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Bismuth film electrodes for heavy metals

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Microsyst Technol (2008) 14:491–498
DOI 10.1007/s00542-007-0432-z
TECHNICAL PAPER
Bismuth film electrodes for heavy metals determination
Vlastimil Rehacek Æ Ivan Hotovy Æ Marian Vojs Æ
Fedor Mika
Received: 18 May 2007 / Accepted: 5 September 2007 / Published online: 25 September 2007

Springer-Verlag 2007
Abstract Bismuth film electrodes (BiFEs) have a
potential to replace toxic mercury used most frequently for
determination of heavy metals (Cd, Pb, Zn) by anodic
stripping voltammetry. We prepared a graphite disc elec-
trode (0.5 mm in diameter) from a pencil-lead rod and
developed a nitrogen doped diamond-like carbon (NDLC)
microelectrode array consisting of 50,625 microdiscs with
3 lm in diameter and interelectrode distances of 20 lm on
a highly conductive silicon substrate as a support for
BiFEs. The disc graphite BiFE was used for simultaneous
determination of Pb(II), Cd(II) and Zn(II) by square wave
voltammetry (SWV) in an aqueous solution. We found the
optimum bismuth-to-metal concentration ratio in the
solution to be 20. The dependence of the stripping
responses on the concentration of target metals was linear
in the range from 1 · 10–8 to 1.2 · 10–7 mol/L. Detection
limits 2.4 · 10–9 mol/L for Pb(II), 2.9 · 10–9 mol/L for
Cd(II) and 1.2 · 10–8 mol/L for Zn(II) were estimated. A
bismuth-plated NDLC microelectrode array was used for
Pb(II) determination by differential pulse voltammetry
(DPV) in an aqueous solution. We found that the stripping
current for bismuth-plated NDLC array was linear in the
concentration range of Pb(II) from 2 · 10–8 to 1.2 · 10–7
mol/L. The detection limit 2.2 · 10–8 mol/L was estimated
from a calibration plot.
V. Rehacek (&)
I. Hotovy
M. Vojs
F. Mika
Faculty of Electrical Engineering and Information Technology,
Department of Microelectronics, Slovak University of
Technology, Ilkovicova 3, 812 19 Bratislava, Slovak Republic
e-mail: vlastimil.rehacek@stuba.sk
1 Introduction
General trends for environmentally friendly analytical
methods and alternative materials have continuously been
sought. Bismuth film electrodes are very promising in the
field of electrochemical analysis. The attractive properties
of bismuth films include simple preparation, high sensi-
tivity, excellent peak resolution, insensitivity to dissolved
oxygen in aqueous solutions, negligible toxicity and ability
to operate in highly alkaline media (Svancara and Vytras
2006; Economou 2005). Bismuth has a potential to replace
toxic mercury used most frequently for determination of
heavy metals [such as Cu(II), Pb(II), Cd(II), Zn(II)] by
anodic stripping voltammetry (ASV). High sensitivity of
ASV is mainly given by the first step involving precon-
centration of the analyte species in the bismuth film, which
is carried out under a fixed potential for a predetermined
time. In the second, stripping step, the accumulated species
are stripped from bismuth into the solution by reoxidation.
Current peaks are proportional to the concentration of the
species accumulated in bismuth and, hence, to the con-
centration in the solution. There are two methods of
coating a substrate with a bismuth film which are the most
frequently used. The first method, ex situ plating, involves
electroplating the bismuth before transferring the electrode
into the analyzed solution (Svancara and Vytras 2006;
Hutton et al. 2005). In the second method, in situ plating,
bismuth ions are added into the analyzed solution and
target metals are co-deposited with bismuth on electrode
surface. A general rule is that the Bi(III) concentration
must be at least tenfold higher than analyte concentration
to avoid saturation (Economou 2005; Baldrianova et al.
2006a, b). Bismuth can be plated on the same substrates as
mercury. Glassy carbon (Kefala et al. 2003; Wang et al.
