Journal of Hazardous Materials 171 (2009) 1133–1138

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Simultaneous preconcentration of copper, zinc, cadmium, and nickel in water

samples by cloud point extraction using 4-(2-pyridylazo)-resorcinol and their
determination by inductively coupled plasma optic emission spectrometry
Edson Luiz Silva a,∗ , Paulo dos Santos Roldan b , Maria Fernanda Giné a
a
Centro de Energia Nuclear na Agricultura, Universidade de São Paulo, Av. Centenário, 303, CP 96, 13416-000 Piracicaba, SP, Brazil
b
Universidade Federal de Alagoas, Campus A.C. Simões, Av. Lourival Melo Mota, Tabuleiro do Martins, CEP: 57072-970 AL, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: A procedure for simultaneous separation/preconcentration of copper, zinc, cadmium, and nickel in water
Received 10 March 2009 samples, based on cloud point extraction (CPE) as a prior step to their determination by inductively
Received in revised form 19 June 2009 coupled plasma optic emission spectrometry (ICP-OES), has been developed. The analytes reacted with
Accepted 23 June 2009
4-(2-pyridylazo)-resorcinol (PAR) at pH 5 to form hydrophobic chelates, which were separated and pre-
Available online 30 June 2009
concentrated in a surfactant-rich phase of octylphenoxypolyethoxyethanol (Triton X-114). The parameters
affecting the extraction efficiency of the proposed method, such as sample pH, complexing agent con-
Keywords:
centration, buffer amount, surfactant concentration, temperature, kinetics of complexation reaction, and
Copper
Zinc
incubation time were optimized and their respective values were 5, 0.6 mmol L−1 , 0.3 mL, 0.15% (w/v),
Cadmium 50 ◦ C, 40 min, and 10 min for 15 mL of preconcentrated solution. The method presented precision (R.S.D.)
Nickel determination between 1.3% and 2.6% (n = 9). The concentration factors with and without dilution of the surfactant-rich
Cloud point extraction preconcentration phase for the analytes ranged from 9.4 to 10.1 and from 94.0 to 100.1, respectively. The limits of detection
Water samples (L.O.D.) obtained for copper, zinc, cadmium, and nickel were 1.2, 1.1, 1.0, and 6.3 ␮g L−1 , respectively. The
accuracy of the procedure was evaluated through recovery experiments on aqueous samples.
© 2009 Published by Elsevier B.V.

1. Introduction ages to human body, such as disturbances in energy metabolism

The pollution by heavy metals from natural waters is a great con-
cern nowadays due to their potentially toxic effects on living beings.
Urbanization, industrial development, and heavy traffic lead to con-
tamination of waters with heavy metals [1]. Copper is an element
essential for many biological systems, which plays an important
role in carbohydrate and lipid metabolism. In general, copper at
nearly 40 ␮g L−1 is required for normal metabolism of many living
organisms; however, in higher levels it is considered to be toxic
and severe oral intoxication will affect mainly the blood and kid-
neys [2]. Cadmium is one of the most hazardous elements to human
health, because it can cause adverse effects on metabolic processes
of human beings [3]. Cadmium is highly toxic even at low concen-
trations, causing damages to organs such as the Kidneys, liver, and
lungs [4]. Zinc is an essential trace element of great importance for
humans, plants, and animals [5]. It is a co-factor in more than 200
enzymes and it is necessary for production of insulin in human [6].
However, high concentrations of this metal can cause several dam-
∗ Corresponding author. Tel.: +55 019 34135385; fax: +55 019 34294774.
E-mail address: edsonqmc@hotmail.com (E.L. Silva).
or increasing in oxidative stress [5]. Nickel is a moderately toxic
element and it is known that inhalation of this metal and its com-
pounds can lead to serious problems, including respiratory system
cancer [7].
The trace metals determination comprises one of the most
important targets in analytical chemistry. This interest is also
demonstrated in different areas such as biology and medicine [8].
Inductively coupled plasma optic emission spectrometry (ICP-OES)
is a very attractive technique for determination of inorganic ele-
ments in environmental and biological samples due to the ability of
multi-elemental analysis and high analytical throughput. However,
this technique presents moderate detectability and a preconcen-
tration step is still commonly required for metal determination
at ␮g L−1 levels [9]. Focusing on increasing the sensitivity and/or
selectivity of analytical measurements by ICP-OES, separation and
preconcentration procedures have been extensively explored in
recent years [10].
Separation and preconcentration procedures based on cloud
point extraction (CPE) have been extensively applied to separate
and preconcentrate metallic ions from different matrices [11]. The
use of CPE as an alternative to conventional solvent extraction
technique has presented several advantages, such as excellent con-

