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Cork and Alcoholic Beverages
Joseph A. Maga a; Jean-Louis Puech b
a
Professor Emeritus, Department of Food Science and Human Nutrition, Colorado
State University, Fort Collins, Colorada, USA
b
Research Director, Institut de Recherche Agronomique (INRA), Montepellier,
France

Online Publication Date: 01 January 2005


To cite this Article: Maga, Joseph A. and Puech, Jean-Louis (2005) 'Cork and
Alcoholic Beverages', Food Reviews International, 21:1, 53 - 68
To link to this article: DOI: 10.1081/FRI-200040593
URL: http://dx.doi.org/10.1081/FRI-200040593

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Food Reviews International, 21: 53–68, 2005


Copyright & Taylor & Francis Inc.
ISSN: 8755-9129 (Print); 1525-6103 (Online)
DOI: 10.1081/FRI-200040593

Cork and Alcoholic Beverages

JOSEPH A. MAGA1,* AND JEAN-LOUIS PUECH2


1
Professor Emeritus, Department of Food Science and Human
Nutrition, Colorado State University, Fort Collins, Colorada, USA
2
Research Director, Institut de Recherche Agronomique (INRA),
Montepellier, France

For centuries, cork has been the stopper of choice for various alcoholic beverages. In
this review, cork history, sources, production, physical properties, composition, off-
flavors, and alternatives to cork stoppers are discussed.

Keywords Alternatives, Composition, Production, Properties, Stoppers, Taint

History of Cork Stoppers


Without question, the cork oak tree has been a natural part of forests in certain parts
of the world for many thousands of years. Because of some of the unique properties
associated with cork, over the centuries humans have found various applications for
cork tree bark.
For example, because of its buoyancy, ancient Greek and Roman records dating
back more than 6000 years noted that cork was used for the actual construction of
fishing boats and floats for fishing nets and anchors. Cork was also used for the soles
of sandals and even for entire shoes, especially for winter use, due to the thermal
insulation property that cork possesses (Margalit, 1997).
Relative to the application of cork as a closure for wine containers, Greek wine
amphora’s dating back to the fifth century BC have been found in the Mediterranean
that had cork stoppers covered with pitch. This discovery, to date, is the earliest
known use for cork as a wine stopper, although many believe that cork was used as a
stopper much earlier (Margalit, 1997).
The Romans then followed by also using cork as a wine stopper on occasion, but
it was not until the fifteenth century, along with the introduction of glass wine

*Correspondence: Joseph A. Maga, Department of Food Science and Human Nutrition,


Colorado State University, Gifford Bldg, Fort Collins, CO 80523, USA; E-mail:
magaja@comcast.net.

53
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54 Maga and Puech

bottles, that cork alone began to be used as the stopper of choice. Back then,
handmade glass bottles did not have uniform openings, and thus cork stoppers had
to be individually hand carved to fit each bottle. Eventually, by the end of the
seventeenth century, the use of cork stoppers became more common, especially for
bottled wines that were aged for several years or more (Margalit, 1997).
By the mid-eighteenth century, a cork stopper industry began in Llacostera,
Spain, which is in the Province of Gerona. At this point, the stoppers were entirely
handmade, and each worker could produce 2000 to 2500 cork stoppers per day
(Margalit, 1997).
Mechanization gradually followed, and most of the cork stopper manufacturing
industry eventually migrated to Portugal. By the late 1970s, there were close to 500
commercial cork manufacturer’s in Portugal that employed more than 50,000 people
for the entire process. Based on a total country population of 3 million, the cork
industry became a major economic factor in Portugal. Currently, the cork industry
in Portugal accounts for 3% of its gross domestic product. In turn, this currently
represents approximately one-half of the world’s cork production, and about 85% of
all wine corks produced (Pohl, 2001).
However, alternatives to natural cork stoppers have gradually appeared for
various reasons, and now ‘‘synthetic corks,’’ which are discussed in detail later,
represent 5–10% of the global market for alcoholic beverage bottle closures.
Currently, in excess of 23 billion cork stoppers are used annually worldwide
(Margalit, 1997).

Cork Sources
In all probability, the word cork was derived from the Latin word cortex, which
means bark. However, others believe that it was derived from the Spanish word for
cork, namely corcho, which could also have been derived from the word cortex
(Margalit, 1997). Cork is manually removed as the dead outside bark from the
evergreen cork oak tree botanically called Quercus suber. Another closely related
variety or subspecies also commercially used for oak is Quercus occidentalis, which
was identified in 1856. This species is commonly called western oak cork and is
slightly hardier than Q. suber. Normally, a mature cork tree grows to an average
height of 60 ft and has a diameter averaging 4 feet.
If one intentionally removes the bark from most tree species, the tree will die
rather quickly because most tree barks contain the vascular bundles that transport
nutrients for the tree. However, there are basically two different layers of bark on
cork oak trees. The inner layer, called peridium, is alive and serves as the nutrient
transporter. The outer layer, called phellogen, eventually dies over time and
naturally serves as an insulation source thereby protecting the tree from hot dessert
winds called siroccos.
All countries and specific regions within these countries that commercially
harvest cork from oak cork trees have established limitations as to when an oak tree
can first be stripped and how much time passes before the subsequent strippings. On
the average, a new cork oak tree has to be 20–25 years old before the first stripping is
permitted. The next stripping usually takes place 8–12 years later. From a practical
standpoint, the cork from the first two strippings is usually not considered to be of
good enough quality to produce all natural wine corks. Therefore, one has to wait
40–50 years before a ‘‘new’’ cork oak tree can be effectively used for bottle stoppers.
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Cork and Alcoholic Beverages 55

