Assessment of Groundwater Pollution with Heavy Metals in North West Bank/Palestine by ICP-MS

doi:10.4236/jep.2014.51007

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Journal of Environmental Protection, 2014, 5, 54-59

Published Online January 2014 (http://www.scirp.org/journal/jep)

http://dx.doi.org/10.4236/jep.2014.51007

OPEN ACCESS JEP

Assessment of Groundwater Pollution with Heavy Metals

in North West Bank/Palestine by ICP-MS

Husam Malassa1,2, Mohamad Hadidou n3, Mahmoud Al-Khatib4, Fuad Al-Rimawi4,

Mutaz Al-Quto b 1,2*

1Departmen t o f Earth an d En vironmental st ud ies, Facult y of Science an d Techno logy, Al-Qud s Universit y, East Jerusale m, Palest ine;

2Aquatic and Aquaculture Research Laboratory, Al-Quds University, East Jerusalem, Palestine; 3Palestinian Water Authority, Ra-

mallah, Palestine; 4Faculty of Science and Tech nology, Al-Quds University, East Jer usalem, Pal es tine.

Email: *qutob@planet.edu

Received November 21st , 2013; revised December 18th, 2013; accepted January 6th, 2014

which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. In accor-

ABSTRACT

Groundwater of North West Bank in Palestine was assessed for pollution with trace metals by ICP/MS. The

samples were analysed for their pH, electrical conductivity, total dissolved solids, and different trace metals con-

tent. The pH, electrical conductivity, and total dissolved solids of all water samples were found to be within the

US Environmental protection Agency limits. Results showed that the concentration of nine trace metals (Cr, Mn,

Ni, Cu, Zn, Mo, Pb, Cd, and Al) is within the WHO limits in drinking water (50, 500, 20, 2000, 3000, 70, 10, 3,

and 200 ug/L, respectively), however six metals of them (Cr, Mn, Ni, Cu, Mo, and Al) were detected in 100% of

the samples, while Pb, Cd, and Zn were detected in 80%, 60%, and 20% of the samples, respectively. On the

other ha nd, Tl which is a very toxic heavy metal with allowed WHO limits of 0.01 - 1 ug/ L is detected in 100% of

the water samples analysed with a range of 0.02 - 0.12 ug/L. It indicates that such concentration levels of Tl

would be har mful to the human be ing drin king the water. In general, 82% of all samples analysed contained one

or more of the 12 metals studied each in varying concentration. Results of this study suggest a possible risk to the

people of the study area given the toxicity of heavy metals, and the fact that for many people in the study area,

groundwate r is a main sourc e of their w ater supply.

KEYWORDS

Heavy Metals; Ground Water; Palestine; Pollution; ICP-MS

1. Introduction

Heavy metals in groundwater are toxic even at low con-

centrations [1-3]. Human activities have increased the

concentrations of heavy metals in the environment. For

example, industry, agriculture, and solid waste disposal

increase the contents of heavy metals in water, soil, air,

fruits, vegetable s, fish, etc. [4-6].

There are 35 metals that concern us because of occu-

pational or residential exposure, of which 23 are heavy

metals: antimony, arsenic, bismuth, cadmium, cerium,

chromium, cobalt, copper, gallium, gold, iron, lead,

manganese, mercury, nickel, platinum, silver, tellurium,

thalli um, ti n, urani um, va nadium, and zinc [7]. Although

small amounts of these are common in our environment

and diet and some are necessary for good health, large

amounts of any of the m may cause ac ute or chronic tox-

icity.

Health risks of heavy metals include reduced growth

and d evelop ment, cancer, organ d amage, nervous syste m

damage, and in extreme cases, death. Exposure to some

metals, such as mercury and lead, may also lead to

autoimmunity. Heavy metals become toxic when they are

not metabolized by the body and accumulate in the soft

tissues. As noted above, heavy metals may enter the hu-

man body via food, water, air, or absorption through the

skin in agriculture, industrial, or residential setting s [ 8,9].

*Corresponding author.

