KAJ( Kurdistan Academicians Journal, March 2006, 4(1( part A( (147- 152(

1( ‫ ذ‬-147
A ‫) بةشى‬152 ( ‫لثةرة‬
4 ‫بةرط‬ ) ‫ ئازاري‬- 2706 ‫ نةوروزي‬-‫طؤظارى ئةكاديميانى كوردستان‬
,2006

Solid- Phase Preconcentration Technique for the

Determination of Lead in Water

Khalid M. Omer
Chemistry Department, College of Science, University of Sulaimani, Kurdistan region, Iraq

Abstract
Column solid-phase extraction (SPE) using [1-(2-pyridylazo)-2-naphthol] (PAN) loaded activated
alumina was used to the preconcentration of traces of lead from water samples prior to its measurement
by flame atomic absorption spectrometry. This complex lead-[1-(2-pyridylazo)-2-naphthol] is adsorbed
on activated alumina in the pH range 8.4-9.7 from large volumes of aqueous solutions, with
preconcentration factor 50. The solid mass consisting of lead complex and activated alumina is packed
into a fixed column and then washed with 5ml DMF and the metal was determined by flame atomic
absorption spectrometry. The combination of the proposed preconcentration method with atomic
absorption spectrometry permits the detection of 0.02 µg.ml-1 . Five replicate determinations of 5 µg.ml-1
of lead gave a relative standard deviation of 2%. Various parameters such as flow rate, pH and the
interferences of a number of metal ions on the determination of lead have been studied in detail to
optimize the conditions for determination of lead in water samples. Average lead in Sulaimani water was
found to be 35µg/L which is well below the tolerance levels internationally accepted which were 50µg/L.
The results indicated that, the suggested method is suitable for environmental study for the determination
of lead in water with reliable selectivity and sensitivity.

Keywords: Solid-phase , Lead, Preconcentration.

Introduction g.L-1 . The level of lead concentration in

Lead is one of many heavy metals that
are toxic to human being. Biological
interest in lead has centered principally on
its properties as a highly toxic cumulative
poison in man and animals. Children are
much more sensitive to lead exposure than
are adults [1, 2]. As a result of world wide
accumulation, lead presents a serious
environmental and health hazard [3]. In
natural waters, lead concentrations often
range from 1 to 50 µg.L-1. Hence highly
sensitive analytical techniques are
necessary to determine it in water [4,5]. It
is well known that lead occurs widely in
nature in water, the atmosphere and food
stuffs, which is harmful to human beings
especially children. According to the
stipulation of the Centre of Disease
Control(USA) and the Department of
Health (UK), typical levels of lead in
blood for children are of the order of 100µ
Email: khalidmomer@yahoo.com
plants is in the range 500-3000µg.L-1 [6-
7].
It is necessary to determine lead at
trace and ultra trace levels. The limitation
of analytical sensitivity associated with
co-existing interference has required the
use of separation and preconcentration
techniques. Different techniques have
been used with preconcentration step to
improve the sensitivity, like
Electrothermal atomic absorption
spectrometry with inductively coupled
plasma[8], Anodic stripping
oltammetry[9], Flame Atomic Absorption
Spectrometry[10,11], Second derivative
Spectrophotometry[12,13]and FIA-AAS-
ICP-Mass spectrometry[14].
Separation and Preconcentration of
metallic traces include the use of materials
that can retain the metallic ions.
Appropriate for trace collection are ion
exchangers and sorbents. Among the

