Electrochemistry Communications 7 (2005) 976–982

www.elsevier.com/locate/elecom

Voltammetry of chromium(VI) at the liquid|liquid interface

Aoife M. OÕMahony a, Micheál D. Scanlon a, Alfonso Berduque a, Valerio Beni a,
Damien W.M. Arrigan a,*, Enrico Faggi b, Andrea Bencini b
a
Tyndall National Institute, Lee Maltings, University College, Cork, Ireland
b
Dipartimento di Chimica, Università di Firenze, Via della Lastruccia 3, 50019 Sesto Fiorentino, Firenze, Italy

Received 16 June 2005; accepted 30 June 2005

Available online 8 August 2005

Abstract

The voltammetry of hexavalent chromium (ammonium dichromate) at the interface between two immiscible electrolyte solutions
is reported. Detection of Cr(VI) by ion transfer voltammetry is possible by use of an organic phase ionophore, which facilitates the
transfer of Cr(VI) from the aqueous into the organic phase. The ionophore was the penta protonated form of polyamine macrocycle
2,5,8,11,14-pentaaza[15]-16,29-phenanthrolinophane (NeoTT). Cyclic voltammetry showed an increase of the peak current on
increasing the concentration of Cr(VI). Square wave voltammetry with background subtraction was employed for low level concen-
tration detection. The lowest concentration detected was 0.25 parts per million of Cr(VI).

2005 Elsevier B.V. All rights reserved.

Keywords: Liquid|liquid interface; ITIES; Hexavalent chromium; Facilitated ion transfer; Ammonium dichromate

1. Introduction chromium is relatively harmless and plays an essential

Speciation is one of the major challenges in analytical
chemistry, particularly metal speciation [1], wherein
analysis of species containing chromium is of great envi-
ronmental relevance due to the different possible oxida-
tion states in which this element can exist [2] and to the
dramatically different effects of such oxidation states on
health and the environment. In solution, chromium may
exist as Cr(III) and Cr(VI) [3] and these two oxidation
states have a contrasting impact in environment and
health. Hexavalent chromium is quite toxic due to its
high oxidation potential and its relatively small size,
which enables it to penetrate biological cell membranes.
It is limited in groundwater by the World Health Orga-
nisation (WHO) provisional guideline value of 50 parts
per billion (lg kg
1, ppb) [2,4]. However, trivalent
*
Corresponding author. Tel.: +353 21 4904079; fax: +353 21
4270271.
E-mail address: damien.arrigan@tyndall.ie (D.W.M. Arrigan).
role in biological processes, and it is about 100–1000
times less toxic than the hexavalent state [5]. The acute
toxic effects of chromium include immediate cardiovas-
cular shock, with later effects on the kidney, liver and
blood-forming organs [6,7]. The main sources of chro-
mium pollution in ground water are plating industries,
cooling towers, timber treatment, leather tanning, wood
preservation and steel manufacturing [2,8]. Moreover,
chromium particles in air play an important role in the
oxidation of sulphur dioxide and formation of acidic
aerosols involved in global acid rain [9].
Two basic electrode systems are generally used for
stripping voltammetric measurements of Cr(VI), the
mercury-film electrode (MFE) and hanging mercury
drop electrode (HMDE). However, because of the toxic-
ity of mercury, alternative electrode materials are
sought, particularly to meet the growing demands for
on-site environmental monitoring of trace chromium
[10]. Thus, mercury electrodes have been replaced by so-
lid electrodes [2]. Direct electrochemical reduction of