After the third stripping, most cork oak trees have a commercial life span of 100–150
years. However, some of these trees have lived to be more than 300 years old
(Margalit, 1997).
Due to unique environmental and climatic conditions, Q. suber and
Q. occidentalis only grow commercially over an area about the size of the state
of New Jersey. Specifically, the region of commercial growth is located around
the western Mediterranean Sea on land directly influenced by the Atlantic Ocean.
The unique combination of ideal climatic conditions includes little rainfall, much
sunlight, and high atmospheric humidity. It has been determined that cork oak trees
at one time grew around the entire rim of the Mediterranean. However, the
ancient civilizations of Phenicia, Asia Minor, and the Balkin Peninsula located in
the eastern Mediterranean left only traces of cork oak trees.
The major European countries that possess these climatic conditions on the
northern Mediterranean covers more than 1500 miles in length and includes portions
of Portugal, Spain, France, and Italy. Countries on the southern Mediterranean that
also commercially grow cork oak trees included Algeria, Morocco, and Tunisia,
which cover a narrow belt of land extending for more than 1000 miles. Most of the
commercial oak tree forests in northern Africa are quite young relative to the forests
in Portugal and Spain. Interestingly, when the area in northern Africa was under
French control, the French government sponsored a cork forestation program that
would ultimately supply cork for the French wine industry. Obviously, as these trees
become older, cork yield should increase. A total of approximately 5.5 million acres
are devoted among the seven countries listed previously for the production of cork
oak trees, with around 30% of the total acreage being in Portugal. However, due to
differences among the countries in annual harvest yields, Portugal normally
produces 50–55% of all the cork in the world, with total annual cork production
usually being more than 3 million tons (Margalit, 1997).
Portugal is rather unique in that cork oak trees can be found throughout the
country, but by far the most productive portion in Portugal is south of the Tagus
River, which produces close to 90% of their total production (Casquilho, 1990).
Also, where many of the cork oak trees are commercially grown, the trees are
not rather close together because the land is normally used for the production of
other crops, including vineyards. Many of these areas also raise pigs among the cork
trees, with the pigs seeking out the fallen cork oak acorns as a food source.
Interestingly, the commercial growth of Q. suber has been attempted throughout
the world, including the eastern Mediterranean along the Black Sea, and in
Argentina, Uruguay, Chile, South Africa, Australia, California, and Arizona.
In most of these locations, the trees grew but they were not able to effectively
produce commercial amounts and quality of cork (Margalit, 1997).

Cork Production
The initial phase of cork production focuses on the traditional labor-intensive
manual removal of cork from the cork tree trunks, and on occasion, from the larger
diameter branches. The process is called stripping and is done during active tree
growth, which normally occurs in June through August (Margalit, 1997).
Workers use a special axe to initially cut the cork around the base of the tree,
and then cut around the tree circumference, about 4 feet up from the base. If during
its early growth, the lower limbs of the tree are pruned, another section of cork can
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56 Maga and Puech

be removed from the tree trunk. After the two horizontal cuts are made, a vertical
cut is made on each side of the tree, and then the axe handle is used to carefully pry
the cork layer from the tree. The outer bark portion, on average, grows about 3 mm
per year, and thus, after approximately 8 years, the harvested cork is 26–28 mm
thick. The curved slabs, which are 1–3 ft wide, depending on the tree diameter, are
then stacked in the open air for 3–12 months to permit the gradual removal of
residual tree sap, moisture, and tannin. Normally, around 60% of the harvested
bark can be used for various forms of cork stoppers (Margalit, 1997).
After the natural curing process, the slabs are visually separated according
to their quality, stacked, tied tightly together, and brought to a cork processing
facility. The first step at the factory usually involves a heat treatment ranging
from boiling the slabs in plain water to boiling in water with added proprietary
chemical additives for an hour or longer, steaming, and/or autoclaving. These
thermal processes serve two basic functions. In theory, the heat/chemical treatments
kill most if not all the naturally occurring microorganisms that are normally present
on raw cork because of its rather porous and irregularly shaped surface. Also, the
raw slabs can become rather easily contaminated because they are stored on the
ground out in open areas. In addition, the heating process makes the slabs quite
pliable so they can be easily flattened for further processing. The slabs are
then stacked to flatten and permitted to dry to a final moisture content of 15–18%.
This phase takes approximately 3 weeks. However, because of the relatively slow
natural drying process open to the atmosphere, the slabs can become covered
with mold, which in turn can influence final cork stopper quality (Margalit, 1997).
At this point, another visual examination is made to separate the slabs relative
to their overall quality and thickness.
The slabs are then cut into strips with the strip width being just slightly larger
than the final cork stopper length. Normally, total automation is used from this
point by most cork stopper producers starting with machines equipped with high-
speed rotating steel tubes to quickly and efficiently punch out the individual corks
from the cut slabs across their grain. This punching process results in cork stoppers
that are the same diameter, lengthwise. If a tapered cork is desired, the ‘‘straights’’
are passed through a tapering machine equipped with a knife to form a tapered cork.
The ends of the punched corks are then trimmed on each end by passing them
through two parallel disc sanders to produce corks of uniform length. Because of
automation, one punching machine can process up to 15,000 cork stoppers per day
(Margalit, 1997). Each processor operates many such machines, thereby providing
literally billions of cork stoppers per year.
To recover residual cork dust, the machined corks are then placed in large net
bags, washed, bleached, and then vacuum or oven dried to a residual moisture
content of 5–10%. Numerous cork processors add a wide range of compounds to the
wash water in an effort to inactivate any viable microorganisms. Historically, the
corks were traditionally washed with chlorinated lime, with any residual chlorine
being neutralized with oxalic acid (Margalit, 1997). This usually results in a white
appearance on the corks due to the deposit of calcium oxalate. Other processors
prefer to wash corks in a hypochlorite solution, which is then neutralized with
sodium oxalate. This process does not produce a white deposit on the corks. Both of
these processes are usually followed by a bleaching step using peroxide, which is
performed in an alkaline or acidic medium. This is followed by a citric acid rinse,
which neutralizes any residual peroxide. Some cork processors expose their cork
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Cork and Alcoholic Beverages 57

