1) were collected during the first quarter of the
year 2011 from the supermarkets and food stores in
Riyadh City, Saudi Arabia. All bottles were stored in a
dark place in their original closed plastic containers at
room temperature. The samples were analyzed for EC,
pH, Ca2+, Mg2+, Na+, K+, Cl, SO42, NO22, NO3,
and F according to Matiti (2004). The bromate
(BrO3) in the bottled drinking water has been investigated using liquid chromatography (ICS-MS 3000 liquid Chromatography System). Also, the concentration

Table 1 The nine areas of Saudi Arabia where sampling of 52


different bottled drinking water brands from various commercial
establishments was carried out
Bottled water sample number

Location of wells used for


bottling drinking water

1, 2, 3, 4, 5, 6, 14, 20, 23, 24,


28, 38, 46, 47, 48, 50, and 52
31, 43, 44, and 34

Riyadh and surrounding

19 and 41

Najran

8, 9, 30, and 40

Abha and Jizan

Kharj and Al-Ahsa

7, 10, and 51

Mecca

11, 13, 15, 16, 21, 22, 26, and 36

Jeddah

45 and 49

Tabuk and Al-Ula

12, 17, 18, 25, 39, and 42

Qassem

29, 27, 32,33, 35, and 37

Hafar al Batin, Dammam,


and Kobar

of As, B, Be, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Se, Sr,
Ti, V, and Zn in the collected bottled water was determined using ICP-Perkin Elmer Model 4300DV. The
hydrochemical characteristics of the mineral water were
evaluated by Piper diagram (Table 1 and Fig. 1).
Geochemical modeling
Interactions between water and surrounding rocks and
soil are considered to be the main processes controlling
the observed chemical characteristics. The deviation of
water from equilibrium with respect to dissolved minerals is quantitatively described by saturation index (SI).
The SI of a mineral is obtained from the following
formula:
SI log IAP=kt

where IAP is ion activity product of dissociated chemical


species in solution and kt is the equilibrium solubility
product of the chemical involved (Alexakis 2011). The
hydrogeochemical equilibrium model, PHREEQC model (Parkhurst and Appelo 1999), was used to calculate
the SI of water with respect to the main mineral phases.

Results and discussions


Bottled water quality comparison and assessment
The average of some laboratory-determined parameter
values and those labeled on the bottles is almost

Environ Monit Assess


Fig. 1 Geological map of
Arabian Peninsula showing
locations of wells used for
bottling drinking water in
Saudi Arabia (map source:
Mohammed et al. 2011)

different for most of bottled water samples (Table 2


and Fig. 2). The average value of bromate determined
in the laboratory was two times more than the average
value labeled on bottles; however, the maximum value
determined in the laboratory dramatically is ten times
more than the value labeled on bottles. Moreover,
Table 3 indicates that the maximum concentrations
of As, B, Se, NO3, F, and BrO3 have exceeded
the permissible limits under KSA, WHO, and USEPA
standards. On the other hand, the average value of these

contaminants was within the acceptable limits sets by


standards used.
The concentrations of BrO3 (Table 3) were so
much higher than acceptable limits (10 gL1) set
either by KSA, WHO, or USEPA standards. Analyses
of bromate indicated that more than 18 % of the
studied water samples exceeded the permissible limits
under standards used; this is due to the high bromide
concentrations in the original source of groundwater
(Bassam and Abdulrazaq 2011). The bromate is a

Environ Monit Assess


Table 2 Comparison of the descriptive statistics of the laboratory analyses of drinking bottled water with those labeled on the
bottles (n=52)
Property

Unit

Determined

Labeled in bottles

Mean

Min

pH

TDS

mg/L

126.098

Ca

mg/L

13.401

Mg

mg/L

3.912

Na

mg/L

7.480

Max

6.700

Mean

Min

Max

8.440

7.20

6.70

7.50

235.000

122.63

43.00

235.00

0.019

41.880

14.31

0.30

40.00

0.038

22.000

4.33

0.50

22.00

20.541

0.300

69.750

18.23

0.30

35.00

mg/L

1.370

0.018

13.400

1.62

0.10

13.40

CL

mg/L

32.483

0.090

88.000

26.25

2.60

88.00
120.00

43.00

HCO3

mg/L

34.720

1.300

135.217

32.88

1.30

SO4

mg/L

23.266

N.D.

90.466

21.91

N.D.

