ARTICLE IN PRESS

Journal of Food Composition and Analysis 21 (2008) 672– 683

Contents lists available at ScienceDirect

Journal of Food Composition and Analysis

journal homepage: www.elsevier.com/locate/jfca

Critical Review

Metals in alcoholic beverages: A review of sources, effects, concentrations,

removal, speciation, and analysis
Jorge G. Ibanez a,c, Alejandra Carreon-Alvarez b, Maximiliano Barcena-Soto a, Norberto Casillas a,
a
Chemistry Department, Universidad de Guadalajara, Blvd. Marcelino Garcia Barragan #1451, Guadalajara, Mexico CP 44430, Mexico
b
Chemical Engineering Department, Universidad de Guadalajara, Blvd, Marcelino Garcia Barragan #1451, Guadalajara, Mexico CP 44430, Mexico
c
Chemical Engineering and Sciences Department, Universidad Iberoamericana. Prol. Paseo de la Reforma 880, 01219 Mexico DF, Mexico

a r t i c l e in f o a b s t r a c t

Article history: A critical review is offered concerning the different sources, effects, concentrations, removal methods,
Received 6 November 2007 speciation, and analysis of metals (e.g., Al, Ca, Cd, Cu, Fe, Pb, Mg, Mn, Ni, K, Na, and Zn) present in a wide
Received in revised form variety of alcoholic beverages.
29 May 2008
& 2008 Elsevier Inc. All rights reserved.
Accepted 19 June 2008

Keywords:
Alcoholic beverages
Electrochemical analysis of metallic ions
Metal ion analysis
Metals in alcoholic beverages
Metal ion removal
Metal ion speciation
Review
Food composition
Food safety

1. Introduction atomic absorption or emission techniques (Pyrzynska, 2007);

The concentration of metals in many alcoholic beverages can
be a significant parameter affecting their consumption and
conservation. This derives from the negative and positive effects
caused directly or indirectly by the presence of metals. Negative
effects include beverage spoilage and hazing, as well as sensorial
and health consequences (Mayer et al., 2003; Green et al., 1997).
Positive effects include the removal of bad odors and tastes (Green
et al., 1997), participation in fermentative processes (Akrida-
Demertzi and Koutinas, 1992), provision of pathways for dietary
intake of some essential minerals (Mayer et al., 2003), and
usefulness for authentication purposes (Kokkinofta et al., 2003).
Because of all this, many metals are carefully monitored and
regulated, which has resulted in the development of a plethora of
analytical techniques for their analysis. Since alcoholic beverages
are complex aqueous matrices containing a wide variety of
organic compounds, such techniques must be attuned to deal
with their presence—usually by the inclusion of a pretreatment
step. Metals in alcoholic beverages are often determined by
however, the high cost of the instruments involved and the long
sample-preparation times required often preclude their wide-
spread use. Electrochemical methods represent a valuable option
for such analyses. The aim of this paper is to review the various
sources and concentrations of metals in alcoholic beverages
(e.g., Al, Ca, Cd, Cu, Fe, Pb, Mg, Mn, Ni, K, Na, and Zn), their
effects, speciation, removal methods, and key electrochemical
alternatives for analysis.
2. Sources of metals in alcoholic beverages
Metals find their way into alcoholic beverages at different stages
and through various sources including raw materials, brewing,
process type and equipment, bottling, aging/storage, and adultera-
tion as discussed below. (An updated, extensive review of the
sources of metals in wine can be found elsewhere, Pohl, 2007b).
2.1. Raw materials

 Corresponding author. Tel.: +52 33 31342222x7585; Several metal ions can be taken up from the surrounding
fax: +52 33 13 78 59 00x7536. soil by plants from which an alcoholic beverage is prepared
E-mail address: ncasa@hotmail.com (N. Casillas). (FSA, 1998). For instance, the type of soil (i.e., its geogenicity), its