1388-2481/$ - see front matter
2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2005.06.011
 A.M. O’Mahony et al. / Electrochemistry Communications 7 (2005) 976–982
Cr(VI) has been studied on gold and carbon electrodes
[2]. Moreover, bismuth film-electrodes have been inves-
tigated as possible alternatives. Bismuth is an environ-
mentally friendly element, with very low toxicity, and
a widespread pharmaceutical use [11]. A sensitive
adsorptive stripping protocol was used to detect Cr(VI)
via its reduction and subsequent complexation with
diethylenetriammine pentaacetic acid (DTPA) at a bis-
muth film electrode [10].
An electrochemical detection strategy which has
hardly been investigated [12] for Cr(VI) voltammetry is
ion transfer across the interface between two immiscible
electrolyte solutions (ITIES) [13–17]. The ITIES may be
used as the basis of voltammetric detection methods be-
cause the transfer of charged analyte species across it re-
sults in current generation [18,19]. Although there are
many examples of cationic species determination by
ion transfer and facilitated ion transfer, the voltammetry
of anions has been hardly addressed [20–22]. Amongst
possible methods for facilitating the transport of anionic
Cr(VI) across the ITIES, complexation with a supramo-
lecular complexation agent and interaction with organ-
ic-phase electrolyte materials (as recently described for
the transfer of silver(I) cations across the ITIES [23])
may be considered. Supramolecular chemistry of anio-
nic species has emerged as an important area of interest
due to the presence of such species in both organic (bio-
logical) and inorganic environments [24]. The use of
non-covalent interactions with positive charged centers,
including the use of polyammonium receptors, and of
coordinative interactions with metal ions, constitute
two major approaches for strong and selective anion
binding [24]. Among carriers used for Cr(VI) transport
in membrane extraction processes, quaternary ammo-
nium salts have been most extensively studied [25–27].
The aim of this work was to investigate if Cr(VI)
transfer across the ITIES was possible using either or-
ganic phase electrolyte-facilitated or macrocyclic iono-
phore-facilitated processes. This study is a preliminary
study toward an electroanalytical methodology based
on voltammetry at the ITIES for the determination of
Cr(VI).
2. Experimental
2.1. Reagents
Reagents used were of maximum purity commer-
cially available. Lithium chloride anhydrous (LiCl), tet-
radodecylammonium tetrakis-(4-chlorophenyl)borate
(herein called ETH 500), bis (triphenylphosphoranylid-
ene) ammonium chloride (BTPPACl) and potassium
tetrakis(4-chlorophenyl-borate) (KTPBCl), hydrochlo-
ric acid 1.040 N, ammonium chloride (99.99%), sulphu-
ric acid 0.5 N, tetraethylammonium chloride (TEACl)
977
and the organic solvents used (1,2-dichloroethane,
DCE; and 1,6-dichlorohexane, DCH) were purchased
from Sigma–Aldrich. Ammonium dichromate atomic
spectroscopy standard solution ((NH4)2Cr2O7,
1000 ppm of chromium) was purchased from BDH Lab-
oratory Supplies (England); due to the low concentra-
tions and the acidic nature of the aqueous phase
electrolytes employed, the dominant Cr(VI) species as-
sumed present is the monoatomic HCrO
4 [2]. Solutions
of LiCl 10 mM, LiCl 10 mM + HCl 1 mM, or HCl 0.1 M
in de-ionised water were used as aqueous phases. The
organic phase contained either bis(triphenylphosphora-
nylidine) ammonium tetrakis(4-chlorophenyl-borate),
BTPPATPBCl, at 10 mM, or ETH 500 (purchased from
Fluka) 10 mM as organic phase electrolytes dissolved in
DCE or DCH. Solutions of hexavalent chromium were
obtained by dilution of the stock solution of ammonium
dichromate in the aqueous phase electrolyte. DCH was
purified as described by Katano et al. [28]; DCE was
used as received. The organic phase electrolyte,
BTPPATPBCl, was prepared by metathesis of
BTPPACl and KTPBCl [29,30].
The ionophore used, the polyamine macrocycle
2,5,8,11,14-pentaaza[15]-16,29-phenanthrolinophane
(NeoTT), was synthesised at the Department of Chemis-
try, University of Florence, Italy [31,32]. This compound
consists of a pentaamine linking the 2,9-phenanthroline
positions. Fig. 1 shows the chemical structure of NeoTT.
In its penta-protonated form, the acidic protons are
localised on the aliphatic amine groups [31]. NeoTT
was prepared as the hydrogen bromide, NeoTT.5HBr
(Mw = 798.1 g mol
1), soluble in water. In order to
make NeoTT soluble in the organic phase and suitable
for use as an organic phase ionophopre, the Br
anions
were substituted by tetrakis(4-chlorophenyl-borate)
anions (TPBCl
), by metathesis, as follows: 5 mol of
KTPBCl (in acetone) were added to 1 mol of
NeoTT.5HBr (in water). After acetone evaporation
(overnight), a yellow jelly-powder was collected and
placed in a desiccator (overnight) to remove water.
Fig. 1. Chemical structure of the ionophore employed in this work,
the penta-protonated form of 2,5,8,11,14-pentaaza[15]-16,29-
phenanthrolinophane (NeoTT) [31].
978 A.M. O’Mahony et al. / Electrochemistry Communications 7 (2005) 976–982

