Arabian Journal of Chemistry (2011) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Assessment of the levels of some heavy metals in water

in Alahsa Oasis farms, Saudi Arabia, with analysis
by atomic absorption spectrophotometry
Fahad N. Assubaie *

Department of Chemistry, College of Science, King Faisal University, P.O. Box 400, Hofuf 31982, Saudi Arabia

Received 12 May 2011; accepted 20 August 2011

KEYWORDS Abstract For the first time, the levels of some heavy metals in water in Alahsa farms, Saudi Arabia
Heavy metals; were examined. Three types of water were analyzed including groundwater, mixed water and waste-
Groundwater; water. The total contents of Mn, Fe, Cu, Zn, Cd and Pb were determined using graphite-furnace
Irrigation water; atomic absorption spectrophotometry. The results obtained were verified through the analysis of
Wastewater a certified reference material, the results of which are in good agreement with the certified consensus
values. As recommended by the Food and Agriculture Organization, the level of heavy metals in
groundwater and mixed water have been found to be suitable for irrigation purpose. However,
the occurrence of some heavy metals that discharged directly from man-made activities without
treatment could result in some environmental problems in the future. On the other hand, the spatial
distribution of Mn and Fe has been found to increase from southeast to northwest.
ª 2011 King Saud University. Production and hosting by Elsevier B.V. All rights reserved.

1. Introduction environments, such as water, soil, air, etc. (Morrison et al.,

1990; Dawson and Macklin, 1998; Ekpo and Ibok, 1998;
The accelerated industrialization process in combination with Hassanzadeh et al., 2011; Mandour and Azab, 2011). For its
rapid population growth and agricultural activities has multipurpose usage, persistence in the environment, bioaccu-
brought the risk of increasing the pollution index in natural mulation and high toxicity, heavy metals are considered as
one of the most serious pollutants in the environment. Heavy
* Fax: +966 3 5886 437. metals are involved in various industrial processes, agricultural
E-mail address: [email protected] activities, domestic waste and vehicles emission. On the other
hand, heavy metals that originated from anthropogenic
1878-5352 ª 2011 King Saud University. Production and hosting by sources could be found in all components of the environment
Elsevier B.V. All rights reserved. (Idris et al., 2007; Idris, 2008; Ayni et al., 2011). Due to the
increasing anthropogenic contribution by heavy metals, more
Peer review under responsibility of King Saud University.
attention has been devoted to the investigation on those pollu-
doi:10.1016/j.arabjc.2011.08.018
tants in the environment (Edmund et al., 2003; Marengo et al.,
2006; Al-Hobaib et al., in press). Low efficiency in industrial
Production and hosting by Elsevier production processes (e.g. energy power plants, petrochemical
and chemical industries, etc.) and the unsuitable handling and

Please cite this article in press as: Assubaie, F.N. Assessment of the levels of some heavy metals in water in Alahsa Oasis farms, Saudi
Arabia, with analysis by atomic absorption spectrophotometry. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.08.018
2 F.N. Assubaie