stoppers to Cobalt-60, and the irradiation process normally totally inactivates any
residual mold spores. Others prefer to wash corks in metabisulfite using a 1–2%
addition of potassium metabisulfite (Margalit, 1997). The dried corks are then
mechanically or visually graded into normally five to nine different categories, based
on the number of voids on each cork stopper surface. On average, ranging from very
high quality to poor quality, only approximately 10% of the cork stoppers produced
are judged to be of very high quality, whereas 15% are of poor quality. However,
around 50% of the corks are normally classified as being of good quality. Many of
the cork processors still rely on human visual quality evaluation, and an experienced
individual examiner can screen up to 35,000 cork stoppers per day (Margalit, 1997).
It is interesting to note that all the residue and dust recovered from the punching
and sanding/trimming operations can be used to produce other types of cork
stoppers, which are discussed later, as well as other cork-based industrial
applications. Alternatively, the residue is processed into fuel cubes that are used
for local heating operations.
After the corks have been separated relative to overall quality, they can be
branded with the names and/or trademarks of their customers. Branding is done
either by using ink or a hot metal branding iron. In addition, most of the corks are
then surface treated with one of several food-grade materials, such as paraffin,
silicon oil, or wax, which aid in cork stopper insertion and removal from the bottle
(Margalit, 1997). Finally, the finished corks are normally sealed in plastic bags that
have added sulfur dioxide to maintain sterility during storage and shipment.

Physical Properties of Cork


From a physical standpoint, cork has three structural axes, which can be visually
described as being radial (horizontal), axial (vertical), and tangential (horizontal
angle). Upon looking at cork structure microscopically, it becomes quite obvious
that its radial cell structure appears to be a hexagonal prism, similar to that of a
honeycomb. In contrast, the axial and tangential dimensions in cork microscopically
appear as stacks of bricks in a wall (Margalit, 1997). The actual number of cells in
cork range from 10–40 million per cubic centimeter. Therefore, any average size wine
cork stopper has approximately 800 million cells. Because of the unique cell structure
of cork, its natural air content ranges from 60–85% of its total volume, which is the
key factor relative to the lightness of cork. Thus, because of its unique cell structure
and high air content, cork can be rather easily compressed to up to half its width
without losing any of its flexibility. Also, when compressed horizontally, as is done
with cork stoppers, there is no vertical expansion in size.
In conjunction with compressibility, cork has very good elasticity or resilience
properties (Margalit, 1997). Relative to most typical wine bottles, the inside
bottleneck diameter is usually around 18 mm, whereas the cork diameter before
insertion is usually 24 mm. When the cork is inserted, the cork stopper diameter is
reduced approximately 25% in radial dimension, which represents 45% of its
volume. Because of its inherent elasticity, the stopper can maintain a tight seal in the
bottle for long periods of time. However, if kept in the bottle for long periods of
time, when removed, it only expands slightly. Most good-quality cork stoppers can
retain some degree of resilience for 5–10 years. Interestingly, for still wines, cork
stoppers are usually reduced in horizontal volume by 45%, whereas when corks are
used to stopper sparkling wines, they are compressed around 65% in order to
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58 Maga and Puech

withstand an internal pressure of up to 2.5 atmospheres. In addition cork stoppers


are quite tolerant to changes in temperature and pressure, which is a key to
maintaining a uniform bottle seal.
Interestingly, good-quality cork stoppers are very impermeable to liquids,
including alcohol. It is believed that this is due to the alternating layers of suberin
and wax, which are structural components of the cell walls. Therefore, wine bottles
can be placed on their sides or even upside down, and the wine will not pass through
a good-quality cork stopper.
Cork does permit a rather slow migration of gases through microscopic channels
in its cell walls that are about 0.06 mmm in diameter. These channels are so small that
liquids cannot pass through, but gases and vapors can. However, when compressed
into a bottleneck, the pressure of the naturally entrapped air inside the cork cells
serves as a very effective barrier to the entry of environmental oxygen (Casey, 1991).
This process over time prevents the oxidation of the alcoholic beverage in the bottle.
This concept can be supported by the fact that a typical good-quality cork stopper
has an internal surface area of 2–3 m2, which has a very good ability to entrap many
forms of molecules, including internal and external environmental compounds. This
property does not permit the loss of volatiles from within the bottle, and entraps the
incoming compounds that could alter the internal volatile composition of the bottle
contents.
Aside from potential off-flavors associated with cork, which are discussed
in detail later, good-quality cork is considered to be very inert and resistant to
rotting and physical deterioration. If wine bottles are stored properly with
good-quality cork stoppers, the stoppers have a normal lifespan of 40–50 years
(Margalit, 1997).

