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Eurasian Journal of Analytical Chemistry

ISSN: 1306-3057
2017 12(7):987-1000
DOI: 10.12973/ejac.2017.00227a

Determination of Trace Amount of Lead (11) and Cadmium

(11) Ions in Real Water and Real Samples by Flame Atomic
Absorption Spectrometry After Cloud Point Extraction
Using Selective Synthesis Ligand2-(3- indolyl) – 4,5 di
phynyl imidazole
Gholamhossein Vatankhah
Department of Chemical Engineering, Islamic Azad University, Bushehr Branch, Bushehr, IRAN
Mahboube Ebrahimi
Department of Agriculture Science, Payame Noor University, Tehran, IRAN
Mostafa Kahani
Department of Chemical Engineering, Shahrood University of Technology, Shahrood, IRAN

Received 25 May 2017 ▪ Revised 20 July 2017 ▪ Accepted 5 August 2017

ABSTRACT
A simple, sensitive and feasible cloud-point extraction (CPE) methodology has been
developed for the separation and preconcentration of cadmium and lead ions in real
samples. The metals in the aqueous solution were complexes with 2-(3- indolyl) - 4,5 di
phynyl imidazole.(IDPI), at pH = 7.0 and Triton X-114 was added as surfactant. The variables
effecting like concentration of Triton X-114 and HNO3, bath temperature, centrifuge rate
and time on the cloud-point extraction were optimized. Under optimum conditions, the
response are linear over concentration range of 0.025-1.3(µg mL-1) for Cd2+, 0.064-1.27(µg
mL-1) for Pb2+ andRSD % (n =5) 1.4 for Cd2+, 1.3 for Pb2+, detection limits (3SDb/m, n =10,
m = slope of calibration) of 0.15 (µg.mL-1) for Cd2+ and 0.13 (µg.mL-1) Pb2+ respectively. The
enrichment factors were 31 for Cd2+ and 37 for Pb2+. The preconcentration factors were 26
for Cd2+ and 31 for Pb2+ respectively.

Keywords: cloud-point extraction,2-(3- indolyl) - 4,5 di phynyl imidazole.(IDPI), separation,

preconcentration

INTRODUCTION
Lead is a nonessential, heavy metal element, assumed to be toxic and a potential danger to
living beings and a pollution source [1, 2]. Its most widespread toxic ions are within industrial
wastewater, emissions from traffic, and pesticide residuals [3]. Cadmium is a toxic heavy metal
of environmental concern as well and classified as a B1 carcinogen by the US Environmental

© Authors. Terms and conditions of Creative Commons Attribution 4.0 International (CC BY 4.0) apply.
Correspondence: Gholamhossein Vatankhah, Department of Chemical Engineering, Islamic Azad University,
Bushehr Branch, Bushehr, Iran.
[email protected]
G. Vatankhah et al. / Determination of Trace Amount of Lead (11) and Cadmium (11)

Protection Agency [4]. Cadmium is widely used in various industries, which widely pollutes
the environment. In order to remove hazardous pollutants from various environmental
sources, e.g. aqueous media, many procedures such as co-precipitation, adsorption, ion-
exchange, filtration, electrochemical techniques, and reverse osmosis were proposed. Because
of their serious detrimental effects, itis important to determine trace levels of lead and
cadmium in almost all matrices as well as to remove these pollutants effectively and cheaply.

Monitoring the presence of toxic trace elements in biological fluids is an extremely

important task to evaluate the occupational and environmental exposure [5–7]. The common
availability of the instrumentation, simplicity of the procedures, speed, precision and accuracy
of the technique still make flame atomic absorption method an attractive alternative [8–10].
Monitoring of trace element concentrations in biological materials, particularly biological
fluids, might be considered a difficult analytical task, mostly due to the complexity of the
matrix and the low concentration of these elements, which requires sensitive instrumental
techniques and often a preconcentration step [11-13].

Several analytical techniques such as flame atomic absorption spectrometry (FAAS) [14],
electro thermal atomic absorption spectrometry (ETAAS) [15], and inductively coupled
plasma-optical emission spectrometry (ICP-OES) [16], and kinetic- Spectrophotometry [17].
However, the detection limit for measurement of low levels of cadmium and lead ions in
samples is not suitable, therefore the preconcentration before measurement with flame atomic
absorption spectrometry is necessary. The old methods of separating for example a liquid-
liquid extraction are used toxic organic solvents which are dangerous to the environment and
humans [18-20].

