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Exploring the effect of elevated storage temperature on wine composition

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Temperature can play a significant role in the development of wine at many stages during its lifetime. Elevated temperature, however, poses a significant risk to the sensory attributes of wine and its resultant shelf-life. Wines often experience difficult environmental conditions during transport and storage, and this can directly impact on the colour, aroma and mouthfeel of the wine. Higher and/or fluctuating temperature can essentially accelerate the ageing process. Unfortunately, these changes often go unnoticed until the wine reaches the consumer. Numerous studies have investigated the impact of elevated temperature on wines, with noticeable effect, such as reduction of sulfur dioxide, colour development (especially browning of white wines) and changes in the profile of volatile compounds, being common. Unfortunately, most of these studies tend to have a narrow scope and tend to focus only on a limited number of wine types or on specific compounds. The chemistry changes involved in heat-affected red wines are generally more complex than they are in white wines, but it is arguable that white wines are more sensitive to the effect of heat and therefore require the same or a greater level of research consideration with respect to temperature effects. The focus of this review is to highlight the common effects that different wine types and styles can experience when subjected to elevated storage temperature that are considered to be beyond the limits that most winemakers and consumers would accept. This review will also summarise the fundamental chemical kinetics that play a significant role in wine development at elevated temperature.
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Exploring the effect of elevated storage temperature on
wine composition
N. SCRIMGEOUR, S. NORDESTGAARD, N.D.R. LLOYD and E.N. WILKES
Commercial Services, The Australian Wine Research Institute, Adelaide, SA 5064, Australia
Corresponding author: Mr Neil Scrimgeour, email neil.scrimgeour@awri.com.au
Abstract
Temperature can play a significant role in the development of wine at many stages during its lifetime. Elevated temperature,
however, poses a significant risk to the sensory attributes of wine and its resultant shelf-life. Wines often experience difficult
environmental conditions during transport and storage, and this can directly impact on the colour, aroma and mouthfeel of the
wine. Higher and/or fluctuating temperature can essentially accelerate the ageing process. Unfortunately, these changes often go
unnoticed until the wine reaches the consumer. Numerous studies have investigated the impact of elevated temperature on wines,
with noticeable effect, such as reduction of sulfur dioxide, colour development (especially browning of white wines) and changes
in the profile of volatile compounds, being common. Unfortunately, most of these studies tend to have a narrow scope and tend to
focus only on a limited number of wine types or on specific compounds. The chemistry changes involved in heat-affected red wines
are generally more complex than they are in white wines, but it is arguable that white wines are more sensitive to the effect of heat
and therefore require the same or a greater level of research consideration with respect to temperature effects. The focus of this
review is to highlight the common effects that different wine types and styles can experience when subjected to elevated storage
temperature that are considered to be beyond the limits that most winemakers and consumers would accept. This review will also
summarise the fundamental chemical kinetics that play a significant role in wine development at elevated temperature.
Keywords:
ageing
,
browning
,
degradation
,
elevated temperature
,
exposure
,
heat
,
kinetics
,
sulfur dioxide
Introduction
Wine is a sensitive and complex combination of chemical com-
ponents. It is a carefully crafted product that reflects the inti-
mate care and attention afforded to it and is the result of a
myriad of considered processing operations and decisions.
Unfortunately, all of this good work can be undone if a wine is
not stored and transported under the conditions required to
maintain its optimal state.
There are many instances in the life of a wine where tem-
perature can play a significant role in its development and, in
some unfortunate cases, chemical degradation. A wine can
experience elevated temperature during crushing, fermenta-
tion, blending, maturation, bottling, shipping and storage. If
temperature is not adequately controlled across these critical
control points, there is a significant risk to the physical, chemical
and sensory attributes that the wine can portray.
Ideally, wines should be stored in cool cellars or air-
conditioned facilities (15–20°C) but more often than desired,
wines may experience less than optimal environmental condi-
tions during transport or other means of storage, where they are
exposed to higher and fluctuating temperature (Robinson et al.
2010, Cejudo-Bastante et al. 2013, Pereira et al. 2014). There is
no ‘ideal’ storage temperature for wine in general because the
development of a wine is a careful balance between allowing
complexity and maturity to develop and preventing oxidative
and temperature-influenced characteristics from taking hold.
Wine held at low temperature (e.g. <10°C) will clearly benefit
from a reduced risk of spoilage, but will also take much longer
to develop.
It has been well described in the literature over the years that
elevated temperature directly impacts and promotes significant
change in the aroma of wines. The change in wine composition
caused by higher or fluctuating temperature is of major concern
to winemakers and consumers, especially the significant change
in sensory profile that can occur. The extensive research in this
area has shown the impact of temperature on wine and that
heating accelerates the effect of ageing, among other changes.
Several significant aesthetic effects are observed when wines
are subjected to elevated temperature. The most notable is the
formation of a haze, resulting from the denaturing of proteins in
white wines (Falconer et al. 2010). If wine is packaged in glass
bottles when subjected to elevated temperature, effects can
include cork push (from volumetric expansion of the wine in
bottle), impact on closure seal integrity and consequential
increase in oxygen transmission rate (OTR) and a significant
reduction in shelf-life. There are also many chemical changes
that can occur in wines subjected to elevated temperature and
unfortunately these often go unnoticed until the wine reaches
the consumer.
In general, studies on the impact of temperature on wines
tend to focus on the effect on antioxidants, such as sulfur
dioxide (SO
2
), colour (especially browning of white wines) and
volatile components (and their perception through sensory
studies). Unfortunately, most of these studies tend to have a
narrow focus (on specific compounds or wine types) and are
relatively disparate in nature.
A complicating factor in this area of research is that few of
these studies tend to focus on the impact of temperature alone;
commonly, many other factors, such as pH, concentration of
alcohol, SO
2
, tannin, storage time, bottle type and closure type,
are included. It then becomes difficult to separate the effect of
temperature from other confounding variables.
