Analytica Chimica Acta 450 (2001) 215–222

Determination of cadmium, copper, lead and zinc

in water samples by flame atomic absorption
spectrometry after cloud point extraction
Jianrong Chen, Khay Chuan Teo∗
Chemistry Department, Natural Sciences Academic Group, National Institute of Education,
Nanyang Technological University, 1 Nanyang Walk, Singapore 637616, Singapore
Received 2 May 2001; received in revised form 23 July 2001; accepted 24 August 2001

Abstract
Cloud point extraction (CPE) has been used for the simultaneous pre-concentration of cadmium, copper, lead and zinc
after the formation of a complex with 1-(2-thiazolylazo)-2-naphthol (TAN), and later analysis by flame atomic absorption
spectrometry (FAAS) using octylphenoxypolyethoxyethanol (Triton X-114) as surfactant. The chemical variables affecting
the separation phase and the viscosity affecting the detection process were optimized. At pH 8.6, pre-concentration of only
50 ml of sample in the presence of 0.05% Triton X-114 and 2 × 10−5 mol l−1 TAN permitted the detection of 0.099, 0.27, 1.1
and 0.095 ng ml−1 cadmium, copper, lead and zinc, respectively. The enhancement factors were 57.7, 64.3, 55.6 and 63.7 for
cadmium, copper, lead and zinc, respectively. The proposed method has been applied to the determination of cadmium, copper,
lead and zinc in water samples and a standard reference material (SRM). © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Cloud point extraction; Flame atomic absorption spectrometry; Surfactant-rich phase

1. Introduction determination of the trace elements by less sensi-

Several analytical techniques such as atomic ab-
sorption spectrometry (AAS), inductively coupled
plasma atomic emission spectrometry (ICP-AES)
and inductively coupled plasma mass spectrometry
(ICP-MS) are available for the determination of trace
metals with sufficient sensitivity for most of applica-
tions. However, the determination of trace metal ions
in natural waters is difficult due to various factors, par-
ticularly their low concentrations and matrix effects.
Pre-concentration and separation can solve these prob-
lems and lead to a higher confidence level and easy
∗ Corresponding author. Tel.: +65-790-3849; fax: +65-896-9432.
E-mail address: kcteo@nie.edu.sg (K.C. Teo).
tive, but more accessible instrumentation such as
flame atomic absorption spectrometry (FAAS). There
are many methods of pre-concentration and sepa-
ration such as liquid–liquid extraction (LLE) [1,2],
ion-exchange techniques [3,4], co-precipitation [5,6],
sorption on the various adsorbents such as activated
carbon [7,8], Amberlite XAD resins [9,10] and other
sorbents [11,12].
Cloud point extraction (CPE) is related to the
conventional LLE and is used in micellar liquid
chromatography (MLC) [13]. The principle and ad-
vantages have been well-established and identified
in recent years [14–16]. Undoubtedly, MLC offers a
simple alternative and yet an effective mean of ex-
tracting compounds into an organic stationary phase