The resultant compound was NeoTT.5TPBCl (as con-
firmed by NMR spectrometry), hereafter referred to as
NeoTT.
2.2. Apparatus
All cyclic voltammetry (CV) and square wave voltam-
metry (SWV) experiments were performed using CH
Instruments electrochemical workstations (CHI 660B,
CHI 620A or CHI 620B) (from IJ Cambria Scientific,
UK). The electrochemical cell used was a customised
four-electrode cell, where the interfacial potential differ-
ence was applied between two Ag|AgCl reference elec-
trodes (prepared by potentiostatic oxidation of silver
wires in a solution of KCl 3 M) and the current was
measured by two platinum mesh counter electrodes.
The geometric area of the interface was 1.005 cm2. A
series of cell configurations was used in this work, as
shown in Scheme 1. Different aqueous and organic
phases were used to investigate the transfer of hexava-
lent chromium across the interface. According to the
interface polarisation convention adopted in the experi-
mental setup, the transfer of anionic species from the
aqueous phase into the organic phase occurs on the neg-
ative-going potential direction, producing a negative
current. In the CV experiments the forward scan was
that going from more positive to more negative poten-
tial and the SWV experiments were performed by sweep-
ing the potential from more positive to more negative
potential.
3. Results and discussion
3.1. Cyclic voltammetry
Initial experiments were focused toward establishing
whether electrolyte-facilitated transfer of Cr(VI) was
possible. Because of the low concentrations of Cr(VI)
and the acidic nature of the aqueous phase electrolytes
employed in this work, the dominant Cr(VI) species
present is assumed to be the monoatomic HCrO
4

BTPPA+Cl - 10 mM
BTPPATPBCl 10 mM
aj mM in
Cell 1: Ag (s) AgCl (s) in LiCl 10 mM AgCl (s) Ag (s)
in DCE (org) LiCl 10 mM and
(Luggin capillary) H2SO 4 1 mM

A 10 mM in LiCl 10
ETH 500 10 mM in
aj mM in
Cell 2: Ag (s) AgCl (s) mM (Luggin capillary) AgCl (s) Ag (s)
DCE (org) LiCl 10 mM and
H 2SO4 1 mM

BTPPA+Cl - 10 mM BTPPATPBCl 10 mM aj mM in
Cell 3: Ag (s) AgCl (s) in LiCl 10 mM + X mM NeoTT in AgCl (s) Ag (s)
LiCl 10 mM
(Luggin capillary) DCE (org)

BTPPA+Cl- 10 mM BTPPATPBCl 10 mM aj mM in
Cell 4: Ag (s) AgCl (s) in LiCl 10 mM + X mM NeoTT in AgCl (s) Ag (s)
LiCl 10 mM
(Luggin capillary) DCE (org) and HCl 1 mM

BTPPA +Cl- 10 mM BTPPATPBCl 10 mM aj mM in

Cell 5: Ag (s) AgCl (s) in LiCl 10 mM + X mM NeoTT in AgCl (s) Ag (s)
LiCl 10 mM
(Luggin capillary) DCH (org) and HCl 1 mM

BTPPA+Cl- 10 mM BTPPATPBCl 10 mM aj mM in
Cell 6: Ag (s) AgCl (s) in LiCl 10 mM + X mM NeoTT in AgCl (s) Ag (s)
HCl 0.1 M
(Luggin capillary) DCH (org)