Assessment of Groundwater Pollution with Heavy Metals in North West Bank/Palestine by ICP-MS

OPEN ACCESS JEP

Many studies have investigated the occurrence and

monitoring of heavy metals in groundwater and drinki ng

water. Momodu and Anyakora [1] have assessed ground-

water contamination with heavy metals (Pb, and Cd) and

Aluminum in Nigeria. The results show that there is a

significa nt risk for the population from drinking ground-

water; Pb and Cd were detected in 98% of water samples

analysed in that study. Laniyan et al. [10] as well as

Oyeku and Eludoyin [11] also investigated the occur-

rence of heavy metals in ground water in Nigeria. Momot

and Synzynys [12] have investigated toxic aluminium

and heavy metals in groundwater of middle Russia and

have detected some heavy metals (Hg, Cr, and As) there.

Batayneh [4] has studied heavy metal content in water

springs of the Yarmouk Basin (Jordan) and has shown

that the Basin is contaminated with heavy metals that

might affect human health as well as the health of the

ecosystem. Iqbal and Gupta [13] and Rajappa [14] have

studied the heavy metal pollution of ground wa ter in India,

and have detected some heavy metals in groundwater

samples. Gutierrez et al. [15] have studied the occurrence

of heavy metals in water of San Petro River in Mexico

and have found that the San Pedro River is contaminated

with heavy metals and other contaminants that might

affect human health as well as the health of the ecosys-

te m. K a r et al. [1 6] have stud ied the a sse ssme nt o f hea v y

metals pollution in the surface water of the River Ganges

in West Bengal. The results show that the dominance of

various heavy metals in those waters followed the se-

quence: Fe > Mn > Ni > Cr > Pb > Zn > Cu > Cd. Voica

et al. [17] have determined different heavy metals in

surface water from Transylvania/Romania. The results

showed that toxic heavy metals were detected in water

samples in the range of few ug/L. Ismail and Mat Saleh

[18] have analysed different heavy metals in water sam-

ples from Malaysia. Their results showed that the con-

centrations of heavy metals in water samples were belo w

the detection limit. It is obvious from this literature that

studies on the occurrence and determination of heavy

metals in water (ground, drinking, surface etc) is an im-

portant issue for the human health and for the environ-

ment. In Palestine, the principal water resources available

include groundwater, springs, and harvested rainwater

[19]. However, there are few studies in Palestine that

dealt with pollution of groundwater with different pollu-

tants e.g. pesticides, nitrates, chlorides, heavy metals. A

study by Ghanem and Samhan [20] has focused on the

asses sment o f poll ution o f gro undwate r in T ulkare m area

with nitrate a nd chloride. Their results had indicated that

there are many samples with nitrate concentrations ex-

ceeding the WHO standards of 45 mg/L for drinking

water. Ghanem et al. [21] have also investigated the

groundwater pollution due to pesticides and heavy metals

in North West Bank. The results show that Pb, Cd, and

Cr were detected in the groundwater of North W est B ank.

The concentr ation of P b was found higher t hat the WHO

limit. El-Nahhal [22] has studied the contamination of

ground wat er wit h heav y metal s in Gaza Strip . T he results

showed that the concentration of Cd, Pb, Fe, and Cr are

above the EP A li mits in some well s.

The objectives of the current study are to study the

occurrence of different trace metals (Tl, Pb, Cr, Mn, Co,

Ni, Cu, Zn, Mo, Ag, and Cd) and Al in groundwater of

North West Bank in order to assess its pollution with

metals, as groundwater in the study area is used for

drinking.

2. Experimental

2.1. Study Area

2.1.1. Cl ima te

The climate in the West Bank can be characterized as hot

and dry during the summer and cool and wet in winter

[19]. The climate becomes more arid to the east and

south. Evaporation is high in summer when there is al-

ways a water deficit. The average annual rainfall in the

central highlands is 700 mm and becomes less than 100

mm near the Dead Sea. However, great variations in

rainfall a mount s and distribution exist [1 9].

2.1.2. Groundwate r : Aquifers a nd We lls

The principal water resources available to Palestinians

include groundwater, springs, and harvested rainwater

[20]. Both groundwater and surface water drain either

westwards to the Mediterranean or eastwards to the Jor-

dan River and Dead Sea. The lower Jordan River flows

southwards at the eastern edge of the West Bank from

Lake Tiberias to the Dead Sea [23]. The West Bank lies

over the Mountain aquifer. The Mountain aquifer is di-

vided into the eastern aquifer, the north eastern aquifer,

and the western aquifer. The eastern aquifer and part of

the north eastern aquifer flow east towards the Jordan

River. The western aquifer and part of the north eastern

aquifer flow westerly towards the Mediterranean Sea [24,

25].