0304-3894/$ – see front matter © 2009 Published by Elsevier B.V.

doi:10.1016/j.jhazmat.2009.06.127
1134 E.L. Silva et al. / Journal of Hazardous Materials 171 (2009) 1133–1138
Table 1
Operation parameters for determination of copper, zinc, cadmium, and nickel by
ICP-OES.
Parameter
RF generator power 1.4 kW
Frequency of RF generator 40 MHz (radial view)
Plasma gas flow rate 15 L min−1
Auxiliary gas flow rate 0.5 L min−1
Carrier gas flow rate 0.8 L min−1
Solution uptake rate 1.2 mL min−1
Integration time 5s
Wavelength Cu: 324.742 nm; Zn: 206.200 nm
Cd: 228.802 nm; Ni: 232.003 nm
centration factors, lower cost, higher safety and simplicity, and it
does not need to handle a great volume of organic solvent that is
generally toxic [12].
In very diluted solutions of non-ionic or zwitterionic surfactant,
the monomers are dispersed in the solvent. But above the critical
micellar concentration (CMC) of the surfactant, these monomers
associate spontaneously, forming aggregates of colloidal dimen-
sions termed micelles, due to the diminished solubility of the
surfactant in water [13]. This clouding phenomenon can be induced
by changing the temperature, additive content, or pressure, result-
ing the separation of a single isotropic micellar phase into two
isotropic phases: (i) a surfactant-rich phase of small volume com-
posed mainly of surfactant, and (ii) an aqueous phase containing
surfactant with the concentration level near to CMC [12]. Any
species originally present that associates and binds to micelles can
be extracted and subsequently preconcentrated in a surfactant-rich
phase [14].
Several papers have used as quantification technique for deter-
mination of trace metals after a preconcentration step by CPE the
flame atomic absorption spectrometry (FAAS) [15–31], electrother-
mal atomic absorption spectrometry (ET-AAS) [32–39] or ICP-OES
[40–43]. Most of the procedures developed for preconcentration
of trace metals by CPE do not employ simultaneous extraction
of metallic species. However, if the analytical procedure allows a
simultaneous extraction of some interest species, ICP-OES is an
excellent alternative as technique for analysis, providing an expres-
sive reduction in the time of analysis. In this work, an analytical
procedure for simultaneous separation and preconcentration of
copper, zinc, cadmium, and nickel was developed in order to join
the capability of simultaneous determination provided by ICP-OES
with the advantages offered by CPE.
2. Experimental
2.1. Instrumentation
A model Optima 3000 DV sequential inductively coupled plasma
optical emission spectrometer (Perkin-Elmer – Norwalk, USA) was
used for determination of copper, zinc, cadmium, and nickel. Argon
99.996% (White Martins – São Paulo, Brazil) was used. Analytical
measurements were carried out according to the operational con-
ditions showed in Table 1. For comparative purpose, a model Perkin
Elmer 3110 flame atomic absorption spectrometer (Perkin-Elmer)
was also used for determination of the analytes. Hollow cathode
lamps wavelength, slit width, and burner height were selected
following the manufacturer’s recommended conditions. The aspira-
tion rate of the spectrometer was 6 mL min−1 . The pH values were
measured using a Model Tec-3MP pH-meter (Tecnal – Piracicaba,
Brazil), equipped with a glass-combination electrode. A model 55
centrifuge (Cientec – Piracicaba, Brazil) was used to speed up the
phase separation.
2.2. Reagents, solutions, and samples
High purity water (resistivity 18.2 M cm) obtained by a Milli-
Q® water purification system (Millipore – Bedford, USA) was used
throughout. All chemicals were of analytical-reagent grade and
were used without previous purification. Plastic bottles and lab-
oratory glassware were cleaned by soaking in 1.4 mol L−1 HNO3
solution during 24 h. Later bottles and glassware were rinsed with
high purity water, dried, and stored in a class 100 laminar flow hood.
Stock standard solutions of copper, zinc, cadmium, and nickel
at a concentration of 1000 mg L−1 were prepared by dissolving
appropriate amounts of CuSO4 ·5H2 O, ZnSO4 ·7H2 O, CdO, and NiSO4
(Johnson & Matthey – Royston, England) in diluted acid solution,