147
KAJ( Kurdistan Academicians Journal, March 2006, 4(1( part A(
A ‫) بةشى‬1( ‫ ذ‬4 ‫ بةرط‬,2006 ‫ ئازاري‬- 2706 ‫ نةوروزي‬-‫طؤظارى ئةكاديميانى كوردستان‬
sorbents (coal, silica) and exchanger,
especially interesting are silica gels
modified with various reagent and
chelating agents immobilized on different
supports[15-18]
Column methods have also been
reported for the preconcentration of
metals using various adsorbents. Such as
Activated carbon[19], thiol cotton[20],
cellulose[21], poly thio ether[22].
Although some are fairly effective, the
methods for preparation are lengthy and
also involve rigid conditions. The
desorption of the metal complex is carried
out by a slow process of elution, thus
making the method more time consuming.
The aim of this work is to optimize
conditions for the quantitative column
solid-phase extraction preconcentration of
lead from a large volume of aqueous
phase using [1-(2-pyridylazo)-2-naphthol]
(PAN) and activated alumina as an
adsorbent. The method is sensitive and
selective. A number of parameters have
been evaluated and the developed method
has been applied to the determination of
lead in water samples in Sulaimani city. It
may also be employed for the
determination of lead in environmental
samples.
Experimental:
Reagents:
All reagents used were of analytical
grade. All glasses were washed with 2M
HNO3 then thoroughly with distilled
water. A series solutions of lead ion for
calibration curve was prepared by serial
dilution of the AAS standard solution
( GSB G 62071-90) (1000mg/L). A 0.1%
solution of PAN ( Reidel-De Haen ) was
prepared in ethanol. Buffer solutions of
pH 6-8 and 8-11 were prepared by mixing
appropriate ratios of 0.1M dipotassium
hydrogen phosphate , and 0.5M ammonia
and 0.5M ammonium acetate solutions
respectively.
148
Apparatus:
Atomic Absorption Spectrophotometer
WFX-120 (BRAIC) was used. All
absorption measurements were performed
under the following operating conditions.
Wavelength: 217.0nm, slit setting: 0.2nm,
lamp current: 4mA, PMT voltage: 517V.
burner height: 8mm, flow rate air/fuel
setting: 5/3 L.min-1, pH meter(thermo
Orion 210) was employed for pH
measurements.
Activation of Alumina:
Alumina ( Al2O3.xH2O ) is the most
common adsorbent, displays increased
activity after heating to 1 1000C.
Overnight heating to 4000C in air
produces highly adsorbent activity grade I
alumina which was preferred for our
experiment. It has Lewis acid (electron
acceptor) sites that adsorb unsaturated
compounds quite well. The relative
proportion of acidic sites increases as the
activation temperature is increased.
Activated alumina may react with esters,
anhydrides, aldehydes and ketones [23].
Preparation of loaded PAN-Activated
alumina:
A mixture consisting of 1g of PAN, 20g
of activated alumina, 10ml of water and
100ml of acetone was stirred on a stirrer
hot plate arrangement at ∼ 400C for a few
minutes to obtain nearly a clear solution
of the reagent and alumina. It was then
mixed with 1000-1500ml of distilled
water at room temperature. The
coprecipitated mixture was further stirred
for 3h and allowed to stand for 12h at
room temperature. The supernatant
solution was drained off with siphon and
the mixture was washed twice with
distilled water. The final adsorbent was
slurry of PAN-activated alumina in water
and was stored in a bottle [12].
KAJ( Kurdistan Academicians Journal, March 2006, 4(1( part A(
A ‫) بةشى‬1( ‫ ذ‬4 ‫ بةرط‬,2006 ‫ ئازاري‬- 2706 ‫ نةوروزي‬-‫طؤظارى ئةكاديميانى كوردستان‬
General Procedure:
An aliquot of lead solution (250ml)
containing 50µg of lead was put in a
beaker. The pH of this solution was
adjusted to 9.5 with the addition of 2ml of
buffer solution. The column loaded with
PAN-activated alumina adsorbent was
conditioned to pH 9.5 with 2-5ml of
buffer and then the metal ion solution was
passed through the column at a flow
1ml.min-1. The solid mass, consisting of
the metal complex along with activated
alumina, was dissolved out of the column
with 5ml of Dimethylformamide DMF.
The solution was aspirated into an air-
acetylene flame and then absorbance was
measured at 217.0nm against reagent
blank. The absorbance of s amounts of
lead in the sample were measured on a
calibration curve which was constructed
against a reagent blank prepared in a
similar manner.
Results and Discussion
Reaction conditions:
The reaction conditions were
investigated with 5µg of lead. Adsorption
was performed at different pH values,
keeping the other variables constant. It
was found that lead complex was
quantitatively adsorbed on activated
alumina in the pH range 8.4-9.7.For
further studies pH 9.5 was chosen.
The reagent concentration was also
varied. It was observed that adsorption
was quantitative for 0.1-6.0ml of 0.1%
reagent. Consequently, 1.0ml of reagent
solution was used in subsequent studies.
Flow rates of 0.1-9.0 ml.min-1 were
studied. It was found that a flow rate of
0.1-7.0ml did not affect adsorption. A flow
rate of 1ml.min-1 was recommended in all
experiments.
The volume of the aqueous phase was
varied in the range of 50-500ml under the
optimum conditions, keeping the other
149
variables constant. It was found that the
peak height was almost constant up to
250ml. Therefore a preconcentration
factor 50 (preconcentration factor = 250ml
of aqueous phase solution divided by 5ml
of final DMF solution=50) can be
achieved by the column.
120
100
%recovery
80
60
40
20
0
6 7 8 8.2 8.4 8.5 8.7 9 9.2 9.5 9.5 10 11
PH
Fig(1): Influence of PH on solid phase
extraction recovery
Choice of solvent
It is essential to select a solvent ın
whıch the chelate ıs hıghly soluble. Some
common solvents were studied (Water,
Acetic acid, Dimethyl sulfoxide, butanol,
tolouen, and chloroform). DMF was
preferred because of the high solubility
and stability, thus increasing the
sensitivity of the method.
Retention capacity of the adsorbent
The retention capacity of the adsorbent
was determined by a batch method. The
experiment was performed by putting 500
mg of lead, 2ml of buffer solution
(pH= 9.5) and 40ml of water into a beaker.
This solution was transferred into a
separating funnel and then 2.5g of PAN-
activated alumina was added. The
separating funnel was shaken vigorously
on a mechanical shaker for 5 min. The
solid mass was separated by filtration and
lead was determined from the filtrate by
atomic absorption spectrometer. The
maximum amount of lead retained was
4.2mg.g-1 of PAN in the adsorbent.
KAJ( Kurdistan Academicians Journal, March 2006, 4(1( part A(
A ‫) بةشى‬1( ‫ ذ‬4 ‫ بةرط‬,2006 ‫ ئازاري‬- 2706 ‫ نةوروزي‬-‫طؤظارى ئةكاديميانى كوردستان‬