0003-2670/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 3 - 2 6 7 0 ( 0 1 ) 0 1 3 6 7 - 8
216 J. Chen, K.C. Teo / Analytica Chimica Acta 450 (2001) 215–222
comprises of the critical micellar (CM) assemblies.
The key to the success of the MLC is very much laid
on the selection of the surfactant and the aqueous
phase physicochemical conditions. Factors that are
important in the formation of the CM include surfac-
tant concentration, temperature and the choice of a
compatible pH buffer and/or the maintenance of the
needed ionic strength for the aqueous phase. The last
two factors could have a critical effect in the formation
of the metal chelate and on the stability of the chelate.
Once the aqueous system of the surfactant reaches the
critical micelle concentration (CMC) under a warmer
temperature condition, the well-organized phase of
CM can be separated from the aqueous phase on cool-
ing. This is often referred to as the cloud point (CP).
The cloud shall then aggregate and settle to form the
stationary phase of the MLC. The process of the sepa-
ration of the CM phase is an effective means of taking
the metal chelates from the aqueous phase. CPE is a
powerful approach comparable with other established
methods. Like for all other established LLE meth-
ods, the metal ion is required to be in the uncharged
chelated form prior to its extraction to the organic
phase. Concentration by CPE has been established for
a number of trace organic pollutants from an aqueous
phase [17–22].
The phase separation phenomenon has been also
used for the extraction and pre-concentration of metal
ions after the formation of sparingly water-soluble
complexes [23–26]. U [27], Er [28], and Gd [29] were
determined by spectrophotometry, Pd [30] by room
temperature phosphorescence, Cu [31], Cd [32], Ni
and Zn [33], Ag and Au [34], Cr(III) and Cr(VI) [35]
by FAAS after CPE using complexing agents. Gold
and lead were extracted efficiently without a com-
plexing agent, using a non-ionic surfactant such as
poly-oxyethylene-nonyl-phenyl-ether (PONPE 7.5).
Gold [36] in the aqueous phase was determined by
ICP-MS and in the surfactant-rich phase by a cal-
culation based on mass balances. Lead [37] in the
surfactant-rich phase was determined by FAAS af-
ter diluting with ethanol. Recently, determination
of trace elements by X-ray fluorescence spectrome-
try [38,39] and ultrasonic nebulization ICP-MS [40]
using phase separation with a surfactant have been
reported. Sanz-Medel et al. [41] reviewed the use of
surfactant-based organized assemblies in analytical
atomic spectrometry.
In our previous papers, we reported the useful-
ness of this methodology for the pre-concentration
of manganese [42], cobalt and nickel [43]. This pa-
per reports the results obtained in a study of the CP
simultaneous pre-concentration of cadmium, copper,
lead and zinc after the formation of a complex with
1-(2-thiazolylazo)-2-naphthol (TAN), and later anal-
ysis by FAAS, using octylphenoxypolyethoxyethanol
(Triton X-114) as surfactant. The proposed method is
also applied to the determination of cadmium, cop-
per, lead and zinc in water samples and a standard
reference material (SRM).
2. Experimental
2.1. Apparatus
A Shimadzu AA-680 atomic absorption/flame
emission spectrometer equipped with deuterium back-
ground correction was used with cadmium, copper,
lead and zinc hollow-cathode lamps as radiation
sources. The operating conditions were those recom-
mended by the manufacturer, unless specified other-
wise. The acetylene flow rate and the burner height
were adjusted in order to obtain the maximum ab-
sorbance signal, while aspirating the analyte solution
in methanol containing 0.1 mol l−1 nitric acid. For dis-
crete volume sampling, a volume of 100 ␮l of the final
solution was introduced into the nebulizer of the spec-
trometer by a manual sample injector that was con-
nected to the nebulizer by the sample aspiration tubing.
Absorbance signals as peak height were measured. A
MP4 centrifuge (International Equipment Company,
USA) was used to accelerate the phase separation.
2.2. Reagents and solutions
The non-ionic surfactant Triton X-114 was obtained
from Sigma and was used without further purifica-
tion. Stock standard solutions of cadmium, copper,
lead and zinc at a concentration of 1000 ␮g ml−1
were obtained from Spectrosol. Working standard so-
lutions were obtained by appropriate dilution of the
stock standard solutions. A solution of (1.0 × 10−3 M)
of TAN (Lancaster, Morecambe, Lancs, England) in
Triton X-114 was prepared from the commercially
available product. A stock buffer solution 0.1 mol l−1 ,
 J. Chen, K.C. Teo / Analytica Chimica Acta 450 (2001) 215–222 217

