964

Stripping Voltammetry of Pb(II), Cu(II), and Hg(II) at a

Na®on-Coated Glassy Carbon Electrode Modi®ed by Neutral
Ionophores
Zuliang Chen, Zahra Pourabedi, and D. B. Hibbert*
Department of Analytical Chemistry, The University of New South Wales, Sydney, 2052, Australia

Received: January 14, 1999

Accepted: April 14, 1999

Abstract
The analysis of Pb2‡, Cu2‡ and Hg2‡ by stripping voltammetry using a Na®on-coated glassy carbon electrode modi®ed with diethyl-
dithiocarbamic acid (DDTC) or 1,4,7,10,13,16-hexaoxacyclooctadecane(18-crown-6) is described. Metal ions were accumulated at the
electrode by complexing with the ionophore, reduction and detected by differential pulse anodic stripping voltammetry. A ®ve-fold increase
in the voltammetric response was achieved at the modi®ed electrode compared to a bare glassy electrode. Parameters and conditions such as
the modi®er composition, the pH of supporting electrolyte, deposition potential, deposition time, and stripping mode were optimized. For
®ve minutes preconcentration at DDTC in 100 mM KNO3, pH 2.5, linear calibration plots in the range 0.5 mM to 50 mM were obtained with
a detection limit of 10 nM. For 18-crown-6, after accumulation at open circuit for 1 minute, a linear plot between 2 and 40 mM was achieved.
The lifetimes of each electrode were more than three weeks.
Keywords: Na®on modi®ed electrode, Heavy metal analysis, Stripping voltammetry

1. Introduction potential interfering ions have no electrochemistry (alkali and

Stripping voltammetry, employing various chemically modi-
®ed electrodes (CMEs), is widely used in the determination of
trace metals and organic compounds [1]. Many CMEs have been
reported that are based on the speci®c accumulation of a target
compound at the electrode prior to the voltammetric determina-
tion. Accumulation occurs by reaction between modi®er and the
analyte in several ways, e.g., ion-exchange, complexation, bioac-
cumulation, covalent attachment and hydrophobic interaction, as
described in a review by Arrigan [2]. Recently, there have been
several reports of CMEs used for accumulationystripping voltam-
metric determination of trace metals based on the use of macro-
cyclic reagents. These reagents offer a de®ned cavity for metal ion
complexation and hence the possibility of enhanced sensitivity and
selectivity. A new CME using a-benzoinoxime has been devel-
oped for the determination of Cu2‡ [3]. CMEs modi®ed with
Krypto®x-222 [4] and mercaptoacetic acid [5] were used for
selective accumulation of Hg2‡. CMEs for the determination of
Pb2‡ were constructed with ligands such as diphenylthiocarba-
zone [6] and benzoin [7].
The use of macrocyclic reagents for stripping voltammetric
analysis of metals has received little attention. Recently, a CME
modi®ed polymeric calixarene has been successfully used for the
accumulation of Pb2‡, Cu2‡ and Hg2‡ ion with subsequent anodic
stripping voltammetry [8]. Humic acids have also been incorpo-
rated into modi®ed carbon paste electrode and employed for
stripping voltammetry of Pb2‡, Cu2‡ and Hg2‡ [9]. Similarly,
glyoxal bis(2-hydroxyanil) has been used in a CME for voltam-
metry of Hg2‡ and Ag‡ [10]. Macrocyclic compounds that can
bind heavy metals including lead [11±17], cadmium [18], mercur-
y(II) [17, 19, 20] have been reported. The simple oxygen crowns,
such as 18-crown-6, bind a number of ions, including Hg2‡ [21].
However, when used in ion selective electrodes their lack of
selectivity (in particular their tendency to bind alkali metal ions)
is considered a drawback. In voltammetry, however, many of the
alkaline earth metals) or are discriminated in the stripping
voltammogram. Prabhu et al. have demonstrated the use of
crowns (dibenzo crowns) and cryptands for the analysis of lead
[22]. Dithiocarbamates form stable complexes with various metal
ions such as Pb2‡, Cu2‡ and Hg2‡ [23]. Polymeric ion-exchangers
such as Na®on have attracted particular interest for CMEs. Na®on
is inert and conducting, and provides both hydrophobic regions to
stabilize ligands, and hydrophilic regions to allow the permeation
of aqueous cations [24]. Its ability to reject anions is useful when
analyzing cations in different matrix solutions. Na®on has been
used as an active matrix in electrochemical analysis, for example
the voltammetric analysis of metal cations [25, 26] and for
monitoring nitric oxide in physiological conditions [27]. Combin-
ing the complexing ability of ionophores and the sensitivity of
stripping voltammetry requires suf®ciently strong binding to
accumulate the metal, and a matrix in which the metal ion may
be reduced, and subsequently re-oxidized. Na®on ful®ls these
requirements, and the model ionophores, 1,4,7,10,13,16-hexa-
oxacyclooctadecane(18-crown-6) and diethyldithiocarbamic acid
(DDTC) are both available, stable in the proposed environment,
and have the requisite complexing ability. It must also be observed
that as the use of mercury for anodic stripping voltammetry is
rapidly coming to a close on health and safety grounds, for the
technique to continue as a cheap, rapid method for the analysis of
trace metals in solution, new electrode systems must be found.
In this article we demonstrate the use of the electrodes based on
glassy carbonyNa®ony18-crown-6 or DDTC for the anodic strip-
ping voltammetry of lead, copper and mercury. Parameters
affecting the voltammetric response are optimized.
The reaction at a Na®on-coated glassy carbon electrode may be
written schematically:
‰CarbonÿÿNafion SO3 Na†2 ÿÿIonophoreŠ ‡ Hg2‡ >
1†
‰CarbonÿÿNafion SOÿ 2‡
3 †2 Ionophore Hg Š ‡ 2 Na
ÿ
ÿ ‡