Cork Composition
The major compositional components of cork have been reported to be
approximately 45% suberin, 25% lignin, 15% cellulose, and 5% each of tannins,
waxes, and minerals (Margalit, 1997). As can be seen, most of these components are
polymers, with suberin being unique to cork. Structurally, suberin is similar to lignin
and is composed of phenolic fragments that are linked together by both long-chain
C-18 and C-22 fatty acids, and hydroxy fatty acids, which in turn are esterified by
high-molecular-weight alcohols (Mazzoleni et al., 1994). Because of their complex
structure and rather large molecular weights, most of the major components of cork
are quite inert and thus, do not directly contribute to the flavor properties of cork.
However, several research groups (Boidron et al., 1984; Mazzoleni et al., 1993,
1994; Rigaud et al., 1984), using various isolation and concentration techniques,
have in combination reported on the presence of slightly more than 100 volatile
compounds identified in cork. For example, using Freon 113, Chromosorb 101, and
Freon 11, a total of 29 volatiles were identified in cork (Boidron et al., 1984).
Another group used pentane to extract the volatiles from cork and was able to
identify approximately 50 volatiles (Rigaud et al., 1984). Other research groups
(Mazzoleni et al., 1993, 1994) used a dynamic headspace technique to isolate,
separate, and identify 107 volatile compounds in several forms of cork.
The most extensive study (Mazzoleni et al., 1994) evaluated cork of various
types including (1) new one-piece stoppers that had no added surface lubricant or
printing; (2) cork bark from Spain, northern Portugal, and southern Portugal, which
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Cork and Alcoholic Beverages 59

the researchers boiled in distilled water before analysis; (3) used stoppers that had
been in contact with red wine in the necks of bottles for a minimum of 12 months;
and (4) new one-piece stoppers that were fabricated from cork with wide versus
narrow growth rings. All the samples were frozen in liquid nitrogen and ground into
a powder. Then, 2 g of each powder were exposed to standard dynamic headspace
extraction/concentration, and were separated and identified using capillary gas
chromatography-mass spectrometry.
Among all the samples, a total of 107 compounds were identified, but the
analytical techniques used did not permit quantitation. Specific classes of identified
compounds included aliphatic and aromatic hydrocarbons, alcohols, carboxylic
acids, aldehydes, ketones, esters, ethers, furans, chlorinated compounds, nitrogen,
and sulfur compounds (Mazzoleni et al., 1994).
When the identified compounds from different cork sources were compared,
several interesting differences were observed. For example, when volatiles in a new
cork stopper were compared with those found in cork bark, a total of 13 aliphatic
hydrocarbons were identified, which included saturated hydrocarbons along with
some terpenoids. More hydrocarbons were found in the bark as compared with the
new stoppers. Relative to terpenes, b-pinene was only found in the bark (Mazzoleni
et al., 1994)
A total of 23 aromatic hydrocarbons, which included five naphthalenes, were
identified in both bark and new stoppers. It was proposed that the naphthalenes
were actually chemical contaminants coming from the environment. Also, an
extensive series of 23 alcohols were identified, including low molecular weight,
primary aliphatics, aromatics, and terpenols. The aliphatic alcohols were found more
often in the new stoppers than the bark (Mazzoleni et al., 1994). Also, the compound
1-octen-3-ol, which has a characteristic mushroom-like aroma, was found in only
one of the bark samples. It was concluded that this compound was a mold
metabolite. A total of 11 saturated carboxylic acids were identified both in the bark
and new stoppers. In addition, a series of five chlorinated compounds were found
both in the bark and new stoppers. It was concluded that this latter group of
compounds were derived from the previous chemical treatments commonly
performed on cork (Mazzoleni et al., 1994).
It was postulated that overall, most of the compounds identified were naturally
associated with cork or were derived via enzymatic or chemical degradation during
normal cork processing. For example, compounds that had a benzene ring along
with a linear structure could have been derived from suberin and lignin (Mazzoleni
et al., 1994).
When the compounds found in fast-growing bark (wide growth rings) vs.
slow-growing bark (narrow growth rings) were compared, it was observed that the
fast-growing bark had fewer allyl substituted benzenes and carboxylic acids than
slow-growing bark. These differences were probably due to the fact there are
structural differences between fast and slow-growing bark. Also, noted composi-
tional differences among bark samples could have resulted from variable extraction
rates relative to bark type/source.
As would be expected, due to climate, soil, and possible environmental
differences, barks from different areas had different volatile compositions. For
example, fewer volatiles were found in bark from northern Portugal as compared
with bark from southern Portugal. In contrast, bark from Spain had more volatiles
than any of the barks from Portugal (Mazzoleni et al., 1994).
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60 Maga and Puech