2001a, b; Charalambous and Economou 2005), carbon
123
492
paste (Baldrianova et al. 2006a; Kefala et al. 2003), carbon
fibre (Hutton et al. 2005; Baldrianova et al. 2006b; Wang
et al. 2000), impregnated graphite (Kefala et al. 2003),
pencil-lead (Demetriades et al. 2004), gold (Svancara
and Vytras 2006; Baldrianova et al. 2006b), platinum
(Svancara and Vytras 2006) and other have been reported
(Svancara and Vytras 2006; Economou 2005).
In this work, a graphite electrode (pencil-lead) and a
nitrogen-doped diamond-like carbon (NDLC) microelec-
trode array were investigated as a support for deposition of
a bismuth film for in situ determination of heavy metals
[Pb(II), Cd(II) and Zn(II)] by ASV.
2 Experimental
The pencil-lead graphite disc electrode was prepared from a
pencil-lead rod (HB, 0.5 mm in diameter) which was
inserted into a polyethylene tube and fixed by epoxy glue.
The tip of this electrode (Fig. 1) was mechanically polished.
Before use, the disc electrode was rinsed only with deion-
ized water and dried. The NDLC microelectrode array was
prepared by vacuum pulse sputtering of graphite on a highly
conductive (0.008–0.024 X cm) silicon substrate. The areas
which act as working electrodes (an array of 50,625
microdiscs with 3 lm in diameter and distance 20 lm
between them) were defined photolithographically (Fig. 2).
The composition of NDLC film was analyzed by Raman
spectroscopy. Generally, DLC is characterized by low
conductance. The electrical properties can be controlled
during sputtering by doping with nitrogen or different
metallic elements. Nitrogen atoms incorporated during
layer sputter-deposition affect the bonding formation (ratio
between sp2 and sp3 bonded carbon) in the diamond-like
carbon structure. Usually, an excess of N atoms will lead to
Fig. 1 Graphite disc electrode in the middle ([ = 0.5 mm)
123
Microsyst Technol (2008) 14:491–498
Fig. 2 Detail of the NDLC microelectrode array
graphitization of DLC and, hence, the conductance of
NDLC will rise (Liu and Liu 2005). For successful utili-
zation of NDLC in electrochemical applications in aqueous
solutions, NDLCs with conductance as high as possible are
required, of course. NDLC with the highest conductance
was reached when the layer was sputtered at a nitrogen flow
rate of 11 sccm. In this case, the graphite component
intensity was higher than that for disordered graphite
(Fig. 3). Electrochemical properties of the graphite elec-
trode as well as NDLC electrode array were investigated by
cyclic voltammetry (CV). All the stock solutions were
prepared from analytical grade chemicals (Bi(NO3)3
5H2O,
99.999%; Pb(NO3)2, 99.0%; Cd(NO3)2
4H2O, 99.0%;
Zn(NO3)2
6H2O, 99.0%; CH3COOH, 99.8%; CH3COONa,
99.0%; KNO3, 99.0%) in 18 M X cm deionized water. A
three-electrode arrangement was used in all experiments.
As a reference, a homemade Ag/AgCl/agar Cl– (3 mol/L)/
agar NO3– (1 mol/L) electrode and, as a counter electrode, a
platinum wire were used. Voltammetric experiments were
Fig. 3 Raman spectra of NDLC; layer thickness of 150 nm; D
disordered graphite, G graphite
Microsyst Technol (2008) 14:491–498
performed with an electrochemical sensor interface
(PalmSens, Palm Instruments BV) in combination with a
personal computer. SWV or DPV were used in the mea-
surement of the stripping voltammograms.