0889-1575/$ - see front matter & 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.jfca.2008.06.005
 ARTICLE IN PRESS
J.G. Ibanez et al. / Journal of Food Composition and Analysis 21 (2008) 672–683
agrochemical treatments (e.g., the use of pesticides and fungi-
cides), and the surrounding environmental pollution have
implications in the mineral content of many beverages (Salvo
et al., 2003; Pohl, 2007b). In this way, wines from vineyards in
coastal areas are richer in Na (Pohl, 2007b). Pesticides, fungicides,
and fertilizers containing Cd, Cu, Mn, Pb, and Zn compounds can
derive in increased contents of these metals in the alcoholic
beverage (Pohl, 2007b; Guerrero et al., 1996). Most of the Mg
found in beer can be introduced with the malt (Weiner and Taylor,
1969). Cu in beer comes mainly from raw materials (Mayer et al.,
2003); on the contrary, only a small percentage of the final Cu
content in whiskey comes from the barely from which the spirit is
distilled (Adam et al., 2002).
2.2. Substances added during brewing
Hops, acids, bases, silica gel, dilution water, flavoring agents,
additives, and stabilizers are potential sources of metal ions in the
brewing process (Mayer et al., 2003). For example, the main
source of Cu in wine is the CuSO4 added to remove sulfidic odors
(Green et al., 1997). The acidity of the liquor to be distilled may be
important in this regard (e.g., in whiskies), since more acidic
beverages tend to contain more Cu (Adam et al., 2002). Addition
of fining and clarifying substances (e.g., flocculants) to reduce
turbidity can bring about an increase in Na, Ca or Al in wine (Pohl,
2007a).
2.3. Process type
Major differences in metal content (i.e., Ni) have been found
among alcoholic beverages depending on their processing. In this
way, certain fermented beverages (e.g., wine and beer) contain
several times more Ni than distilled beverages (e.g., brandy,
whiskey, and vodka) (Dugo et al., 2004).
2.4. Process equipment
This is frequently a key source of metal ions in the final
products. Several examples follow.
 The concentration of Cu coming from process equipment in
vodka is twice as much that coming from the raw materials
(Trawinska et al., 1979).
 The main source of Cu in whiskey is the copper still used for its
distillation (Adam et al., 2002).
 Corrosion of tequila-distillation equipment (made of Cu)
provokes the presence of this metal in the final product
(Carreon et al., 2001).
 Storage of vodka in metal containers (e.g., low-quality steel or
Cu alloys) results in their corrosion with the concomitant
introduction of metals into the liquor (Krasnopol’skii and
Tishchenko, 1984; Trawinska et al., 1979). This is also the case
with acidic wine vinegars (Guerrero et al., 1996).
 The Zn, Fe, and Cu contained in home-produced alcoholic
drinks can be essentially unrelated to the material fermented
as it primarily depends on the vessel materials (Reilly, 1972).
 The temperature in the distillate and the degree of still
utilization affect the Cu content in whiskey (Reaich, 1998).
 Extremely high concentrations of Cu, Zn, and Fe in home-
produced beers and spirits can be largely traced to the use of
galvanized metal fermentation drums, when these replace old
clay and wooden vessels (Reilly, 1973).
 The Fe-content in pulps and musts increases due to the Fe
in concrete tanks used for the storage of raw materials
(Trawinska et al., 1979).
673
 Contact of wine with process equipment, pipes, casks, and
barrels is the usual source of Al, Cd, Cr, Cu, Fe, and Zn
(Pohl, 2007b).
 The main sources of heavy metals in the production of an anis-
type beverage are the bronze pot stills (Moutsatsou et al.,
2003).
 Lead plumbing can add Pb to beverages (Green et al., 1997).
Metal addition from process equipment (e.g., stills) can
be prevented by the use of high-quality steel or glass,
although some organoleptic properties may be altered by the
absence of certain metal ions added during distillation (e.g., the
lack of minute amounts of Cu in tequila affects negatively its
flavor).
2.5. Bottling process
Bottling water and equipment may also introduce metals in
beverages. For example, the content of Ca, Mg, and Na in
brandies depends on the quality of water used for dilution
after distillation (Varju, 1972). The modification of certain
imported alcoholic beverages ‘‘for the purpose of bottling
and sale by the addition of distilled or otherwise purified water
to adjust the beverage to a required strength’’ is sometimes
allowed (DJC, 2005). It is noteworthy that when metallic capsules
seal alcoholic beverage bottles, some Pb may be carried over
(Mena et al., 1997).
2.6. Aging/storage
Possible effects caused by metals during these stages are
multiple. For example, Fe(III) and Mn(II) affect the stability of
old wines and modify their sensorial quality after bottling
(Pohl, 2007a) since they are believed to activate molecular oxygen
by forming reactive oxygen species (e.g., hydroxyl radicals)
(Pohl, 2007a); this is possible due to their electronic configura-
tions involving unpaired electrons that may interact quantum
mechanically with the dioxygen triplet. Likewise, Fe catalyses
the oxidation of polyphenolic substances and Mn facilitates
acetaldehyde formation; the products of these reactions yield
undesirable precipitates. Metal complex formation is also
common at this aging/storage state, which may alter a signifi-
cant number of beverage parameters (Pohl, 2007a). Customer-
accessible containers for alcoholic beverages include metal
cans, glass bottles, plastic containers, and paperboard cartons,
and the containers themselves sometimes are a source of metal
ions in the beverage. For example, Cu and Zn can be introduced
into beer by welded cans (Mayer et al., 2003). In fact, the Zn
concentration in a specific brand of bottled beer was measured
at 0.33 ppm, whereas in canned beer it reached 0.87 ppm
(Weiner and Taylor, 1969). On the contrary, the Ni content in
canned beer as compared with glass-bottled beer is not higher
(Dugo et al., 2004).
2.7. Adulteration
This term comes from the Latin word adulterare (i.e., to defile
or falsify), and means to make something impure by the addition
of extraneous, inferior, or improper ingredients. As far back as
1875, legislation has prohibited the adulteration of drinks
(MacRae and Alden, 2002). Unfortunately, Pb and other metallic
impurities can enter beverages during adulteration practices
(Ijeri and Srivastava, 2001). For example, adulterated vodka
has been found to contain an excess of Ca and Mn ions (Servadio
et al., 1975).
 ARTICLE IN PRESS
674 J.G. Ibanez et al. / Journal of Food Composition and Analysis 21 (2008) 672–683
3. Effects of metals present in alcoholic beverages
These effects can be classified according to the final subject
they act upon.
3.1. Effects on the beverages
These include negative or positive aspects as described below.
3.1.1. Negative aspects
Minerals may generate irreversible turbidities in liquors; the