was prepared by dissolving appropriate amounts of solution of methanol containing 0.1 mol l−1 HNO3
Na2 B4 O7 ·10H2 O in water. Nitric acid (Merck) and was added to the surfactant-rich phase. The samples
methanol (Merck) were used. Water was doubly dis- were assayed as described above.
tilled and purified with a Milli-Q system (Millipore
Corp., Bedford, MA). The materials and vessels used
for trace analysis were kept in 10% nitric acid at least 3. Results and discussion
24 h and subsequently four times in Milli-Q water.
SRM 1640 was obtained from the National Institute of 3.1. Effect of pH
Standards and Technology (NIST), Gaithersberg, MA.
CPE of cadmium, copper, lead and zinc was per-
2.3. Procedures formed in different pH buffer solutions. The separation
of metal ions by the CP method involves prior forma-
For the CPE, aliquots of the cold solution contain- tion of a complex with sufficient hydrophobicity to
ing the analyte, Triton X-114 and TAN buffered at a be extracted into the small volume of surfactant-rich
suitable pH were kept for 15 min in the thermostatic phase, thus obtaining the desired pre-concentration.
bath maintained at 40◦ C. Since the surfactant density Extraction yield depends on the pH at which complex
is 1.37 g ml−1 therefore, the surfactant-rich phase can formation occurs.
settle through the aqueous phase. The phase separation Fig. 1 shows the effect of pH on the extraction
is accelerated by centrifuging at 5000 rpm for 15 min. of cadmium, copper, lead and zinc complexes. It
On cooling in an ice-bath, the surfactant-rich phase was found that for copper and zinc in the pH range
became viscous and was retained at the bottom of the 7.0–10.0, lead in a range 7.0–9.0 and cadmium in the
tubes. The aqueous phases can readily be discarded range 8.0–10.0, extraction was quantitative. Hence,
simply by inverting the tubes. Later, in order to de- a middle range of pH at 8.6 was chosen for these
crease the viscosity and facilitate sample handing prior analytes.
to the FAAS assay, 200 ␮l of an acidified methanol so-
lution containing 0.1 mol l−1 HNO3 was added to the 3.2. Effects of buffer concentration and
surfactant-rich phase. The viscous phase reverted to its ionic strength
normal fluidity. A volume of 100 ␮l of the final solu-
tion was introduced into the nebulizer of the spectrom- The influence of buffer amount was carried out
eter via a manual sample injector that was connected in which the other experimental variables remained
to the nebulizer by the sample aspiration tubing.
Prior to the above pre-concentration procedure, all
the water samples were filtered through a 0.45 ␮m pore
size membrane filter to remove suspended particulate
matter and were stored at 6◦ C in the dark. To a 50 ml
water sample, 1.0 ml of a solution containing 2.6%
Triton X-114 and 1.0 × 10−3 mol l−1 TAN and 1.0 ml
of 0.1 mol l−1 Na2 B4 O7 ·10H2 O buffer solution (pH
8.6) were added. After phase separation, 200 ␮l of
a solution of methanol containing 0.1 mol l−1 HNO3
was added to the surfactant-rich phase. The samples
were assayed as described in the previous section.
25 ml of SRM 1640 was adjusted with 0.5 mol l−1
NaOH to pH ca. 8.0 and diluted with Milli-Q water
to 50 ml; 1.0 ml of a solution containing 2.6% Tri-
Fig. 1. Effect of pH on the extraction recovery. Conditions:
ton X-114 and 1.0 × 10−3 mol l−1 TAN and 1.0 ml 20 ng ml−1 Cd and Zn, 40 ng ml−1 Cu and Pb, 2 × 10−5 mol l−1
of 0.1 mol l−1 Na2 B4 O7 ·10H2 O buffer solution (pH TAN and 0.05% Triton X-114. Other experimental conditions as
8.6) were added. After phase separation, 200 ␮l of a described in Section 2.3.
218 J. Chen, K.C. Teo / Analytica Chimica Acta 450 (2001) 215–222
Fig. 2. Effect of TAN concentration on the extraction recovery.
Conditions: 20 ng ml−1 Cd and Zn, 40 ng ml−1 Cu and Pb, 0.05%
Triton X-114, pH 8.6. Other experimental conditions as described
in Section 2.3.
constant. The results showed that above 0.5 ml of
buffer solution added to 50 ml of solution, no variation
took place in the extraction yield. Thus, 1.0 ml buffer
solution was added in all subsequent experiments.
Ionic strength had no significant effect upon extrac-
tion efficiency and sensitivity up to 0.5 mol l−1 .
3.3. Effect of TAN concentration
The extraction yield as a function of the concen-
tration of the complexing agent is shown in Fig. 2.
For the four cations studied, 50 ml of a solution
Fig. 3. Effect of Triton X-114 concentration on the absorbance. Conditions: 20 ng ml−1 Cd and Zn, 40 ng ml−1 Cu and Pb, 2 × 10−5 mol l−1