Almost all published studies on temperature effects involve
bottling of wine(s) under different closures, in order to examine
the specific effect of temperature over time during storage. Wine
closures all have the propensity to allow diffusion of oxygen
Scrimgeour et al.
Elevated storage temperature and wine composition 713
doi: 10.1111/ajgw.12196
© 2015 Australian Society of Viticulture and Oenology Inc.
from the external environment into the wine (bottle), and there
is a vast array of oxidation and reduction reactions that occur in
wine through this mechanism. It is therefore impossible to
de-couple the effect of temperature exposure alone from the
impact of transmitted oxygen on the wine chemistry in these
studies, where the potential impact of closures has not been
carefully controlled.
The impact of temperature exposure on white wines and red
wines has been investigated in equal measure, but the changes
in chemistry involved in heat-affected red wines is much more
complex than that in white wines, where the predominant
focus is on browning, loss of SO
2
and a more noticeable impact
on sensory characteristics. In all cases, the wine type chosen for
study is a significant factor in the resultant trends observed
because of the different chemical composition of the wines
involved.
The focus of this review is to highlight the common effects
that different wine types and styles can experience when sub-
jected to elevated temperature that are considered to be beyond
the limits that most winemakers and consumers would accept.
This review will also summarise the fundamental chemical
kinetics that play a significant role in wine development at
elevated temperature.
The role of chemical equilibria and kinetics in
wine development
Changes in the chemical and sensory properties of a wine are a
consequence of a range of complex chemical reactions. The
effect of temperature on all of these chemical reactions can be
understood and analysed using established physical chemical
principles.
Two of the key characteristics of a chemical reaction are
the equilibrium and the kinetics. The equilibrium describes the
maximum extent to which a reaction can proceed, while the
kinetics describes the speed at which it will proceed. Both are
influenced by composition and temperature (Smith et al. 1996).
With respect to the equilibrium, considering the reversible
reaction, where compounds Aand Bcan form products Mand N:
aA bB mM nN++
(
1)
If a reaction is exothermic, the equilibrium constant K
C
decreases as temperature increases, that is, this favours reten-
tion of compounds Aand B. If the reaction is endothermic, the
equilibrium constant increases with temperature and this
favours formation of products Mand N.
With respect to the kinetics, the reaction rate of component
A(−r
A
) can often be described in terms of a separate
temperature-dependent rate constant, k, and concentration
terms (Fogler 1999, Levenspiel 2004) as follows if reaction (1) is
assumed to be essentially irreversible:
−=− =
()
rdC
dt kTC C
A
A
AB
αβ
(
2)
The temperature-dependent rate constant is almost always
modelled with what is now known as the Arrhenius equation
(Laidler 1984):
kT ke
o
E
RT
act
()
=
(
3)
where E
act
is the Arrhenius (1889) activation energy and k
o
is a
pre-exponential factor, both of which can usually be treated as
being independent of temperature over the small temperature
range (Richardson and Peacock 1994) likely to be relevant in
most wine reactions.
The Arrhenius equation can usefully be rearranged to elimi-
nate the pre-exponential factor and allow the calculation of
relative reaction rates between the two temperature values at an
instant in time assuming the same starting concentration, based
on just the value of the Arrhenius activation energy:
==
r
r
kCC
kCC
ke C C
ke
AT
AT
TAB
TAB
o
E
RT AB
o
E
act
act
,
,
2
1
2
1
2
αβ
αβ
αβ
RRT AB
E
RT T
CC
e
act
1
21
11
αβ
=−−
(
4)
The commonly employed rule of thumb is that reaction rate
doubles for every 10°C increase in temperature. This should be
used with caution, however, as the relative reaction rate will
depend on the specific reaction, the temperature and the asso-
ciated Arrhenius activation energy, as illustrated in Figure 1.
The Arrhenius equation has been successfully applied in
many fields since its derivation more than 100 years ago. It is
widely regarded as one of the most important equations in
physical chemistry (Logan 1982), although there are some
critics of its blanket use without careful consideration (Peleg
et al. 2012).
In published studies relating to wine, the Arrhenius equa-
tion has been applied to the kinetics of processes, including
oxidative browning (Berg and Akiyoshi 1956, Ough 1985,
Cilliers and Singleton 1989, Boulton et al. 1996, Serra-Cayuela
et al. 2014), volatile ester hydrolysis and formation (Ramey and
Ough 1980), co-pigmentation (Baranowski and Nagel 1983,
Kunsági-Máté et al. 2009), ethyl carbamate formation (Ough
et al. 1988), sotolon formation (Silva Ferreira et al. 2005) and
wine protein unfolding (Falconer et al. 2010).
Reactions in wine are often complex with numerous steps,
interactions and parallel pathways that are not perfectly defined.
While it is best if these reactions are fully understood, even if they
are not, useful apparent reaction rate expressions can still some-
times be developed. Reaction rates are determined by the rate
limiting step, so ultimately what is required is a rate expression
that directly or indirectly approximates that step rather than
necessarily describing the entire chain of reactions involved.
0
1
2
3
4
5
6
7
8
9
10
10 20 30 40 50
Relave reacon rate
Temperature (°C)
Figure 1. Influence of Arrhenius activation energy on relative reaction rate.
Reaction rates relative to those at 10°C for the Arrhenius activation energy
5kJ ( ), 10 kJ ( ), 25 kJ ( ), 50 kJ ( ), 100 kJ ( ), 200 kJ
() and 500 kJ ( ).
714 Elevated storage temperature and wine composition Australian Journal of Grape and Wine Research 21, 713–722, 2015
© 2015 Australian Society of Viticulture and Oenology Inc.