formation of sediments is a long lasting process that may depend
on the contents of all metals and substances present, the redox
potential, pH, and temperature. Thus, the establishment of
absolute limiting values for metal contents is rather difficult
(Trawinska, 1977). Turbidity typically increases with metal
concentrations. For example, maximum turbidity in soplica liquor
was observed with the addition of Ca after more than 2 months of
storage, whereas a smaller Ca addition (i.e., 20 mg Ca/L) barely
changes a Winiak liquor’s clarity; Fe can likewise contribute to
turbidity. Some metal ions promote the development of turbid
colloids during cognac storage (Russu et al., 1985).
Small amounts of Cu (ca. 3 mg Cu/L) cause maximum turbidity
after 5 months of storage of some beverages (Trawinska, 1977); it
can also be a factor in the formation of hazes (called copper casse)
in wine and in beer (Mayer et al., 2003; Green et al., 1997). In the
case of wine, the basis of this phenomenon is attributed to the
Cu-promoted flocculation of negative hydrophobic colloids
formed by protein-tannins moieties, and also to the interaction
of these Cu cations with HS-groups resulting from protein
denaturation (Esparza et al., 2007). Cu also contributes to the
oxidation of beer and imparts a coppery, unpleasant metallic taste
(Mayer et al., 2003); here, even small amounts of this metal
(e.g., 0.15 mg Cu/L) can cause gushing (Mayer et al., 2003). Radical
formation in sugar cane spirits depends mainly on the Cu content,
as detected by electron spin resonance (Bettin et al., 2002).
Color changes in some alcoholic beverages (e.g., wine) can be
attributed to different factors (Esparza et al., 2005): (a) complex
formation of Fe, Cu, Al or Mg with anthocyanins and tannins,
(b) the presence of metal–polyphenol complexes, (c) hyperchro-
mic of batochromic effects originating from copigmentation
processes, and (d) an exogenous contribution of selected metal
cations that might result in favorable color modification.
Examples of additional color changes include the following. Cu
can increase the rate of oxidative spoilage of wine, which
ultimately results in its browning (Pohl, 2007b). There is a
relationship between the color of a brandy and its Fe and Cu
contents (Varju, 1972); if the concentration of metals in brandy
reaches a critical limit, they promote precipitation (Varju, 1972).
Although a significant correlation is not found between the
content of metals (e.g., Fe, Cu, and Zn) and the color development
in sake (a traditional Japanese drink) during the first 2 years of
storage, more extensive darkening is observed after 3 years
(Kondo, 1966).
Another effect involves the influencing of key organoleptic
properties by high concentrations of certain metals. A case in
point is the negative influence of Zn in wines (Salvo et al., 2003).
3.1.2. Positive aspects
Contrary to the above, some metals enhance the flavor of wine
(Esparza et al., 2005). One plausible indirect pathway for this
effect involves the binding of sulfur derivatives to reduce the
sulfury flavor (e.g., Cu in whiskey, sugar cane spirits, and cognac),
as confirmed by thermal desorption gas chromatography (Reaich,
1998; Richter et al., 2001). Cu is also involved in the reduction and
formation of congeners throughout the distillation of whiskey
(Reaich, 1998; Nedjma and Hoffmann, 1996). Key concentration
ratios of K, Na, and Ca to Cu can speed up the fermentation
kinetics of a solution composed of raisin extract and sucrose
(Akrida-Demertzi and Koutinas, 1992); this may be attributed
to the increase of the glucose uptake rate. On the other hand a
higher concentration of Ca2+ ions results in their uptake
by Saccharomyces cerevisiae cells, which reduces cell growth
(Akrida-Demertzi and Koutinas, 1991). Yeasts consume Ca, Cu,
Fe, K, Mg and Zn and therefore their concentrations tend to
decrease (Pohl, 2007b); a substantial cofactor role occurs in some
cases (Esparza et al., 2005).
Another useful aspect of the presence of specific metals in
alcoholic beverages involves their use in quality analysis and in
authentication (fingerprinting) due to their typical stabilities
(Guerrero et al., 1996; Nuñez et al., 2000). Chemometrics and
pattern recognition methods are used for the distinction of
beverages according to their origin, quality, variety, type, and
other features (Kokkinofta et al., 2003; Nuñez et al., 2000). For
example, the Cu concentration in a malt Scotch whiskey is ca.
1.5–3.5 times greater than that in a blended (grain) Scotch
whiskey (Adam et al., 2002). Another case in point is the metal
content in zivania (a Cypriot traditional drink), which allows
its differentiation from spirits produced in other countries
(Kokkinofta et al., 2003). Likewise, the analysis of Na and Mg is
often sufficient to discriminate among different wines; even the
analysis of Mg alone may serve such a purpose (Kokkinofta et al.,
2003). In the same manner, the metal profile of brandies depends
on their elaboration process; accordingly, the content of metals is
sometimes used as a chemical descriptor for classifying different
kinds of brandies. Statistical techniques are most helpful here,
since classification procedures based on artificial neural networks
lead to a predictive ability up to 90% (Camean et al., 2001).
3.2. Effects on humans
Metal ion effects on humans can be quite varied, and their
detailed coverage falls beyond the scope of the present review;
key information can be found in toxicology treatises. To exemplify
this issue, among the best known effects are those of the toxic
Pb(II) and Cd(II) ions. In fact, Benjamin Franklin in the eighteenth
century noticed that certain homemade rum was causing human
paralysis; he successfully traced the problem to Pb-containing
equipment (UMA, 2005). Chromium—specifically Cr(VI)—can also
be toxic; fortunately, dangerous concentrations are not common
in alcoholic beverages. For instance, in a wide sampling of
beverages (including wine, beer, cider, brandy, rum, whiskey,
gin, vodka, anisette, and liquors) its concentration was found to be
below 0.025 mg/L (Lendinez et al., 1998).
On the contrary, the presence of certain metal ions in alcoholic
beverages is beneficial in that it may provide an intake path for
necessary nutrients in consumers (Mayer et al., 2003). For
example, moderate wine consumption provides important
amounts of nutritional requirements of several essential metals
like Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Ni, and Zn (Pohl, 2007b).
4. Metal concentrations and limits
The concentrations of metals in alcoholic beverages can vary
widely, as exemplified by the concentrations of Cu summarized in
Fig. 1. Other metal concentrations are condensed in Table 1. As
shown here, metals are sometimes present in alcoholic beverages
at rather high concentrations. In fact, extreme metal ion
concentrations in home-produced beer and spirits from different
parts of Africa, India, Europe, and Canada revealed concentrations
 ARTICLE IN PRESS