TAN, pH 8.6. Other experimental conditions as described in Section 2.3.
containing 1 ␮g of Cd and Zn, 2 ␮g of Cu and Pb in
0.05% Triton X-114 and at a medium buffer of pH 8.6
containing various amounts of TAN were subjected to
the CP pre-concentration process. The yield increases
up to a TAN concentration of 8 × 10−7 mol l−1 for
Cd, Pb, Zn and 1.2 × 10−6 mol l−1 for Cu and reaches
near quantitative extraction efficiency. A concentra-
tion of 2 × 10−5 mol l−1 was chosen to account for
other extractable species.
3.4. Effect of Triton X-114 concentration
A successful CPE would be that which maximizes
the extraction efficiency through minimizing the phase
volume ratio thus, maximizing its concentrating factor.
The variation in extraction efficiency within the Tri-
ton X-114 range of 0.03–0.2% (w/v) was examined.
Quantitative extraction was observed when the Triton
X-114 concentration was >0.05%. Fig. 3 highlights the
differences observed in the respective atomic absorp-
tion signals at different surfactant concentrations. With
increase of Triton X-114 concentration above 0.05%,
the signals decrease because of the increment in the
overall analyte volumes and the viscosity of the sur-
factant phase. The optimum surfactant concentration
used for the four metals was the same, 0.05% Triton
X-114, in order to achieve the optimal analytical sig-
nal in conjunction with the highest possible extraction
efficiency.
 J. Chen, K.C. Teo / Analytica Chimica Acta 450 (2001) 215–222
3.5. Effects of equilibration temperature and time
It was desirable to employ the shortest equili-
bration time and the lowest possible equilibration
temperature, as a compromise between completion of
extraction and efficient separation of phases. It was
found that 40◦ C is adequate for these analyses. The
dependence of extraction efficiency upon equilibra-
tion time was studied for a time span of 5–30 min. An
equilibration time of 15 min was chosen the optimal
to achieve quantitative extraction.
3.6. Effect of viscosity on the analytical signal
Since the surfactant-rich phase obtained after CPE
is rather viscous, methanol containing 0.1 mol l−1
nitric acid was added to the surfactant-rich phase
after the separation of phases in order to facilitate
its introduction into the nebulizer of the spectrome-
ter. Fig. 4 shows the changes of the analytical signal
normalized as a function of the volume of methanol
added to the surfactant-rich phase obtained after
phase separation. There is an optimum volume of
methanol (100–200 ␮l) with respect to the cadmium,
copper, zinc and lead absorbance signals. For smaller
added volumes of acidified methanol, the signals
are lower because the viscosity remains high and
clearly predominates over dilution whereas, for larger
added volumes of acidified methanol, the decrease in
Fig. 4. Effect of added methanol volume on absorbance.
Conditions: 20 ng ml−1 Cd and Zn, 40 ng ml−1 Cu and Pb,
2 × 10−5 mol l−1 TAN, 0.05% Triton X-114, pH 8.6. Other exper-
imental conditions as described in Section 2.3.
219
Fig. 5. Effect of injection volume on absorbance. Conditions:
20 ng ml−1 Cd and Zn, 40 ng ml−1 Cu and Pb, 2 × 10−5 mol l−1
TAN, 0.05% Triton X-114, pH 8.6. Other experimental conditions
as described in Section 2.3.
viscosity of the resulting analyte solution is small
enough for nebulization. However, further dilution
beyond the threshold region would lead to a re-
duction of signal. An optimal volume of 200 ␮l of
methanol containing 0.1 mol l−1 HNO3 was added to
surfactant-rich phase. This added volume of methanol
was chosen in order to ensure a sufficient volume of
sample for aspiration.
3.7. Effect of injection volume on the
analytical signal
The influence of injection volume on the analytical
signal was studied in which the other experimen-
tal variables remained unchanged. The results are
shown in Fig. 5. The analytical signal increases up
to an injection volume of 100 ␮l, reaching a plateau.
An injection volume of 100 ␮l was therefore chosen
in order to obtain a good analytical signal and en-
sure a sufficient volume of sample for four element
determination.
3.8. Calibration, precision and detection limits
Calibration graphs were obtained by pre-concentra-
ting 50 ml of sample in the presence of 0.05%
Triton X-114 in a medium buffered at pH 8.6. A vol-
ume of 100 ␮l of the final solution was introduced
into the nebulizer of the spectrometer by a manual
220 J. Chen, K.C. Teo / Analytica Chimica Acta 450 (2001) 215–222