Temperature effect on the concentration of active
preservatives
Sulfur dioxide is the most common additive used for wine
preservation. It inhibits the growth of microorganisms and
protects wine against the effects of oxidative reactions
(Ribéreau-Gayon et al. 2006). The concentration of SO
2
decreases with time in a sacrificial process that is retarding wine
oxidation; the apparent concentration of free SO
2
is often used
as a marker for shelf-life.
Sulfur dioxide exists in three free forms in wine: molecular
SO
2
, bisulfite (HSO
3
) and sulfite (SO
32-
) as shown in Figure 2.
The equilibrium between these forms is dependent on the spe-
cific pH of a wine, but bisulfite is always the principal form,
followed by molecular SO
2
and a small amount of sulfite
(Boulton et al. 1996). It is generally considered that molecular
SO
2
is the form responsible for the antimicrobial function of SO
2
.
It is bisulfite that is now thought to react indirectly with oxygen
in wine causing the level of SO
2
to decrease with time. This
occurs via a complex pathway involving other wine constitu-
ents, which is still the subject of considerable research [e.g.
Danilewicz (2012, 2014), Waterhouse (2012)]. Bisulfite also
binds with other molecules to form ‘bound SO
2
’. This includes
binding with acetaldehyde and with quinones, reducing and
delaying enhanced concentration of aldehydic characters and
browning, respectively (Boulton et al. 1996). The binding of
bisulfite, however, reduces the quantity of SO
2
available as an
antimicrobial and antioxidant agent.
Temperature influences both the SO
2
equilibrium in wine
and the kinetics of oxidative reactions, in which it is involved as
an inhibitor. With regard to equilibrium, at higher temperature,
a greater fraction of SO
2
is in the antimicrobial molecular SO
2
form. At the time of bottling, wines can actually be sterilised at
a moderate temperature of 45–50°C, in part because of this
effect (Ribéreau-Gayon et al. 2006). Similarly, the equilibrium
between free and bound bisulfite can change meaningfully with
temperature for some bisulfite-binding compounds (but not for
acetaldehyde, which is in a relatively stable bound form).
There are surprisingly few published studies that have sys-
tematically studied the effect of temperature on the kinetics of
oxidation reactions and SO
2
concentration in real wine, given its
practical importance, but most practitioners would be aware
that the rate of SO
2
drop and browning increases with increasing
temperature. Boulton et al. (1996) provide a valuable table of
oxidation-related reaction rates (Table 1), relative to those at
10°C, based on data from three earlier published studies (e.g.
the rate of browning is 2.9 times faster and the rate of total SO
2
decline is 1.2 times faster at 20°C relative to that at 10°C for a
white wine—based on data from Ough 1985).
These values would have been calculated using the relative
Arrhenius equation provided in Equation 4, and apparent
Arrhenius activation energies calculated for disappearance of
dissolved oxygen in white wine [137.7 kJ/mol, Ribéreau-Gayon
(1933)], white wine browning [66.4 kJ/mol, Berg and Akiyoshi
(1956) and 74.6 kJ/mol, Ough (1985)] and total SO
2
decline
[35.7 kJ/mol for red wine and 13.4 kJ/mol for white wine,
Ough (1985)].
These values assume pseudo-first-order kinetics for the con-
centration dependence with respect to the disappearance of the
dissolved oxygen (the reaction order is not explicitly stated for
the other reactions). A rate expression that is a continuous
function of concentration and temperature is a valuable tool. It
is easy for a wine producer to specify a conservatively low-
storage temperature, but when this is not met because, for
example, a refrigeration plant has failed or an uninsulated ship-
ping container has been held up by customs, a reliable rate
expression is useful in determining possible consequences.
A limitation of the analysis provided by Boulton et al.
(1996) is that the source data available were limited. For
example, the only data relating to SO
2
depletion were sourced
from Ough (1985), and that study was performed with only one
white and one red wine (each at two concentration values of
SO
2
). Different rates of decline might reasonably be expected in
other wines depending on the concentration of phenolic sub-
stances, metals, alcohol, dissolved oxygen, ionic strength and
wine pH.
Ascorbic acid is another antioxidant preservative employed
in wine production—perhaps more so in Australia than in the
USA or Europe (Bradshaw et al. 2003). It is generally used in
combination with SO
2
, both because ascorbic acid has negligible
antimicrobial effect and because when ascorbic acid reacts with
dissolved oxygen, hydrogen peroxide is produced. Sulfur
dioxide can then react with this and prevent the hydrogen
peroxide from causing other undesirable oxidation products.
Limited data are available on the effect of temperature on ascor-
bic acid degradation directly in wine, but a strong temperature
dependency has been previously observed in a non-wine acidic
solution (Finholt et al. 1965, Bradshaw et al. 2011).
Effect of elevated temperature on volatile
compounds
Flavour and aroma are arguably the most important contribu-
tors to perceived wine quality. The aroma of wine is influenced
by a range of volatile compounds that originate from the grapes
or as a result of the winemaking process, as well as ageing and
storage. Some of the classes of volatile compounds present in
Molecular bisulfite sulfite
2+2++3
↔2 ++3
2−
pKa=1.81 pKa=7.2
Figure 2. Equilibrium between molecular, bisulfite and sulfite forms of sulfur
dioxide in wine.
Table 1. The relative reaction rates of selected reactions in wines†.
Reaction Relative rate at temperature (°C) relative to 10°C
5°C 10°C 15°C 20°C 25°C 30°C 35°C 40°C
Oxygen uptake 0.35 1.00 2.76 7.35 18.9 47.3 114 270
Browning 0.57 1.00 1.73 2.94 4.91 8.07 13.0 20.7
Browning 0.60 1.00 1.63 2.62 4.13 6.42 9.84 14.9
Total SO2decline (red wine) 0.76 1.00 1.30 1.67 2.15 2.72 3.43 4.28
Total SO2decline (white wine) 0.90 1.00 1.10 1.21 1.35 1.46 1.59 1.73
†Boulton et al. (1996). SO2, sulfur dioxide.