respectively. Working standard solutions were obtained daily by
stepwise dilution from stock solution. A 10 mmol L−1 PAR solution
(Merck – Hohenbrunn, Germany) was prepared by dissolution of
the chelating agent in 0.25 mol L−1 NaOH solution. A 2.5% (w/v) Tri-
ton X-114 solution (Sigma – St. Louis, USA) was used as surfactant
agent. A acetate buffer solution was prepared by mixing 0.2 mol L−1
sodium acetate solution (Merck – Darmstadt, Germany) and con-
centrated acetic acid (Merck – Darmstadt, Germany) in an adequate
ratio. This buffer was used to adjust the sample pH from 3 to 5.
A Sörensen buffer solution was obtained by mixing 0.064 mol L−1
Na2 HPO4 and 0.066 mol L−1 KH2 PO4 (both from Merck – Darmstadt,
Germany) in an adequate ratio, which was used to adjust the pH
between 6 and 7. A 0.1 mol L−1 tris(hydroxymethyl)aminomethane
solution (Merck – Darmstadt, Germany) was used as buffer for
the pH interval of 8–10. A aqueous solution containing 0.5 mol L−1
HNO3 (Merck – Rio de Janeiro, Brazil) and 1% (v/v) ethanol (Merck –
Darmstadt, Germany) was used to dilute the surfactant-rich phase.
Lake water samples were collected from a lake at ESALQ (Piraci-
caba, São Paulo state, Brazil), mineral water samples were acquired
from a local market, and drinkable water samples were collected
directly at the laboratory. These samples were filtered before anal-
yses through a cellulose membrane (Millipore) of 0.45 ␮m pore
size.
2.3. Procedure for simultaneous separation and preconcentration
of copper, zinc, cadmium, and nickel by CPE
An aliquot of 0.3 mL of acetate buffer solution was added to the
analytical solution containing the analytes and 0.6 mmol L−1 PAR,
and its pH was adjusted at pH 5 by the addition of diluted HCl or
NaOH solution. After 40 min, it was added Triton X-114 to a final
concentration of 0.15% (w/v). The final volume of micellar solution
was 15 mL. The sample or standard solutions were transferred to
centrifuge tubes and kept for 10 min in a thermostated bath at 50 ◦ C
to start the process of extraction and preconcentration of analytes
in the surfactant-rich phase.
In order to minimize the time, raise the efficiency, and facilitate
the separation process, the samples were centrifuged for 10 min at
4800 rpm. After the centrifugation, the tubes containing the two
separated phases were placed in an ice bath for 5 min to increase
the viscosity of the surfactant-rich phase, so the aqueous phase
was removed by inverting the tubes. Afterwards, 1.5 mL of an aque-
ous solution containing 0.5 mol L−1 HNO3 and 1% (v/v) ethanol
was added to the separated micellar phase in order to decrease
its viscosity and facilitate its introduction into the nebulizer-burner
system of the inductively coupled plasma optic emission spectrom-
eter by using a peristaltic pump.
2.4. Procedure to obtain recovery and concentration factors of the
analytes
To obtain the recovery factors, a standard solution contain-
ing 100 ␮g L−1 of zinc and copper, 200 ␮g L−1 of cadmium, and
 E.L. Silva et al. / Journal of Hazardous Materials 171 (2009) 1133–1138
Fig. 1. Effect of pH on the preconcentration of 15 mL of a solution containing
250 ␮g L−1 of Cu(II), Zn(II), Cd(II), and Ni(II), 1 mmol L−1 PAR, and 0.2% (w/v) Triton
X-114.
500 ␮g L−1 of nickel and a blank solution were submitted to
the proposed extraction procedure. After the separation step, the
surfactant-rich phase of the standard solution was diluted with
1.5 mL of aqueous solution containing 0.5 mol L−1 HNO3 and 1%
(v/v) ethanol. The surfactant-rich phase of the blank solution was
diluted in a similar way as the standard solution, but the solu-
tion to dilute the blank was spiked with the same analytes mass
as that present in the preconcentrated standard solution volume.
Analytical measurements of the spiked blank solution were con-
sidered 100%. Recovery factors were obtained by comparison of
analytical signals between the blank and standard solution. The
concentration factors (CF) were obtained by the following equa-
tion: CF = RF(VS /VE ), where RF is the recovery factor, VS is the
volume of preconcentrated micellar solution, and VE is the volume
of surfactant-rich phase. The volume of surfactant-rich phase with