Electroanalysis 1999, 11, No. 13 # WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999 1040±0397/99/1309±0964 $17.50‡:50=0
Stripping Voltammetry of Lead(II), Copper(II), and Mercury(II) 965

2eÿ ‡ ‰CarbonÿÿNafion SOÿ 2‡ ‡

3 †2 Ionophore Hg Š ‡ 2 Na !
ÿ
ÿ 18-crown-6 electrodes was carried out at open circuit by dipping
‰CarbonÿÿNafion SO3 Na†2 ÿÿIonophore 0
Hg Š
2†
‰CarbonÿÿNafion SO3 Na†2 ÿÿIonophore Hg0 Š !
2eÿ ‡ ‰CarbonÿÿNafion SOÿ 2‡
3 †2 Ionophore Hg Š
ÿ
ÿ
3†
If the stripping (Eq. 3) is performed in electrolyte not containing
Hg2‡ the equilibrium of Equation 1 will reverse with removal of
Hg2‡ from the electrode. This is important for the regeneration of
the electrode for subsequent determinations.
2. Experimental
2.1. Apparatus and Reagents
Voltammetry measurements were performed with a BAS-100B
electrochemical analyzer (BAS, Lafayette, USA). The three-
electrode system consisted of a modi®ed glassy carbon disk
working electrode (3 mm diameter, BAS, Lafayette, USA), a
AgyAgCl reference electrode (BAS) and a platinum wire
(0.5 mm) auxiliary electrode.
All solutions were prepared with doubly distilled water. The
ionophores 18-crown-6 and DDTC were supplied by Aldrich
(Gillingham, Dorset, UK). A stock solution of 10 mM of iono-
phore was made in ethanol and added to the polymer solution as
required. The Na®on polymer used in this study was per¯uorinated
ion-exchange powder 5 % wyw solution in a mixture of lower
aliphatic alcohols and 10 % water (Aldrich) which was then
diluted to 1 % with methanol for modi®cation of the electrode.
The ionophore and Na®on solutions were prepared in HPLC-grade
solvent and mixed in appropriate ratio to give the modifying
solution. All metal nitrate solutions and pH buffer solutions
were made in doubly distilled water and metal nitrate solutions
were stored in polyethylene bottles. The supporting electrolyte
was 0.1 M acetate buffer made of sodium acetate and acetic acid
made by dilution of glacial acetic acid (Ajax).
the electrode into 20 mL of a stirred, buffered solution of nitrates
for a given time (the accumulation time). The electrode was
removed from the cell, washed thoroughly with distilled water
and dried with a soft tissue. It was then transferred to a cell
containing fresh electrolyte (0.1 M acetate buffer, pH 4.0). The
solution was deaerated by bubbling nitrogen through it while a
potential of ÿ1.1 V was applied to the electrode for about 20
seconds in order to reduce complexed metals. The differential
pulse voltammograms were recorded from 0 to ‡600 mV or
‡1.0 V against AgyAgCl at a scan rate of 20 mV sÿ1 and a pulse
amplitude of 50 mV. During measurements a continuous stream of
nitrogen gas was passed through the solution. After each measure-