Scrimgeour et al.
Elevated storage temperature and wine composition 715
© 2015 Australian Society of Viticulture and Oenology Inc.
wine considered to be the most important to flavour are those
arising from the fermentation process, which include ethyl
esters, acetate esters, higher alcohols, fatty acids and aldehydes
(Recamales et al. 2011).
In general, most published studies have investigated the
effect of accelerated ageing, promoted by heat treatment, on
the volatile profile of white wines. Fewer studies have assessed
the effect of heat treatment on aroma compounds in red
wine or in fortified wines, most likely because these wines
are generally considered more resistant to the effect of
temperature.
Robinson et al. (2010) examined the direct effect of tem-
perature on the volatile composition of red and white wine by
subjecting six types of wines to simulated temperature condi-
tions that would likely occur during transportation, such as
shipping, over a 21-day period. The study found that a constant
40°C heat treatment had a greater impact on the aroma and
volatile composition of the wines compared with that of the
20°C/40°C cycled treatment, which in turn had a greater impact
on that of wines stored at a constant 20°C.
There was a significant difference between the wines at the
higher temperature, with a higher concentration of 1,1,6-
trimethyl-1,2-dihydronaphthalene (TDN), vitispirane 1 and 2
(Figure 3) and a lower concentration of isoamyl acetate, hexyl
acetate (Figure 4) and 2-phenyl acetate. It is evident from this
study that as a direct result of heat, the fruity acetate com-
pounds in the wines are disappearing and aged-like characters
have developed. A high concentration of TDN is often observed
in aged Riesling, imparting a kerosene-like flavour and it nor-
mally forms over long periods of time from precursors in the
young wine. In this case, it was shown that TDN developed
prematurely at increased concentration because of the heat
treatment. These results matched those that were previously
reported by Leino et al. (1993), Marais and Pool (1980) and
Ramey and Ough (1980).
A study by Pérez-Coella and González-Viñas (2003) also
showed a decrease in important fruity ethyl esters and acetates
such as isoamyl acetate with respect to uncontrolled storage
temperature and time compared with storage at 5°C. Some
esters, such as ethyl lactate, diethyl succinate, ethyl
monosuccinate and diethyl malate, increased in the wine after
exposure to the fluctuating temperature treatment. Although
the exact temperature in the uncontrolled environment was not
documented, they suggested that storage at 5°C increases the
shelf-life of a young white wine, with less chemical and sensory
changes occurring over time which may be because reaction
rates are slower at the lower temperature. The reality is that
wines are often stored in environments with uncontrolled tem-
perature such as retail outlets and thus wines are susceptible to
changes in their aroma profile post-bottling.
A loss of fruity and floral aromas in young white wines that
have been subjected to elevated temperature has been reported
frequently in the literature. This presumably reflects the loss of
mainly ester and acetate compounds that impart pleasant fruity
aromas such as strawberry and banana type characters. These
compounds appear to be more sensitive and susceptible to
changing temperature conditions than other volatile compo-
nents. During storage, the volatile composition of wine changes
because of different reactions taking place, in particular ester
hydrolysis/esterification reactions. Changes in ester composition
will occur during storage and the reaction rate is influenced by
the storage temperature. Acetates are hydrolysed faster than the
ethyl esters of short chain fatty acids, which, as a result, may
lead to the loss of fruitiness in a young white wine. Hydrolysis
of esters appears to be accelerated with increasing temperature
and pH. Wines that were stored at chilled conditions (0, 5 or
10°C) were shown to have prolonged life, retaining their youth-
ful wine aromas (Pérez-Coella and González-Viñas 2003,
Robinson et al. 2010).
Recamales et al. (2011) provide similar conclusions, as well
as referencing other studies (Sivertsen et al. 2001, Pérez-Coella
and González-Viñas 2003) that support their findings and
showed that this loss in fruitiness can be minimised if the wine
is stored at low temperature. They investigated the storage of
white wine at constant temperature of 15–20°C and variable
temperature between 10.5 and 25.3°C. Principal component
analysis and linear discriminant analysis revealed that tempera-
ture had the greatest impact on the volatile compounds com-
pared with the other factors studied, including time and bottle
positioning. Isoamyl acetate was observed to decrease as a result
of predominantly variable temperature between 10.5 and
25.5°C compared with a storage temperature of 15–20°C, which
may be the reason for an observed loss of fresh and floral odour
of the wine after 12 months. Of interest, however, is the fact
that ethyl butyrate, ethyl lactate and diethyl succinate actually
increased after 12-month storage, and this may explain why
overripe and spice characters were developed over this period
(Recamales et al. 2011). These studies emphasise the impor-
tance of controlling storage temperature for the maintenance of
fresh fruity aromas and reducing the effect of accelerated ageing
and for wines developing aged type characters, either negative
or positive.
Both time and temperature factors have been shown to
influence changes to the volatile profile of Chardonnay white
wines (Cejudo-Bastante et al. 2013). Both standard conditions
(18°C for 1 year) and accelerated ageing conditions (80°C for
7 days) led to the formation of dioxanes, dioxolanes and TDN
and the disappearance of some alcohols, terpenes and furanic
compounds. Different chemical classes were monitored but
there was a decrease in the volatiles associated with positive
attributes in wine, such as β-damascenone, esters and terpenes.
There was also an increase in the concentration of those
volatiles that may exert a negative influence on aroma, such as
long chain fatty acid ethyl esters and furanic compounds. Accel-
erated ageing at 80°C resulted in higher concentration of both
β-damascenone and TDN (Cejudo-Bastante et al. 2013), which
supports previous studies where both of these compounds were
found to increase in aged wine.