When used corks were compared with new corks, additional compounds were
found in the used corks, including a series of alcohols, ethyl esters of fatty acids, and
butyl and amyl esters of acetic acid. All these additional compounds are commonly
found in wine, and thus, apparently the stoppers had absorbed them while they were
in contact with the wine (Mazzoleni et al., 1994).
The number and diversity of volatile compounds reported in certain studies
(Boidron et al., 1984; Mazzoleni et al., 1993, 1994; Rigaud et al., 1984) were quite
impressive. However, from a more practical standpoint, it could not be determined,
based on compound concentration and odor threshold, which compounds made a
significant positive or negative contribution to the overall odor properties of cork
stoppers.
The presence of various types of phenolic compounds in cork has also been
reported (Mazzoleni et al., 1998). In general, free benzoic and cinnamic acids do not
have significant positive or negative odor properties, but they do serve as precursors
for the formation of compounds such as vanillin, which possess a low odor threshold
usually considered to be desirable in alcoholic products.
Cork slabs were harvested from the same location and from same-age trees
(Mazzoleni et al., 1993). Once harvested, analyses were performed at different steps
of aging and processing. For example, samples were taken immediately after
stripping versus slabs that were stored for 1 year in the open air. Relative to
subsequent processing, samples were taken at various times during the traditional
boiling process in water, after the slabs were dried, and from resulting cork stoppers.
The samples were frozen in liquid nitrogen, ground into a powder, and 66 g of each
resulting powder were placed in 1 L of 12% ethanolic solution adjusted to pH 3.2.
The phenolic compounds of interest were then extracted, concentrated, and analyzed
using high-performance liquid chromatography. Standard solutions of increasing
concentrations of specific phenolics were also analyzed to obtain relative
quantitative data (Mazzoleni et al., 1993).
As would be expected, phenolic content was significantly different between
unaged and aged cork slabs, with aging resulting in a decrease in benzoic acids and
an increase in cinnamic acids and vanillin. Also as expected, the degree of boiling
significantly modified phenolic concentrations. Increases in boiling time decreased
the amount of extractable cinnamic acids but increased the amount of vanillin
present. The loss of cinnamic acids due to boiling is significant because they
normally serve as precursors for potentially negative flavor compounds. Also,
another potential positive aspect of boiling was the increase in the concentration of
vanillin (Mazzoleni et al., 1994).
Another study also quantitated the amounts of low-molecular-weight phenolics
from various stages of cork processing (Peña-Neira et al., 1999). Samples were
obtained from raw cork slabs that were aged for 6 months in the open air, after
boiling and the manufacture of cork stoppers with no chemical treatment, stoppers
bleached with hydrogen peroxide, and another group that were bleached and then
lubricated with paraffin and silicon waxes. Also, corks used as wine stoppers were
analyzed. This phase included stoppers used for red wines from three different wine-
producing regions in Spain, along with white wine from another region in Spain.
It was found that boiling caused significant decreases in gallic and ellagic acids.
They obviously were soluble in water and were discarded with the water. Bleaching
also resulted in lower levels of phenolics, probably due to their oxidation by
hydrogen peroxide. Interestingly, lubrication caused an increase in phenolics, but
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Cork and Alcoholic Beverages 61

this was probably due to the fact that their extraction was more efficient due to the
added lubricants. The used wine stoppers had a wide range of differing phenolics
among all the regions evaluated and between red and white wines (Peña-Neira et al.,
1999).
In summary, to date, conclusive research has not been conducted for one to
be able to conclude which class of compounds, or which specific compound, is a key
indicator of good cork quality. However, this may not be an important issue
because cork stoppers for alcoholic beverages have been in use for centuries, and
are usually well accepted by all, with the final judge being the consumer.

Off-Flavors Associated with Cork


Historically, on occasion cork stoppers have been found, usually upon opening a
bottle of alcoholic beverage, which possesses a rather wide range of objectionable
odors (Pereira et al., 2000). Generally, these odors in wine can be characterized as
being moldy, musty, burnt, medicinal, mushroom-like, earthy, or smoky, and are
commonly called cork taint or corkiness (Margalit, 1997). Also, in general terms, the
word ‘‘taint’’ can cover a wide range of sensory sensations, including odor, taste,
aftertaste, and mouth feel, that are not normally expected in a product.
In general, cork taint can originate from several sources. One such source is the
fact that if cork is not boiled or steamed sufficiently, a rather strong cork flavor can
be present in corks, which can simply migrate into alcoholic beverages when the
liquid and cork are in contact (Margalit, 1997). Another potential pathway for the
development of cork taint is the simple environmental migration of various
agricultural chemicals such as insecticides, herbicides, and pesticides that are
commonly used in the polyculture of agricultural products, including cork oak trees
(Margalit, 1997). Probably one of the most common pathways for the appearance of
cork taint is the presence of metabolites resulting from the potential of microbial
growth on cork during various phases of harvesting, storing, and processing of cork
stoppers (Margalit, 1997). To further complicate this situation, some of these same
objectionable odors may actually be present in faulty alcoholic beverages, and thus,
are not of cork origin (Margalit, 1997).
From a logical standpoint, if an entire case of bottled alcoholic beverages is
found to possess a detectable cork taint, it would seem logical that probably the taint
originated in the beverage itself, due to the use of faulty barrels or moldy grapes in its
manufacture. However, if only several bottles per case have a defective odor, it is
quite more likely that tainted corks were responsible.
Even more frustrating is the fact that within a specific lot of cork stoppers, not
all the stoppers can be defective from an odor standpoint, thus making it quite
difficult for the cork processor to guarantee that every cork they sell will be totally
free of objectionable aromas when used. This in turn can potentially provide
significant public embarrassment and economic loss to wine and alcohol producers
who are unfortunate enough to use tainted cork stoppers for their products.
Therefore, many of the larger producers of alcoholic beverages throughout the world
who use cork stoppers have attempted to develop in-house statistical sampling
procedures from a quality evaluation standpoint before they cork their bottles
(Wiley, 2000).
Because of the potential economic loss associated with tainted cork stoppers, a
vast amount of research has been conducted regarding cork taint. Without question,
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62 Maga and Puech

