Analyst, January 1997, Vol.
122 (1–5) 1
Determination of Lead and Copper in Wine by Anodic
Stripping Voltammetry With Mercury Microelectrodes:
Assessment of the Influence of Sample Pretreatment
Procedures
M. Antonietta Baldo, Carlo Bragato and Salvatore Daniele*
Department of Physical Chemistry, University of Venice, Calle Larga S. Marta 2137, I-30123
Venice, Italy
The results obtained using different pretreatment
procedures for determining total lead and copper in wine
by anodic stripping voltammetry were compared. The
measurements were performed by employing mercury
microelectrodes as the working electrode and linear sweep
voltammetry as the voltammetric technique in the
oxidation step. The pretreatments considered were (A)
wine plus concentrated HCl to pH 1.5; (B) wine plus 30%
m/m H2O2 (2.5 : 1 v/v) and UV irradiation for 2 h; and (C)
wine plus concentrated HCl to pH 1.5 and UV irradiation
for 4 h. The three procedures gave different results, and
the efficiency of the different procedures in releasing the
cations from inorganic and organic complexes can be
ranked as B > C > A. Moreover, data obtained with
procedure B agreed within 15% with the values found by
AAS measurements. For the quantification of the metal
ions, both the multiple standard addition method, based
on current or charge versus concentration graphs, and an
absolute method, based on the charge involved in the
stripping peak, were employed. The latter procedure
allowed measurements to be carried out even when the
calibration plots were not linear. When all the
quantitative methods could be applied, data agreement
within 5% was found.
Keywords: Wine analysis; sample pretreatment; heavy
metals; mercury microelectrodes; anodic stripping
voltammetry
Anodic stripping voltammetry (ASV) has been widely used for
trace metal measurements in food samples.1,2The remarkable
sensitivity of this technique is attributed to its effective in situ
preconcentration of the metal of interest, generally into a
mercury drop or film of both conventional and, more recently,
microscopic dimensions.3
In the application of stripping methods to food analysis, the
major challenge is often the sample pretreatment, which is
generally required to extract the analyte or to destroy the
organic matrix, which can interfere with the electrochemical
processes.2 The choice of the procedure depends to some extent
on the target element, food matrix and speed of analysis.2,4,5
For liquid food, such as most wines and other beverages with
low sugar content, simple and relatively fast sample pre-
treatment procedures are usually employed in order to release
the metal ions bound in inorganic and organic complexes. These
treatments consist in acidification or UV irradiation in the
presence of an oxidant3,4,6–10 and, owing to this, the total
amount of metal ions is claimed to have been determined.3,8,10
In fact, the compositions of the solutions resulting from the
above two pretreatments are very different: whereas organic
matter is still present in the sample after the former treatment, it
is almost completely destroyed with the latter procedure.10
Consequently, in view of the influence of organic compounds
on the electrochemical processes, different results by ASV may
be expected.
The aim of this work was to assess the influence of different
pretreatment procedures on the ASV responses obtained from
different varieties of Italian wines. The target elements
considered were lead and copper, which are typical contami-
nants determined in this matrix.
The measurements were conducted employing platinum-
based spherical mercury microelectrodes, which allow the
experimental apparatus to be simplified and the performance of
the ASV technique to be improved.11 For instance, mercury
microelectrodes make it possible to achieve the preconcentra-
tion step in a quiescent solution, so improving the reproduci-
bility of the procedure, to employ small sample volumes for the
analysis and to take measurements directly in low ionic strength
media without any pretreatment and in the absence of a
supporting electrolyte.12 Under these last conditions, the labile
metal fractions in the untreated samples can be also achieved.
In this investigation, linear-sweep voltammetry was em-
ployed as the voltammetric technique for the oxidation of the
metal during the anodic process. This allows the evaluation of
the charge involved in the stripping process by the integration of
the current–potential diagram. An absolute method, based on
the stripping charge, for determining the labile metal fraction
can therefore also be applied.11
Experimental
Reagents and Samples
Titrisol lead and copper standards (Merck, Darmstadt,
Germany) were used to prepare stock standard solutions (1000
mg l21) of these metal ions. Hydrochloric acid to acidify the
wine samples was of Suprapur grade (Merck); hydrogen
peroxide, 30% m/m solution in water (Aldrich, Milwaukee, WI,
USA), and the other chemicals used were of analytical-reagent
grade. All the solutions were prepared with water purified with
a Milli-Q system (Millipore, Bedford, MA, USA). Nitrogen
(99.99%), pure from SIAD (Bergamo, Italy) was used to
remove oxygen from the test solutions.
The samples analysed were the following Italian wines:
Barbera (dry red wine, alcohol 13% v/v) from the vintage of
1993, a mixture of Sauvignon Blanc and Nosiola Galetti (dry
white wine, alcohol 10.5% v/v) from the vintage of 1993,
Passito Bianco (sweet white wine, alcohol 14.5%v/v, sugar 90
g l21) from the vintage of 1988 and Chardonnay (sparkling dry
white wine, alcohol 12% v/v) from the vintage of 1993. The
samples, kindly provided by the Research Laboratory of the
Istituto Agrario di S. Michele all’Adige (Trento, Italy), were
chosen on the basis of their dominant quality factors, such as
variety, time of harvesting and climatic conditions, which lead
to different sugar content on the finished products, and method
of production, on which depends the making of red or white,
2 Analyst, January 1997, Vol. 122
still or sparkling wines.13 Barbera is an example of a red table
wine with high amounts of tannin and colouring matter. All the
varieties of the three white wines considered require late