New substances can appear in young wines when they have
been subjected to an elevated temperature; these tend to
develop from precursors present in the wine, producing aged-
type characters earlier than expected. Typical aged characters
TDN Vispirane
Figure 3. Volatile compounds 1,1,6-trimethyl-1,2-dihydronaphthalene
(TDN) and vitispirane.
Isoamyl acetate Hexyl acetate
Figure 4. Volatile compounds isoamyl acetate and hexyl acetate.
716 Elevated storage temperature and wine composition Australian Journal of Grape and Wine Research 21, 713–722, 2015
© 2015 Australian Society of Viticulture and Oenology Inc.
such as TDN can be observed in young Riesling wines at a
concentration one would normally expect to see in the chemical
profile of a ripe aged Riesling, if the wines have been stored at
higher temperature. Wines stored at a lower temperature gen-
erally have a longer shelf-life, with fresh/fruity aromas pre-
served in young wine if optimal conditions are maintained.
In Merlot and Cabernet Sauvignon wines, Robinson et al.
(2010) reported substantial changes in the aroma profile, with
30 out of 47 volatile compounds analysed altered as a result
of temperature. Wines exposed to a constant 40°C showed a
lower concentration of linalool, ethyl octanoate, nonanoate,
decanoate and dodecanote, methyl octanoate and decanoate,
isoamyl octanoate and decanoate, isopentyl hexanoate and
ethyl-9-decanoate, compared that of the same wines stored at
20°C. Conversely, there was a higher concentration of ethyl-2-
furoate, ethyl phenylacetate, dehyroxylinalool oxide A,
p-cymene, TDN and vitispiranes. Evidence in the literature sug-
gests that increases in TDN and vitispiranes in wines can be
attributed to the hydrolysis of multiple glycosylated precursors
under acidic conditions, which can be accelerated by elevated
temperature, as referenced in Robinson et al. (2010).
Leino et al. (1993) also reported precursor hydrolysis as a
contributor to changes in Chardonnay and Semillon wine
aroma brought about by heat treatment (45°C for 20 days). The
concentration of volatile norisoprenoids, TDN and vitispirane
was higher in the heat-treated wines, which was likely caused
by the hydrolysis of glycosidic precursors. Thermal treatment of
wine demonstrated alterations in ester composition and in vola-
tile norisoprenoids. The authors also reported a decrease in
ethyl dodecanoate in the heated wines, and an enhancement in
ethyl esters of C
4
,C
6
,C
8
and C
10
acids and volatile acids was
observed.
Hopfer et al. (2012) studied the effect of heat-treated Char-
donnay wine at 10, 20 and 40°C for a period of 3 months. They
too observed an increase in compounds associated with age or
with heat-affected wine such as TDN and furfuryl ether particu-
larly in wines stored in bag-in-boxes at 40°C. Similar to
Robinson et al. (2010), wines stored at 20 and 40°C were higher
in the volatiles diethyl succinate, ethyl-3-methyl butanoate,
furfuryl ether, 2-phenethyl alcohol and TDN. A higher concen-
tration of hotrienol, linalool, 2-phenylethanol acetate, 3-methyl
butanol acetate, 1-hexyl acetate was observed in wine kept at
10°C.
A study to investigate the combined effect of storage tem-
perature (10, 20 and 40°C) and packaging configuration in
Cabernet Sauvignon was described by Hopfer et al. (2013). After
6 months, several volatile compounds varied significantly
between samples with increasing storage temperature with the
largest observed changes in acetates and alcohols, with some
compounds increasing and others decreasing. Those volatiles
that increased with increasing storage temperature included
ethyl acetate, ethyl-2-methyl propanoate, ethyl butanoate,
ethyl 2-methylbutanoate, ethyl 3-butanoate, 1-octen-3-ol and
vitispiranes. Compounds that decreased as a result of increasing
storage temperature included the acetates isoamyl acetate,
hexyl acetate, 2-phenylethyl acetate, the ethyl esters ethyl
octanoate and ethyl decanoate, and octanoic acid.
Another group of important volatile compounds in white
wine known to be affected by temperature is the varietal thiols.
A research study by Herbst-Johnstone (2010) specifically
monitored the concentration of the varietal thiols
3-mercaptohexanol (3-MH) and 3-mercaptohexylacetate
(3-MHA) in Sauvignon Blanc wine after being stored at elevated
temperature. A loss of both of these thiols was observed at 16°C.
At an elevated temperature of 45°C and low pH, 3-MHA is
hydrolysed to 3-MH, causing the decline of 3-MHA (Figure 5).
As mentioned above, acetate esters undergo hydrolysis in wine
and this is likely to be the mechanism by which degradation of
3-MHA is occurring.
A study dating back to 1956 by Deibner and Bernard, ref-
erenced in Cutzach et al. (2000), noted the importance of the
Maillard reaction in the aroma of sweet fortified wines subjected
to heat treatment. The Maillard reaction is a chemical reaction
between amino acids and reduced sugars and is associated with
the browning of food. These studies reported that many factors
have a role in Maillard formation and thus have an impact on
the final colour and aroma. Factors considered important
include pH, types of amino acids and sugars, temperature,
time, presence of oxygen, water, water activity and other
components.
Accelerated ageing of red and white sweet fortified wines
was investigated by Cutzach et al. (1999) in which the
wines were heated at 37°C for 12 months. The volatile com-
pounds sotolon [3-hydroxy-4,5-dimethyl-2(5H)-furanone],
5-ethoxymethylfurfural, 5-hydroxymethylfurfural (HMF),
acetylformoin and hydroxymaltol increased with elevated
storage temperature and furfural decreased with higher
temperature.
Changes in the volatile content of Fino Sherry wines sub-
jected to 45°C have also been reported (Benitez et al. 2006),
revealing that the wines exposed to heating exhibit a reduction
in esters, acids and alcohols and an increase in furfural and
benzaldehyde. This is important to note because the esters are
associated with fruity or favourable characters in Fino wines.