J.G. Ibanez et al. / Journal of Food Composition and Analysis 21 (2008) 672–683 675

2.5

2.0
.
1.5
. .
1.0 .
. .
. .

log CCu , mg/L

0.5
. .
0
. . . . .
.
-0.5 . .
-1.0 . .
. .
-1.5

-2.0
. ND
-2.5
Beverage spirits

Brandy

Cachaza

Cognac

Gin

Rum

Scotch whiskey

Sherry brandy

Sugar cane spirits

Tequila

Vodka

Whiskey

Wine, fruit wine, cocktails

Beer

Fig. 1. Copper content in selected alcoholic beverages. (Note: quotas in lines symbolize maximum and minimum concentrations. ND ¼ not detectable.)

of up to 58, 68, and 245 mg/L of Cu, Zn, and Fe, respectively then adding tannins or tannic acids and allowing the mixed
(Reilly, 1973). Homemade—but commercially available—alcoholic substances to react for several days. Finally, gelatin and
beverages in Tanzania can have up to twice the World Health bentonite are added to react with the metal tannates and the
Organization recommended maximum for Zn in drinking water mixture is stirred, decanted, and filtered. Large reduction
(i.e., 5 mg/L), and one brewed beverage was found to contain toxic factors in Cu, Fe, and Zn concentrations are thus obtained
amounts of Mn (12.8 mg/L) (Nikander et al., 1991). These instances (Bakalov et al., 1989; Ionescu, 1980).
dramatically demonstrate that the establishment of limits is  Ion exchange resins decrease the metal content of certain
indispensable. Table 2 shows examples of metal concentration distillates to the allowable limits (Hodejeu et al., 1972).
limits established by various regulatory agencies for selected (As a case in point, we have obtained up to 99.6% removal of
beverages. Cu from tequila.)
Note that limits imposed for alcoholic beverages are higher  MgCO3 and CaCO3 can act as cationic exchangers to remove
than those established for water utilized in human consumption. Cu(II) from sugar cane spirits (Almeida Neves et al., 2007).
This reflects the lower intake of the former (Green et al., 1997). For  Cu is removed from spirituous beverages by precipitation with
example, alcoholic drinks usually contribute only marginally to rubeanic acid (Peña et al., 2004).
typical dietary Cu intakes (0.05 mg/day) (Sadhra et al., 2007).  Some metal ions (e.g., Cu and Fe) are removed from alcoholic
Regrettably, marked absences in legislation do exist (Baldo and beverages by adding polymers that contain metal-binding
Daniele, 2005). groups (Detering et al., 1991; Kern, 1987).
Metal ion concentrations in wastewaters of breweries and  Electroless cementation (Ibanez et al., in press) is under testing
alcoholic beverage factories are typically below the limits for Cu removal from tequila by cementation on Fe. We have
established for the introduction of such concentrations into removed up to 60% of Cu with Fe (from a 10 ppm Cu solution).
municipal treatment systems. Metals that are sometimes present  Electrolysis for Cu removal from a variety of matrices is widely
in concentrations near the upper regulation limits include Hg and practiced (Rajeshwar and Ibanez, 1997). (We are currently
Cu (Koller and Sahlmann, 1987). testing it for the removal of Cu(II) from tequila, whereby
preliminary results indicate that ohmic drop losses prevent a
removal higher than 50%.)
5. Metal removal  Certain chelating agents (e.g., the trisodium salt of nitrilo
tris-methylenephosphonic acid) in wine and cognac can
Methods for metal removal from alcoholic beverages can be precipitate Fe, Al, and Cu within 1 week (Romantseva et al.,
exemplified by the following cases: 1982). The same compound can be used in brandy to
precipitate Fe and Al (Cu does not precipitate here) (Mekhuzla
 Cu in whiskey may form complexes that bind to wood et al., 1978).
during storage and aging; Cu is thus removed from the  Potassium hexacyanoferrate (II) binds some metals and
liquor (Adam et al., 2002). On the contrary, the contents of sulfides present in alcoholic beverages, although it cannot be
Ca and K in sherry brandy increase with aging (Camean et al., used in applications where the Cu content exceeds that of Fe;
2000). besides, it may release poisonous HCN.
 An alternative metal removal scheme consists in raising the pH  A cross-linked, insoluble, powdery polymer may circumvent
(e.g., in wine and brandy) with NaHCO3 or CaCO3 to ca. 4.5–5, some of the problems described earlier. It is produced with
 676
Table 1
Summary of sample metal concentrations in various alcoholic beverages

Alc. beverage Concentration, mg/L

Al Ca Cd Cu Fe Pb Mg Mn Ni K Na Zn Ref.

Anisette 0.086–0.445 Mena et al. (1997)

J.G. Ibanez et al. / Journal of Food Composition and Analysis 21 (2008) 672–683
Beer 0.1–58 0.2–25 ND–0.245 0.1–68 Reilly (1973), Mena et al.
(1997)
Beverage 0.4 0.7 0.165–0.390 0.3 Maranda (1986), Mena
spirits et al. (1997)
Brandy ND–14.8 2.0–14.6 ND–2.30 ND–0.224 2.0 3.0 Cyro (1976), Bakalov et al.
(1989), Mena et al. (1997),
Soufleros et al. (2004)

ARTICLE IN PRESS
Cachaza 1.36–44.6 0.04–14.3 0.01–2.24 ND–0.421 Bettin et al. (2002),
Soufleros et al. (2004)
Cognac 6.0–11 0.005–5.31 0.1 0.008–0.420 2.0 0.016–3.0 Cyro (1976), Soufleros
et al. (2004), Barbeira and
Stradiotto (1998)
Finnish berry o0.005 o0.1 Harju and Ronkainen
liqueurs (1984)
Gin 1.0 0.5 ND ND–0.035 0.5 0.5 Cyro (1976), Mena et al.
(1997)
Rum 4.0 0.5 1.0 ND–0.070 2.0 3.0 Cyro (1976), Mena et al.
(1997)
Scotch whiskey 0.5–4 0.1–1.7 0.02–28 o0.005 0.02–4 0.002–0.6 2–24 0.02–20 Adam et al. (2002)
Sherry brandy 0.02–1.58 ND–14.8 5.31–0.30 0.22–5.31 ND–2.03 0.008–0.073 0.06–11.20 0.11–70.06 17.8–635 Camean et al. (2001)
Sugar cane 0.04–7.0 0.01–1.28 Bettin et al. (2002),
spirits Soufleros et al. (2004)
Tequila 0.38–11.80 Carreon-Alvarez et al.
(2008)
Vodka 3.0 0.5 ND 0.5 ND Cyro (1976)
Whiskey 4.0 0.23–0.5 ND–0.1 0.02–0.195 1.0 0.5 Cyro (1976), Mena et al.
(regular) (1997), Soufleros et al.
(2004)
Wine, fruit 0.017–14.3 3.50–241 ND–0.052 ND–7.62 ND–23.7 ND–1.125 7.8–718 ND–5.5 0.073–19.4 265–3056 ND–310 ND–8.9 Bulinski et al. (1995),
wine, Mena et al. (1997),
cocktails Soufleros et al. (2004),
Pohl (2007b), Dugo et al.
(2005), Barbeira and
Stradiotto (1996)

Note: ND ¼ not detectable.