harvesting of the grapes, i.e., the fruit must be fully matured
before harvesting (at a Brix of 22–23°); Passito is characterized
by a high sugar content, while Chardonnay and Sauvignon
Blanc are dry. Sparkling Chardonnay contains an excess of
carbon dioxide produced by fermentation of residual sugar from
the primary fermentation.
Instrumentation
Chronoamperometric and linear-sweep ASV (LSASV) experi-
ments were carried out with a Model 283 potentiostat/
galvanostat (EG&G PAR, Princeton, NJ, USA), controlled with
a Hewlett-Packard (Avondale, PA, USA) 486/33 MHz personal
computer via EG&G PAR 270 software. The same software was
also used for integrating the areas of the anodic stripping peaks.
Measurements were performed in a two-electrode cell, main-
tained in a Faraday cage made of sheets of aluminium to avoid
external noise. The reference electrode was an Ag/AgCl
electrode, which was separated from the cell by a glass frit to
prevent contamination by leakage from the electrode tip.
UV irradiation of wine samples was performed in closed 200
ml quartz glass tubes in an air-cooled device equipped with a 1.2
kW mercury UV lamp (Ace Glass, Vineland, NJ, USA).
A Metrohm (Herisau, Switzerland) Model 605 pH meter was
used for pH measurements.
AAS determinations were performed with a Perkin- Elmer
(Norwalk, CT, USA) Model 5000 spectrometer.
Microelectrode Preparation and Procedures
Mercury microelectrodes were prepared by ex situ electrode-
position of mercury on a platinum microdisc electrode of 10 mm
radius, fabricated by sealing a 20 mm diameter wire into
glass.
Deposition of mercury was performed under potentiostatic
conditions at 0.0 V (versus Ag/AgCl) for 600 s from 5 mm
Hg2(NO3)2 and 1m KNO3 solution at pH 1 (acidified with nitric
acid). The height h of the deposit, which would adopt a spherical
segment shape,11 was calculated on the basis of the plating
charge recorded during the electrodeposition step. Under the
experimental conditions employed, the plating charge was 26.4
± 0.7 mC and the corresponding height of the deposit was 15.1
± 0.2 mm.
For stripping analysis of the wine samples, the electrochem-
ical cell was a laboratory-made PTFE cup of volume 3 ml,
which was cleaned before the experiments using recommended
procedures for trace analysis.14
The samples were kept quiescent during the preconcentration
step and no rest period was applied before the anodic scan. The
LSASV measurements were conducted at a scan rate of 50
mV s21; the mercury deposit was renewed before each series of
experiments and each day.
The pretreatment procedures employed for the quantification
of heavy-metal contents in the wine samples by ASV were (A)
acidification with concentrated HCl to pH 1.5 and leaving the
solution to equilibrate for 24 h; (B) addition of 20 ml of 30%
H2O2 ( to 50 ml of sample) followed by UV irradiation for 2 h;
and (C) acidification with concentrated HCl to pH 1.5 followed
by UV irradiation for 4–5 h.
The determination of the labile metal fraction was performed
in the untreated wine samples as withdrawn from the bottle,
after equilibration at room temperature and deareation.
For AAS measurements, the samples, according to official
methods for the analysis of wines,15 were mineralized by
employing the classical wet digestion procedure in the presence
of a mixture of concentrated strong acids.
Methods Employed for Quantitative Analysis
The determination of copper and lead was carried out by
applying two methods. The first was the classical multiple
standard addition, which was applied when linear plots of
current (ip), or charge (Qs), of the stripping peak as a function of
concentration were obtained. In the other cases, an absolute
method based on the evaluation of the charge associated with
the stripping peak was used. The latter approach is based on the
following equation:11
Qs = knFDCr[td + (Ep 2 Ed)/v] (1)
which comes from the assumption that steady-state conditions
are achieved in the preconcentration step, and that the diffusion
limiting current is given by the equation
id = knFDCr (2)
where r is the radius of the microdisc, k is a parameter which
depends on the h/r ratio11,16 and D and C are the diffusion
coefficient and bulk concentration of the cation in solution,
respectively. In eqn. (1), td is the deposition time, Ep and Ed are
the stripping peak and deposition potentials, respectively, and v
is the scan rate. The additive term in brackets represents the
scanning period during which plating of the metal continues.11
From eqn. (1) and the experimental stripping charge, the
concentration of the analyte can be determined, provided that
the other parameters are known. The parameters k, r, td, Ep, Ed
and v are obtained on an experimental basis.11. For the diffusion
coefficient values of the cations, it was assumed that they are
equal to those found in aqueous solutions, corrected for the
change of viscosity from water to wine, on the basis of the
Stokes–Einstein relationship.17
Results
Determination of Lead and Copper in Pretreated Wine
Samples
(A) Wine + hydrochloric acid
The different varieties of wines analysed after acidification with
concentrated HCl to pH 1.5 were characterized by a similar
ASV behaviour. Fig. 1 shows, for instance, typical stripping
voltammograms recorded in the sample of Sauvignon–Galetti,
after deposition for 1 min at 20.6 V for copper (full line) and for
10 min at 20.8 V for lead (dashed line), in a quiescent solution.
Under these conditions, the LSASV peaks of Cu and Pb were
well defined, and appeared at about 20.110 and 20.370 V,
respectively.
For each wine sample and metal ion, the experimental
parameters td and Ed were properly optimized, in order to
achieve the best conditions with respect to signal-to-noise ratio,
repeatability and speed of analysis. The optimized values are
given in Table 1. Because the lead and copper levels differ by
Fig. 1 Linear-sweep anodic stripping voltammograms obtained at a
mercury microelectrode for the wine sample Sauvignon–Nosiola acidified
with HCl to pH 1.5. td = 1 min, Ed 20.6 V (full line) and td = 10 min, Ed
20.8 V (dashed line). Scan rate, 50 mV s21.
 Analyst, January 1997, Vol. 122 3