2.1.3. Geography and Geology

North of West Bank including Nablus and Jenin have a

highly varying topography and altitude, with the highest

point at 940 m above sea level and the lowest at 150 m

above sea level for Nablus. The same goes for Jenin that

has a peak height of 750 m above sea level while the

lowest level is at 90 m above sea level. In terms of geol-

ogy, the majority of the Nablus and Jenin area is rocky

mainly comprised of carbonate sediment such as limes-

tone, carbonate, chalk and marl. The geological rock age

formations range from Cretaceous to Eocene [19].

2.2. Sampling and Analysis

Five groundwater wells which are used for drinking were

Assessment of Groundwater Pollution with Heavy Metals in North West Bank/Palestine by ICP-MS

OPEN ACCESS JEP

selected as representative wells of the study area. Figure

1 shows location of the wells in the study area that were

analysed in this study. Three samples were obtained from

each well at different times. A total of 15 water samples

were collected from the five wells. The water samples

were collected in 1-liter high densit y polyeth ylene b ottles

(pre-cleaned with 10% nitric acid followed by repeated

rinsing with bi-distilled water). The collected samples

have been stabilized with ultrapure nitric acid (0.5%

HNO3), preserved in a cool place (about 4˚C) and trans-

ported to the lab of Al-Quds Unive rsit y for fur ther a nal y-

sis. pH, electr ical conductivity, and total d issolved solids

were measured in the lab immed iately after the arr ival of

the samples according to standard methods [26]. The

samples were then analysed for the following metals (Tl,

Pb, Cr, Mn, Co, Ni, Cu, Zn, Mo, Ag, Cd, and Al) which

are dissolved in water by ICP/MS (Agilent technologies

7500 series).

For accurate quantitative determination of heavy met-

als in water samples, an internal standard method was

used using Nd as internal standard and a multi-standard

calibration method: (22 metals standard (Ag 10 mg/L, Al

50 mg/L, B 50 mg/L, Ba 10 mg/L, Bi 100 mg/L, Ca 10

mg/L, Cd 10 mg/L, Co 10 mg/L, Cr 50 mg/L, Cu 10

mg/L, Fe 10 mg/L, K 100 mg/L, Li 50 mg/L, Mg 10

mg/L, Mn 10 mg/L, Mo 50 mg/L, Na 50 mg/L, Ni 50

mg/L, Pb 100 mg/L, Sr 10 mg/L, Tl 50 mg/L, Zn 10

mg/L, matrix 5% HNO3). Samples were prepared by di-

lution of 1.0 mL of the water samples to 10.0 mL with

0.3% ultrap ure nitric acid and analysed by ICP/MS. Each

sample was analysed three times and the results are ex-

pressed as mean ± SD (SD: standard deviation). Relative

standard deviation (RSD) of the three results are calcu-

lated and found to b e less than 5% for all sa mples for all

metals analysed in this study, reflecting the precision of

Figure 1. Map of West Bank and the study area showing

location of the gro und w ells an aly zed i n this st udy (Ara bba,

Jaba, Al Badhan, Ruje e b, and Met ha lon).

the method for the analysis of these heavy metals. Cali-

bration curves for all metals analysed were constructed

by plotting the ratio o f the int ensity of the analyse metal

to that of the internal standard (Nd) vs. concentration of

the trace metal (in ug/L), and results showed that the ca-

libration curves are linear with cor relation co efficient (r2)

greater than 0.999 for the trace metals analysed.

3. Results and Discussion

This study was conducted to investigate the quality of

groundwater which is domestic wells used for drinking in

the study area. The people of the study area depend

mainly on the groundwater and on the rain water har-

vested and stored in cisterns or wells. The pH of all water

samples ranged between 6.9 - 7.8 which is within the

allowed WHO limit (6.5 - 8.5). Electrical conductivity

and total dissolved solids of all water samples ranged

from 394 - 1432 µS/cm, and 225.0 - 816.0 mg/L respec-

tively. The limit for total dissolved solids in drinking

water according to WHO is 1000 mg/L [27], where our

results sho wed that all water s amples are withi n this lim-

it.