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J.G. Ibanez et al. / Journal of Food Composition and Analysis 21 (2008) 672–683
Table 2
Examples of metal concentration limits for selected beverages
Metal Beverage Concentration limit, mg/L
Cu Wine 0.5
Pb Wine 0.2
Cu Beer 0.05
Cd Wine 0.1
Cu Wine 1.0
Pb Wine 0.2
Zn Wine 0.5–5
Cu Cachaza 5 MAL
Cu Fruit distillate 5 MAL
a
MAL ¼ maximum acceptable limit.
N-vinylimidazole, N-vinyl-2-pyrrolidinone and N,N0 -divinyl-
imidazolidin-2-one under the BASF trade name of divergan
HM. This polymer can be used in matrix filter sheets at
different stages during wine treatment; for example,
a dose of less than 1 g/L can bind ca. 90% of the Cu and Fe in
immature wines, and 75% of the Cu and Fe in mature wines
(USFDA, 2003).
 Some of the Mg in beer is removed by the yeast itself (Weiner
and Taylor, 1969).
6. Speciation
The chemical form in which an element, ion or compound is
found in a given medium depends on the physicochemical
conditions of the system. Thus, the distribution of species in an
aqueous medium (e.g., an alcoholic beverage) is contingent on pH,
composition, temperature, and the oxidation-reduction potential
of the solution. These variables define precipitation, dissolution,
redox, and complexation reactions. Biological phenomena
(e.g., bioaccumulation) frequently depend on the chemical form
or speciation of a metallic ion.
The redox environment can determine some properties
of metallic and non-metallic species. For example, when
arsenic is present in oxic (oxidizing) environments as As(V), its
toxicity is very low; however, its reduced form, As(III) is highly
poisonous. The opposite occurs with Cr(VI), which is much
more toxic than its reduced counterpart, Cr(III). Solubility can
also be severely affected by the redox environment. Examples
of this are Fe(II) and Mn(II) species, typically soluble in
aqueous solutions deficient in dioxygen, whose oxidized forms
precipitate quite easily. Similarly, ligand speciation may drasti-
cally affect the nature and physicochemical properties of the
metallic complexes they form. Bioavailability and toxicity of
metal ions in aqueous systems are often proportional to the
concentration of the free metal ion and thus decrease upon
complexation. However, some metal compounds are more
dangerous than the metallic element itself (e.g., methyl mercury
vs. mercury) (Ibanez et al., 2007).
Because of the aforementioned reasons, determination of the
total concentration of a metal in a given matrix often does not
adequately or effectively characterize it; as a result, speciation has
gained considerable ground. Speciation is the process that yields
evidence of the atomic or molecular form of an analyte. It can be
defined either functionally (e.g., the determination of species that
have certain specific functions), or operationally (e.g., the deter-
mination of the extractable forms of an element from a given
matrix) (Ibanez et al., 2007). A thorough review of the develop-
ment of chemical speciation and fractionation analysis of metals
in wine is available, including a description of the methods to
identify ionic, labile and tightly bound species (Pyrzynska, 2007).
677
Obligatorietya Reference
Recommended Green et al. (1997)
Recommended Green et al. (1997)
Recommended Mayer et al. (2003)
MAL Salvo et al. (2003), Dugo et al. (2005)
MAL Salvo et al. (2003), Dugo et al. (2005)
MAL Commission of the European Communities (2006), Dugo et al. (2005)
MAL Salvo et al. (2003), Dugo et al. (2005)
Richter et al. (2001)
Soufleros et al. (2004)
Examples of the importance of speciation in alcoholic beve-
rages include the following:
 Metals can be either in a state ‘‘bound’’ to the wine matrix, or
‘‘unbound’’ in solution. Some analytical methods (e.g., anodic
stripping voltammetry, ASV see below) may not detect the total
amount of the metal in the sample, but merely identify the
unbound fraction. This problem has been circumvented by
means of the standard addition method (SAM) used for their
quantification (Akkermans et al., 1998). Nevertheless, one must
be careful when interpreting results since the added metal ions
may perturb the equilibrium distribution of species in the
target matrix (Green et al., 1997). In fact, this method is not
recommended for metal ions that strongly bind the alcoholic
matrix (Green et al., 1997).
 The concentration of metals in distillates may be affected by
complex formation in the stills, given that such complexes may
be less volatile than the metal ions themselves and thus their
final concentration in the distillate would be smaller than what
could be predicted (Adam et al., 2002).
 Bioavailability is usually more important than the total
concentration of a metal (Green et al., 1997). Labile metal
complexes (ML) are normally more toxic because they are
more easily absorbed by organisms (Arcos et al., 1993).
 In the case of Cu in wine, its chemical form—rather than the
total concentration—may be a better indicator of its potential
for spoilage, since Cu sometimes produces spoilage even at low
concentrations (Green et al., 1997). Additionally, some Cu
complexes are stable even at pH ¼ 1 and their stability
increases if the wine is young and the organic matter is not
very oxidized (Arcos et al., 1993). Cu in white wine is mainly
complexed by thiol groups (Wiese and Schwedt, 1997); in fact,
this principle is used in determining it by differential pulse
ASV (dPASV, see below) when forming a complex on the
surface of a mercury drop (Ensafi et al., 2001). Tannine,
peptide, and protein groups also highly influence the formation
of Cu complexes in white wine (Wiese and Schwedt, 1997).
 Organic complexes of Cu are present in residues of the
distillation process of Scotch whiskies (Adam et al., 2002). Cu
and Zn form soluble complexes in the spent wash of whiskey
distilleries. Cu is believed to be bound to an organic fraction
containing carbohydrate and ninhydrin, whereas Zn is com-
plexed by a lower molecular weight fraction containing hexose
and phenolic moieties (Quinn et al., 1982).
 Red wine has a high complexation capacity for Pb, as it rapidly
and strongly binds it (Green et al., 1997).
 Ultrafiltration removes the species that complex Pb ions in
wine, which means that such species are macromolecules
(e.g., polyphenols or polyuronides) (Green et al., 1997).
 Fe can complex certain triketones, the main bittering com-
pounds in beer. In doing so, it may induce their deprotonation
 ARTICLE IN PRESS