51.00

NNO3

mg/L

5.731

N.D.

35.718

3.40

N.D.

20.00

mg/L

1.040

0.050

BrO3

g/L

4.733

N.D.

5.000

0.89

0.05

5.00

111.600

1.76

N.D.

9.99

N.D. not detected

major by-product of bromide, and the level of bromate


formed during ozonation usually depends on the
amount of bromide found in the source of water, the
dosage of ozone, and the pH of water in addition to
some other factors. Control bromate formation is
therefore important whenever ozone-based technologies are used for drinking water processes (Bassam
and Abdulrazaq 2011; Kruithof 1998; Von Gunten et
al. 2006; Song et al. 1997; Kruithof et al. 2007). The
following equations summarize the bromate formation
from bromide in the ozonation process (Von Gunten
and Hoigne 1993; Song 1996; Minear and Amy
1996):

Direct/indirect:
O3
OH
disproportionation
O3
Br 
!HOBr =OBr ! OBr ! BrO
!BrO
2 
3

Indirect/direct:
OH
O3
disproportionation
O3
Br 
! Br 
! OBr ! BrO
! BrO
2 
3


Direct:
O3
O3
O3
! HOBr=OBr 
! BrO
! BrO
Br 
2 
3
Fluoride and nitrate were also found in high concentration in some of studied water samples. About 30
and 20 % of the samples fall over the acceptable limits

Fig. 2 Comparison of the determined parameters in laboratories and labeled in bottles of drinking water (n=52): a mean values, b
maximum values

Environ Monit Assess


Table 3 Descriptive statistics of chemical composition of drinking bottled water and permissible limits (n=52)
Property

Unit

Mean

Min

Max

SD

Permissible limits
KSA

WHO

USEPA

Nitrite

mg/L

0.005

N.D.

0.033

Bromide

mg/L

0.082

0.014

0.680

0.091

Al

mg/L

0.007

N.D.

0.145

0.2

0.2

As

mg/L

0.003

N.D.

0.033

0.01

0.01

0.01

mg/L

0.327

0.019

1.656

0.349

0.5

0.5

Ba

mg/L

0.004

N.D.

0.061

0.7

0.7

Be

mg/L

N.D.

N.D.

N.D

Cd

mg/L

N.D.

N.D.

N.D.

0.003

0.003

0.003

Co

mg/L

N.D.

N.D.

N.D.

Cr

mg/L

0.001

N.D.

0.009

0.05

0.05

0.1

Cu

mg/L

N.D.

N.D.

N.D.

1.3

Fe

mg/L

N.D.

N.D.

N.D.

0.3

0.3

0.3

Mn

mg/L

N.D.

N.D.

N.D.

0.1

0.2

0.05

Mo

mg/L

0.002

N.D.

0.009

0.07

Ni

mg/L

N.D.

N.D.

N.D.

0.02

Pb

mg/L

0.008

N.D.

0.024

0.01

0.01

Se

mg/L

0.008

N.D.

0.086

0.01

0.01

Sr

mg/L

0.105

N.D.

0.382

Ti

mg/L

N.D.

N.D.

N.D.

mg/L

0.000

N.D.

0.010

Zn

mg/L

0.001

N.D.

0.029

pH

7.480

6.700

8.440

0.385

6.58.5

6.58.5

6.58.5

TDS

mg/L

126.098

43.000

235.000

30.208

500

600

755

Ca

mg/L

13.401

0.019

41.880

8.358

Mg

mg/L

3.912

0.038

22.000

3.743

Na

mg/L

20.541

0.300

69.750

9.925

100

200

mg/L

1.370

0.018

13.400

1.744

Cl

mg/L

32.483

0.090

88.000

17.596

150

250

250

HCO3

mg/L

34.720

1.300

135.217

21.410

SO4

mg/L

23.266

N.D.

90.466

16.319

150

400

250

NNO3

mg/L

5.731

N.D.

35.718

6.511

10

10

10

mg/L

1.040

0.050

5.000

0.550

1.5

1.5

BrO3

g/L

4.733

N.D.