More recently, in a study by Pereira et al. (2014), the volatile
profile changes of Madeira wines with respect to the baking
process, estufagem, which is utilised in the production of these
wines, was investigated. Tinta Negra and Malvasia wines were
heated at 45°C for 3 months (standard) and 70°C for 1 month
(baked). One hundred and ninety volatile compounds were
identified, with 53 of them found only in the baked wines. All
furans and a majority of the ester compounds that were meas-
ured increased as an effect of the heat treatment, at standard
heating conditions and at baked conditions. Esters that did show
a decrease in concentration in all heat-treated wines at both
standard and baked conditions were isoamyl acetate, hexyl
acetate and phenlethyl acetate, which are compounds that
appear to be susceptible to heat treatment.
Monoterpenic alcohols were not detected after the baking
process. Heating to 70°C resulted in increased formation
of aroma compounds, such as phenylacetaldehyde,
β-damascenone, 5-ethoxymethylfurfural, ethyl butyrate, ethyl
2-methylbutyrate, ethyl caproate, ethyl isovalerate, guaiacol,
5-hydroxymethylfurfural and γ-decalactone. These aroma com-
3-Mercaptohexyl acetate 3-Mercaptohexan-1-ol Acec acid
Figure 5. Hydrolysis of 3-mercaptohexyl acetate to 3-mercaptohexan-1-ol (Herbst-Johnstone 2010).
Scrimgeour et al.
Elevated storage temperature and wine composition 717
© 2015 Australian Society of Viticulture and Oenology Inc.
pounds produce a mixture of volatiles that are associated with
negative characters in wine and some that are associated with
positive characters. It is interesting that floral and fruity volatiles
phenylacetaldehyde and β-damascenone are present in higher
concentration at this extreme temperature but not at the stand-
ard heating temperature of 45°C (Pereira et al. 2014).
Changes in wine composition because of temperature can
have an impact on fortified wines but may not be as noticeable
as they are normally well characterised by a variety of ‘aged’
aromas; however, accelerated ageing caused by temperature still
appears to cause deterioration in the bouquet of these wines.
The impact of heat on non-volatile compounds in
wine
While volatile compounds are important for aroma perception
in wine matrices, non-volatile compounds play an important
role in the palate characteristics of a wine and, in many cases,
these can be equally sensitive to the impact of temperature.
There are a range of important classes of non-volatile
compounds typically found in wines (organic acids,
polysaccharides, sugars and proteins), and the group of com-
pounds most sensitive to the impacts of heat exposure is the
phenolic substances.
Phenolic substances are a large and complex group of com-
pounds (Figure 6). They include the predominant species that
give rise to red wine colour (anthocyanins) and mouthfeel
[flavan-3-ols, tannins and phenolic acids; Arnold et al. (1980),
Robichaud and Noble (1990)]. In grapes and wine, the most
important sub-class is the flavonoids, although phenolic acids
such as caftaric acid are known to play an important role in
white wine chemistry. Within the flavonoid class of compounds,
the most sensitive to temperature are the flavanols and
anthocyanins.
For white wines, the most important phenolic substances
include gallic acid, caftaric acid and caffeic acid. These com-
pounds readily react with oxygen, performing an antioxidant
role in the winemaking process. When oxidised, they can form
brown pigments that may eventually precipitate (Harbertson
2015).
In red wines, the key phenolic substances originate pre-
dominantly from the grape skins and seeds, including flavan-3-
ols (catechins), anthocyanins and tannins (Peynaud 1984,
Margalit 2004). The concentration of these compounds in
grapes and the level of skin contact during fermentation are the
key factors that affect their ultimate concentration in the wine
produced.
The evolution of phenolic substances during the ageing
process can be influenced by the method of maturation, storage
temperature, presence of oak and other additives, light expo-
sure, oxygen content and storage time (Lago-Vanzela et al.
2014). Trials incorporating UV radiation as well as elevated
temperature on wines (e.g. by storage in an external environ-
ment) have shown that this combination can introduce specific
effects on wine pigmentation (Maury et al. 2010) and that the
type/colour of glass used to store the wine can influence the
colour development, especially in white wines.
The most common effect on non-volatile compounds caused
by exposure to elevated temperature in red wines is a decrease
in anthocyanin concentration and a corresponding increase in
tannin-bound anthocyanins (polymeric pigments), such as the
adduct shown below in Figure 7. This process allows the more
unstable (and SO
2
bleachable) colour component in wine to be
converted into its more stable (and non-SO
2
bleachable) form.
Monomeric anthocyanins are known to be intricately
involved in ageing reactions, specifically in the formation of
polymeric pigments via the condensation reaction with tannin
species. The speed of this process has been shown to increase at
elevated temperature (Gómez-Plaza et al. 2000).
Monomeric anthocyanins have been shown to diminish
over time in red wines, even at typical cellar storage tempera-
ture, through the ageing process (Somers 1971), and polymeric
pigments increase, with a corresponding colour change from
purple to red/orange occurring in the wine (Fulcrand et al.
2006). In this context, temperature exposure appears to accel-
erate the ageing process. Interestingly, temperature appears to
be a more influential factor on the concentration and fate of
anthocyanins than pH, SO
2
, alcohol or storage time (Dallas and
Laureano 1994).
The effect of temperature on the stability of anthocyanins in
model systems and food products has been studied extensively
and the indications are that anthocyanins can be degraded by
heat (Markakis 1982). The exact mechanism, however, for this
degradation reaction in aqueous media is still the subject of
debate. Given the proliferation of polymeric pigments in red
wines, it appears clear that the presence of compounds such
as tannins provide an alternative reaction pathway for
anthocyanins when elevated temperature is introduced.