3 Results and discussion
3.1 Characterization of pencil-lead graphite electrode
and NDLC microelectrode array
The behaviour of the graphite electrode and of the
NDLC microelectrode array was characterized by cyclic
voltammetry in an 0.1 mol/L acetate buffer (pH = 4.5) or
0.1 mol/L KNO3 solution. In a potential range from –1.3 to
–0.4 V at a scan rate of 50 mV/s, the effect of the bismuth
film was investigated (Fig. 4). In the case of the graphite
electrode (with or without bismuth film), the difference
between voltammograms was negligible despite the fact that
various concentration of Bi(III) were used (1 · 10–6 to 1 ·
10–5 mol/L). A remarkably different I–V curve was recorded
in the case of NDLC, when the NDLC was preplated with a
bismuth film. In the case of bare NDLC the currents are
much lower, most likely due to the higher resistance of
NDLC.
3.2 Effect of SWV parameters
The SWV parameters which affect the response of the
sensor are SW step increment, SW pulse height and SW
frequency (Kefala et al. 2003; Charalambous and Econo-
mou 2005). These parameters were investigated using a
solution with Pb(II), Cd(II) and Zn(II) concentration of
Fig. 4 Cyclic voltammograms of graphite electrode and NDLC
microelectrode array with and without bismuth film
493
1 · 10–8 mol/L of each in an 0.1 mol/L acetate buffer. The
effect of the step increment was investigated in the range
from 2 to 30 mV (Fig. 5). The best stripping response was
obtained at 12 mV step increment for Pb(II) and Cd(II),
and at 25 mV for Zn(II). For all metals the peak positions
as well as the peak widths were independent of the step
increment. The SW pulse height was investigated in the
range from 20 to 120 mV (Fig. 6). When the pulse height
increased, the stripping response gradually increased. The
peak positions were shifted to the cathode direction by
about 20–30 mV per pulse height increment (20 mV) for
all metals. The peak widths were not influenced by the
pulse height. The SW frequency had a significant effect on
the stripping response (Fig. 7). The peak heights for Pb(II)
and Cd(II) increase up to 120 Hz. Over this frequency, the
stripping responses decreased. A negligible effect of fre-
quency on response was found for Zn(II). The peak
positions for all metals were shifted to the cathode direc-
tion by about 10 mV per frequency increment (20 Hz). In
accordance with the observed results, a step increment of
12 mV, pulse height 80 mV and frequency 120 Hz were
chosen for SWV experiments with the pencil-lead graphite
electrode.
3.3 Effect of the bismuth concentration
The concentration of Bi(III) used for in situ formation of
the bismuth film on graphite electrodes is known to influ-
ence the height of the stripping peaks of the target metals
(Baldrianova et al. 2006b; Demetriades et al. 2004; Kefala
et al. 2003; Wang et al. 2000; Charalambous and Econo-
mou 2005). Stripping voltammograms with the pencil-lead
graphite electrode for the solution with 1 · 10–8 mol/L
Fig. 5 Dependence of stripping response on step increment of SWV
in 0.1 mol/L acetate buffer; concentration of each of metals: 3 ·
10–7 mol/L, Bi(III): 1 · 10–6 mol/L, preconcentration time: 60 s
123
494
Fig. 6 Dependence of stripping response on pulse height SWV in
0.1 mol/L acetate buffer; concentration of each of metals: 3 ·
10–7 mol/L, Bi(III): 1 · 10–6 mol/L, preconcentration time: 60 s
Fig. 7 Dependence of stripping response on frequency of SWV in
0.1 mol/L acetate buffer; concentration of each of metals: 3 ·
10–7 mol/L, Bi(III): 1 · 10–6 mol/L, preconcentration time: 60 s
concentration of each of Pb(II), Cd(II) and Zn(II) in
0.1 mol/L acetate buffer are shown in Fig. 8. They were
recorded at different contents of Bi(III) from 3.3 · 10–8
(bismuth-to-metals ratio of 3.3:1 ) to 1 · 10–6 mol/L
(bismuth-to-metals ratio of 100:1). In Fig. 9 there are
shown the dependences of the stripping current on the
concentration ratio of Bi(III) to metals in the solution. As
the Bi(III) concentration increased, all the peaks increased
in height up to a ratio of 20:1. After a slight decrease for
Cd(II) and Zn(II) peaks, the current responses of all metals
became independent of additional increasing of Bi(III).