111.600

2.451

10

10

10

N.D. not detected

of KSA, WHO, and USEPA standards for F and


NO3, respectively. On the other hand, the TDS, pH,
and maximum concentrations of Be, Cr, Cu, Fe, Mn,
Mo, and Zn in the studied bottled water were found to
be in the acceptable limits with respect to the KSA,
WHO, and USEPA standards (Alfadul and Khan
2011). Some attention should be paid to As, B, and
Se since measured concentration in less than 5 % of

samples was approximately more than the standard


value (Fig. 2 and Tables 2 and 3).
Hydrochemical facies
The chemical data of the water samples are plotted on
a Piper trilinear diagram (Piper 1944; Fig. 3). This
diagram provides a convenient method to classify

Environ Monit Assess


Fig. 3 Piper trilinear diagram showing the major
ionic composition of the
sampled mineral water

and compare bottled water types collected from groundwater, based on the ionic composition of different water
samples (Semerjian 2011; Baba et al., 2008). This diagram reveals that there are different types of mineral
water in Saudi Arabia. Four main mineral water types
have been identified on the basis of the major ion concentrations as in Aly and Benaabidate (2010) and Baba
et al. (2008). The first is rich in sodium chloridesulfate
water types which correspond to 66.7 % of water samples. The second is rich in calcium sulfatechloride
water type corresponding to 15.7 % of water samples.
The third is rich in sodium bicarbonate water type
corresponding to 15.7 % of water samples. The fourth
is rich calciummagnesium bicarbonate water type
corresponding to 1.9 % of water samples. In the study
area, the type of water that predominates is NaCl, which
is mainly due to the geology of the area which comprises
halite (Fig. 3).
Geochemical modeling
The SI is the form most commonly used for groundwater. Water is in equilibrium with a mineral when the
SI of this mineral is equal to 0. It is undersaturated if
this index is below 0 and it is oversaturated when the
SI is above 0. However, these factors result in an

inaccuracy in the calculation of the saturation index:


the inaccuracy on the pH measurements due to measuring devices, the variation of this parameter when
the water flows toward the surface, and the error that
could occur during chemical analysis. Therefore, it is
recommended to consider that the saturation is
obtained in a wider area such that 1<SI<+1 (Daoud
1995).
Figure 4 shows the mineral SI of water calculated
by the PHREEQC model (Alexakis 2011). The minerals which are distinguished by the model were:
anhydrite (CaSO 4 ), aragonite (CaCO 3 ), calcite
(CaCO3), dolomite (CaMg(CO3)2), fluorite (CaF2),
gypsum (CaSO42H2O), and halite (NaCl). The use
of the SI showed that almost all studied waters are
undersaturated with respect to the previous minerals;
consequently, the minerals tend to dissolve (Alexakis
2011; Aly et al. 2011). Therefore, there is a possibility
for further Ca2+, Mg2+, Na+, CO32, F, SO42, and
Cl concentration increase in the studied water samples due to the dissolution of anhydrite, aragonite,
calcite, dolomite, fluorite, gypsum, and halite. With
the exception of sample 37 which was oversaturated
for dolomite, samples 5, 17, 20, 30, 33, 34, 37, and 38
were saturated for aragonite, samples 5, 12, 17, 18, 19,
20, 21, 30, 31, 32, 33, 34, 35, 37, and 38 were

Environ Monit Assess


Fig. 4 The mineral saturation indices (SI) of studied
water samples

saturated for calcite, and samples 5 and 33 were saturated for dolomite (Fig. 4).

Conclusion
Many people prefer to use bottle water than tap water
for drinking. However, not all bottled waters are of
high qualities. Analysis of 52 bottled mineral waters in
Saudi Arabia shows considerable difference between
the laboratory-determined values of some parameter
and the respective value labeled on the bottles. Eighteen percent of studied water samples indicate that the
concentration of bromate exceeded the allowable limits according to the KSA, WHO, and USEPA Standards (bromate 10 gL1). On the other hand, most
collected waters were within the permissible limits for

most parameters determined. Thus, this study recommends that in bottled drinking water treated by ozone,
bromate should be tested to identify the suitability of
bottled water for drinking. The hydrochemical analysis shows that the studied water samples corresponded
mainly to sodium chloridesulfate water types which
are mainly due to the geology of the study area comprising halite. The geochemical modeling shows that
all water samples were undersaturated with respect to
anhydrite, gypsum, and halite; however, some samples
were saturated for calcite, dolomite, and aragonite, and
only two samples were oversaturated for dolomite.
Acknowledgments The authors wish to thank King Saud
University, Deanship of Scientific Research, College of Food
and Agriculture Science, Research Center for supporting the
research work

Environ Monit Assess

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