Baranowski and Nagel (1983) observed that storage tem-
perature affected the degradation and polymerisation mecha-
nisms associated with malvidin 3-glucoside (the most common
anthocyanin in red wine). Villamor et al. (2009) showed that
the prominence of this effect on anthocyanins is affected by the
wine type studied; this is a common observation for all classes of
phenolic substances, as the chemical matrix of red wines is
extremely complex and varied between wine types.
POLYPHENOLS
Flavo noids
Phenol ic
acids St ilbenes
FlavanonesFlavanolsIso-flavonesFlavones FlavonolsAnthocyanins
Flavan-3-ols
(catechins)
Proanthocyanidins
(condensed tannins)
Figure 6. Structural classes of phenolic substances in wine.
Figure 7. Ethyl-linked anthocyanin-flavanol adduct.
718 Elevated storage temperature and wine composition Australian Journal of Grape and Wine Research 21, 713–722, 2015
© 2015 Australian Society of Viticulture and Oenology Inc.
Loss of anthocyanins over time in different food products is
commonly observed to be logarithmic in nature (Markakis
1982, Bakker 1986). This tends to be more pronounced as
temperature increases, reflecting the higher reaction rates asso-
ciated with the relevant Arrhenius activation energy required to
achieve either conversion or degradation of the anthocyanins at
that elevated temperature (Lago-Vanzela et al. 2014). Figure 8
highlights this effect for Violeta wine in a 2014 study investi-
gating the effect of accelerated ageing conditions on phenolic
composition, colour and antioxidant activity. This acceleration
effect is common in many temperature impact studies, for both
volatile and non-volatile components.
Other components in wine, such as SO
2
concentration and
pH, are known to play a significant role in the impact of tem-
perature on anthocyanins and pigmentation products. It is con-
sidered that SO
2
may play a part in hindering the condensation
reaction between flavan-3-ols (catechins) and tannins via by
binding to the flavylium ion through its bisulfite form. Dallas
and Laureano (1994) showed that wines with a higher concen-
tration of SO
2
experienced a slower decrease in anthocyanins
than the same wines with lower SO
2
, when storage temperature
was increased. A similar effect was seen with the polymeric
pigments in this study, with increases in both SO
2
and pH
correlated with a slower increase in polymeric pigments formed.
Sims and Morris (1984) observed a similar trend in that wine
with lower pH was able to incorporate more anthocyanins in the
polymeric pigment form and browns less than wine at a higher
pH.
Most individual anthocyanins have been shown to decrease
with increasing temperature exposure, but not all show the
same level of response. Dallas and Laureano (1994), for
example, showed that peonidin and malvidin-3-glucoside-p-
coumarate were affected by increasing temperature.
Baranowski and Nagel (1983) showed that the concentration of
malvidin-3-glucoside decreased with increasing temperature
exposure and showed first-order kinetics, both with and
without the presence of acetaldehyde. Arapitsas et al. (2014)
showed that for Sangiovese wines stored under fluctuating daily
temperature (20–27°C), formation of pinotin A-like pigments
(Figure 9) and the hydrolysis of flavonol glycosides occurred
more rapidly, in relation to the same wines stored at relatively
stable cellar temperature (15–17°C).
Tannins are important for their impact on mouthfeel, espe-
cially in red wines. As a class of phenolic substances in wine,
they can be separated into condensed and hydrolysable forms.
Condensed tannins are the most abundant class of phenolics
found in grapes and wine and are polymers of flavan-3-ols,
commonly found in the skin and seeds of grapes. Hydrolysable
tannins are derived from the non-flavonoid ellagitannins found
in oak, from barrels and adjuncts used to modify the flavour and
mature wines.
The concentration of tannins in red wines appears to
decrease because of temperature exposure. This is consistent
with the faster formation of polymeric pigments commonly seen
with elevated temperature (Somers and Evans 1986), as well as
changes in colour and phenolic composition (Somers and
Pocock 1990), which affect the measured tannin concentration.
Vidal et al. (2002) considered that changes in tannin concentra-
tion caused by elevated temperature could be a result of high
molecular mass tannins forming via acid-catalysed C-C bond
cleavage.
Villamor et al. (2009) showed that small polymeric pigments
(SPP) increased with heat exposure over time, but large poly-
meric pigments (LPP) did not. Both trends were consistent for
two wines; a Merlot and a Cabernet Sauvignon. Total tannin
concentration exhibited a small, but non-significant change
over time for the Merlot wine and a small but significant
decrease for Cabernet Sauvignon wine; this is likely to be a
reflection of the extent of polymerisation that occurs with dif-
ferent wine types.
Arapitsas et al. (2014) observed that temperature exposure
resulted in wines developing approximately four times faster
(wine aged for 6 months at a fluctuating 20–27°C being com-
parable to wine aged for 2 years at a controlled 15–17°C).
Higher storage temperature influenced the formation of
monosulfonated flavanols; a direct reaction between tannins
and the SO
2
present in its bisulfite form. The difference between
wines stored at different temperature was more pronounced
from 12 to 24 months, suggesting an increasing role for SO
2
in
this process over time.
The most obvious effect of elevated temperature on white
wines is the formation of brown pigments, commonly referred
to as browning. Browning in white wines is commonly attrib-
uted to the mechanisms involved with the oxidation of phenolic
substances and many studies have shown that the formation of
quinones has a significant influence in the browning process
(Berg and Akiyoshi 1956, Macheix et al. 1991, Cheynier et al.
1993). Trans-caftaric and caffeic acids (Cilliers and Singleton
1989, 1991) are also known to play an important role, with
oxidation of catechin, epicatechin, caffeic acid and other
hydroxycinnamic acids leading to browning. Singleton and
Kramling (1976) developed an accelerated browning test, which
0
200
400
600
800
1000
1200
1400
1600
1800
0 20 40 60 80 100 120
Total anthocyanin cont ent (mv-3-glc, mg/L)
Time (days)
Figure 8. Degradation of anthocyanins (measured as malvidin-3-glucoside
equivalents) in Violeta red wine aged over 120 days at 15 ( ), 25 ( ), 35 ( )
and 50°C ( ) (adapted from Lago-Vanzela et al. 2014).