about one order of magnitude, to obtain good repeatability the
metal cations were determined using two separate preconcentra-
tion steps. In fact, when copper was accumulated for deposition
times longer than 5 min, the stripping peaks obtained were
poorly reproducible, probably because of the saturation of the
amalgam with copper.18 Under the experimental conditions
adopted, five replicate measurements gave RSDs lower than 4%
for both species.
For Sauvignon, Barbera and Passito wines, multiple standard
additions gave linear graphs of current or charge against
concentration both for copper and lead. Table 2 shows the linear
regression parameters of the graphs obtained for these wines
over the indicated concentration ranges of the metals added to
the samples. Table 3 collects the evaluated metal contents
obtained by the multiple standard addition procedure based on
Qs–C plots (method I), together with those calculated by eqn.
(1) (method II); agreement between the two procedures within
5% is obtained.
The determination of the metal content in the acidified
Chardonnay wine was complicated by matrix effects. In this
Table 1 Experimental conditions employed in the ASV analysis of acidified
wine samples
wine, in fact, the standard addition plots, based on both current
and charge of the stripping peak, were not linear, and displayed
trends similar to those found in the determination of the
complexing capacity of natural waters.19 Moreover, a large
dependence of Qs (and ip) on the deposition potential was
observed, as reported in Table 4. The large increase in charge
(and current) of the stripping peak when the deposition potential
is made more negative suggests that the nature of the species
undergoing the electrochemical process changes on changing
the deposition potential. In fact, if the nature of the reducible
species were the same at any potential, only a relatively small
increase in Qs (or ip ) would be expected as a consequence of a
small increase in the deposition time, when the difference
between deposition and stripping peak potentials becomes
wider.20 The correspondence between deposition potential and
time arises from the unique properties of microelectrodes,
which allow deposition to occur while scanning.9,11,12
These results suggest that, in spite of acidification of the
sample, the effect of the organic matrix on complexation or
adsorption phenomena on the electrode surface is still relevant.
Therefore, to quantify the metal levels in the latter sample, only
eqn. (1) was employed, and the results obtained are given in
Table 3.