Generally, the concentration of Bi(III) in the solution
controls the thickness of the bismuth film. Since bismuth–
metal alloying occurs mainly on the surface (Baldrianova
et al. 2006b), without any diffusion of the metals into
123
Microsyst Technol (2008) 14:491–498
Fig. 8 Square wave stripping voltammograms obtained at graphite
disc BiFE in 0.1 mol/L acetate buffer (pH = 4) with 1 · 10–8 mol/L
concentration of each of metals and different concentration of Bi(III)
from 3.3 · 10–8 to 1 · 10–6 mol/L; preconcentration time: 120 s
Fig. 9 Dependence of stripping response of graphite disc BiFE on
concentration ratio of Bi(III) to metals in 0.1 mol/L acetate buffer
bismuth film, an increase of bismuth film thickness should
have a little effect on metal stripping. The dependence of
the stripping response on Bi(III) concentration at low bis-
muth-to-metals ratios (\20) and low target metal
concentrations (1 · 10–8 mol/L) is probably a special fea-
ture of in situ prepared electrodes. We suppose that under
these conditions the surface of graphite electrode is not
covered by bismuth completely.
3.4 Effect of the preconcentration time
To improve the electroanalytical performance (especially
the sensitivity) of the in situ bismuth electrode, the pre-
concentration time should be optimized for the stripping
Microsyst Technol (2008) 14:491–498
responses not to be influenced by saturation. The effect of
the preconcentration time was studied with the pencil-lead
graphite electrode in the range from 60 to 600 s for a solu-
tion with concentration 1 · 10–7 mol/L of each of target
metals and 1 · 10–6 mol/L Bi(III) in 0.1 mol/L acetate
buffer. The peak heights increased linearly with time up to
360 s (Fig. 10). At a longer preconcentration time the peak
heights deviate from linearity due to surface saturation.
3.5 Analytical performance of bismuth film electrodes
Excellent performance of the bismuth film electrode for
determination of Pb(II), Cd(II) and Zn(II) on various car-
bon substrates was already demonstrated (Kefala et al.
2003; Wang et al. 2000, 2001a, b).
3.5.1 Pencil-lead graphite BiFE
The ability of using the BiFE for simultaneous determi-
nation of Pb(II), Cd(II) and Zn(II) is illustrated in Fig. 11.
All the peaks are well resolved and increase linearly with
the metal concentration in the range from 1 · 10–8 to
1.2 · 10–7 mol/L. The resulting calibration plots (Fig. 12)
were used for estimating the detection limits. The cali-
bration data are given in Table 1. On the basis of criteria
for calculation of the detection limit (Yintercept + 3 · SD)
the detection limits were estimated as 2.4 · 10–9 mol/L for
Pb(II), 2.9 · 10–9 mol/L for Cd(II) and 1.2 · 10–8 mol/L
for Zn(II). In addition, one of the features of BiFE is good
precision. Moreover, a calibration measurement was car-
ried out under conditions, when the concentration ratio of
each metal to bismuth in the solution was constant (1:20)
Fig. 10 Dependence of stripping response of graphite disc BiFE on
preconcentration time in 0.1 mol/L acetate buffer (pH = 4), concen-
tration of each of metals: 1 · 10–7 mol/L, Bi(III): 1 · 10–6 mol/L
495
Fig. 11 Square wave stripping voltammograms obtained at graphite
disc BiFE in 0.1 mol/L acetate buffer (pH = 4) at different concen-
tration of metals from 1 · 10–8 to 1.2 · 10–7 mol/L of each;
concentration of Bi(III): 2 · 10–7 mol/L, preconcentration time:
120 s
for the whole calibration range. We have found worse
performance of BiFE at determination of Pb, Cd and Zn