3.1. Heavy Metals Conte nt

Results showed that eleven heavy metals (Tl, Pb, Cr, Mn,

concentratio n of Tl, Pb, Al, Cr, Mn, Co, Ni, Cu, Zn, Mo,

Ag, and Cd), and Al were detected in one or more water

sample analysed in this study. The concentration of Tl,

Pb, Al, Cr, Mn, Co, Ni, Cu, Zn, Mo, Ag, and Cd in the

five wells analysed in this study were ranged from: 0.02 -

0.12, 0.0 - 1.35, 0.28 - 30.11, 0.07 - 1.77, 0.02 - 8.96,

0.03 - 0.06, 0.13 - 4.62, 0.52 - 16.11, 0.0 - 16.36, 0.38 -

8.75, 0.0 - 0.03, and 0.0 - 0.04 ug/L, respectively, see

Table 1. Results showed that the concentration of nine-

trace metals (Cr, Mn, Ni, Cu, Zn, Mo, Pb, Cd, and Al) is

within the allowed WHO limits in drinking water (50,

500, 20, 2000, 3000, 70, 10, 3, and 200 ug/L, respective-

ly), however six metals of them (Cr, Mn, Ni, Cu, Mo,

and Al) were detected in 100% of the samples, while Pb,

Cd, and Zn were detected in 80%, 60%, and 20% of the

samples, respectively. In general, 82% of all samples

analysed contained one or more of the 12 metals studied

each in varying concentrat i on.

There is no limit for Ag in dr inking water acco rding to

WHO, however it is usually found in drinking water in

the range of 5 - 50 ug/L. Our results showed that all

samples are within this limit. Co has also no limits in

drinking water by WHO. Howe ver, this metal was de-

tected in 100% of the water samples analysed in this

study. Thallium (Tl) is a highly toxic element that hu-

mans are exposed to mainly by consumption of drinking

water and vegetables grown in soil with high thallium

content but also throu gh inhalation of par ticles in the air.

Assessment of Groundwater Pollution with Heavy Metals in North West Bank/Palestine by ICP-MS

OPEN ACCESS JEP

Table 1. Trace metals concentrations which are detected in the groundwater samples analyzed in this study (minimum,

maxi mum, ave rage, stan dard deviation (SD), and relative standard deviation (RSD)), as well as their WHO limits, and % of

the samples that found to contain p articular hea v y metal.

Heavy meta l concentrati on (ppb)

Bi Pb Cd Ag Mo Zn Cu Ni Co Mn Cr

1.33 12.94 0.0 0.0 0.0 22.19 21.93 9.15 0.34 4.56 22.6 Minimum

96.52 486.4 2.19 149.7 6.17 302.98 925.5 87.28 4.93 552.3 165.5 Maximum

32.8 45.8 1.17 39.7 11 .3 111.8 143.6 26.7 3.16 11 2.6 56.1 Average

14.1 14.3 0.8 13.7 3.6 29.7 36.3 4.1 1.5 11 .8 6.1 SD

43.0 31.2 68.3 34.5 31.9 26.6 25.2 15.4 47.5 10.5 10.9 RSD (%)

100 100 38 18 37 100 100 100 100 100 100

% of samp les that

found to contain that

hea v y metal

limits

10 3 No limits* 70 3000 2000 20 No limits 500 50 Limits

100 0

4.5 (exceeded

50 ppb)

0 0 0 34 / 4.5 59

% of samp les that

exce eded the li mit

*usually found in con ce ntration of 5 - 50 ppb.

Thallium is also present in fossil fuels, alloys, and in

electronic utilitie s. The increasing use of the element and

emissions from notably energy production has lead to a

higher load on the surface of the Earth. The allowed

WHO limits of T l in water is 0 .01 - 1 ug/L (IPCS, 1996).

Our results showed that Tl is detected in 100% of the

water samples analysed with a range of 0.02 - 0.12 ug/L,

which indicates t hat such concentra tion level of T l would

be harmful to human being consuming this groundwater.

A one way ANOVA statistical test was used to test if

the concentration of the analysed metals is significantly

different between the five groundwater wells. Results

sho wed t hat t he five wells i n t his st udy are d i ffer e nt fr om

each other at 95% confidence level in terms of trace met-

al content. These findings confirm locational variations

of the metals in t he wells analysed in this study.

3.2. Sources of Heavy Metals in the

Groundwater Samples

Heavy metals exist in water in colloidal, particulate and

dissolved phases [28] with their occurrence in water bo-

dies being either of natural origin (e.g. eroded minerals

within sediments, leaching of ore deposits and volcanism

extruded products) or of anthropogenic origin (i.e. solid

waste disposal, industrial or domestic effluents) [3]. The

most common metals that humans are exposed to are

Aluminium, Arsenic, Cadmium, Lead and Mercury.