Wine Metal td/min Ed/V (B) Wine + hydrogen peroxide + UV digestion

Sauvignon Cu 1 20.6 The mineralization of wines via UV irradiation was accompli-
Pb 10 20.8 shed in the presence of a relatively high concentration of
Barbera Cu 2 20.8 hydrogen peroxide, which provides oxygen free radicals for the
Pb 20 20.8 oxidation process of organic matter.10,21
Passito Cu 2 20.8 After this pretreatment, all the wines were clear, colourless
Pb 10 21.0 and typically smelled of acetic acid. The stripping voltammo-
Chardonnay Cu 1 20.8
Pb 15 21.0
grams both of copper and lead were sharp and reproducible, and
a typical stripping response is shown in Fig. 3. In this case, the

Table 2 Parameters of ip versus C and Qs versus C graphs obtained for wines acidified and spiked with Cu2+ and Pb2+

ip versus C Qs versus C

Concentration Slope 3 103/ Intercept/ Slope 3 103/ Intercept/

Wine Cation range/mg l21 nA l mg21 nA r2 nC l mg21 nC r2
Sauvignon Cu2+ 50–400 2.250 0.863 0.992 3.887 1.457 0.999
Pb2+ 20–300 22.89 0.801 0.999 19.50 0.710 0.998
Barbera Cu2+ 30–200 4.784 0.228 0.999 9.048 0.422 0.999
Pb2+ 5–100 9.624 0.084 0.996 8.446 0.072 0.997
Passito Cu2+ 30–200 3.383 0.274 0.999 10.07 0.777 0.999
Pb2+ 5–100 5.507 0.028 0.999 10.94 0.056 0.999

Table 3 Results obtained for the analysis of wines after different sample pretreatments

Concentration/mg l21 †

Sauvignon Barbera Passito Chardonnay

Sample
Technique pretreatment* Cu Pb Cu Pb Cu Pb Cu Pb
LSASV Procedure A (I) 375 (2.7) 36.4 (2.1) 46.6 (1.5) 8.52 (6.8) 77.1 (3.9) 5.12 (8.0) — —
(II) 359 (2.6) 37.0 (1.5) 47.3 (1.4) 8.09 (5.2) 78.5 (3.2) 5.31 (6.4) 71.2 (2.3) 9.05 (8.9)
Procedure B (I) 891 (1.9) 78.0 (3.4) 90.9 (2.7) 120 (3.3) 715 (0.9) 30.5 (2.1) 285 (3.1) 54.8 (4.8)
(II) 902 (1.4) 74.4 (3.0) 87.7 (2.7) 123 (2.9) 711 (0.5) 29.2 (1.3) 271 (2.3) 54.0 (4.1)
Procedure C (I) 479 (1.6) 67.1 (3.9) — 57.3 (9.2) 448 (2.8) 16.2 (5.4) — 24.0 (4.9)
(II) 475 (1.1) 66.3 (3.8) — 55.6 (8.8) 459 (2.3) 16.8 (4.8) 123 (3.5) 22.9 (3.7)
Natural sample (I) — 3.75 (9.5) — — — — — —
(II) 42.5 (2.2) 3.68 (3.2) 25.3 (8.0) — 36.2 (5.6) — 27.6(14.7) —
AAS Wet digestion15 855 (0.8) 72.5 (5.7) 101 (2.6) 129 (6.3) 720 (3.1) 27.2 (11.0) 281 (4.7) 60.1 (9.3)
* (I) values determined by means of multiple standard addition method, based on Q versus C graphs; (II) values determined by means of eqn. (1) (see
s
text). † Mean with RSD (%) in parentheses for three separate determinations.
4 Analyst, January 1997, Vol. 122