678 J.G. Ibanez et al. / Journal of Food Composition and Analysis 21 (2008) 672–683

and thus contribute to changes in beer quality during ageing
(Blanco et al., 2003).
 Metals can be present in beer as cations (e.g., Mn2+) or as
complex anions (e.g., Fe(III) with cyclic triketones) (Blanco
et al., 2003). Strong interactions between the metal cations and
ligands in alcoholic beverages are believed to play a key role in
some properties of the final product (Blanco et al., 2003).
 Metals in the waste from an alcoholic anis-type beverage
facility have been found in complexed form in the solution. The
existence of metals in the amorphous phase (as shown by SEM)
indicates the presence of metal–organic complexes (as verified
by HPLC). Complexation data can be used for selecting
the proper wash treatment method. The formation of large
molecules favors precipitation and chemisorption treatment
methods (Moutsatsou et al., 2003).
Finally, some confusion in the literature as for the use of the terms
labile or stable complexes should be noted. Traditional usage implies
that the labile/stable status is defined on the grounds of kinetic
stability (e.g., Cotton and Wilkinson, 1976), whereas recent publica-
tions use this distinction on the basis of thermodynamic stability
(Wiese and Schwedt, 1997). Thus, one must be careful as to the
meaning of these terms; in the present review we have maintained
their meanings as they are used in each original publication.
7. Determination of metals in alcoholic beverages
Analytical methods frequently require sample preconcentra-
tion and/or pretreatment for the destruction of the organic matrix
such as wet digestion, dry ashing, and microwave oven dissolution
(Salvo et al., 2003; Dugo et al., 2004). Common analytical methods
include atomic absorption spectrometry (AAS), atomic emission
spectrometry (AES) and inductively coupled plasma–optical
emission spectrometry (Camean et al., 2001). Ion chromatography
is also used for the analysis of metals, for example in vodka
(Obrezkov et al., 2000). The SAM can be used with some of these
schemes; for example, Cu is determined in cachaza with SAM–AAS
(Farias-Almeida et al., 2003). Another alternative involves a
previous fractionation step of the metals from the beverage
matrix using either ionic resins or adsorbents before analyzing
food or wine samples (Pohl, 2007a). Unfortunately, most of these
methods involve rather expensive instrumentation (with its
concomitant high-cost maintenance) that precludes their wide-
spread use among alcoholic beverage producers. Electrochemical
methods have gained considerable ground in the analysis of
alcoholic beverages because of their simplicity, rapidity, and
relative low cost. The principles, advantages and challenges
involved as well as their proposed solutions are discussed below.
 In many cases, electrochemical measurements can be per-
formed in the natural medium without sample pretreatment
(e.g., in potentiometric stripping analysis, PSA) (Green et al.,
1997).
 Organometallic complexes of many metal ions can adsorb onto
Hg drops, and therefore they are—in principle—suitable for
electrochemical analysis using Hg surfaces (Dugo et al., 2004).
 Electrochemical methods are effective for metal speciation
studies (Green et al., 1997).
 Frequently all the metal ions need to be in the same form prior
to analysis. An example for solving this problem before an
electrochemical analysis is as follows: Cu is typically analyzed
in alcoholic beverages by adding a high concentration of
chloride ions to ensure that all the Cu is in the same form
(i.e., CuCl
2 ) (Green et al., 1997). Quite interestingly, the
catalytic properties of free and labile Cu(II) ions can be
exploited for determining the element since the oxidation of
an azine does not occur in the presence of stable Cu complexes
and thus depends directly on the free metal ions (Wiese and
Schwedt, 1997).
7.2. Potentiometric methods
These are based on the potentiometric response of the target
analytes. The PSA is the most important method in this group.
The principles of two key potentiometric methods are depicted in
Figs. 2 and 3.
In the PSA, reoxidation plays a key role since an oxidizing
agent is necessary (see Fig. 2). For example, O2 is used in the
determination of Pb, Cd, and Cu in water and in some alcoholic
beverages (Macca et al., 1997), and of free and total Cu in wines
(Green et al., 1997). Hg(II) is also used as oxidizer in PSA (Mayer
et al., 2003; Ensafi et al., 2001; Marken et al., 1997; Jagner, 1978;
+
n n+
M(aq) + L(aq) [ML](aq)
Electrochem. redn.
Ered(const.) Plot E vs. dt/dE
ENRICHMENT
M0/M0L(amalgam)
Chemical oxidation
STRIPPING (with Hg2+, O2)
n+
M(aq)+ products
Fig. 2. Derivative potentiometric stripping analysis.