Cloud point extraction (CPE), employed in analytical chemistry to separate and

preconcentrate organic compounds and metal ions, has been well reviewed [21] Cloud point
extraction is the process in which the surfactant is added to the aqueous solution which
containing the component or components that must be extracted [22].

Surfactants are usually organic compounds that are amphiphilic, meaning they contain
both hydrophobic groups (their tails) and hydrophilic groups (their heads). Therefore, a
surfactant contains either a water insoluble (or oil soluble) component and a water soluble
component. The tail of most surfactants is consisting of a hydrocarbon chain which can be
linear, branch or aromatic. [23, 24]. Suitable amount of surfactant shall be added to provide
the micelles in the solution. It means that the final concentration of the surfactant shall be
exceeding from its CMC (Critical Micelle Concentration). Then for micelle or cloud solution
formation, conditions (such as increase or decrease in temperature, increase in salt or other
surfactants) are changed and with applying the suitable conditions, surfactant molecules form
micelles. In order to speed up the separation of two phases, centrifugation can be used. Finally
phase separation is done and a surfactant-rich phase and an aqueous phase will observe. [25,
26] The general procedure of cloud point extraction process is shown in Scheme 1 as following:

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Scheme 1: Cloud point extraction procedure

In this present work a simple , selection and sensitive CPE method for preconcentration
and determination of Pb2+ and Cd2+ ions in various real sample using 2-(3- indolyl)- 4,5 di
phynyl imidazole(IDPI)as selective and sensitive complexing agents in basic media was
established. Cloud point extraction procedure was presented for preconcentration of lead(II)
and cadmium(II) ions in various samples after complexation by 2-(3- indolyl) - 4,5 di phynyl
imidazole(IDPI) with lead and cadmium ions are quantitatively extracted in TritonX-114.

EXPERIMENTAL
Reagents
All solutions were prepared with deionized water. Analytical-grade methanol, acids,
and other chemicals used in this study were obtained from Merck. A 1.0% (w/v) Triton X-114
from E. Merck (Darmstadt, Germany) was prepared by dissolving 1.0 g of Triton X-114 in a
100 mL volumetric flask with stirring. All chemicals such as nitrate of Cd(II), Pb(II) and other
cations were of analytical grade purchased from Merck. The 2-(3- indolyl) – 4,5 di phynyl
imidazole.(IDPI) was synthesized, purified and characterized according to the literature[27].

Synthesis of Ligand2-(3- indolyl) – 4,5 di phynyl imidazole (IDPI)

A mixture of benzil (1mmol), ammonium acetate (3mmol) and substituted
benzaldehydes (1mmol), was added silica-bonded N-propylsulfamic acid (0.1 g) in solvent
free condition at 80 0Cfor the appropriate time, and heated at 800C in an oil bath. After
completion of the reaction, as indicated by TLC, the reaction mixture was filtered and
remaining washed with warm ethanol (2-5 mL). After cooling, the corresponding 2,3-
dihydroquinazolinone products were obtained which purified by recrystallization from hot
ethanol. The recovered catalyst was dried and reused for subsequent runs. The product was
purified by column chromatography on silica gel [eluent: EtOAc/n-hexane (1:3)] to give
pure2-(3- indolyl) – 4,5 di phynyl imidazole.(IDPI)in 90% yield. (Scheme2) was synthesized
according to literature [27].

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Ph
N

Ph N
H NH

Scheme 2: 2-(3- indolyl) – 4,5 di phynyl imidazole (IDPI)

Mp: 302-305 ºC
1H-NMR (DMSO-d6,400 Hz) δ: 7.05-7.16 (m, 3H), 7.23-7.28 (m, 3H), 7.37 (d, 3H, J=7.8 Hz),
7.44 (d, 2H, J=7.3 Hz), 7.56 (d, 2H, J=7.1 Hz), 7.93 (d, 1H, J=2.5 Hz), 8.40 (d, 1H, J=8.6 Hz), 11.29
(s, 1h), 12.20 (brs, 1H).
13C-NMR (DMSO-d6, 100 MHz) δ: 106.8, 111.6, 119.7, 121.5, 121.8, 123.7, 125.1, 126.8,
128.1, 128.7, 136.2, 143.7, 145.3, 171.7.

IR(KBr) (cm-1): 3412, 3055, 1621, 1598, 1491, 1451, 1336, 1208, 1182, 1049, 940, 854, 761,
749, 696.

Elemental analysis: C, 82.36; H, 5.11; N, 12.53.

Found: C, 82.17; H, 5.17; N, 12.29.