and without dilution was approximately 1.5 and 0.15 mL, respec-
tively.
Recovery factors were also obtained by the following procedure:
concentration factors were calculated as the ratio of the slopes of
the calibration curves obtained with and without the preconcentra-
tion procedure, being the recovery factors obtained by the following
equation: CF = RF(VS /VE ) [8]. There was no considerable difference
between the results of both procedures.
3. Results and discussion
Parameters of the proposed extraction procedure were opti-
mized by the univariate method, taking to account the sensitivity
and precision of the analytical measurements. All analyses were
carried out in triplicate and the volume of each replicate was a
sufficient amount to provide three analytical signals as emission
intensities expressed in counts per second.
3.1. Effect of pH on the extraction performance
According to the literature [44], the reagent PAR in buffered solu-
tion with sodium acetate from pH 3 to 6 can complex zinc, cadmium,
cobalt, nickel, mercury, manganese, and other metals. The extrac-
tion of metal ions by surfactant micelles generally occurs after the
formation of a complex with enough hydrophobicity. Since the pH is
one of the main parameters for chelation reactions, it was the first
variable optimized in the extraction procedure. The effect of pH
on the metals recovery is presented in Fig. 1, which shows higher
recoveries at pH 4 for copper, zinc, and nickel and pH 6 for cadmium.
Based on these results, a pH value of 5 was selected throughout,
1135
which is in agreement with the literature [44], resulting in R.S.D.
values ranging from 1.7% to 2.9%. This good reproducibility can
probably be attributed to the separation stage, because the chelat-
ing agent PAR in the surfactant-rich phase provided an increase
of viscosity, facilitating the separation between the two phases by
inversion of the centrifuge tube. Moreover, it is important to point
out that the precision of the method is very influenced by this stage;
since the cloud point is considered a reversible phenomenon and
by decreasing the temperature, the two separated phases can form
again a homogeneous solution [12].
3.2. Effect of PAR concentration on the extraction performance
PAR is a pyridylazo compound which acts as a tridentate ligand.
It complexes the metal ions through the pyridine nitrogen atom,
the azo-nitrogen atom, and the o-hydroxyl group. The stoichimetry
of metal:chelate is 1:2 [26]. The extraction efficiency as a function
of the complexing agent concentration was studied. As illustrated
in Fig. 2, the recovery for copper, zinc, and nickel increased up to
a concentration of 0.32 mmol L−1 , except for cadmium that went
up to 0.6 mmol L−1 . Above this concentration, there was a decrease
on the recovery of analytes, but no very expressive difference was
observed in the concentration range of 0.6–1.6 mmol L−1 . A con-
centration of 0.6 mmol L−1 was selected as optimum in order to
guarantee maximum recovery of analytes. The R.S.D. values at this
concentration ranged between 1.8% and 3.4%.
3.3. Effect of buffer amount on the extraction performance
The influence of buffer amount added to the analytical solution
on the analytes recovery by the proposed procedure was investi-
gated. The extraction efficiency was higher when 0.3 mL of acetate
buffer solution was added to a final volume of 15 mL of analyti-
cal solution. Above 0.3 mL, there were both decrease and variation
on the recovery of analytes. In this stage, it was observed that the
solution became more limpid with the increase of buffer amount.
An aliquot of 0.3 mL of acetate buffer solution was selected for all
subsequent experiments.
3.4. Effect of Triton X-114 concentration on the extraction
performance
In order to raise the efficiency of the extraction procedure, the
concentration of Triton X-114 was optimized evaluating concentra-
tions between 0.05% and 0.3% (w/v). As showed in Fig. 3, maximum
Fig. 2. Effect of PAR concentration on the preconcentration of 15 mL of a solution
(pH 5) containing 250 ␮g L−1 of Cu(II), Zn(II), Cd(II), and Ni(II) and 0.2% (w/v) Triton
X-114.
1136 E.L. Silva et al. / Journal of Hazardous Materials 171 (2009) 1133–1138