Scheme 1. Cell configurations used, where a is ammonium dichromate, of j concentration; A is tetradodecylammonium chloride and X is the
concentration of NeoTT ionophore used.
 A.M. O’Mahony et al. / Electrochemistry Communications 7 (2005) 976–982 979

species [2]. A quaternary ammonium salt organic phase As can be seen from Fig. 3, the addition of Cr(VI) re-
electrolyte (cell 2 in Scheme 1) and a non-quaternary sults in the disappearance of the signal previously re-
ammonium salt organic phase electrolyte (cell 1 in corded in the absence of Cr(VI) (curve 1) and in the
Scheme 1) were examined. No additional complexing appearance of a new peak signal at higher potential
agent or ionophore was added. Cyclic voltammetry (curves 2–6). This second signal is probably due to the
(CV) showed that Cr(VI) (as the salt ammonium dichro- transfer of Cr(VI) and to formation of the complex
mate) did not transfer across the ITIES under these con- NeoTT=HCrO
4 . The fact that the signal recorded in
ditions, as no transfer peaks were observed. In the the presence of Cr(VI) is at higher potential than those
absence of an ionophore, Cr(VI) did not transfer, be- attributed to the ionophore-Cl
complex, and the disap-
cause it is too hydrophilic to transfer within the avail- pearance of this peak following the addition of the
able potential window. Therefore, the ionophore Cr(VI) (even when Cl
is at ca. 350-fold excess) are clear
(NeoTT) was introduced into the organic phase to lower indication of the selectivity of the NeoTT for Cr(VI)
the Gibbs free energy of transfer for Cr(VI) ions. NeoTT over chloride. The peak currents recorded in the pres-
is able to form complexes with anionic species such as ence of Cr(VI) had a linear dependence on the square
sulfate [24]. Although the presence of aromatic groups root of the potential sweep rate, in accord with the
does not favour binding due to repulsion between the Randles-Sevcik equation
anion and the electronic p cloud of the aromatic rings,
ip ¼ ð2.69  105 Þn3=2 ACD1=2 m1=2 ð1Þ
relatively large amine chains (such as the pentaamine
in NeoTT) can form complexes in which the anion is lo- where ip (A) is the peak current, n is the charge of
cated far from the aromatic structure [24]. the ionic species, A (cm2) is the area of the interface,
However, CV of the blank solution (cell 3, Scheme 1, C (mol cm
3) is the concentration of Cr(VI), D
no Cr(VI) in the aqueous phase) containing NeoTT ion- (cm
2 s
1) is the diffusion coefficient of Cr(VI) and m
ophore in the organic phase, produced a peak-shaped (V s
1) is the sweep rate. This linear dependence implies
voltammetric response. These peaks may be due to the that the transfer process was diffusion-controlled. Eq.
complexation of the aqueous phase chloride ions in (1) was used to calculate the diffusion coefficient of
the NeoTT structure. NeoTT itself is not believed to Cr(VI), 1.3 · 10
5 cm2 s
1, in good agreement with a lit-
transfer across the ITIES, as when a hydrophilic version erature value 1.6 · 10
5 cm2 s
1 [2].
of NeoTT (i.e., NeoTT.5HBr) was present in the aque- Furthermore, the addition of further aliquots of
ous phase (not shown) no transfer peaks were recorded. ammonium dichromate to the aqueous phase resulted
Thus, NeoTT (NeoTT.5TPBCl, in the organic phase) in an increase in peak current with Cr(VI) concentration
should not transfer across the interface. Fig. 2 (curve (Fig. 3, curves 2–6 and inset). Thus, Cr(VI) interacts
1) shows an example of the voltammetric response of with the NeoTT receptor in such a manner that it can
the blank containing NeoTT 0.3 mM in the organic be quantified. The inset in Fig. 3 shows the peak current
phase (cell 3, Scheme 1). Curves 2–6 in Fig. 2 show increase with concentration measured from the forward
the voltammetric response at different sweep rates fol- (negative-going) potential sweep (the transfer of Cr(VI)
lowing the addition of Cr(VI) to the aqueous phase. from aqueous to organic phase). Replacing ammonium

25 20
15 y = 106.78x - 1.9778
2
R = 0.934
20 10
Current /µA

5
5
15 0
-5 0 0.03 0.06 0.09 0.12 0.15 0.18 4
10 -10 y = -76.813x + 1.1842
2
3
R = 0.9549
-15 2
Current / µA