Table 1
Analytical characteristics of the method
Element Concentration range (ng ml−1 ) Regression equation R2 R.S.D. (%) LODd (ng ml−1 )

Cd 0.099–50 Aa = 1.2 × 10−2 Cb + 0.014 0.9982 3.1 (10)c 0.099

Cu 0.27–100 A = 4.5 × 10−3 C + 0.016 0.9987 1.6 (20) 0.27
Pb 1.1–160 A = 1.6 × 10−3 C + 0.002 0.9995 3.5 (20) 1.1
Zn 0.095–30 A = 1.9 × 10−2 C + 0.029 0.9992 1.5 (10) 0.095
a
A: absorbance.
C: concentration (ng ml−1 ).
b
c Values in parentheses are the cadmium, copper, lead and zinc concentrations (ng ml−1 ) for which the R.S.D. was obtained; number

of results n = 10.
d LOD: limit of detection, calculated as three times the standard deviation (3σ ) of the blank signal.

sample injector that was connected to the nebulizer Table 2

via the sample aspiration tubing. In this case, linear Effect of foreign ions on the pre-concentration and determination
of cadmium (10 ng ml−1 ), copper (20 ng ml−1 ), lead (20 ng ml−1 )
relationships between the absorbance measured and
and zinc (10 ng ml−1 )
the concentration of metal prepared for the calibration
solution were obtained. Table 1 gives the calibration Ions Concentra- Recovery (%)
tion (mg l−1 )
parameters, the relative standard deviation obtained Cd Cu Pb Zn
for 10 analyte samples subjected to the complete pro- Na+ 10 × 103 105.0 98.9 100 104.1
cedure and the detection limits. Pre-concentration of K+ 10 × 103 104.2 97.8 103.2 104.8
only 50 ml of sample in the presence of 0.05% Triton Ca2+ 10 × 102 103.5 97.8 98.2 102.2
X-114 permitted the detection of 0.099, 0.27, 1.1 and Mg2+ 10 × 102 99.1 100 96.8 101.1
Al3+
0.095 ng ml−1 for cadmium, copper, lead and zinc,
10 99.2 100.8 100.0 96.8
Mn2+ 0.5 100.7 101.0 102.0 98.8
respectively. The enhancement factors calculated as Co2+ 0.5 103.4 102.1 99.1 99.2
the ratio of absorbance of pre-concentrated samples Ni2+ 0.5 96.5 100.6 103.6 98.4
to that obtained without pre-concentration were 57.7, Fe3+ 0.5 99.3 98.4 103.2 97.8
64.3, 55.6 and 63.7 for cadmium, copper, lead and Cd2+ 0.5 98.0 102.3 103.0
Cu2+ 0.5 98.1 102.0 101.6
zinc, respectively. Pb2+ 0.5 98.4 100.0 98.6
Zn2+ 0.5 100 101.5 98.8
3.9. Interferences
react with TAN and extracted to the micelle phase
In the view of the high selectivity provided by were studied. The results are shown in Table 2. Cad-
FAAS, the only interferences studied were those re- mium, copper, lead and zinc recoveries were nearly
lated to the pre-concentration step. Cations that may quantitative in the presence of other cations.

Table 3
Determination of Cd, Cu, Pb and Zn (ng ml−1 ) in water samplesa
Metal Tap water River water Sea water SRM 1640

Certified value Our value

Cd ndb nd nd 22.79 ± 0.96 22.52 ± 0.84

Cu 13.4 ± 0.4 3.71 ± 0.15 2.24 ± 0.12 85.2 ± 1.2 85.5 ± 1.3
Pb nd 4.81 ± 0.21 3.64 ± 0.15 27.89 ± 0.14 26.68 ± 0.71
Zn 10.7 ± 0.2 9.85 ± 0.24 0.52 ± 0.02 53.2 ± 1.1 53.4 ± 1.0
a Mean ± S.D. (n = 3).
b nd: not detected.
 J. Chen, K.C. Teo / Analytica Chimica Acta 450 (2001) 215–222 221

Table 4
Cd, Cu, Pb and Zn recovery (n = 3)
Samples Added (ng ml−1 ) Measured (ng ml−1 ) Recovery (%)

Cd Cu Pb Zn Cd Cu Pb Zn Cd Cu Pb Zn

Tap water – – – – nda 13.4 nd 10.7 – – – –

10 10 10 10 10.4 23.2 10.4 20.6 104 98 104 99
River water – – – – nd 3.71 4.81 9.85 – – – –
10 10 10 10 10.2 13.8 15.0 19.7 102 101 102 98.5
Sea water – – – – nd 2.24 3.64 0.52 – – – –
10 10 10 10 10.2 12.1 13.5 10.9 102 98.6 98.6 104
a nd: not detected.