7.1. Electrochemical methods: principles, advantages, challenges,

and proposed solutions
POTENTIAL-ASSISTED
COMPLEXATION ADSORPTION
Electroanalytical techniques are either passive or active
(i.e., dynamic), depending on whether or not the process of
excitation/response forces concentration changes at the electro- L(aq) Edep(const.)
n+ n+ n+
M(aq) [ML](aq) [ML](ads)
de–electrolyte interface. In this way, potentiometric techniques
tdep
(that measure the solution potential as a response to physico-
chemical variables) are passive, whereas voltammetric techniques
REDUCTION
(that observe redox behavior as a consequence of dynamic DISSOCIATION (STRIPPING)
potential changes) are active (Rajeshwar and Ibanez, 1997). EQUILIBRIUM istrip(const.)
Advantages of the electrochemical methods include the following:
n+ n+
 They are straightforward, fast, sensitive and inexpensive, and M(aq)+ L(aq) M0L(amalgam)
they tend to encompass simple requirements (Mayer et al.,
2003; Barbeira and Stradiotto, 1996, 1998a). Fig. 3. Adsorptive stripping chronopotentiometric analysis.
 ARTICLE IN PRESS
J.G. Ibanez et al. / Journal of Food Composition and Analysis 21 (2008) 672–683
Nan et al., 1994). However, besides the health threats posed by Hg
(see below), this element does not allow the detection and
adequate reproducibility for the quantitation of certain metal ions
(e.g., Cu) (Macca et al., 1997; Daniele et al., 1989) due to their low
solubility in Hg (Ostapezuk et al., 1997). Mercury-free, solid-state
electrodes are useful alternatives (Wang and Tian, 1993).
The selection of the oxidizer depends on the supporting
electrolyte, as in the case of high HCl concentrations in which
O2 cannot be used (Green et al., 1997). If the deposition time is
extended, the analytically useful response is enhanced (Ostapezuk
et al., 1997). Proteins may interfere with the electrochemical
processes involved (Mayer et al., 2003), which often prevents the
use of PSA when determining metals in alcoholic beverages.
Adsorptive stripping chronopotentiometry (AdSCP, see Fig. 3) is
used in the analysis of tea, coffee, fruit juice, coca cola, white and
red wines, beer, brandy, whiskey, and vodka (Dugo et al., 2004).
Derivative anodic stripping chronopotentiometry is used for the
2
determination of inorganic anions (Cl, NO 3 , SO4 ) and metal
2+ 2+ 2+
cations (Cd , Pb , Zn ) in wine (Dugo et al., 2005).
Advantages of the potentiometric methods include the following:
 The analysis is not affected by the adsorption of organic
compounds when the stripping is performed by a chemical
oxidant (Green et al., 1997).
 They are suitable for direct measurement of labile metal ion
concentrations in alcoholic systems with a high organic
content (Green et al., 1997).
 Maintenance costs are low, and the methods are highly
sensitive, accurate and precise; there is often no need for an
extraction step, and disposable electrodes may be used (Dugo
et al., 2004; Wang and Tian, 1993; Andruzzi et al., 1983).
 dPSA allows the direct determination of many metals in wines
without any sample pretreatment (other than pH adjustment),
because the glassy carbon-Hg film working electrode (GCMFE)
remains inert to organic molecule interferences during the
signal collection phase (Salvo et al., 2003).
 The optimum adsorption potential can be found by analyzing
the response of the system at various applied adsorption
potentials. For example, in the case of Ni analysis, H2O
molecules and interfering ions can also be adsorbed at various
potentials (Dugo et al., 2004).
 The transformation of E vs. t data into a E vs. dt/dE format
(i.e., derivative dPSA) allows for the elimination of the capacitive
current and reduces the influence of the adsorbed species, see
Fig. 2 (Dugo et al., 2004). The area under the peaks then reflects
the time required for the corresponding (faradaic) reduction
processes, whereas the area under the baseline represents the
charging time for the double layer (Dugo et al., 2004).
 dPSA allows the direct determination of Cd(II), Cu(II), Pb(II),
and Zn(II) in acidified wine samples (Salvo et al., 2003).
 Analysis of Cu by PSA can yield essentially the same results as
AA (Richter et al., 2001).
Challenges posed by these methods include the following:
 They require toxic Hg to plate the working electrode.
 The also toxic Hg(II) is often utilized for the chemical stripping
(oxidation) step.
 The use of dioxygen as the chemical oxidizer is precluded in
those cases where a high Cl concentration is utilized, since
this lowers the solubility of the gas in the stripping medium
(Green et al., 1997).
7.3. Voltammetric methods
Here, the potential is changed at will and the system responds
in the form of a measurable current; this offers a powerful tool for
679
mechanistic and diagnostic studies. The most popular voltam-
metric method is cyclic voltammetry, where a potential ramp is
applied to the system normally from the point of zero current up
to a desired potential, limited by the decomposition of the solvent.
In this way, the redox behavior of the system can be mapped to
include oxidations and reductions of the analyte, coupled
chemical or electrochemical reactions, electrode participation in
redox processes, the kinetic facility of reactions involving analyte
species (i.e., reversibility/sluggishness), the kinetics of charge
transfer at the electrode/electrolyte interface, and the measure-
ment of the concentration of analyte species (Rajeshwar and
Ibanez, 1997).
Voltammetric methods have been widely used in the food
industry for the analysis of metals, vitamins, additives, antiox-
idants, among others (PAR, 1982). For example, the fraction of
labile ML to the total metal content in alcoholic beverages can be
estimated electrochemically. This is done by analyzing the metal
under the natural conditions of the beverage; then, the results are
compared with those found after the addition of specific reagents
that produce the necessary conditions for the rupture of virtually
any other complex present (i.e., all the complexed, bound metal is
liberated) (Salvo et al., 2003; Green et al., 1997; Daniele et al.,
1989) and for the avoidance of insoluble oxide formation (Salvo
et al., 2003). Typical reagents include acidic solutions of highly
concentrated chlorides (Daniele et al., 1989), and a combination of
HClO4, H2O2, and UV (Richter et al., 2001). This is exemplified
below as
ML þ 2Hþ "M2þ þ H2 L (1)
This step is of paramount importance for the analysis of the
metal because at a higher pH and low Cl concentration, for
example, no useful Cu peaks are obtained in stripping voltam-
metry (Green et al., 1997). When identical results are obtained
with and without such ‘‘uncomplexing’’ reagents, the conclusion
is that the metal ion complexes are totally labile (Richter et al.,
2001). Examples of labile metal fractions in an alcoholic beverage
are given in Table 3.
Stripping voltammetry coupled to quantum mechanical calcu-
lations is a powerful tool in the elucidation of complex
stoichiometries as well as structural, thermodynamic, and kinetic
information on ML (Esparza et al., 2005). It is also used as a gauge
of the vinification stage in certain wines (Esparza et al., 2007).
Even though stripping voltammetry is more susceptible than
stripping chronopotentiometry to interferences by electroactive
organic molecules and by capacitive currents (Dugo et al., 2004),
its use seems to be more widespread.
7.3.1. Polarography
Polarography is a branch of voltammetry where the working
electrode is an Hg drop (Wang, 2000; Monk, 2001). It is simple
and fast, and—by a judicious selection of the working conditions—
it can also be made highly selective. Polarography is widely used
in the determination of metals and sometimes in the determina-
tion of the ethanol content of an alcoholic beverage (Song et al.,
2000; Dechsuwan and Vaneesorn, 1997). Other examples of
Table 3
Labile metal fractions in wine (Green et al., 1997; Daniele et al., 1989)
Metal % as labile metal content
Pb 53
Cu 64–78
Cd 67
Zn 85
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680 J.G. Ibanez et al. / Journal of Food Composition and Analysis 21 (2008) 672–683

metals analyzed in alcoholic beverages include Cd, Cu, and Pb in
beer (Nguyen et al., 2003), Fe, Zn, Cu, and Pb in wine (Vasyutinskii
et al., 1967; Fournier et al., 1998), and Pb in white spirits (Jin et al.,
2001). Reported detection limits for Pb in the later case range
from 0.021 to 0.1 mg/L, and for Cd it is given as 0.5 mg/L (Jin et al.,
2001; Zhang et al., 2002).
Polarographic methods used in alcoholic beverage analysis—
other than classical polarography—include:
 Differential pulse polarography in the determination of metal
traces (Kobori and Sugiyama, 1995; Kobori and Matsuyama,
1994; Shukla and Pitre, 1998), and of ethanol (Dechsuwan and
Vaneesorn, 1997), where a smaller standard deviation than
that obtained with square wave voltammetry was evidenced.
 Adsorptive wave polarography for the determination of Mn
(Liang and Li, 1992).
 Square wave polarography for the determination of Mn in sake
(Kondo and Yamada, 1967).
 Anodic stripping polarography for the analysis of Cu, Pb, Cd,
and Zn in wine (Cobo and Zamora, 1985).
Sample data for comparison with similar optical absorption
analyses are given in Table 4.
The main advantages in using Hg as the working electrode
include the following (Wang, 2000; Monk, 2001; Mikkelsen and
Schrøder, 2003):
 Hg is an effective working electrode since it has a high
overpotential towards hydrogen evolution as compared to
other common electrodes, which provides a large poten-
tial window for its usage; as a result, many metals can be
analyzed.
 Hg presents a renewed electrodic surface to the solution in each
drop, which eliminates or minimizes contamination effects due
to undesired adsorption phenomena. This avoids interference
from possible residues from previous determinations.
 The use of fresh Hg drops eliminates the need to clean the
electrodic surface with more chemicals.
The main disadvantages in using Hg include the following:
 As discussed earlier, Hg is highly toxic (Monk, 2001).
 Many metals cannot be analyzed since Hg is oxidized at
positive potentials.
 The set up and its operation become complicated because of
the need to house liquid Hg.
 Hg cleaning (normally by triple distillation) is costly.
 Due to the inconveniences mentioned above, mercury amal-
gams have been developed—although this does not completely
preclude its associated toxicity (Lovrić et al., 1991).
7.3.2. Rotating disk electrode
Here, a rotating disk enhances mass transport for the
electrodeposition of a target substrate. Advantages include
mercury avoidance, simplicity, and reproducibility of results. An
example is the analysis of Cu in tequila using a Pt rotating disk
electrode with the SAM. The obtained results compare well to
those with AAS (Carreon-Alvarez et al., 2008).
7.3.3. Stripping analysis
The quantitation of metals in alcoholic beverages may be
achieved by stripping voltammetric analysis. Here, a judiciously
selected potential is applied during a preselected time to reduce
and deposit the metal from the liquid matrix onto the electrode
surface. Then, a potential is applied such that the metal is
reoxidized, see Fig. 4. The amount of metal reduced and then
reoxidized is proportional to its concentration in the liquid
(Wang, 2000; PAR, 1991; Bard and Faulkner, 2001).
Advantages of this technique include its sensitivity (1010 M in
some cases), accuracy, cost effectiveness, and speediness; typi-
cally, no pretreatment of the sample is required. Quantitation is
achieved by measuring the area under the oxidation curve. Metals
commonly analyzed with this technique include Cu, Cd, Pb, Zn,
and Ni, although Tl, Sn, Bi, and Sb have also been reported. Typical
results compare well with those obtained by AAS.
Several techniques derive from this stripping analysis; the
main differences involve the nature of the parameters monitored.
The principal stripping techniques used for the quantitation of
metals in alcoholic beverages include:
 PSA, used in the quantitation of metals and estimation of their
labilities in cachaza, German wine, and white wine (Green
et al., 1997; Richter et al., 2001; Ostapezuk et al., 1997;
Mikkelsen et al., 2004).
 dPSA in beer, and white and red wines (Salvo et al., 2003;
Mayer et al., 2003; Mikkelsen and Schroder, 2002).
 ASV in wines and grappa (Baldo and Daniele, 2005; Arcos et al.,
1993; Baldo et al., 1998).
 Sono-ASV in beer (Agra-Gutierrez et al., 1999).
 Differential pulse voltammetry in wines and in synthetic
alcoholic beverages (Ijeri and Srivastava, 2000), and in cognacs
(Barbeira and Stradiotto, 1998a).