Figure 9. Chemical structure of pinotin A.
Scrimgeour et al.
Elevated storage temperature and wine composition 719
© 2015 Australian Society of Viticulture and Oenology Inc.
is a standardised test commonly used to assess the browning
capacity of white wines. This test directly measures the impact
of heat exposure on brown pigment formation. In these studies,
browning has consistently been shown to increase with elevated
temperature exposure.
Benitez et al. (2006) showed that there was a decrease in
gallic, vanillic, caftaric, coutaric and fertaric acids from heat
exposure, along with a decrease in epicatechin and
protocatechuic acid. Caffeic acid, syringaldehyde, trans-coumaric
acid, ferulic acid, catechin and procyanidins B1 were observed to
increase. The trends are consistent with the affinity of these
compounds for oxidation (Singleton 1987, Macheix et al. 1991,
Mayen et al. 1997); however, Ferreira-Lima et al. (2013) found
some opposing trends, with quercetin and gallic acid increasing,
but catechin, epicatechin and trans-caftaric acid decreasing.
Kallithraka et al. (2009) observed that hydroxycinnamic
and gallic acids increased fivefold in a series of selected Hellenic
varietal white wines, while epicatechin decreased, when sub-
jected to the accelerated browning test (55°C over 10 days).
These opposing trends are likely to represent the complexity of
the different white wine matrices present in various wine types.
Hernanz et al. (2009) showed that many phenolic substances
were impacted by temperature exposure, with the impact on
the phenolic profile significantly influenced by wine type.
Recamales et al. (2011) showed that light and temperature
may contribute to the degradation of flavan-3-ol (catechin) and
caftaric acid and that this could be related to polymerisation
reactions that occur during browning (Hernanz et al. 2009).
Fabios et al. (2000) suggested that several compounds influenc-
ing browning (referred to as the browning peaks) are synthe-
sised in substantial amounts when wines age.
Non-volatile compounds in both white and red wines are
susceptible to the effect of heat exposure, predominantly affect-
ing the colour characteristics of the wines, often quite dramati-
cally. Elevated temperature can also produce a noticeable
impact on the palate attributes of the wines, as phenolic profiles
change and tannin composition is affected. This process some-
what mimics the natural ageing process, but often results in
excessive polymerisation and degradation of the phenolic sub-
stances present in the wines and a consequentially dramatic
reduction in shelf-life.
Closing remarks
It is clear from the available published literature that elevated
storage temperature accelerates the ageing process that wines
typically experience over time. The chemical profile of wine can
change significantly with elevated storage temperature, indicat-
ing that the reaction mechanisms and Arrhenius activation
energies involved are highly sensitive to temperature.
The most common and noticeable impact on wines that
have been stored under high temperature conditions is the loss
of SO
2
. This is more apparent in white wines than in reds, as red
wines have a higher concentration of compounds that are able
to alleviate the effect of higher temperature (and ongoing
oxygen exposure) without relying on the antioxidant properties
of the SO
2
alone.
White wines brown much faster at higher temperature and
the aroma profile tends to show significant changes, with the
development of undesirable attributes in the wine and loss in
intensity of the desirable fruity/floral characters, imparted by
the ester and acetate compounds present. Red wines are pre-
dominantly impacted by a reduction in the concentration of
anthocyanins and an increase in polymeric pigments. Red pig-
mentation appears to become more stable with increasing tem-
perature and the formation of brown pigments and undesirable
aroma characteristics can also occur in red wines, especially in
lighter style wines.
Many other components in wine, such as SO
2
and pH, have
been shown to play a significant role in influencing the impact
of temperature on white and red wines, and it is clear that
different wine types can have different responses to tempera-
ture, depending on the complexity of the wine matrix. All of
these studies emphasise the importance of carefully controlled
storage temperature for the maintenance of fresh fruity aromas
and reducing the effect of premature ageing.
At this stage, it is difficult to obtain a clear understanding of
what actual compounds make wine more or less vulnerable to
heat impacts, and it is therefore difficult to predict how a par-
ticular wine will cope with elevated temperature. Unfortu-
nately, in most cases, once a wine starts to exhibit noticeable
changes because of temperature, the chain of events (reactions)
that leads to ultimate deterioration of the wine is already under
way and requires some form of intervention to mitigate its
impact.
In order to provide the wine industry with practical tools
and information that can be applied to the issue of temperature
exposure, scientifically rigorous studies are required. These
should ideally include a broad range of wine styles and a range
of temperature that represents typical supply chain conditions.
The collection of comprehensive chemical and sensory analyti-
cal data would allow relatively simplistic prediction tools to be
developed. If temperature impact data can be gathered and
modelled using known Arrhenius activation energies, this may
allow estimation of the future condition of a wine with a known
starting chemical composition, based on the time–temperature
profile that it experiences.
Acknowledgements
This work is supported by Australian grapegrowers and
winemakers through their investment body Wine Australia,
with matching funds from the Australian Government. The
Australian Wine Research Institute is a member of the Wine
Innovation Cluster in Adelaide. The authors thank the numer-
ous colleagues, wineries and wine industry personnel who have
been involved in the work outlined. The authors also wish to
acknowledge Michael Downie, Anne Lord, Ella Robinson,
Annette Freeman and Con Simos for their editorial support and
constructive commentary.
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Manuscript received: 24 August 2015
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722 Elevated storage temperature and wine composition Australian Journal of Grape and Wine Research 21, 713–722, 2015
© 2015 Australian Society of Viticulture and Oenology Inc.
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