the compound most responsible for a musty/moldy odor in alcoholic beverages is


2,4,6-trichloroanisole, which is commonly called TCA. On average, TCA accounts
for 80–90% of all cork taints found in objectionable corks. Although TCA had been
identified as an objectionable odor in other foods as a result of fungal activity, it was
not until 1982 that its presence in off-flavored bottled wine was verified (Buser et al.,
1982). By the late 1980s, it was estimated that 2–5% of all worldwide cork bottled
wines had cork taint from their cork stoppers (Simpson, 1990). In brandy, TCA was
described as possessing a walnut-like aroma. Interestingly, in brandy, the odor of
TCA is not detected until from 5–30 min after consumption (Butzke et al., 1998).
One of the interesting properties of TCA is that it possesses a rather low odor
threshold. By its direct intentional addition to wine (Buser et al., 1982), it was
determined that its odor threshold in wine was 10–30 ng/L, whereas commercially
produced cork tainted wines were found to contain 20–370 ng/L of TCA.
The reactions involved in the formation of TCA in cork stoppers are rather
intriguing. Initially, phenols that are commonly found in cork, as described
previously, are chlorinated when corks are intentionally bleached with calcium hypo-
chlorite, thereby forming 2,4,6-trichlorophenol (Margalit, 1997). This compound
in turn can then be naturally methoxylated by commonly occurring fungal activity
during the gradual drying of boiled cork slabs to form TCA.
A wide range of mold genera has been identified in various phases of cork
production. These include the presence of Penecillium, Aspergillus, Alternaria,
Mucor, Monilia, Trichoderma, Cladosporium, Paecilomyes, and Rhizoctonia, all of
which can proliferate due to varied environmental conditions during the outside
aging and subsequent processing of cork (Margalit, 1997).
Another TCA formation pathway, which is not highly likely to occur during
cork processing, but can rather easily occur in oak wine barrels for example, involves
its synthesis by direct microbial activity from carbohydrates and subsequent
chlorination as a means of sanitizing barrels (Mawean et al., 1985).
As a result of the previously mentioned TCA pathways, some cork processors
avoid using hypochlorite as a bleaching agent and have instead turned to using
hydrogen peroxide. Also, some wineries avoid using chlorine-derived sanitizing
agents.
The location of TCA relative to cork stoppers was investigated (Howland et al.,
1997), and it was reported that TCA was primarily found on the entire exterior
surface of the cork stopper surface, which would indicate that biomethylation
resulting in the formation of TCA had occurred after the corks were punched from
the bark strips. Thus, it would appear in this situation that the punching devices were
contaminated, or there was a significant degree of environmental contamination
within the processing facility.
Aside from TCA, other chloroanisoles have been identified in tainted wines and
corks (Pollnitz et al., 1996). These included 2,4- and 2,6-dichloroanisole, 2,3,4,6-
tetrachloroanisole, and pentachloroanisole, all of which were assumed to be derived
via methylation of compounds formed by the nonenzymatic chlorination of phenols.
A rather unique and interesting microbial study focused on the isolation and
identification of 187 bacteria and 36 yeast strains that were found in various types of
cork slabs and their resulting cork stoppers (Jäger et al., 1996). As a result, they
concluded that fungi were not the only microbial source of TCA. Their samples
included soil located directly beneath stored slabs, slabs in contact with soil, and
slabs not having contact with soil. Also evaluated were slabs that were boiled in a
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Cork and Alcoholic Beverages 63