ment the 18-crown-6 electrode was regenerated for its next use by
cycling the potential between 0.0 and ‡600 mV at 20 mV sÿ1 until
no peaks appeared (usually three cycles) con®rming the complete
removal of the electroactive material from the electrode surface.
Ions were accumulated and simultaneously reduced at the DDTC
electrode by holding the electrode at ÿ1.0 V in 0.1 M KNO3 pH
2.0 solution for the required accumulation time (30 s to 1 min). The
electrode was regenerated in fresh 0.1 M KNO3 pH 2.0 solution by
cycling at 100 mV sÿ1 between ÿ1.0 V and ‡1.0 V.
3. Results and Discussion
3.1. Voltammetric Behavior
Initial studies showed that differential pulse voltammetry gave
superior peaks and baseline than linear sweep voltammetry, and all
work reported here was performed in the differential pulse mode.
Figure 1 shows the differential pulse stripping voltammograms for
the test metals using the procedure described above with a bare
glassy electrode, a Na®on-coated electrode and an electrode
modi®ed with Na®on and DDTC. The sensitivity increased
dramatically when the ionophore was introduced into the modify-
ing coat. We note that the voltammetric responses to Hg2‡ and

2.2. Preparation of Electrodes

The glassy carbon electrode was polished, rinsed with deio-
nized water, sonicated in dilute nitric acid solution for 3 minutes,
washed using deionized water, and then air-dried prior to being
coated with the modifying solution. A solution containing 1 %
Na®on was prepared by dilution of the stock solution with ethanol.
This was mixed with an equal volume of a 10 mM solution of the
crown or a 2 mM solution of DDTC. 5 mL was applied to a
polished glassy carbon electrode and left to dry in air. A freshly
prepared modi®ed electrode was tested by performing ®ve, 60 s
accumulationy voltammetry cycles in a solution containing 50 mM
of Pb2‡, Cu2‡ and Hg2‡ to ensure a repeatable response. The
electrode was then suitable for use in the various experiments
undertaken.

2.3. Procedure Fig. 1. Differential pulse anodic stripping voltammograms (100 mV sÿ1)
of Pb2‡, Cu2‡ and Hg2‡ at a) glassy carbon, b) glassy carbon ‡ Na®on,
Two procedures were employed to accumulate ions at the and c) glassy carbon ‡ Na®on ‡ DDTC. 30 s accumulation time at
electrodes. Chemical accumulation of the test metal ions on the ÿ1.0 V. Electrolyte 0.1 M KNO3 pH 2.0 plus 50 mM of each ion.

Electroanalysis 1999, 11, No. 13

966 Z. Chen et al.

Cu2‡ were also slightly improved at an electrode modi®ed only

with Na®on, which re¯ects the ion-exchange properties of Na®on.
This con®rms the results seen in the cyclic voltammetry of Hg2‡
and Cu2‡ at a Na®on-modi®ed electrode [25].