deposition times needed to obtain detectable stripping peaks of
lead were shorter than those required with procedure A. A
deposition time of 5 min and a deposition potential of 21 V
were the optimum stripping conditions for the determination of
both cations in all the samples considered.
The standard addition graphs were linear in all cases, as
shown in Table 5, which gives the regression parameters
relevant to Qs versus C plots over the indicated concentration
ranges. Table 3 gives the values found for all the wines analysed
with this procedure together with those evaluated using eqn. (1);
the agreement is within 3%.
(C) Wine + hydrochloric acid + UV digestion
To our knowledge, this pretreatment procedure has never been
applied to wines, although it has been employed with natural
waters.22
After this pretreatment, the white wines were very cloudy,
and the Barbera red wine still showed a red colour, even if less
intense, and a large amount of solid material at the bottom of the
tube. Therefore, before the measurements, the solid matter was
Table 4 Dependence of ip and Qs on Ed for the stripping of copper and lead
in acidified Chardonnay wine
removed by filtration through a cellulose acetate membrane
filter of 0.45 mm pore size.
The measurements were performed by adopting, unless stated
otherwise, the same experimental conditions as employed with
procedure A (see Table 1). For the three white wines, the
stripping peaks of both lead and copper were well defined. They
were lower, however, than those obtained in the presence of
H2O2, but much higher than those recorded in the same samples
only acidified. For Barbera, no stripping peak of copper was
observed, even if a deposition time of 40 min (unusual for wine)
was employed. To explain this unexpected result, we speculate
that almost all the copper was bound to the solid particles found
at the bottom of the tube after this pretreatment, and therefore
eliminated by filtration.
The multiple standard addition was employed for quantifying
the contents of both lead and copper in Passito and Sauvignon
wines, and only lead in Barbera and Chardonnay wines. The
relevant linear regression parameters of the plots (Qs versus C)
are summarized in Table 5. In Chardonnay, no linear plot was
obtained for copper, so its quantification was accomplished by
using eqn. (1).
The metal levels obtained following the above procedure are
given in Table 3. Eqn. (1) was also employed for determining
the concentration of the cations in all the samples, and data
agreement within 4% was found.

Cu* Pb† Quantification of the Labile Fractions in Natural Wine

Samples
Ed/V ip/nA Qs/nC ip/nA Qs/nC
The labile fractions of lead and copper in the different natural
20.8 0.46 0.85 0.15 0.12 wines were also detected.
21.0 1.05 1.96 0.36 0.28 The stripping peak corresponding to the oxidation process of
21.2 1.78 3.31 0.47 0.40
* t = 1 min. † t = 15 min.
copper was recorded for all the samples investigated, by
d d
employing a deposition potential of 21 V and deposition times
ranging between 2 and 5 min. For lead, in contrast, a detectable
stripping peak was obtained only for the dry white Sauvignon
wine, using a deposition time of 30 min and a deposition
potential of 21.4 V. In the other samples, no stripping peak was
observed, even if more negative deposition potentials and
longer deposition times (up to 40 min) were employed.
The multiple standard addition graph for lead in Sauvignon
wine was linear in the concentration range 1–50 mg l21; eg., the
plot of Qs versus C gave a slope of 8.88 3 1023 nC l mg21, an
intercept of 0.033 nC and r2 = 0.999. This indicates that in this
sample the organic matrix exercises the same effects on the
stripping peak over the concentration range tested, and therefore
the labile fraction of lead was quantified by using the multiple
standard addition method. The concentration value determined
Fig. 2 Linear sweep anodic stripping voltammogram obtained at a with this procedure is 3.75 mg l21 .
mercury microelectrode for the wine sample Sauvignon–Nosiola after As far as copper is concerned, the multiple standard addition
addition of H2O2 and UV irradiation. td = 5 min; Ed = 21 V; scan rate, 50 gave no linear plots, considering both current and charge against
mV s21. concentration data. Moreover, the peak heights depended