5 -20 (Scan Rate)1/2 / (Vs-1)1/2 1

0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
-5

-10

-15

-20

-25 Potential / V vs Ag|AgCl

Fig. 2. Cyclic voltammetry of Cr(VI) at the liquid|liquid interface using cell 3. Voltammogram of blank at 5 mV s
1 (1) and voltammograms of
Cr(VI) 58 lM facilitated ion transfer at different scan rates: 7.5 (2); 10 (3), 15 (4) and 25 mV s
1 (5). Concentration of NeoTT: 0.3 mM. Inset. Peak
current vs. the square root of the scan rate. Forward (d) and reverse (}) peak currents.
980 A.M. O’Mahony et al. / Electrochemistry Communications 7 (2005) 976–982

20 0
0 0.025 0.05 0.075 0.1

Peak current / µA
-1

15
-2 y = -21.104x - 1.2399
2
R = 0.9963
-3
10 6
5

Current / µA
-4 Concentration / mM 4
5 3
2
1

0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

-5

-10 Potential / V vs Ag|AgCl

Fig. 3. Cyclic voltammetry of Cr(VI) at the liquid|liquid interface using cell 3. Voltammogram of blank (1) and voltammograms of different
concentrations of Cr(VI): 5 (2); 15 (3), 25 (4) 50 (5) and 100 lM (6). Concentration of NeoTT: 0.3 mM. Inset. Forward peak current (j) vs. the
concentration of Cr(VI). All scan rates: 5 mV s
1.

dichromate with ammonium chloride in cell 3 showed trolyte did lead to a larger potential window probably
no change of the peak current response observed from due to its lower dielectric constant, compared to that
the CV of the blank (i.e., before addition of the ammo- of DCE.
nium chloride). Thus, it can be concluded that the peak
current increase (Figs. 2 and 3) is due to Cr(VI) ion
transfers and not to the ammonium ions. These latter 3.2. Square wave voltammetry
experiments were necessary in order to rule out the pos-
sibility of cation transfer, as it is know that NeoTT can Square wave voltammetry (SWV) is an electrochemi-
interact with and coordinate also with cations such as cal technique commonly used for quantitative purposes
copper [31] and cadmium [32]. due to the better detection limits achievable [33]. Cur-
The use of different organic solvents (DCE and rent measurements in SWV are taken twice per cycle:
DCH) in the organic phase and of different aqueous the forward current sample (if) and the reverse current
phase electrolyte phases (LiCl 10 mM and HCl 1 mM; sample (ir) [33]. A difference current Di results from the
and HCl 0.1 M) was also evaluated. No significant subtraction if
ir. The SWV experiment can thus be
changes were observed on using mixtures of LiCl and represented as three square wave voltammograms show-
HCl or HCl alone in the aqueous phase electrolyte (cell ing difference, forward and reverse currents versus the
6). The use of 1,6-dichlorohexane as organic phase elec- applied potential [33].

40

30 1

20

10
Current / µA

0
0 0.2 0.4 0.6 0.8 1 2 1.2
-10

-20

-30 3

-40
4
-50

-60 Potential / V vs Ag|AgCl

Fig. 4. Square wave voltammetry analysis of Cr(VI) (HCrO
4 ) transfer across the ITIES. Cell 5 (DCH organic solvent, and LiCl 10 mM and HCl
1 mM as aqueous phase electrolyte). SWV of blank: forward current segment (2), reverse current segment (1) and difference current segment (3); and
difference current segment of 0.335 mM Cr(VI) (4).
 A.M. O’Mahony et al. / Electrochemistry Communications 7 (2005) 976–982 981