(Fig. 13) in comparison with calibration procedure car-
ried out at a constant concentration of bismuth (2 ·
10–7 mol/L) (Fig. 12). Lower sensitivity, worse linearity
and higher LOD (2 · 10–8 mol/L for Pb(II) and 3.6 ·
10–8 mol/L for Cd) at determination of Pb(II) and Cd(II)
was obtained (Table 1) even though the linearity of bis-
muth dependence was high (R = 0.9979). In addition, the
calibration of Zn(II) could not be evaluated since the
stripping response of Zn(II) did not increase with increas-
ing concentration of Zn(II). A series of ten repetitive
measurements of a solution with concentration 1 · 10–8
mol/L of each of Pb(II), Cd(II) and Zn(II) and 2 · 10–7
Fig. 12 Calibration plots of Pb(II), Cd(II) and Zn(II) at graphite disc
BiFE; at constant concentration of Bi(III): 2 · 10–7 mol/L
123
496 Microsyst Technol (2008) 14:491–498

Table 1 Calibration data for

Ion Sensitivity Intercept (lA) R SD Electrode Remark
determination of Pb, Cd and Zn
(lA L/lmol)
at graphite BiFE and Bi-NDLC
microelectrode array Pb 35.9 0.465 0.9998 0.029 Graphite cBi = constant
Cd 22.7 0.118 0.9998 0.022 Graphite cBi = constant
Zn 6.0 0.224 0.9967 0.025 Graphite cBi = constant
Pb 23.2 0.262 0.9916 0.154 Graphite cBi/cPb = 20
Cd 15.1 0.274 0.9741 0.180 Graphite cBi/cCd = 20
Pb 2.5 0.005 0.9870 0.019 NDLC cBi = constant

Fig. 14 Differential pulse stripping voltammograms obtained at

Fig. 13 Calibration plots of Pb(II), Cd(II) and Zn(II) at graphite disc Bi-NDLC microelectrode array in 0.1 mol/L KNO3 (pH = 2) with
BiFE; at cBi/cMe = 20 different concentration of Bi(III) from 2.5 · 10–6 to 1 · 10–5 mol/L,
preconcentration time: 120 s

mol/L Bi(III) at 120 s preconcentration time gave highly
reproducible stripping peaks with relative standard devia-
tions 4.5% for Pb(II), 3.4% for Cd(II) and 2.7% for Zn(II).
Good precision is attributed to the reproducible bismuth
film (2.8%).
3.5.2 Bismuth-plated NDLC microelectrode array
The bismuth-plated NDLC microelectrode array for in situ
determination of Pb(II) was prepared by co-deposition of
Bi(III) and Pb(II) at –1.3 V in a plating solution of Bi(III) in
a supporting electrolyte with different contents of Pb(II).
Stripping currents from reoxidation of Pb were recorded by
differential pulse voltammetry (scan rate 30 mV/s, pulse
duration 25 ms, step increment 2 mV and pulse height
50 mV). The influence of many parameters, including con-
centration of the plating solution, the kind of supporting
electrolyte and concentration of Pb(II) on the stripping
current responses was analyzed. The influence of the con-
centration of the plating solution on bismuth film formation
for in situ technique was investigated in the range of
2.5 · 10–6 to 1 · 10–5 mol/L Bi(III) in 0.1 mol/L acidified
KNO3 (pH = 2) (Fig. 14). For ASV experiments, a con-
centration of 2.5 · 10–6 or 5 · 10–6 mol/L was chosen
because the stripping current was not increased at concen-
trations higher than 5 · 10–6 mol/L and, additionally, the
bismuth peak shape was distorted. We observed a minimum
effect of different supporting electrolytes (0.1 mol/L acetate
buffer (pH = 4), nitrate (acidified by HNO3) or perchlorate
solutions) in the bismuth plating procedure. The dependence
of the stripping response of bismuth-plated NDLC array on
Pb(II) concentration and a calibration plot is shown in
Figs. 15, 16. The stripping currents were linear in the range
from 2 · 10–8 to 1.2 · 10–7 mol/L concentration of Pb(II)
with sensitivity of 2.5 lA L/lmol, and the estimated
detection limit was 2.2 · 10–8 mol/L.