management of industrial wastes have been recognized as pol- ng/mL levels especially when graphite furnace mode is used
lution sources, which are responsible for producing consider- for atomization. Furthermore, AAS enjoys good selectivity,
able load of heavy metals to the environment (Charlesworth which is due to the use of selective irradiation source.
and Lees, 1999; Hashisho and El-Fadel, 2004; Kuang et al., There is lack of studies on water quality in Alahsa Oasis
2004; Mireles et al., 2004; Banat et al., 2004; Namaghi et al., with the exception of a report on nitrate and nitrite levels in
2011). groundwater (Assubaie, 2004). Therefore, it has been pro-
Nearly, all types of water contain heavy metals, many of posed in the current study to achieve the following objec-
which result from the natural weathering of the earth’s surface tives. (i) To determine the levels of some heavy metals,
(Newcomb and Rimstidt, 2002). In addition, wastewater used namely Mn, Fe, Cu, Zn, Cd and Pb, in water samples using
for irrigation land, besides effluent from city sewage and indus- AAS-GF. Three types of samples including groundwater,
trial wastewater, could significantly affect water quality. Heavy mixed water and wastewater in Alahsa Oasis will be exam-
metals from anthropogenic activities could migrate or infiltrate ined. (ii) To examine the spatial distribution of the levels
into aquifers and interact with groundwater (Dawson and of Mn and Fe in the groundwater. (iii) To identify the
Macklin, 1998; Charlesworth and Lees, 1999). sources of heavy metals in groundwater and finally. (iv)
A number of heavy metals in irrigation water cause toxic To assess the irrigation water quality.
reaction in plants and, therefore, limit its use for irrigation.
Many reports that recommended maximum allowable levels of 2. Methodology
heavy metals in water used for irrigation for a short and long
time are available elsewhere (Todd, 1980; FAO, 1985; Rowe 2.1. Study area
and Abdel-Magid, 1995; Chapman, 1997). Rowe and Abdel-
Magid (1995) reported on the toxicity of some heavy metals to Al-Ahssa Oasis, Saudi Arabia, is one of the largest oases in
plants. For example, lead at high concentration can inhibit plant the world. It forms an ‘‘L’’ shape that covers 320 km2 with
cell growth. In addition, manganese is toxic to a number of crops about 150 m above the sea level. It is situated between
at few-tenths to a few mg/L, but usually only in acid soils. On the 25210 and 25370 northern latitude with 49330 and 49460
other hand, iron is not toxic to plants in aerated soils, but can eastern longitude. The area is located between the rock des-
contribute to soil acidification and loss of availability of essen- ert of As-Summan Plateau in the west and sand dunes cov-
tial phosphorus and molybdenum. Moreover, copper is toxic ering the plain as far as the east border. The climate belongs
to a number of plants at the levels from 0.1 to 1.0 mg/L in nutri- to the subtropical arid zone of the northern hemisphere.
ent solutions. Furthermore, zinc is toxic to many plants at This area includes two cities Al-Hofuf and Al-Mubaraz,
widely varying concentrations. Zinc toxicity is reduced at pH which are densely populated and industrialized, besides more
> 6.0 in fine textured or organic soils. Cadmium is also toxic than fifty villages (Fig. 1). The population increased from
to beans, beets and turnips at concentrations as low as 0.1 mg/ 741,000 in 1980 (Team of Staff, 1995) to 1,408,000 in
L in nutrient solutions. However, such heavy metals as manga- 2000. Now they are more than 2 millions (Central Depart-
nese, zinc and copper in trace levels are important for the phys- ment of Statistics Information, 2011).
iological functions of living tissue and regulate many
biochemical processes.
In Al-Ahssa Oasis, Saudi Arabia, the main source of water
or almost the single source is groundwater since rivers are not
available and rainfalls are scarce. The groundwater in that area
is distributed into three aquifers: (a) Neogen is the upper one
with a depth of up to 180 m, (b) Khobar is the middle one with
a depth ranging from 180 to 250 m and (c) Umm-Arradma is
the bottom one with a depth ranging from 280 to 240 m. Al-
Ahssa Oasis is the largest irrigated agricultural area in Saudi
Arabia. It includes date palm farms, the product of which is
the main popular nutritional food, besides many other farms
that produce vegetables and fruits.
The increasing demand of water for agricultural, industrial
and domestic purposes in the area under study leads to reuse
the wastewater. Wastewater includes emission of industries,
domestic sewage and drainage water (the unconsumed part
of the irrigation water). Unfortunately, wastewater is directly
mixed with groundwater at a ratio of 1–3, respectively, with
no treatment. Not least but more, most of industries in that
area emit wastes without management.
On the other hand, atomic absorption spectrophotometry
(AAS) is widely used as a routine technique for elemental anal-
ysis in water samples. In this issue, the extensive worldwide use
of AAS is attributed to its popularity, familiarity, ease of use
and cost-effectiveness comparing with other elemental tech-
niques such as inductively coupled plasma. Moreover, AAS
is a sensitive technique, which can detect elements in up to Figure 1 Saudi Arabia map showing Al-Hufuf city.