3.10. Determination of cadmium, copper, lead
and zinc in water samples
In order to test the reliability of the proposed
methodology suitable for the assay of the four tar-
geted metal ions, it was applied to determine their
concentrations in tap water, river water, sea water and
a SRM.
For this purpose, 50 ml of each of the samples were
pre-concentrated with 0.05% Triton X-114 and 2.0 ×
10−5 mol l−1 TAN following the proposed method.
The results are shown in Table 3. For calibration pur-
poses, the working standard solutions were subjected
to the same pre-concentration procedure as used for
the analyte solutions.
In addition, recovery experiments for different
amounts of Cd, Cu, Pb and Zn were carried out. The
results shown in Table 4 confirm the validity of the
proposed method.
4. Conclusions
CPE is an easy, safe, rapid and inexpensive method-
ology for pre-concentration and separation of trace
metals in aqueous solutions. Triton X-114 was chosen
for the formation of the surfactant-rich phase due to
its excellent physicochemical characteristics: low CP
temperature; high density of the surfactant rich phase,
which facilitates phase separation easily by centrifuga-
tion; commercial availability and relatively low price;
and the lack of electro-active groups in its molecule
and low toxicity. TAN is a very stable, and fairly se-
lective complexing reagent. The surfactant-rich phase
can be introduced into the nebulizer of a flame atomic
absorption spectrometer by a manual injector con-
nected to a nebulizer after dilution with methanol.
One can improve the detection limit by an order
of magnitude of one or two with such a simple CP
pre-concentration procedure. The proposed method
can be applied to the determination of trace metals in
various water samples.
Acknowledgements
The authors gratefully acknowledge the National In-
stitute of Education, Nanyang Technological Univer-
sity for providing a scholarship for Chen Jianrong to
pursue post-graduate study and research.
References
[1] P.L. Malvankar, V.M. Shinde, Analyst 116 (1991) 1081.
[2] P.S. More, A.D. Sawant, Anal. Lett. 27 (1994) 1737.
[3] S.Y. Bae, X. Zeng, G.M. Murray, J. Anal. At. Spectrom. 13
(1998) 1177.
[4] N. Prakashi, G. Csanady, R.A. Michaelis, G. Knapp,
Mikrochim. Acta 3 (1989) 257.
[5] M. Vircaus, V. Rone, A. Palne, D. Vircava, Anal. Chim. Acta
299 (1994) 291.
[6] L. Elçi, U. Sahin,
˛ S. Özta˛s, Talanta 44 (1997) 1017.
[7] S.
˛ Güçer, M. Yaman, J. Anal. At. Spectrom. 7 (1992) 179.
[8] M. Soylak, I. Narin, M. Dogan, Anal. Lett. 30 (1997) 2801.
[9] M. Soylak, L. Elçi, Int. J. Environ. Anal. Chem. 66 (1997) 51.
[10] M. Soylak, U. Sahin,
˛ L. Elçi, Anal. Chim. Acta 322 (1996)
111.
[11] R.M.C. Suttun, S.J. Hill, P. Jones, J. Chromatogr. A 739
(1996) 81.
[12] B. Mohammad, A.M. Ure, D. Littlejohn, J. Anal. At.
Spectrom. 7 (1992) 695.