Instrumentation
A SensAA GBC double beam atomic absorption spectrometer (AAS) with hollow
cathode lamp operating at 7, 5 and 4 mA was used to determine cadmium and lead in the
surfactant-rich phase. The selected wavelengths were 228.8 and 217.0 nm, for Cd and Pb,
respectively. An adjustable-capillary nebulizer and supplies of acetylene and air were used for
the generation of aerosols and atomization. Deuterium lamp background correction was
employed to correct for the non-specific absorbance. Operation in a double beam-background
correction mode was essential due to the complexity of the aspirated sample, which apart from
the target metal and excessive chelating agent, causing a suppression of the signal.
Measurements were performed in the integration mode.

Shimadzu double beam UV-Vis spectrophotometer UV-1700 (Japan) , shimadzu single

beam UV-Vis spectrophotometer UV-1000-02 (Japan) , shimadzu Testscan FTIR 8400 series,
shimadzu AA6300 (Italy),

A centrifuge (Shimifan) was used to accelerate the phase separation process. A Jenway
model 3510 pH-meter was used for pH measurements. An electronic analytical balance
(220LA) was used for weighting the solid materials. A thermostated water bath (Fater Ltd.)
model W610B was employed to maintain the experimental temperature.

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Spectrophotometric Titrations
Standard stock solutions of IDPI (3.5 × 10-6mol/L) and the metal ions (5.o × 10-5mol/L)
were prepared by dissolving appropriate and exactly weighed (accuracy of ± 0.0001 g)
amounts of pure solid compounds in pre-calibrated 25.0 mL volumetric flasks, and diluting to
the mark with MeOH. Working solutions were prepared by appropriate dilution of the stock
solutions. Titration 1mL of the IDPI (3.5 × 10-6mol/L) and solution was carried out by the
addition of micro-liter amounts of a concentrated standard solution 1mL of the metal ion (5.o
× 10-5mol/L) using a pre-calibrated micro-syringe, at 25°C, with the spectrum subsequently
recorded.

Procedure
For CPE, an aliquot of 15 ml of a solution containing cadmium and lead ions, 0.1 %
Triton X-114 and 0.26 mM of IDPI was adjusted to pH 7.0 with HCl. The mixture was kept for
20 min in the thermostatic bath maintained at 50º C. The phase separation is accelerated by
centrifuging at 4000 rpm for 15 min. The whole system was cooled in an ice-bath so for 15 min
that the surfactant rich phase would regain its viscosity. In this way, the bulk aqueous phase
was easily decanted. The remaining micellar phase was dissolved in 500 μl of 2.0 M HNO3 in
methanol and then the cadmium and lead ions content were readily evaluated by FAAS.

Preparation of Real Samples

Water samples

Tap, well, natural mineral and sea water samples were collected in acid-leached
polyethylene bottles. Bushehr tap water sample was collected from our Lab (Bushehr, Iran).
The natural mineral water, well water samples and sea water sample was prepared from
Persian Gulf (Iran) were selected from Bushehr and Persian Gulf, respectively in Iran. Al water
samples were collected (if needed), filtered through 0.45 µm Millipore cellulose acetate
membrane filters to remove particles and diluted with distilled water to the ratio of 1:1. The
samples were then adjusted to pH7.0 and immediately analyzed [28].

Soil samples

Accurately weighed 1.0 g of soil samples from near Bushehr petrochemical center (less
than 200 meshes), dried at 110 °C were poured into a 250-mL beaker and 10 ml concentrated
nitric acid was added to it. The mixture was gently heated under a hood until drying. After
complete dry and the mixture was cooled to room temperature, A second 10-mLportion of
concentrated nitric acid was added and the procedure. Then 10 mL concentrated hydrochloric
acid was added to the beaker and the mixture was gently heated until complete drying. After
cooling, the residue was dissolved in 10 mL of 1 M HCl and the solution was then filtered into
a 100-mL calibrated flask, using a syringe filter (0.45 µ m pore sized). The sample was
neutralized by proper amounts of a 1 M NaOH solution and finally diluted to the mark with
water [29].

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Blood samples

Homogenized blood sample 20 mL was weighed accurately and in a 200 mL beaker was
digested in the presence of an oxidizing agent with addition of 10 mL concentrated HNO3 and
2 mL 70 % HClO4 was added and heated for 1 hour. The content of beaker was filtered through
a Whatman No. 40 filter paper into a 250 mL calibrated flask and its pH was adjusted to 7.0
and diluted to mark with deionized water [30].