traditional cork processing facility as compared with slabs boiled in a facility that
had high levels of sanitation. Internal cork temperatures during boiling were also
monitored, and were found to only reach 87 C after 115 min of boiling. In addition,
they sampled a series of new cork stoppers, including those that were not chemically
treated, along with those treated with hydrogen peroxide, as well as those initially
treated with hydrogen peroxide and then neutralized with citric acid.
They established model systems composed of the pulverized cork samples and
wine that were incubated, with the resulting odor properties being subjectively
classified. A wide range of distinctive and objectionable aromas was noted. The
microbes that were present in the tainted samples were then isolated and identified.
Before grinding the cork stoppers, they were subjected to low-temperature scanning
electron microscopy, and both bacteria and yeast were covered with mucous or
fibrous substances and were located in the cork lenticela. Because of their coatings,
the organisms were rather thermal stable and they were able to survive the boiling
process, the peroxide treatments, and the alcohol in wine. Overall, they were able to
identify five yeast isolates that were capable of methylating 2,4,6-trichlorophenol
into TCA.
Apparently, cork has the ability to effectively absorb chloroanisoles (Capone
et al., 1999). A series of chloroanisoles, including 2,4-dichloroanisole, 2,6-
dichloroanisole, TCA, 2,3,4,6-tetrachloroanisole, and pentachloroanisole, at a
concentration of 40 ng each, were intentionally added to 200 mL of white wine in
a 250-mL glass container. Then, four new cork stoppers were placed into the wine,
and the container was sealed with aluminum foil and stored for 24 and 48 h. After
24 h, 80% of the added TCA was absorbed from the wine into the stoppers, whereas
after 48 h, 90% had been absorbed. The amount of added tetra- and pentachlor-
oanisoles was absorbed at a slightly higher rate than TCA, whereas the
dichloroanisoles were absorbed into the stoppers at a lower level than TCA.
Also, deuterium-labeled TCA was added to 750-mL bottles of white wine, sealed
with new commercial cork stoppers, and the bottles were stored on their sides for 30
months before analysis. The labeled TCA could then be segregated analytically from
any inherent TCA in the stoppers. Results showed that approximately 90% of the
labeled TCA was absorbed into the stoppers.
It was reported in another study (Barker et al., 2001) that new cork stoppers can
effectively absorb TCA from various environmental sources, primarily associated
with the shipping and storage of new corks. Conditions included the atmospheric
migration of TCA into cork stoppers from contaminated wooden shipping/storage
pallets, the floors and walls of shipping containers, and even cardboard cartons used
for the packaging of stoppers. TCA from these sources usually result from the use of
polychlorophenol-based biocides. They also exposed new cork stoppers to an
atmosphere containing labeled TCA. Up to 90% of the labeled TCA was initially
found in the outer 2 mm of the stoppers, but after 24 h of exposure, a significant
amount of TCA had migrated to the cork stopper interior. Also, they demonstrated
that the desorption of TCA from cork stoppers can occur by simply blowing air
around stoppers containing high levels of TCA. However this process took
approximately 50 days before a significant loss in TCA from the stoppers was
observed.
Many mold strains have been isolated from various stages of cork processing
that can eventually lead to the formation of TCA, but it is believed that the fungal
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64 Maga and Puech

genus Trichoderma has the highest ability to produce TCA (di Falco and Sampò,
1993).
Interestingly, an individual cork stopper in its dry state that has a significant
level of TCA in and on it usually cannot be humanly smelled as being tainted by
untrained evaluators. Also, most new corks have a typical green/woody aroma that
has to be subjectively separated from any potential cork taints. It has been reported
(Simpson and Veitch, 1993) that normal typical cork stopper aroma is due to the
presence of an extensive series of monoterpenes, with the compound camphor being
the most prevalent. As a result, most of the subjective tests designed to detect cork
taint in new stoppers are usually performed in neutral dry white wine or water.
Randomly selected stoppers of varying numbers are soaked in liquid for 6 h up to
several days, and then the composite wine odor is subjectively evaluated to determine
if cork taint is present.
The presence of cork taint due to TCA has been extensively studied in wine as
described previously. Also, its presence in tainted cognac has been reported
(Cantagrel and Vidal, 1990), along with the presence of 1,2-dibromobenzene,
3,4-dimethylphenol, and 2,3,4,6-tetrachlorophenol. An evaluation was performed on
the fate of intentionally added TCA to white wine before the traditional double
distillation of cognac. Interestingly, the final distilled spirit had a TCA content that
was seven to eight times higher than the original wine. Therefore, it can be concluded
that TCA easily withstands the distillation process, and thus, if tainted wine is
commercially used for distillation, high levels of TCA that are well above its odor
threshold can be detected in the final distilled product.
Another interesting compound that had been found in numerous cork tainted
wines is 2-methoxyphenol, which is commonly known as guaiacol. Its odor
properties have been described as being burnt, smoky, and medicinal (Simpson,
1986).
One of its chemical formation pathways begins with the thermal degradation of
lignin to ferulic acid, which then goes through a decarboxylation step resulting in
4-vinylguacol. This compound is then oxidized to vanillin and vanillic acid, which is
then decarboxylated to guaiacol (Maga, 1978). Guaiacol can also be biochemically
formed via oxidation by certain soil bacteria as well as yeasts. Its odor threshold has
been reported to be 20 mg/L, and up to 2600 mg/L have been found in tainted wine.
The ketone 1-octen-3-one and its corresponding alcohol, 1-octen-3-ol, are also
related to cork taint. Their odor thresholds are 20 ng/L and 20 mg/L, respectively
(Simpson, 1990). They possess a mushroom-like and metallic odor. It has been
demonstrated that these compounds can result from the microbial action of molds
on linoleic acid (Wurzenberger and Grosch, 1984).
Geosmin (trans-1,10-dimethyl-trans-9-decalol) and 2-methylisoborneol are also
two other compounds that have been isolated from cork taint (Margalit, 1997). They
both possess earthy, musty, and muddy odor properties and have odor thresholds
of 25 and 30 ng/L, respectively (Simpson, 1990). They are naturally occurring
compounds from soil bacteria and can be commonly found in water supplies.
In summary, all the compounds associated with cork taint can be formed by the
traditional processes used in the production of cork stoppers ranging from outside
cork slab storage, to the boiling/heating and subsequent drying procedures, the use
of certain chemicals in processing, and via environmental contamination during the
processing and transportation of the finished corks.
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Cork and Alcoholic Beverages 65