Please cite this article in press as: Assubaie, F.N. Assessment of the levels of some heavy metals in water in Alahsa Oasis farms, Saudi
Arabia, with analysis by atomic absorption spectrophotometry. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.08.018
Assessment of the levels of some heavy metals in water in Alahsa Oasis farms 3

2840 Table 1 Locations of samples collected in Alahssa Oasis’s

Districts.
2835 Sample number District name Longitude Latitude
1 Oyoon 2535.30 4934.50
2830 2 Oyoon 2535.30 4934.50
3 Oyoon 2535.30 4934.50
Distance from south to north (km)

4 Morah 2536.20 4934.80

2825
5 Morah 2536.00 4935.00
6 Morah 2537.20 4935.10
2820 7 Mitairfi 2528.30 4933.50
8 Mitairfi 2528.40 4933.90
9 Mitairfi 2528.40 4934.10
2815
10 Mubaraz 2524.20 4935.10
11 Mubaraz 2524.10 4935.20
2810 12 Mubaraz 2524.00 4935.30
13 Gara 2525.00 4940.70
14 Gara 2524.50 4940.60
2805 15 Gara 2524.60 4940.60
16 Gara 2524.60 4940.60
2800
17 Sowaidra 2522.20 4937.30
18 Sowaidra 2522.20 4937.20
19 Sowaidra 2522.10 4936.90
20 Sowaidra 2521.90 4937.20
355 360 365 370 375 380 385 390
21 Seefa 2522.50 4934.50
Distance from west to east (km) 22 Seefa 2522.50 4934.40
23 Seefa 2522.10 4934.40
Figure 2 Post plot of 22 groundwater samples collected from 24 Qatar Road 2519.60 4938.10
Al-Ahssa Oasis from south to north (y-axis) and from east to west 25 Qatar Road 2519.70 4938.10
(x-axis). 26 Qatar Road 2518.40 4938.60
27 Qatar Road 2519.00 4938.60
28 Gowaiba 2517.80 4937.50
2.2. Sampling
29 Gowaiba 2517.60 4937.50
30 Gowaiba 2601.70 5021.50
During August and September 2010, a total of thirty water
samples including groundwater, mixed water and wastewater
were collected from Al-Ahssa Oasis. The hypothesis governing was used to verify the accuracy of results obtained in the cur-
the campaign is to provide good spatial coverage in the studied rent study
area (Fig. 2). The latitude and longitude values for all locations Thousand milligrams per litre standard solutions of each of
are introduced in Table 1. The groundwater samples were col- Mn, Fe, Cu, Zn, Cd and Pb, which were prepared from nitrate
lected from the outlets of the wells after flushing water for 10– salts, were supplied from BDH (Poole, England) and used for
15 min in order to remove the stagnant water. Samples from calibration purpose. Mixed working standard solutions con-
the dug wells were collected using water sampler. Mixed water taining all metals were prepared by dilution in appropriate ways
and wastewater samples were collected using grab sampler at a using double distilled deionized water. Measurement for each
depth of 10 cm below the surface. solution was done in triplicate and the average was taken.
Tight-capped high quality polyethylene bottles were used
for sample storage. Before use, the bottles were washed by dis- 3. Results and discussion
tilled deionized water and rinsed overnight in 10% (v/v) nitric
acid. Samples were filtered through the Whatmann filter pa- The adopted reference material was used to verify the results
pers number 42. To prevent precipitation of metals and biolog- obtained for Mn, Fe, Cu, Zn, Cd and Pb. The certified and
ical growth, few drops of concentrated nitric acid were added analytical values along with the relative standard deviation
to samples to obtain pH around 2 (Kramer, 1994; Eaton, values for triplicate measurements, besides the recovery values,
1995). Thereafter, samples were immediately transported to are introduced in Table 2. It has been found that the recovery
the laboratory in iceboxes and stored at 4 C up to analysis. values are in the range of 87.5–104.3%. The analytical values
obtained are within the range of certified values. This outcome
2.3. Materials indicates good quality of results that are obtained in the cur-
rent study.
AA-6800 atomic absorption spectrophotometer (AAS) cou- The summary statistics of the concentrations of heavy met-
pled with GFA-EX7 graphite furnace atomizer and ASC- als in the groundwater, mixed water and wastewater are intro-
6100 auto sampler from Shimadzu (Koyoto, Japan) was uti- duced in Table 3. In general, the concentrations of Mn, Fe, Cu,
lized for heavy metal analysis. A high-density graphite tube Zn, Cd and Pb in groundwater are lower than those in mixed
was used for atomization. Normal single hollow cathode lamps water and wastewater.
were used for irradiation. Some studies that reported the allowable limits of the levels
Reference seawater from the National Research Council, of some heavy metals in irrigation water are available else-
Canada (NRCC, open ocean seawater standard NASS-5) where (Todd, 1980; FAO, 1985; Rowe and Abdel-Magid,