3.2. Optimization of Analytical Parameters

The electrode composition was optimized for the amount of
Na®on and the loading of the ionophore. As the mass of Na®on
increases at constant ionophore loading (1 mL of 10 mM) and
constant (2 mL) volume of coating solution, the voltammetric
peaks go through a maximum at about 1 wt. % in alcohol solution
(Fig. 2).
Similarly as the ionophore content is increased at constant
weight of Na®on the peaks also pass through a maximum at
about 15 wt. % of DDTC in ethanol (equivalent to 1 mM, see Fig.
3). There will be a general increase in the amount of ion
accumulated as both Na®on and ionophore are increased.
However, at high loadings of ionophore, the Na®on will be
disrupted by the nonconducting ionophore and it is possible that Fig. 3. The effect of increasing DDTC content of the coating solution at
not all the accumulated ion will be available for the electroche- constant Na®on concentration (1 mL of 1 wt.%). Deposition time: 30 s,
mical steps. As the total loading of the electrode increases the coat deposition potential: ÿ1200 V. Supporting electrolyte: 0.1 M KNO3, pH:
becomes thicker and eventually the transport of ions within the 4.0, sweep rate: 100 mV sÿ1; j) Pb2‡; u) Cu2‡, and s) Hg2‡ 50 mM.
electrode will become dif®cult with the complexation taking place
largely at the electrodeysolution boundary with electrons for the
electrochemical processes being available at the carbonycoat appears to be no adverse effects on the ionophore from this
boundary. procedure. A chemical accumulation at open circuit is necessary
The pH of the electrolyte is important when analyzing metal when the method is used in the ®eld, for example, analyzing water
ions with ionophores with groups that can be protonated. Too high samples. The electrode is simply dipped in the water for the
a pH leads to hydrolysis of the ion, particularly with Hg2‡, and as required length of time, and the subsequent analysis may be
the pH is lowered ionophores such as the crown ethers will done in a portable apparatus nearby, or the electrode may be
protonate at the oxygen atoms reducing the complexing ability stored and stripped back in the laboratory. When a potential was
of the ionophore. Figure 4 illustrates this for Hg2‡ at a DDTC applied during accumulation, the subsequent stripping current was
electrode and a 18-crown-6 electrode. It is seen that the DDTC greater as the accumulation potential was made more negative. A
electrodes could be operated in lower pH solutions with resulting potential of ÿ1.0 V was chosen for the experiments reported here.
higher peak currents. Figure 5 shows the effect of accumulation time of Hg2‡ at a
There are some advantages to depositing metal simultaneously DDTC electrode for simultaneous accumulation and reduction,
with accumulation. The analysis becomes a two step process and at a 18-crown-6 electrode for separate accumulation. The
(accumulationyreduction and stripping) as in conventional ASV, stripping currents increased with accumulation time to a plateau as
the deposition time and the overall time is shortened and there

Fig. 4. The voltammetric peak as a function of electrolyte pH. Filled

squares: Na®onyDDTC modi®ed electrode; 50 mM Hg2‡, accumulation
Fig. 2. The effect of increasing Na®on concentration at constant iono- time 30 s at ÿ1.0 V; electrolyte 0.1 M KNO3 (current60.1). Open
phore loading (5 mM 18-crown-6). The current is the peak current of a squares: a Na®ony18-crown-6 modi®ed electrode, 1 mM Hg2‡ accumu-
solution of 10 mM Hg2‡. Accumulation time: 1 min. lation time: 2 min; electrolyte 0.1 M acetate buffer.