Vegetable sample

Spinach sample was bought from Bushehr, Iran. Afterwards, they were taken in small
mesh. A 40 g sample was heated in silica crucible for 3 hours on a hot plate and the charred
material was transferred to furnace for overnight heating at 650◦C. The residue was cooled,
treated with 10 mL concentrated nitric acid and 3 mL 30% H2O2 and again kept in furnace for
2 hours at the same temperature so that no organic compound traces are left. The final residue
was treated with 3 mL hydrochloric acid and 2–4 mL 70% perchloric acid and evaporated to
fumes, so all the metals change to respective ions. The solid residue was dissolved in water,
filtered and by keeping the pH at7.0 made up to 15 mL by addition of KOH [31].

RESULTS AND DISCUSSION

Spectrophotometric Investigation
A typical kinetic Spectrophotometric method experiment required the following steps:
In order to investigate the complexation process between Ligand2-(3- indolyl) – 4,5 di phynyl
imidazole.(IDPI) and the Cd2+ and Pb2+ cations, the spectrophotometric titration was utilized
and the complexation procedures were analyzed in acetonitrile at 25°C due to the absorbance
alteration which occurs with the cation to ligand ([M]/[L]) ratio conversion. The electronic
absorption spectra of ligand (3.5 × 10-6mol/L) without and in the presence of the metals (5.0 ×
10−5 mol L−1) ions to the volumetric flask, the time of the reaction beginning is recorded, The
spectra of IDPI with the addition of Cd2+ and Pb2+ ions, corresponding mole ratio plot and
curve fitting at wavelengths of 498 or 495 nm, are depicted in Figures 1 and 2, respectively.
complexation occurs through binding of Cd2+ and Pb2+ ions to nitrogen atoms, leading to the
ML, or ML, ML2 models. Formation constants and stoichiometries of complexes were
calculated using the Kinfit program [32, 33] and results are shown in Table 1.

Effect of pH
A complex with sufficient hydrophobicity is required for separation of metal ions. The
mentioned complex can be extracted in a small volume of surfactant-rich phase. The extraction
efficiency is dependent on the pH at which complex formation occurs. Therefore, pH is the
most important parameter affecting the extraction efficiency and it is necessary to choose the
optimum pH at first [34-36]. The effects of pH on to extract metal complexes are given in Figure
3. In the pH range of 6.5-7.0, extraction was quantitative. The decrease in recoveries at pH >7.0
is probably due to the precipitation of metal ions in the form of hydroxide, and at pH < 6.5

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Figure 1. U.V- Visible spectra for titration of IDPI (3.5 × 10-6mol/L) with Cd2+ (5.o × 10-5mol/L) in MeOH
(T = 250C ) and I = 0.05 M) (a) molar ratio plot at 495 nm (b)

Figure 2. U.V- Visible spectra for titration of IDPI (3.5 × 10-6mol/L) with Pb2+ (5.o × 10-5mol/L) in MeOH
( T = 250C ) and I = 0.05 M ) (a) molar ratio plot at 495 nm (b)

may be due to competition from hydronium ion toward ions for complexation with IDPI or
decomposition of complex at pH <7.0, which led to the decrease in recoveries. In later
experiments a pH of 7.0 was selected.

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Table 1. Stepwise stability constsnts of complexation between metal ions and IDPI in Me

Metal ion Log K1 Log K2 M/L

Cd2+ 5.70 + 0.23 1.24 + 0.39 1:1 , 1:2
Pb2+ 4.46 + 0.33 1.06 + 0.27 1:1 , 1:2

Figure 3. Effect of pH on the extraction recovery of cadmium and lead ions. Conditions: 0.01 mg mL-1,
0.26 mM IDPI, 0.1% (w/v) Triton X-114. Other experimental conditions are described in Procedures

Effect of IDPI Concentration

The absorbance of extracted metal ions as a function of the concentration of IDPI is
shown in Figure 4. As can be seen, increasing IDPI concentration up to a 0.26 mM causes
increasing absorbance. Thus, a IDPI concentration of 0.26 mM was chosen to optimize other
variables. At lower than 0.26 mM of IDPI, insufficient concentration leads to incomplete
complexation. A possible explanation for the decrease in absorption with higher
concentrations may be attributed to the formation of charged complexes with excess IDPI in
the medium or with remaining excess IDPI in aqueous solution, competing with surfactant-
rich phase for formation of complex with metal ions in aqueous phase.