Table 2
Properties of merit obtained by the proposed method.

Ion R.S.D.a (%) L.O.D.b (␮g L−1 ) RFc (%) CFd CFe

Cu 1.3 1.2 97.7 9.77 97.7

Zn 1.7 1.1 100.1 10.1 101
Cd 1.9 1.0 93.6 9.36 93.6
Ni 2.6 6.3 97.9 9.79 97.9
a
Relative standard deviation.
b
Limit of detection.
c
Recovery factor.
d
Concentration factor with dilution of the surfactant-rich phase.
e
Concentration factor without dilution of the surfactant-rich phase.

3.6. Effect of temperature and time on the extraction performance

The clouding phenomenon is frequently induced by changing

Fig. 3. Effect of Triton X-114 concentration on the preconcentration of 15 mL of
a solution (pH 5) containing 250 ␮g L−1 of Cu(II), Zn(II), Cd(II), and Ni(II) and
0.6 mmol L−1 PAR.
recoveries of analytes were attained at concentrations between 0.1%
and 0.15%, resulting in R.S.D. values from 0.7% to 1.8%. Above 0.15%
(w/v), there was an expressive decrease on the recovery of analytes.
Therefore a concentration of 0.15% (w/v) Triton X-114 was chosen as
appropriate; hence this concentration resulted in higher recoveries.
3.5. Effect of ionic strength on the extraction performance
The addition of an electrolyte to aqueous solutions of non-ionic
surfactant usually alters the cloud point due to the salting-out
effect. Some electrolytes reduce the cloud point temperature while
others present a contrary effect [12]. The effect of ionic strength
on the recovery of analytes was investigated using NaCl at con-
centrations from 0.1 to 1 mol L−1 . The electrolyte was added to
working solutions containing 250 ␮g L−1 of copper, zinc, cadmium,
and nickel. Fig. 4 shows that the recoveries of copper, zinc, and
nickel in relation to NaCl concentration were practically constant up
to 0.75 mol L−1 NaCl, and above this concentration it was observed
a decrease on the recovery of chelates. When growing amounts of
NaCl were added to the micellar solution, it was observed a constant
decrease in recovery for cadmium. According to the results given
in Fig. 4, only the preconcentration of cadmium was substantially
influenced by the ionic strength of the micellar solution. Probably
chelate of cadmium is less stable than chelate of cupper, zinc, and
nickel in solution of surfactant containing NaCl.
the temperature. In this work, the temperature of the thermostatic
bath was investigated within a range of 20–60 ◦ C. It was observed
higher extraction efficiency at a temperature of 50 ◦ C for all the
analytes, and this temperature was selected for the proposed pro-
cedure.
Complexes formation is the rate-determining step in several
chelate extractions [12]. Thus, the kinetics of the complexation reac-
tion between analytes and PAR before adding the surfactant agent
to the analytical solution was investigated. This parameter influ-
enced the extraction efficiency of analytes. A time of 40 min was
considered as appropriate for equilibration time and thus it was
used for subsequent experiments.
The incubation time of the micellar solution was investigated in
order to employ a shortest incubation time. The recovery of analytes
was practically constant between 10 and 40 min, so an incubation
time of 10 min was considered appropriate for subsequent experi-
ments.
3.7. Analytical properties of merit
The analytical properties of merit were obtained by preconcen-
trating 15 mL of analytical solution in aforementioned experimental
conditions. The proposed extraction procedure provided linear cal-
ibration curves according to the following equations:
S = 149.8 + 35.94[Cu2+ , ␮g L−1 ],
with r = 0.9926 in the 10–500 ␮g L−1 range;
S = 151.1 + 31.41[Zn2+ , ␮g L−1 ],