Electroanalysis 1999, 11, No. 13

Stripping Voltammetry of Lead(II), Copper(II), and Mercury(II)
Fig. 5. The peak current for stripping Hg2‡ at a DDTC electrode and a
18-crown-6 electrode as a function of accumulation time. Filled squares:
Na®onyDDTC modi®ed electrode; 50 mM Hg2‡, accumulation: ÿ1.0 V;
electrolyte 0.1 M KNO3 pH 2 (current60.1). Open squares: a Na®ony18-
crown-6 modi®ed electrode, 1 mM Hg2‡, 0.1 M acetate buffer.
the ®lm became saturated, this occurring sooner when a potential
was applied during accumulation.
3.3. Calibration
Calibration plots were linear for solutions of Hg2‡ of 0.5 mM to
100 mM at an 18-crown-6 electrode, for 1 minute accumulation
time at open circuit. The slope was 1.2  0.03 (95 % con®dence
interval) mA mMÿ1. Similar results were obtained from the
Na®onyDDTC electrodes. For example the slopes of the calibra-
tion lines for 5 minutes accumulation were 6.1, 5.8 and 4.5 mA
mMÿ1 for Pb2‡, Cu2‡ and Hg2‡, respectively. The electrodes were
regenerated between each run as described above. Relative
standard deviation for ®ve measurements was 6.1 % for one
minute accumulation of 10 mM Hg2‡ at a Na®ony18-crown-6
electrode and 3.0 to 5.0 % for 50 mM samples of Pb2‡, Cu2‡ and
Hg2‡ at a Na®onyDDTC electrode.
The detection limit, calculated from the standard error of the
calibration curve by the recommended ISO procedure, was 1.9 mM
[28]. This is considerably greater than that calculated from three
times the baseline noise (100 nM), but it is considered to be more
realistic in rejecting type II errors (i.e., accepting that an excursion
from the baseline is a peak when, in fact, it is not). Using the
baseline method, for longer accumulation times the detection limit
of the Na®ony18-crown-6 electrode was estimated to be 10 nM for
10 minutes accumulation of Hg2‡ and about 1 nM for 5 minutes of
accumulationydeposition of Pb2‡, Cu2‡ and Hg2‡ at a
Na®onyDDTC electrode.
3.4. Interferences
The effect of interfering species can be twofold, by competing
with the analyte for the ionophore, and by overlapping the
voltammetric wave of the analyte. The latter was not a problem
with the interfering ions investigated. Cd2‡ at ÿ800 mV is the
nearest to Pb2‡ at ÿ600 mV and these were easily resolved in the
voltammetry.
Addition of equimolar amounts of Cu2‡, Pb2‡, Zn2‡, Mn2‡,
Cd2‡ and Ag‡ to 10 mM Hg2‡ solution did not affect the
voltammetric response of a Na®ony18-crown-6 electrode,
967
neither did the 0.1 M Na‡ in the supporting electrolyte. The
determination of 100 nM of Pb2‡, Cu2‡ and Hg2‡ at a
Na®onyDDTC electrode was not affected by the addition of
10 mM of Co2‡, Ni2‡, Zn2‡, Cd2‡, Mn2‡, and Mg2‡. However,
the stripping currents were reduced by about 15 % in the presence
of the 10 mM Ag‡. The af®nity of sulfur bearing ionophores for
silver ions is well known [16].
A Na®ony18-crown-6 electrode was used each day for three
weeks. The calibration range and linearity for Hg2‡ was main-
tained but the calibration slope fell to 1.1 mA mMÿ1 after two
weeks and 0.8 mA mMÿ1 after three weeks indicating some
leaching of the ionophore.
4. Conclusion
We have demonstrated that glassy carbon electrodes modi®ed
with Na®on and a neutral ionophore can be used for the stripping
voltammetry of mercury and other heavy metals. The Na®on acts
as both a suitable conducting medium and matrix for the iono-
phore, and an ion exchanger. The stability of the ionophores and
the ability of the Na®on to extract cations into the membrane leads
to an electrode that is precise and accurate. The analyte ion may be
preconcentrated by chemical interaction with the electrode at open
circuit potential, with subsequent electrochemical reduction, or by
applying a cathodic potential during accumulation for simulta-
neous reduction.
A Na®ony18-crown-6 modi®ed electrode had a linear range of
0.5 mM to 100 mM Hg2‡, for 1 minute accumulation time at open
circuit. The slope was 1.2  0.03 (95 % con®dence interval) mA
mMÿ1, with a detection limit of 1.9 mM, determined from the
calibration plot, or 100 nM determined from 3  sbaseline . Higher
slopes were found with Na®ony diethyldithiocarbamic acid for
Pb2‡, Cu2‡ and Hg2‡, namely 6.1, 5.8 and 4.5 mA mMÿ1,
respectively, for a 5 minute preconcentration with simultaneous
reduction at ÿ1.0 V.
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