Effect of Triton X-114 Concentration

Triton X-114 was used as extractant and the concentration of this surfactant affects both
the extraction efficiencyand the volume of the surfactant-rich phase. In order to obtain easy
phase separation and maximum extractionefficiency the optimum amount of Triton X-114
should be determined [37]. The variation in absorbance of extracted Cd2+ and Pb2+ ions within
the Triton X-114 concentration range of 0.01 - 0.15% (w/v) was examined and results shown
in Figure 5. The results show that quantitative extraction was obtained with an optimum
Triton X-114 concentration of 0.1% (w/v), at which the highest absorbance for extracted Cd2+
and Pb2+ ions were obtained. For concentrations lower than 0.1% (w/v), the preconcentration
efficiency of the formed complexes was very low, since the assemblies at low concentration

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Figure 4. Effect of IDPI concentration on the extraction recovery of cadmium and lead ions. 0.01 mg mL-
1
, 0.1% Triton X-114, pH 7.0. Other experimental conditions are described in Procedures

Figure 5. Effect of Triton X-114 on cadmium and lead ions Recovery, Condition: 15 mL 1.0 μg mL-1
cadmium ion at various Triton X-114, 0.26 mM IDPI, pH=7.0, 0.2 % (w/v) KCl, eluting solution 0.5ml of
2.0 M HNO3 in methanol

were probably inadequate to preconcentrate trace amounts of Cd2+ and Pb2+ ions [38]. The
decreasing of absorbance at a concentration higher than 0.1% (w/v) is due to the remaining of
some part of Triton X-114 and IDPI in aqueous solution as this phase can compete with
surfactant-rich phase to draw analyte ions.

Effect of Temperature and Equilibrium Time on CPE

It was desirable to employ the shortest equilibration time and the lowest possible
equilibration temperature as a compromise between completion of extraction and separation
of phases. The dependence of extraction efficiency upon equilibration temperature and time
above the cloud point in the range 30-70ºC and 5-30 min were thoroughly optimized,

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Figure 6. Effect of temperature on cadmium and lead ions recovery, Condition: 15 mL 1.0 μg mL-1
cadmium and lead ions at various temperature, 0.1% (w/v) Triton X-114, 0.26 mM IDPI, pH=7.0, 0.2%
(w/v) KCl, eluting solution 0.5ml of 2.0 M HNO3 in methanol

respectively [39]. Holding the sample solutions for 25 min at 50ºC was found to be satisfactory
to achieve a small volume of the surfactant-rich phase, quantitative extraction and
experimental convenience.

Effects of Added Electrolyte

The cloud point of micellar solutions can be controlled by addition of salts, alcohols, non-
ionic surfactants and some organic compounds (salting-out effects) [40]. To date, most of the
studies conducted have shown that ionic strength has no appreciable effect on the extraction
efficiency. An increase in the ionic strength in the CPE does not seriously alter the efficiency
of extraction of the chemical forms. Moreover, the addition of a salt can markedly facilitate the
phase-separation process, as demonstrated with some non-ionic surfactant systems, since it
alters the density of the bulk aqueous phase [41, 42]. In this way, 2.0 M KCl concentration was
used in all further experiments.

Effect of Methanol
Since the surfactant-rich phase obtained after the cloud point pre-concentration contains
a high concentration of Triton X-114 and, at the same time, the volume obtained is rather small
(500µl), methanol containing 2.0 mol L-1 HNO3 was added to the surfactant-rich phase after
phase separation. Moreover, it was necessary to decrease the viscosity of the rich phase
without excessive dilution of the micelle to facilitate the introduction of the sample into the
atomizer of the spectrometer. There is an optimum volume (500µl) with respect to the
cadmium ion recovery. Smaller volumes of methanol were not tested because in this case it
was not possible to quantitatively transfer the rich phase from test tubes to the graduated tubes

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Table 2. Optimum Conditions for the Presented CPE Method

Parameter Optimum Value for ions

pH 7.0
IDPI concentration (mM) 0.26 mM
Triton X-114(w/v) 0.1 % (w/v)
Eluting agent 0.5 mL 2.0 mol L-1 HNO3 in methanol
Bath temperature 500C
Temperature time 20 min
Centrifuge time 15 min
Centrifuge rates 4000 rpm

Table 3. Specification of Method at Optimum Conditions for Each Element

Element
Parameters
Pb Cd
Linear Range (µg mL-1) 0.064-1.27 0.025-1.3
Correlation Coefficient 0.9985 0.9993
Detection Limit (µg.mL-1) (n =10) 0.13 0.15
Enrichment factor 37 31
Preconcentration factor 31 26
RSD % (n =5) 1.3 1.4
Recovery % 99 99

and measuring the absorbance. Larger volumes of acidified methanol dilution are clearly
predominated resulting in a gradual absorbance reduction. A 500µl volume of methanol was
therefore used throughout the remaining experiments.