222 J. Chen, K.C. Teo / Analytica Chimica Acta 450 (2001) 215–222
[13] G.L. McIntire, Crit. Rev. Anal. Chem. 21 (1990) 257.
[14] H. Watanabe, in: K.L. Mittal, E.F. Fendler (Eds.), Solution
Behaviour of Surfactants, Vol. 2, Plenum Press, New York,
1982, pp. 1305–1313.
[15] B. Moreno Cordero, J.L. Pérez Pavón, C. Garcı́a Pinto, M.E.
Fernández Laespada, Talanta 40 (1993) 1703.
[16] W.L. Hinze, E. Pramauro, CRC Crit. Rev. Anal. Chem. 24
(1993) 133.
[17] C. Garcı́a Pinto, J.L. Pérez Pavón, B. Moreno Cordero, Anal.
Chem. 67 (1995) 2606.
[18] S.R. Sirimanne, J.R. Barr, D.G. Patterson Jr., L. Ma, Anal.
Chem. 68 (1996) 1556.
[19] E. Evdokimov, R. Von Wandruszka, Anal. Lett. 31 (1998)
2289.
[20] A. Eiguren Fernández, Z. Sosa Ferrera, J.J. Santana
Rodriguez, Analyst 124 (1999) 487.
[21] R.L. Revia, G.A. Makharadze, Talanta 48 (1999) 409.
[22] R. Carabias-Martı́nez, E. Rodrı́guez-Gonzalo, J. Dominguez-
Alvarez, J. Hernández- Méndez, Anal. Chem. 71 (1999) 2468.
[23] H. Watanabe, H. Tanaka, Talanta 25 (1978) 585.
[24] H. Watanabe, T. Kamidate, S. Kawamorita, K. Haraguchi, M.
Miyajima, Anal. Sci. 3 (1987) 433.
[25] T. Saitoh, Y. Kimura, T. Kamidate, H. Watanabe, K.
Haraguchi, Anal. Sci. 5 (1989) 577.
[26] H. Watanabe, T. Saitoh, T. Kamidate, K. Haraguchi,
Mikrochim. Acta 106 (1992) 83.
[27] M.E.F. Laespada, J.L. Perez Pavón, B. Moreno Cordero,
Analyst 118 (1993) 209.
[28] M.F. Silva, L. Fernández, R. Olsina, D. Stacchiola, Anal.
Chim. Acta 342 (1997) 229.
[29] M.F. Silva, L. Fernández, R. Olsina, Analyst 123 (1998) 1803.
[30] S. Igarashi, K. Endo, Anal. Chim. Acta 320 (1996) 133.
[31] C.H. Wang, D.F. Martin, B.B. Martin, J. Environ. Sci. Health
A 31 (1996) 1101.
[32] C. Garcı́a Pinto, J.L. Pérez Pavón, B. Moreno Cordero, E.
Romero Beato, S. Garcı́a Sánchez, J. Anal. At. Spectrom. 11
(1996) 37.
[33] M.C. Cerrato Oliveros, O. Jimenes de Blas, J.L. Pérez
Pavón, B. Moreno Cordero, J. Anal. At. Spectrom. 13 (1998)
547.
[34] M.A. Mesquita da Silva, V.L. Azzolin Frescura, F.J. Nome
Aguilera, A.J. Curtius, J. Anal. At. Spectrom. 13 (1998) 1369.
[35] E.K. Paleologos, C.D. Stalikas, S.M. Tzouwara-Karayanni,
G.A. Pilidis, M.I. Karayannis, J. Anal. At. Spectrom. 15
(2000) 287.
[36] S. Akita, M. Rovira, A.M. Sastre, H. Takeuchi, Sep. Sci.
Technol. 33 (1998) 2159.
[37] M.O. Luconi, M.F. Silva, R.A. Olsina, L.P. Fernández, Talanta
51 (2000) 123.
[38] S. Igarashi, A. Takahashi, Y. Ueki, H. Yamaguchi, Analyst
125 (2000) 797.
[39] A. Takahashi, S. Igarashi, Y. Ueki, H. Yamaguchi, Fresenius
J. Anal. Chem. 368 (2000) 607.
[40] M.A. Mesquita da Silva, V.L. Azzolin Frescura, A.J. Curtius,
Spectrochim. Acta Part B 55 (2000) 803.
[41] A. Sanz-Medel, M.R. Fenandez de la Campa, E. Blanco
Gonzales, M.L. Fernandez-Sanchez, Spectrochim. Acta Part
B 54 (1999) 251.
[42] K.C. Teo, J.R. Chen, Analyst 126 (2001) 534.
[43] J.R. Chen, K.C. Teo, Anal. Chim. Acta 434 (2002) 325.