Please cite this article in press as: Assubaie, F.N. Assessment of the levels of some heavy metals in water in Alahsa Oasis farms, Saudi
Arabia, with analysis by atomic absorption spectrophotometry. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.08.018
4 F.N. Assubaie

Table 2 Results and statistics of the analysis of certified

reference material for heavy metals.
Metal Certified value (mg/L) Analytical value (mg/L) Recovery
Mn 0.919 ± 0.057 0.937 ± 0.035 101.9
Fe 0.207 ± 0.035 0.216 ± 0.014 104.3
Cu 0.297 ± 0.046 0.276 ± 0.011 92.9
Zn 0.102 ± 0.039 0.098 ± 0.009 96.1
Cd 0.023 ± 0.003 0.021 ± 0.002 91.3
Pb 0.008 ± 0.005 0.007 ± 0.001 87.5

1995; Chapman, 1997). As recommended by the Food and

Agriculture Organization (FAO) guidelines, the maximum
allowable limits of heavy metal concentrations in water used Figure 3 Maximum concentration of heavy metals in ground-
for irrigation are depicted in Fig. 3. The maximum concentra- water and mixed water in Al-Ahssa Oasis, besides the maximum
tions of those metals in groundwater and mixed water are de- allowable concentration for irrigation use as recommended by
picted as well. It has been found that the levels of Mn, Fe, Zn FAO.
and Pb in both groundwater and mixed water are suitable for
irrigation use. However, the levels of Cu and Cd in mixed water
are to some extent higher than the FAO’s allowable limits. High study. It could be concluded that the levels of Mn, Fe, Cu, Zn,
levels of those two metals could be attributed to the contribution Cd and Pb in the groundwater and mixed water in Alahsa Oasis
from anthropogenic sources. Industrial and/or domestic activi- are suitable for irrigation purpose. On the other side, low rela-
ties may be the source of contribution by Cu in the environment tive standard deviation (%RSD) of heavy metals in mixed water
of the study area. On the other hand, the source of Cd could be is an indicator of efficient mixing process. The wide range of the
from phosphate fertilizer that is usually used in that area. An- levels and the high level of %RSD of Fe, Cu, Zn, Cd and Pb in
other study conducted in Australia recommended ranges of wastewater reflect that some sites in the study area could be en-
some heavy metal concentrations that are fit for irrigation con- riched from man-made effluents.
sumption. Those ranges are 0.2–10.0, 0.2–10.0, 0.2–5.0, 2.0–5.0, In more detail, the average values of heavy metal concen-
0.01–0.05 and 2.0–5.0 mg/L, for Mn, Fe, Cu, Zn, Cd and Pb, trations in each aquifer were calculated. Fe recorded a higher
respectively. In the current study, it has been also found that level in the upper aquifer than that in the middle and bottom
the levels of all heavy metals are in the range of the Australian aquifers while Mn concentrations were distributed evenly in