Characteristics of the Method

Calibration graphs were obtained by preconcentrating 2.0 mL of standard solution in the
presence of pH 7.0, 0.1% (w/v) Triton X-114, 0.26 mM IDPI with 0.2% (w/v) KCl, under the
experimental conditions specified in the optimized procedure section. The solutions were
introduced into the flame by conventional aspiration. The characteristics of the proposed
method are shown in Table 2.

Table 3, gives the characteristic performance of the proposed method of standard

solutions subjected to the entire procedure. Limits of detection and quantification according
to IUPAC are also included. The limit of detection and the linear range of the proposed method
are comparable to other methods that also employed FAAS.

Interferences
In view of the high selectivity provided by flame atomic absorption spectrometry, the
only interferences studied were those related to the preconcentration step. Cations that may
react with IDPI, and anions that may form complexes with the metal ions were studied [43-
46]. The results were shown in Table 4. It was proved that cadmium and lead ions recoveries
were almost quantitative in the presence of foreign cations.

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Table 4. Effects of the matrix ions on the recoveries of the examined metal ions (N=3)

Ions Added As Tolerance Limit, mg L-1

Cl-, K+, Na+, KCl, NaCl, MgCl2, 800
Zn2+, Ba2+ Nitrate salts 300
PO43- Na3PO4 800
Cu , Ni2+, Cr3+, Hg2+
2+ Nitrate salts 200
Ca2+, Mg2+ Nitrate salts 50
Ti+, Al3+, Nitrate salts 150
HCO3 - NaHCO3 800

Table 5. Determination of analyte ions in soil, blood and vegetable

Ion lood Soil Vegetable

Added Found RSD Recovery Found RSD Recovery Found RSD Recovery
(μg.mL-1) (μg mL-1) % % (μg mL-1) % % (μg mL-1) % %
Cd 0 0.09 1.4 - 1.23 0.9 - 0.14 1.2 -
0.15 0.20 1.1 96 2.51 1.0 94 0. 30 1.3 101
Pb 0 0.03 1.3 - 0.23 1.1 - 0.13 1.3 -
0.15 0.07 1.5 103 0.39 1.1 99 0.19 1.3 99

Determination of Metal Ions in Real Samples

To validate the proposed method, the developed procedure was applied to the
determination of metal ions in real samples. For this purpose, 15 mL of each of the samples
were pre-concentrated with 0.1% (w/v) Triton X-114 and IDPI concentration of 0.26mM in pH
7.0, following the proposed procedure. The results are shown in Table 5 and 6.

CONCLUSIONS
The proposed cloud point extraction method, using ligand 2-(3- indolyl) - 4,5 di phynyl
imidazole.(IDPI), as a stable and fairly selective complexing agent offers a simple, rapid,
inexpensive and environmentally benign methodology for preconcentration and separation of
Cd2+ and Pb2+ ions in aqueous solutions. This method gives very low LOD, good RSD and was
applied to the determination of trace amounts of Cd2+ and Pb2+ ions in various real samples.
In a full comparison of presented results in this paper with those previously reported, it is
found that this method is superior in terms of linear range, detection limits and selectivity. For
comparison, the analytical performance data of similar method reported in literature have
been listed in Table 5 and 6. As it can be seen, the figures of merit of the developed method
are comprisable or better than the reported methods.

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Table 6. Determination of analyte ions in water samples

Water Ion Added Found RSD Recovery

Samples (µg mL-1) (µg mL-1) % (n=5) %
Tap Cd 0 0.13 1.2 -
0.15 0.28 1.3 98
Pb 0.0 0.20 1.3 -
0.15 0.32 1.1 102
Mineral Cd 0 0.10 1.3 -
0.15 0.25 1.4 98
Pb 0 0.12 1.2 -
0.15 0.33 0. 9 99
Sea Cd 0 0.12 1.4 -
0.15 0.26 1.5 96
Pb 0 0.45 1.3 -
0.15 1.12 1.2 99

ACKNOWLEDGEMENTS
The authors gratefully acknowledge partial support of this work by the Islamic Azad
University, Branch of Bushehr, Iran.

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