Table 5 Parameters of Qs versus C graphs obtained for wine samples after pretreatment procedures B and C

Procedure B Procedure C

Concentra- Concentra-
tion range/ Slope 3 103/ Intercept/ tion range/ Slope 3 103/ Intercept/
Wine sample Cation mg l21 nC l mg21 nC r2 mg l21 nC l mg21 nC r2
Sauvignon Cu2+ 50–1000 5.696 3.628 0.997 50–500 2.622 1.256 0.999
Pb2+ 20–400 18.53 1.033 0.996 20–400 5.169 0.347 0.998
Barbera Cu2+ 50–1000 4.217 0.274 0.999 — — — —
Pb2+ 20–400 8.504 0.729 0.999 20–200 13.03 0.746 0.995
Passito Cu2+ 50–1000 2.722 1.390 0.998 50–500 1.998 0.897 0.989
Pb2+ 20–200 14.50 0.316 0.999 10–100 8.229 0.133 0.992
Chardonnay Cu2+ 50–1000 23.96 4.879 0.999 — — — —
Pb2+ 20–200 8.687 0.340 0.999 20–200 14.93 0.358 0.997

strongly on the time elapsed between addition of the cation and
measurements. These results indicate a strong matrix effect on
the anodic stripping peak of copper. For the quantification of
this cation, the method based on eqn. (1) was employed, and the
results are given in Table 3.
Atomic Absorption Measurements
Data obtained for copper and lead contents by ASV were
compared with those found in the same wine samples by AAS
measurements, which, as is well known, allow one to quantify
the total metal contents of the matrices.23 As can be seen from
the data in Table 3, the values found by AAS measurements
show good agreement with those obtained by voltammetric
analysis for the samples pretreated with H2O2 + UV irradiation.
The discrepancies between these two methods never exceeded
15%.
Discussion and Conclusions
The data in Table 3 show that the different procedures employed
to prepare the wine samples for total copper and lead
determination by ASV yield very dissimilar results. Based on
the amount of metal ions determined, the efficiency of the
pretreatment procedures can be ranked as B > C > A. The
comparison between data obtained by ASV and AAS corrobo-
rates this conclusion.
The treatment with HCl, often employed for total metal
determination, seems to be inadequate for releasing all the metal
ions bound to organic matter still present in the solution. This is
suggested from the larger amounts of both cations obtained
from treatment C, which operates at the same pH as A, but in a
solution where organic matter is destroyed to some extent.
The effects of organic substances on ASV measurements
have been discussed in numerous papers,1 and the problem is
still under debate. Their influence is not easily predictable, and
the results obtained from the pretreatment procedures A and C
may fall within this situation. It is also well known that, in some
cases, organic interferences can be corrected by the standard
addition method.1 The data relevant to linear calibration plots in
Tables 2 and 5 indicate that this correction applies, at least in the
concentration interval considered for each wine and metal ion.
However, the amounts of metal ions determined by procedures
A and C suggest that, in spite of the low pH, the complexing
action of the organic substances towards the metal cations is still
important. This explanation provides a reason for the results
obtained with the acidified Chardonnay wine reported in Table
4, where a large dependence of the stripping peak on the
deposition potential is observed. Thus the application of
multiple standard additions, even when linear plots apply, does
not ensure that the metal determined corresponds to the total
amount present.
The lack of linearity of the multiple standard addition plots
recorded with the natural samples can instead be attributed to
organic substances adsorbed on the electrode surface;1 in these
cases quantifications based on calibration plots are impractical.