Table 3 Summary statistics of the concentration (mg/L) of some heavy metals in groundwater, mixed water and wastewater in Al-
Ahssa Oasis.
Samples type Mn Fe Cu Zn Cd Pb
Groundwater (n = 22) Min
0.063 0.101 0.011 0.010 0.009 0.005
Max
0.151 0.145 0.017 0.018 0.013 0.008
Mean
0.120 0..28 0.014 0.014 0.010 0.007
%RSDa
0.024 0.026 0.00 0.004 0.003 0.003
Mixed water (n = 10) Min
0.091 0.214 0.217 0.051 0.031 0.031
Max
0.153 0.315 0.262 0.153 0.066 0.042
Mean
0.137 0.263 0.200 0.110 0.050 0.030
%RSD
0.030 0.041 0.018 0.002 0.008 0.006
Wastewater (n = 10) Min
0.090 0.133 0.192 0.093 0.052 0.034
Max
0.174 0.481 0.353 0.232 0.091 0.091
Mean
0.144 0.310 0.270 0.150 0.063 0.054
%RSD
0.020 0.203 0.181 0.002 0.006 0.006
a
Relative standard deviation.

Please cite this article in press as: Assubaie, F.N. Assessment of the levels of some heavy metals in water in Alahsa Oasis farms, Saudi
Arabia, with analysis by atomic absorption spectrophotometry. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.08.018
Assessment of the levels of some heavy metals in water in Alahsa Oasis farms 5

Figure 4 Spatial distribution of Mn content in groundwater of Al-Ahssa Oasis.

Figure 5 Spatial distribution of Fe content in groundwater of Al-Ahssa Oasis.

the three aquifers. With the exception of Mn, the levels of hea- nificant positive correlation was recorded for Mn with Fe, Mn
vy metals in wastewater are higher than those in mixed water with Cu, Fe with Cu and strong correlation between the con-
and groundwater. This may be an indicator of anthropogenic tents of Mn, Fe, Cu and Zn in the mixed and waste waters.
contribution by heavy metals in the environment of the study Insignificant negative correlation was recorded for Pb with
area (Todd, 1980). Hence, it could be proposed that Khobar other metals except Zn.
and Umm-Arradma aquifers are also free from Mn and Fe
contamination. To some extent, a slight increase in the level
of Fe in the groundwater of Neogen aquifer was recorded. This
may be attributed to a slight enrichment to this upper aquifer Table 4 Correlation coefficients of heavy metals concentra-
by man-made activities. Contamination of groundwater with tion in mixed and waste water in Al-Ahssa Oasis.
Fe is most probably due to multipurpose usage of Fe in indus- Pb Cd Zn Cu Fe Mn
trial and domestic activities.
Pb 1.00 – – – – –
On the other side, Figs. 4 and 5 depict the spatial distribu-
Cd 0.43 1.00 – – – –
tion of Mn and Fe in groundwater. The figures exhibit that the Zn 0.35 0.16 1.00 – – –
content of those metals increases from southeast to northwest. Cu 0.55 0.42 0.80 1.00 – –
Furthermore, the correlation coefficients between the concen- Fe 0.29 0.35 0.71 0.79 1.00 –
trations of the heavy metals in mixed water and wastewater Mn 0.43 0.53 0.26 0.72 0.57 1.00
were calculated and the results are introduced in Table 4. Sig-

Please cite this article in press as: Assubaie, F.N. Assessment of the levels of some heavy metals in water in Alahsa Oasis farms, Saudi
Arabia, with analysis by atomic absorption spectrophotometry. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.08.018
6 F.N. Assubaie

4. Conclusions Central Department of Statistics Information. 2011. Kingdom of

Saudi Arabia, <http://www.cdsi.gov.sa/>.
The current manuscript reports for the first time the investiga- Chapman, D. 1997. Water quality assessments, a guide to the use of
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Eaton, A.D., Clesceri, L.S., Greenberg, A.E., 1995. Standard Methods
 The levels of heavy metals under study in water used for for the Examination of Water and Wastewater, nineteenth ed.
irrigation purpose are below the maximum allowable limits American Public Health Association, Washington.
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are also within the ranges recommended by a previous Aus- Environ. 310, 25.
Ekpo, B.O., Ibok, U.J., 1998. Environ. Geochem. Health 20, 113.
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Please cite this article in press as: Assubaie, F.N. Assessment of the levels of some heavy metals in water in Alahsa Oasis farms, Saudi
Arabia, with analysis by atomic absorption spectrophotometry. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.08.018