Aluminium has been associated with Alzheimer’s and

Parkinson’s disease, senility and presenile dementia. Ar-

senic exposure can cause among other illness or symp-

toms cancer, abdominal pain and skin lesions. Cadmium

exposure produces kidney damage and hypertension.

Lead is a commutative poison and a possible human car-

cinogen [ 29].

The quality of groundwater sources are affected by the

characteristics of the media through which the water

passes to the ground water zone of saturation [30], thus,

the heavy metals discharged by industries, traffic, mu-

nicipal wastes, hazardous waste sites as well as from

fertilizers for agricultural purposes and accidental oil

spillages from tankers can result in a steady rise in con-

tamination of ground water [31]. Additionally, ground-

water quality is influenced considerably by the quality of

the recharge source. Variations in natural and human

activities reflect spatial variations of the aquifer and the

hydro chemical parameters of the groundwater. Pollution

sources are classified as point sources and diffuse

sources. Point sources are sources that can be clearly

identified and pinpointed (such as landfill leachate). Dif-

fuse sources cannot be pinpointed and are distributed

over a large surface area (application of fertilizers and

pesticides in a gric ulture).

In Palestine, groundwater is one of the major sources

of water. Efficient management of this resource requires

a good understanding of its status. Groundwater man-

agement in the West bank is affected by the randomly

distributed dumping sites, solid waste landfills, cesspits,

especially in rural communities, as well as agricultural

and industrial practices. Accordingly, the shallow aquifer

in the eastern and western groundwater basins is deteri-

orated; high concentrations of nitrate and sulphate were

detected larger than the WHO standards. Microorganisms

were detected in some springs inside rural communities

in Ramallah area [20,21]. This could be reflected on the

water suppl y for the se co mmu nities for t he fac t tha t these

water sources are the major sources for drinking and

agricultural purposes [21].

Assessment of Groundwater Pollution with Heavy Metals in North West Bank/Palestine by ICP-MS

OPEN ACCESS JEP

In West Bank and especially in rural areas, people d is-

pose their wastewater using cesspits which is one of the

main pollution sources to groundwater. Most of these

cesspits are emptied by vacuum tankers and disposed

into wadis or to improper dumping sites. These dump-

ing sites are located in agricultural lands and their sites

were selected randomly without any consideration to the

soil characteristics, topography and climate as well as

groundwater. As none of the existing dumping sites is

designed to collect leachate from solid waste degradation,

the leachate always finds its way through the soil to the

groundwater, increasing concentration of pollutants in-

cluding heav y metals to the water. In additio n to munici-

pal wastes and cesspits, urban, agricultural and indus-

trial activities in t he st ud y area may also co ntr ibute to the

contamination of the groundwater with heavy metals

[20,21]. Our recommendations are that uncontrolled dis-

posal of wastes and incineration of solid waste should be

banned and responsible authorities have to monitor and

control the quality of groundwater periodically (e.g.

heavy metals content) in West Bank as this water is used

for drinking especially in regions suffering from water

scarcity.

4. Conclusion

Groundwater from North West Bank contains eleven

heavy metals (Tl, Pb, Cr, Mn, Co, Ni, Cu, Zn, Mo, Ag,

and Cd) and one metal (Al) in 82% of samples analysed

from five wells, with nine trace metals (Cr, Mn, Ni, Cu,

Zn, Mo, P b, Cd, and Al) is withi n the allowed WH O li m-

its in drinking water. H owev e r, six metals of them (Cr,

Mn, Ni, Cu, Mo, and Al) were detected in 100% of the

samples. Although Co has no limit s in drinkin g water b y

WHO, this metal was detected in 100% of the water

samples analysed in this study. Thallium (Tl), a highly

toxic element with a WHO limit of 0.01 - 1 ug/L, is de-

tected in 100% of the water samples analysed with a

range of 0.02 - 0.12 ug/L. It indicates that such concen-

tration level of Tl would be harmful to the human being

consuming this groundwater. There are locational varia-

tions in the concentration of metals in the wells analysed

in this study.

Acknowledgements

The authors thank the German Research Foundation

(Deutsche Forschungsgemeinschaft), DFG for their fi-

nancial support through TRIO N project.

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