PRECONCENTRATION STRIPPING

n+
Edep Estrip n+
M(aq), dilute o
M(s, ads or amalgam) M(aq), concentrated
tdep

Edep < Eo` < Estrip

Fig. 4. Anodic stripping voltammetric analysis.

Table 4
Amount of metals analyzed by polarography, as percentage of the corresponding amount obtained by optical absorption techniques (e.g., atomic absorption)

Liquor Percentage of metal analyzed by polarography, % Reference

Pb Cd Mn Fe

White spirit 99.9–100.1 97.0–104.8 Zhang et al. (2002)

White spirit 99.9–100.2 Jin et al. (2001)
Alc. beverages 93.6 86.7 92.9 Dugo et al. (2004)
Alc. beverages 93.2–101.9 90–105 Cao (1993)
 ARTICLE IN PRESS
J.G. Ibanez et al. / Journal of Food Composition and Analysis 21 (2008) 672–683
 DPASV in white wine and in synthetic alcoholic beverages
(Ijeri and Srivastava, 2001; Wiese and Schwedt, 1997; Daniele
et al., 1989).
Stripping analysis is also used for metal determination in other
foodstuffs such as Pb and Cu in butter (Szlyk and Szydlowska-
Czerniak, 2004), in Sicilian olive oil (Pera et al., 2002), and in the
determination of Cd, Cu and Pb in Coca Cola (Andruzzi et al.,
1983). A typical challenge when using stripping analysis is that
sample decomposition is often required for the removal of
interfering substances prior to measurement (Green et al., 1997).
There are several factors in ASV that affect the analysis of
metals in alcoholic beverages. Representative examples are
discussed below.
Sample pretreatment can in some cases increase the analytical
response of a metal in the reoxidation step (Arcos et al., 1993); a
case in point is wine digestion. However, when the sample is
strongly acidified with HCl-or when it is diluted-the response to
reoxidation is not the same. In the latter case such a response is
probably due to a lowering of the metal concentration below its
detection limit (e.g., Cd in wine) (Ostapezuk et al., 1997).
A variety of electrodes are in use for ASV, including the
following:
 Hg drop—the most typical electrode—is used for Zn, Pb, and
Cu in whiskey, rum, and cachaza (Barbeira et al., 1995; Barbeira
and Stradiotto, 1997; Barbeira and Stradiotto, 1998b).
 Reticulated vitreous carbon (RVC) is covered with Hg prior to
use in ASV (Mayer et al., 2003; Macca et al., 1997; Marken et al.,
1997; Ostapezuk et al., 1997; Agra-Gutierrez and Compton,
1998).
 Pt microelectrodes (1 mm in diameter) covered with Hg
increase mass transfer and reduce preconcentration time
(Daniele et al., 1989).
 Dental amalgam electrodes are used for the analysis of metals
in wines (Mikkelsen et al., 2004; Mikkelsen and Schroder,
2002; Mikkelsen and Schroder, 2000).
 Solid normal electrodes (e.g., Pt, Au, RVC) are used in the
determination of Cu in alcoholic beverages (Barbeira and
Stradiotto, 1999).
 Other working electrodes used for this purpose include
GCMFE, chemically modified electrodes, CD-trodes, carbon
disc microelectrodes, and Hg microelectrodes.
Additional factors to be taken into account for the determina-
tion of metals in alcoholic beverages by this method include:
 Deposition time, td: When this is increased, the reoxidation
response also increases. Longer times are recommended when
analyzing Cd since it is usually found at low concentrations
(Ostapezuk et al., 1997). td affects the peak potential, Ep and the
peak current, ip as both increase with td (Arcos et al., 1993).
 pH: This may play a role in the different equilibria present in a
given matrix. For example, when Cu and Pb are analyzed, the
pH of the sample should be made rather acidic so as to obtain a
larger response signal (Green et al., 1997).
8. Conclusions
Metals find their way into alcoholic beverages through many
possible sources discussed here. Their effects on the beverages as
well as on humans after consuming such beverages are quite
varied. This then necessitates that metals be subject to regula-
tions. Electrochemical techniques offer distinct advantages for
their analysis.
681
Acknowledgements
JGI acknowledges financial support from Universidad Ibero-
americana and Universidad de Guadalajara during a sabbatical
leave. We are thankful to CONACyT for their support through
Grant 62066 for the scholarship of Alejandra Carreon-
Alvarez. This paper is dedicated to Prof. Margarita Watty
(U. Iberoamericana) on the occasion of her 80th birthday.
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