The aim of these studies was to determine the limit of defined peak on this blank voltammogram. Furthermore
detection and the linear range of concentration depen- after the additions of ammonium dichromate to the
dence for Cr(VI) detection by voltammetry at the ITIES. aqueous phase, difference (Fig. 4, voltammogram 4),
As seen in Fig. 4, the characteristics of the difference, forward and reverse (not shown) currents have the same
forward and reverse voltammograms for the detection response behaviour. The only difference recorded is that
of Cr(VI) by NeoTT-facilitated ion transfer are quite in this cases a new signal, in the high potential region, is
complex in comparison to SWV at conventional elec- recorded. This new peak increases with the increase of
trodes. Voltammogram 2 in Fig. 4(a) is the forward cur- Cr(VI) concentration. In order to improve the quality
rent sample of the blank solution, using cell 5 (the of the data analysis the background subtraction ap-
concentration of NeoTT in the organic phase was proach [18] was adopted. To achieve this, initial SWVs
0.3 mM) and a negative sweep from 1.05 to 0.05 V. Re- of blank (no Cr(VI) added) were subtracted from the
sults showed a negative peak response at around 0.64 V, SWVs after additions of Cr(VI). It was also found that
possibly due to the transfer of chloride (as already dis- use of the forward current was better than using either
cussed for the CV experiments). However, voltammo- the difference or the reverse current with background
gram 1, which is the reverse current sample, also yields subtraction.
a negative peak at 0.64 V, of lower intensity than the Fig. 5(a) shows examples of SWV peak after back-
peak in voltammogram 2. Therefore, the subtraction ground subtraction, based on the forward current sam-
if
ir leads to a current Di (voltammogram 3) that does ples. The peak around 0.8 V is associated with the
not improve the peak definition but leads to a less-well Cr(VI) transfer process, as indicated in Fig. 4, voltam-