Cations/Anions Tolerance
Calibration Curve limit(mg(
The calibration curve was performed CH3COO- 200
under the optimum conditions. It was SCN- 10
observed that the curve was linear from C2O42- 15
0.1µg.ml-1 to 5µg.ml-1 Pb in DMF solution SO42- 100
Cl- 100
with a correlation coefficient 0.9907 and a Cd2+ 5
detection limit 0.02µg.ml-1. Co2+ 0.8
y = 0.1881x + 0.0753 Zn2+ 3
R2 = 0.9907 Cr3+ 7
1.2
1
Fe3+ 2
0.8 Ni2+ 2.5
Cu2+ 4
A.A

0.6
0.4
0.2
0
0 1 2 3 4 5
Conc. Pb2+ microgram/ml
Fig(2): Calibration curve
Study of interferences
Various anions and cations were added
individually to a solution containing 5µg
lead and the general procedure was
applied. The tolerance limit was set as the
amount of ion required to cause ±5% error
in lead determination. The results obtained
are listed in Table (1). This indicates that
the proposed method is selective for
determination of lead in water samples
without any prior separation. It is obvious
from the table that the cations have more
effect than anions and that relate to the
ability of the positive ions for
complexation with the reagent PAN.
Table 1: Effect of anions and cations
Determination of lead in water samples
6 Using the proposed method, the lead
concentration and the recoveries from tap
water was determined in different sources
in Sulaimani city that are used for
drinking purposes. Table (2) gives the
results for lead determination in various
water samples. The recoveries of 0.05µg
of lead added to the samples were 92-98%
Conclusion
From table (2), it can be seen that the
developed method can easily be
performed and affords good precision and
accuracy when applied to real samples.
It is obvious from the experimental
data that water of Sulaimani is pure as
far as pollution by lead is concerned,
because they are within the permission
range which is (50µg/L)[4,5].

Table2: Lead concentrations and recoveries of 0.050µg Pb added to natural

waters from various sources.
Samples Pb in samples µg.ml-1 Pb found µg.ml-1 Recovery%
Tap water 0.051 0.048 96
Azadi well(1( 0.030 0.047 94
Azadi well(2( 0.025 0.049 98
Aziz aga (spring( 0.035 0.046 92
Majid beg 0.041 0.047 94
Shex mahmood 0.038 0.046 92

References

150
KAJ( Kurdistan Academicians Journal, March 2006, 4(1( part A(
A ‫) بةشى‬1( ‫ ذ‬4 ‫ بةرط‬,2006 ‫ ئازاري‬- 2706 ‫ نةوروزي‬-‫طؤظارى ئةكاديميانى كوردستان‬

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151
‫(‪KAJ( Kurdistan Academicians Journal, March 2006, 4(1( part A‬‬
‫طؤظارى ئةكاديميانى كوردستان‪ -‬نةوروزي ‪ - 2706‬ئازاري ‪ ,2006‬بةرط ‪ 4‬ذ (‪ )1‬بةشى ‪A‬‬