with r = 0.9980 in the 10–700 ␮g L−1 range;

S = −78.68 + 19.72[Cd2+ , ␮g L−1 ],

with r = 0.9982 in the 20–2000 ␮g L−1 range;

S = −23.68 + 3.872 [Ni2+ , ␮g L−1 ],

with r = 0.9942 in the 50–2500 ␮g L−1 range;

where S is the analytical signal as emission intensities expressed in

Fig. 4. Effect of NaCl concentration on the preconcentration of 15 mL of a solution
(pH 5) containing 250 ␮g L−1 of Cu(II), Zn(II), Cd(II), and Ni(II), 0.6 mmol L−1 PAR, and
0.15% (w/v) Triton X-114.
counts per second and r is the linear correlation coefficient.
Table 2 contains other figures of merit obtained by the precon-
centration procedure. The precision of the method was evaluated
for a solution containing 100 ␮g L−1 of copper and zinc, 200 ␮g L−1
of cadmium, and 500 ␮g L−1 of nickel (n = 9). The limit of detection
(L.O.D.) was defined as the analyte concentration which resulted in
a response equivalent to three times the standard deviation (S.D.)
 E.L. Silva et al. / Journal of Hazardous Materials 171 (2009) 1133–1138 1137

Table 3 samples by CPE, using Triton X-114 as surfactant and PAR as chelat-
Recovery of copper, zinc, cadmium, and zinc added to aqueous samples by the pro-
ing agent, has shown to be an efficient, simple, and safe method.
posed procedure.
This procedure presented as main advantage the union of the capa-
Aqueous matrix Cu2+ added ICP-OES FAAS bility of simultaneous extraction and preconcentration offered by
(␮g L−1 )
CPE with the use of a multi-elemental determination by ICP-OES.
Cu2+ found Ra (%) Cu2+ found R (%)
PAR was an efficient ligand for extraction and preconcentration of
(␮g L−1 ) (␮g L−1 )
copper, zinc, cadmium, and nickel by CPE. The analytical procedure
Drinkable water 100 97.3 ± 8.1 97.3 104.6 ± 8.3 104.6 also shows low limits of detection and good precision and accuracy.
200 201.7 ± 3.0 100.9 204.2 ± 11.7 102.1
Mineral water 100 98.6 ± 6.0 98.6 103.6 ± 7.8 103.6
200 205.6 ± 6.3 102.8 213.9 ± 10.5 107.0 Acknowledgements
Lake water 100 101.8 ± 5.3 101.8 100.3 ± 9.0 100.3
200 207.0 ± 7.7 103.5 202.1 ± 12.3 101.1
The authors are thankful to Centro de Energia Nuclear na Agri-
Aqueous matrix Zn2+ added ICP-OES FAAS cultura (CENA), Conselho Nacional de Desenvolvimento Científico e
(␮g L−1 ) Tecnológico (CNPq), and Fundação de Amparo à Pesquisa do Estado
Zn2+ found R (%) Zn2+ found R (%) de São Paulo (FAPESP) for support and fellowships.
(␮g L−1 ) (␮g L−1 )

Drinkable water 100 112.9 ± 5.1 112.9 114.8 ± 5.8 114.8

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