30 a

20

10

0
Current / µA

0 0.2 0.4 0.6 0.8 1

-10

-20

-30 1 2
3
-40 4 5

-50

-60 Potential / V vs Ag|AgCl

60
b

50
y = 8.2576Ln(x) + 47.57
Peak Current / µA

R2 = 0.9505
40

25
Peak Current / µA

30 20
15
10 y = 0.348x + 4.5747
20
5 R2 = 0.9789

0
10 0 10 20 30 40 50 60
Concentration / µM

0
0 0.5 1 1.5 2 2.5 3 3.5

Concentration / mM

Fig. 5. (a) SWV forward current segments analysis after background subtraction and using cell 5 (DCH organic solvent, and LiCl 10 mM and HCl
1 mM as aqueous phase electrolyte). Concentrations of Cr (VI): 43.2 lM (1), 52.7 lM (2), 148.9 lM (3), 242.1 lM (4) and 335.4 lM (5). (b) Peak
current (in absolute value) vs. concentration. Inset: peak current vs concentration in the linear range. The concentration of NeoTT was 0.3 mM. SWV
sweeps from 0.84 to 0.1 V.
982 A.M. O’Mahony et al. / Electrochemistry Communications 7 (2005) 976–982
mogram 4. The large positive peak around 0.6 V is be-
lieved to be an artefact associated with the Cl
transfer
process which is not negated by the background sub-
traction procedure employed. Fig. 5(b) shows the back-
ground-subtracted forward current sample response
versus concentration of Cr(VI). The current response
is linear with Cr(VI) concentration in the lower range,
and reaching a plateau at higher concentrations. The
linear response range, as shown by the inset in
Fig. 5(b) was in the range 4.8–148 lM (or 0.25–7.7 parts
per million, ppm, mg kg
1). The lowest detectable con-
centration was 4.8 lM of Cr(VI), or 0.25 ppm. In pH
control experiments, it was found that there was no dif-
ference in signal for aqueous phases containing LiCl
10 mM with pH adjusted to the range pH 2–3 or in
HCl 0.1 M.
4. Conclusion
Preliminary results presented show that hexavalent
chromium, in the form of HCrO
4 , can be transferred
across the ITIES when a suitable ionophore, in this case
NeoTT, is present in the organic phase. The ionophore
was the penta protonated form of polyamine macrocy-
cle 2,5,8,11,14-pentaaza[15]-16,29-phenanthrolinophane
(NeoTT). The ability to transfer Cr(VI) in this way
can be useful as the basis of an analytical methodology
for the determination of this toxic species. The lowest
concentration detectable was 0.25 ppm Cr(VI). Further
investigations are required to elucidate the transfer
mechanism undergone by the ionophore–chromate
complex.
Acknowledgements
The authors acknowledge Science Foundation Ire-
land (02/IN.1/B84) for support.
References
[1] I. Turyan, D. Mandler, Anal. Chem. 69 (1997) 894–897.
[2] C.M. Welch, O. Nekrassova, R.G. Compton, Talanta 65 (2005)
74–80.
[3] V. Orescanin, L. Mikelic, S. Lulic, M. Rubcic, Anal. Chim. Acta
527 (2004) 125–129.
[4] Guidance for Drinking Water Quality, second ed., vol. 1,
Recommmendations, Geneva, WHO, 1993, pp. 45–46.
[5] R.M. Cespón-Romero, M.C. Yebra-Biurrun, M.P. Bermejo-
Barrera, Anal. Chim. Acta 327 (1996) 37–45.
[6] E. Vassileva, K. Hadjiivanow, T. Stoychev, C. Daiev, Analyst 125
(2000) 693–698.
[7] P.V. Oliveira, E. Oliveira, Fresenius, J. Anal. Chem. 371 (2001)
909–914.
[8] R.J. Kieber, J.D. Willey, S.D. Zvalaren, Environ. Sci. Technol. 36
(2002) 5321–5327.
[9] M.V. BalaramaKrishna, K. Chandrasekaran, S.V. Rao,
D. Karunasagar, J. Arunachalam, Talanta 65 (2005) 135–143.
[10] L. Lin, N.S. Lawerence, S. Thongngamdee, J. Wang, Y. Lin,
Talanta 65 (2005) 144–148.
[11] J. Wang, J. Lu, S.B. Hocevar, P.A.M. Farias, B. Ogorevc, Anal.
Chem. 72 (2000) 3218.
[12] Y.-W. Choi, S.-H. Moon, Electroanalysis 16 (2004) 932.
[13] Z. Samec, V. Mareček, J. Weber, J. Electroanal. Chem. 100 (1979)
841–852.
[14] P. Vanýsek, Anal. Chem. 62 (1990) 827A–835A.
[15] H.H. Girault, Modern Aspects of Electrochemistry, vol. 25,
Plenum Press, New York, 1993, pp. 1–62.
[16] P. Vanýsek, R.P. Buck, J. Electrochem. Soc. 131 (1984) 1792–1796.
[17] P. Vanýsek, Trends Anal. Chem. 12 (1993) 357–363.
[18] V. Beni, M. Ghita, D.W.M. Arrigan, Biosens. Bioelectron. 20
(2005) 2097–2103.
[19] Z. Samec, E. Samcová, H.H. Girault, Talanta 63 (2004) 21–32.
[20] T. Shioya, S. Nishizawa, N. Teramae, J. Am. Chem. Soc. 120
(1998) 11534.
[21] S. Nishizawa, T. Yokobori, R. Kato, K. Yoshimoto, T. Kamaishi,
N. Teramae, Analyst 128 (2003) 663.
[22] R.A.W. Dryfe, S.S. Hill, A.P. Davis, J.B. Joos, E.P.L. Roberts,
Org. Biomol. Chem. 2 (2004) 2716–2718.
[23] A. Sherburn, M. Platt, D.W.M. Arrigan, N.M. Boag, R.A.W.
Dryfe, Analyst 128 (2003) 1187.
[24] P. Arranz, A. Bencini, A. Bianchi, P. Diaz, E. Garcı´a-España, C.
Giorgi, S.V. Luis, M. Querol, B. Valtancoli, J. Chem. Soc., Perkin
Trans. II (2001) 1765–1770.
[25] F.J. Alguacil, A.G. Coedo, M.T. Dorado, A.M. Sastre, Hydro-
metallurgy 61 (2001) 13–19.
[26] I. Svancara, P. Foret, K. Vytras, Talanta 64 (2004) 844–852.
[27] P. Venkateswaran, K. Palanivelu, Separ. Purif. Technol. 40 (2004)
279–284.
[28] H. Katano, H. Tatsumi, M. Senda, Talanta 63 (2004) 185–193.
[29] H.J. Lee, H.H. Girault, Anal. Chem. 70 (1998) 4280–4285.
[30] S. Ulmeanu, H.J. Lee, D.J. Fermin, H.H. Girault, Electrochem.
Commun. 3 (2001) 219–223.
[31] C. Bazzicalupi, A. Bencini, V. Fusi, C. Giorgi, P. Paoletti, B.
Valtancoli, Inorg. Chem. 37 (1998) 941–948.
[32] A. Bencini, A. Bianchi, P. Fornasari, C. Giorgi, P. Paoletti, B.
Valtancoli, Polyhedron 21 (2002) 1329–1335.
[33] A.J. Bard, L.R. Faulkner, Electrochemical Methods: Fundamen-
tals and Applications, second ed., Wiley, New York, 2001.