Alternatives to Natural Cork Stoppers


Obviously, the use of natural, intact cork stoppers has been associated and well
accepted for centuries as the preferred closure for alcoholic beverages. As a result,
good-quality wines are normally associated with good-quality cork stoppers.
Over the years, the traditional cork stopper industry has developed and supplied
to the alcoholic beverage industry a wide range of cork stoppers varying in quality
and size. For example, for standard-size opening 750-mL wine bottles, the cork
stopper diameter is usually quite uniform, but one can choose stoppers of short
(38 mm), medium (44 mm) or long (48–55 mm) length, depending on how long the
wine is expected to be aged before consumption (Margalit, 1997).
However, over time, because of difficulty in obtaining cork stoppers of uniform
quality, the potential for cork stoppers to support microbial activity that can then
result in cork taint, and the potential for cork stopper breakage, crumbling, and
most important, leakage, has resulted in the introduction and accepted usage of
alternative types of closures. Interestingly, the cork processing industry was in the
unique position of being able to provide other forms of cork-based stoppers as an
alternative to their single-piece cork stopper.
The most popular alternative to traditional intact cork stoppers is called the
agglomerate or composition cork, which is basically made by binding, with a food-
grade adhesive, small pieces of cork byproduct recovered from the traditional cork
punching process (Margalit, 1997). Also, during the initial inspection of cork slab
quality, entire lower-quality cork slabs can be ground and converted into
agglomerate cork. However, it should be noted that because agglomerate corks
are made from natural cork, they are also susceptible to microbial activity. They are
usually denser than traditional cork stoppers, and thus, may not be as effective a
closure as traditional cork stoppers because they normally do not possess as much
expansion capacity when compressed into a bottle neck. Also, agglomerate corks
may have a greater tendency to crumble when being removed from a bottle. From a
practical standpoint, agglomerate corks are usually more uniform in size than
traditional cork stoppers, which makes bottle corking easier (Margalit, 1997).
However, it has been reported (Mas et al., 2002) that agglomerate corks produced
faster wine oxidation than natural corks when the filled bottles were stored vertically
instead of horizontally.
Another form of agglomerate cork has been developed that has one or two
higher-quality intact cork disks glued onto each end of the agglomerate cork
(Margalit, 1997). However, this approach may border on deception to the consumer,
because when one removes the capsule from a bottled wine, it appears that a natural
cork is in place, but when the cork is removed, it becomes apparent to most
individuals that it actually is an agglomerate cork.
Another technique used by some cork producers is to actually punch out corks
from lower-quality cork slabs, and then to fill the cracks and openings in the
stoppers with a combination of cork dust recovered from their processing lines with
the aid of food-grade adhesive. The resulting stoppers are called colmated corks
(Margalit, 1997).
Another alternative, that has both positive and negative properties, is the use of
a metal screw cap closure. For some, this approach obviously has a wine quality
image problem, and thus, most consumers of higher-quality and -priced wines have
difficulty accepting a screw cap closure on a more expensive wine. However, screw
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66 Maga and Puech

caps have found a comfortable acceptance among consumers of inexpensive and jug
wines. Technically, one could demonstrate that wine bottles sealed with screw caps
do not leak as do some of the wines sealed with cork stoppers (Margalit, 1997).
Plastic-based closures are also part of the stopper market. For example, some
sparkling wine producers have used plastic closures since the mid-1950s because loss
of natural and/or added carbonation in sparkling wines can be a problem with
lower-quality cork stoppers. Natural cork stoppers and agglomerate stoppers for
sparkling wines are much larger than wine cork stoppers because they have to
withstand much higher internal pressures in sparkling wines as compared with still
wines. Most plastic stoppers are made from ethylene vinylacetate (Margalit, 1997).
Almost all producers of fortified wines and distilled beverages have adopted
either traditional or agglomerate cork stoppers that have a synthetic phenolic resin
top glued to the top of the closure (Margalit, 1997). Because most of these products
are opened and closed numerous times before the contents of the bottle are finished,
the synthetic top portion makes it much easier for the consumer to open and close
the bottle. The cork portion of these types of stoppers is usually much shorter than
traditional wine corks, which therefore makes it easier to open and close the bottle
without the aid of a corkscrew.
Expanded polymer closures, commonly called synthetic stoppers, are also
another alternative. Their major advantages are that they are very uniform in size,
thus making sealing easier. Also, because they are not of biological origin, the
potential for microbial activity, which can result in cork taint, does not exist.
However, because they are usually made from polyolefines, they do have a strong
ability to absorb objectionable environmental odorants, which can then migrate into
the bottle (Margalit, 1997).

Summary
In conclusion, engineering technology has performed quite well in producing
numerous forms of alcoholic beverage closures, but it is still quite obvious that the
traditional cork stopper industry is still by far the major supplier of alcoholic
beverage bottle closures.
Also, some of the major cork stopper processors and suppliers are continually
involved in proprietary research for means to improve on their existing products.
Because the naturally occurring and potential environmental presence of microbes
can serve as a major source of cork taint, some cork processors have investigated the
use of electromagnetic current and various microwave applications as a means of
thermally eliminating microbes from cork stoppers. Others believe that the
intentional incorporation of certain enzymes during cork processing can eliminate
subsequent methylation that can result in TCA formation.

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