‫ريَطاى دةرهيَنان لةسةر‬‫تةكنيكى فرةكردنى ثةييتى بة ِ‬

‫رةق‬‫رووى ِ‬
‫‪Solid Phase Extraction‬‬
‫رقوشم لة ئاودا‬ ‫بؤ دياريكردنى قو ِ‬
‫خاليد محةمةد عومةر‬
‫بةشى كيميا ‪ /‬كؤليَجى زانست ‪ /‬زانكؤى سليَمانى‪ /‬هةريَمى كوردستان‪ -‬عيَراق‬
‫ثوختة‬
‫دةرهيَنان لةسةر رِووى رِةقى ‪ solid phase extraction‬ئةنجام درا بة بةكارهيَنانى ( ‪2-1‬‬
‫ثايريدايلزؤ نةفتؤل ‪– PAN‬ئةلؤميناى ئةكتيتظ ) بتة مةبةستتى فرةكردنتى ثةيتتى برِى زؤر‬
‫كةمى قورِقشم ثيَش ئةوةى ثيَوانة بكريَت بة هؤى سثيَكتراى مذينى ئةتؤمى ناو بلَيَسة ‪.‬‬
‫ئةم كؤمثليَكستتتة (قورِقشتتتم‪ 2-1 -‬ثايريدايلزؤ نةفتؤل ‪ ) PAN‬لةستتتةر رِووى ئةلؤميناى‬
‫ئةكتيتتتظ رِووةمذينتتتى بةستتتةردا دةهيَنري َتتتت لة مةوداى ‪ pH‬ى ‪ 9.7 -8.4‬لة ناو قةبارةى‬
‫طةورةى طيراوةى ئاوىيةوة وة بتة فاكتةرى ثةيتتى ‪ . 50‬وة بارستتة رِةقةكتة لة ئةلؤميناو‬
‫كؤمثليَكستتتةكة دةخري َتتتتة ناو كؤلَؤميَكةوةو بتتتة ‪ 5‬متتتل لة طيراوةى ‪ DMF‬دةهيَنري َتتتتة‬
‫خوارةوة ‪ ،‬ميتالَةكتتة بتتة ستتثيَكتراى مذينتتى ئةتؤمتتى ناو بلَي َتتسة دياريدةكري َتتت ‪ .‬بتتة يتتة‬
‫ككبةستتى رِيَطةى فرةكردنتى ثةيتتى و ستثيَكتراى مذينتى ئةتؤمتى توانرا كةمتريتن ئاستتى‬
‫ناستتينةوة (‪ ) detection limit‬بطاتتتة ‪ µg.ml 0.02‬وة لدانتتى ثيَوانىيتتى رِيّذةى لة تيَكرِا (‬
‫‪ ) relative standard deviation‬بريتتتى بوو لة ‪ %2‬بتتؤ ثي َتنج جار خؤيَندنةوةى ‪. µg/ml 5‬‬
‫ثاراميتةرى جياواز جياواز نموونتتتة كرا وةك خيَرايتتتى رِؤيشتتتتن ( ‪، flow rate ) ، pH‬‬
‫ئينتةرفيري َتتتتنس ‪.‬دةرةنجامتتتتى كارة ثراكتيكيةكان دةركةوت كتتتتة ئاوى خواردنةوة لةو‬
‫نموونانةى كتتتة وةرطيراون لة ئاستتتتى مةترستتتىداردا نيتتتة‪ .‬وة رِيَطةكةش طونجاوة بتتتؤ‬
‫دياريكردنى رِيَذةي قورِقشم لة ئاودا ‪.‬‬

‫تقنية ازدياد التركيز الرصاص بطريقة الستخلص‬

‫بالحالة الصلبة‬
‫وتقديرها بطيف المتصاص الذرى اللهيبى‬
‫خالد محمــد عمر‬
‫قسم الكيمياء‪ /‬كلية العلوم‪ /‬جامعة السليمانية‪ /‬أقليم كردستان – العراق‬

‫ألخلصة‬
‫استتخدمت طريقتة الستتخلص بالطور الصتلب متع الومينتا المنشتط – ‪ 2-1‬بايريدايلزو‬
‫نفثول ‪ PAN‬لزدباد التركيز الرصاص قبل قياسها بواسطة طيف المتصاص الذرى اللهيبى‬
‫‪ .‬امتزت المعقتد الرصتاص – ‪ PAN‬على ستطح الومينتا المنشتط ‪ .‬يعباء الكتلة الصتلبة متن‬
‫الومينتا و المعقتد متن العمود و يزيتح بواستطة ‪ 5‬ملليتتر متن ‪ . DMF‬ان ربتط الستتخلص‬
‫بالطور الصلب مع طيف المتصاص الذرى تعطى لطريقة ‪ µg.ml 0.02‬كأقل حد للكشف‬
‫و ألنحراف القياستى النستبى ‪ . %2‬درستت متغيرات متعددة مثتل سترعة الجريان و ‪pH‬‬
‫و ايونات متداخلة‪.‬النتائج العمليتتتة أثبتتتتت ان مياه الشرب المأخوذة كنموذج ان نستتتبة‬
‫الرصاص ل تتعدى الحد المسموح ‪ ,‬وان الطريقة المقترحة مناسبة لتقدير ايون الرصاص‬
‫فى الماء ‪.‬‬

‫وةرطيرالة ‪ 2004 /2/9‬دا وثةسةندكرا ‪17/3/2005Received on 2/9 /2004 .Accepted‬‬

‫‪.17/3/2005‬‬
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