Under these conditions, the method based on eqn. (1) appears to
be a reliable means to overcome the difficulty connected with
the evaluation of the metal content in wine. In general, this
approach can be applied for a rapid evaluation of the amount of
metal regardless of the experimental conditions employed; this
may be relevant for speciation studies in these media.
In conclusion, from the above discussion it follows that the
removal or destruction of organic matter is desirable prior to the
Analyst, January 1997, Vol. 122 5
ASV analysis of wines. In this respect, irradiation of the
samples in the presence of H2O2 provides good results. On the
other hand, according to the experimental results obtained here,
irradiation of an acidified sample without H2O2, which would
avoid risks of contamination from the large amount of the latter
reagent needed in the treatment,22 is not effective for complete
destruction of the organic substances. Better results with
procedure C could probably be achieved by employing a longer
UV irradiation period, but in this case the pretreatment
procedure would become much more time consuming.
The authors thank Dr. G. Versini for fruitful discussions, D.
Rudello for skilful experimental assistance and the Research
Laboratory of the Istituto Agrario di S. Michele all’Adige
(Trento, Italy) for providing the wine samples. Financial
support from the Italian National Research Council (CNR) and
Ministry of University (MURST), Rome, is also gratefully
acknowledged.
References
1 Wang, J., Stripping Analysis, VCH, Deerfield Beach, FL, 1985.
2 Mannino, S., and Wang, J., Electroanalysis, 1992, 4, 835.
3 Daniele, S., Baldo, M. A., Ugo, P., and Mazzocchin, G. A., Anal.
Chim. Acta, 1989, 219, 9.
4 Nurnberg, H. W., in Electrochemistry in Research and Development,
eds. Kalvoda, R., and Parsons, R., Plenum Press, New York, 1985,
pp. 121–149.
5 Chang, S. K. C., Holm, E., Schwarz, J., and Rayas-Duarte, P., Anal.
Chem., 1995, 67, 127R.
6 Golimoski, J., Valenta, P., and Nurnberg, H. W., Z. Lebensm.-
Unters. Forsch., 1979, 168, 353.
7 Sipos, L., Golimoski, J., Valenta, P., and Nurnberg, H. W., Fresenius’
Z. Anal. Chem., 1979, 298, 1.
8 Jagner, D., and Westerlund, S., Anal. Chim. Acta, 1980, 117, 159.
9 Mannino, S., Riv. Vitic. Enol. Conegliano, 1982, 6, 297.
10 Golimoski, J., and Golimoska, K., Anal. Chim. Acta, 1996,
325,111.
11 Baldo, M. A., Daniele, S., Corbetta, M., and Mazzocchin, G. A.,
Electroanalysis, 1995, 7, 980.
12 Microelectrodes: Theory and Applications, ed. Montenegro, M. I.,
Queiros, M. A., and Daschbach, J., Nato ASI Series, Kluwer,
Dordrecht, 1991.
13 Amerine, M. A., Berg, H. W., Kunkee, R. E., Ough, C. S., Singleton,
V. L., and Webb, A. D., Technology of Wine Making, Avi, Westport,
CT, 4th edn., 1982.
14 Mart, L., Fresenius’ Z. Anal. Chem., 1979, 296, 350.
15 Office International de la Vigne et du Vin, Recueil des Méthodes
Internationales d’Analyse des Vins et des Mouts, OIVV, Paris,
1990.
16 Stojek, Z., and Osteryoung, J., Anal. Chem., 1989, 61, 1305.
17 Bockris, J. O’M., and Reddy, A. K. N., Modern Electrochemistry,
Plenum Press, New York, 1970, p. 380.
18 Vydra, F., Stulik, K., and Julakova, E., Electrochemical Stripping
Analysis, Ellis Horwood, Chichester, 1976, p. 59.
19 Florence, T. M., Analyst, 1986, 11, 489.
20 Wang, J., Tuzhi, P., and Zadeii, J., Anal. Chem., 1987, 59, 2119.
21 Batley, G. E., and Farrar, Y. J., Anal. Chim. Acta, 1978, 99, 283.
22 Bond, A. M., and Luscombe, D. L., J. Electroanal. Chem., 1986, 214,
21.
23 Bersier, P. M., Howell, J., and Bruntlett, C., Analyst, 1994, 119, 219.
Paper 6/05370J
Received July 31, 1996
Accepted October 11, 1996