There are reports on the use of various types of bare
carbon (glassy carbon, DLC, polycrystalline diamond) for
determination of heavy metals by ASV (Liu and Liu 2005;
Manivannan et al. 2004). Deposition of metals ions results
in a film of atoms, which can occur as a monolayer or
multilayer on the carbon surface (Manivannan et al. 2004).
Results of the determination of the Pb(II) ions in 0.1 mol/L

123
Microsyst Technol (2008) 14:491–498
Fig. 15 Differential pulse stripping voltammograms obtained at
Bi-NDLC microelectrode array in 0.1 mol/L KNO3 (pH = 2) at
different concentration of Pb(II) from 2 · 10–8 to 1.2 · 10–7 mol/L;
concentration of Bi(III): 5 · 10–6 mol/L, preconcentration time:
300 s
Fig. 16 Calibration plot of Pb(II) at Bi-NDLC microelectrode array
KNO3 by DP ASV confirmed our prediction that the sen-
sitivity will be strongly reduced due to the absence of
bismuth with its accumulating capability. We obtained
much lower current responses in comparison with results
obtained on a bismuth-plated microelectrode array
(Fig. 17). Almost no current signal was recorded for con-
centration of Pb(II) 5 · 10–6 mol/L. Similar results, as
regards sensitivity in Pb(II) determination on bare carbon,
were referred (Liu and Liu 2005; Manivannan et al. 2004).
4 Conclusions
BiFEs have a potential to replace toxic mercury used most
frequently for determination of heavy metals (Cd, Pb, Zn)
497
Fig. 17 Dependence of current response of bare NDLC microelec-
trode array on Pb(II) concentration in 0.1 mol/L KNO3
by ASV. We prepared a graphite disc electrode (0.5 mm in
diameter) from a commercial pencil-lead rod. Moreover,
we developed a nitrogen doped diamond-like carbon
microelectrode array consisting of 50,625 microdiscs with
3 lm in diameter and interelectrode distances of 20 lm on
a highly conductive silicon substrate as a support for BiFE.
It was found that the analytical performance of bismuth
film microelectrode array was influenced by the properties
of NDLC. The disc graphite BiFE was used for simulta-
neous in situ determination of Pb(II), Cd(II) and Zn(II) by
SWV in an aqueous solution. The influence of SWV
parameters, Bi(III) concentration and preconcentration
time was investigated. We found the optimum bismuth-
to-metal concentration ratio to be 20. The dependence of the
stripping responses on the concentration of target metals
was linear in the range from 1 · 10–8 to 1.2 · 10–7 mol/L.
Sensitivities of 35.9 lA L/lmol for Pb(II), 22.7 lA
L/lmol for Cd(II) and 6.0 lA L/lmol for Zn(II) were
achieved by the graphite BiFE. The detection limit was
estimated as 2.4 · 10–9 mol/L for Pb(II), 2.9 · 10–9 mol/L
for Cd(II) and 1.2 · 10–8 mol/L for Zn(II). The bismuth-
plated NDLC electrode array was used for in situ Pb(II)
determination by DPV in an aqueous solution. The influ-
ence of the plating solution and supporting electrolyte on
the stripping responses was investigated. We found that the
stripping current for bismuth-plated NDLC array was linear
in the range from 2 · 10–8 to 1.2 · 10–7 mol/L concentra-
tion of Pb(II). The sensitivity 2.5 lA L/lmol and estimated
detection limit 2.2 · 10–8 mol/L were evaluated from the
calibration plot.
Acknowledgments This work was supported by the grant of the
Slovak Grant Agency Vega, Project 1/3095/06 and by Science and
Technology Assistance Agency under the contract No. APVT-
20-021004.
123
498
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