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a r t i c l e i n f o a b s t r a c t
Article history: In champagne and sparkling wine tasting, the concentration of dissolved CO2 is indeed an analytical
Received 21 July 2011 parameter of high importance since it directly impacts the four following sensory properties: (i) the
Received in revised form 30 August 2011 frequency of bubble formation in the glass, (ii) the growth rate of rising bubbles, (iii) the mouth feel,
Accepted 6 October 2011
and (iv) the nose of champagne, i.e., its so-called bouquet. In this state-of-the-art review, the evolving
Available online 14 October 2011
nature of the dissolved and gaseous CO2 found in champagne wines is evidenced, from the bottle to
the glass, through various analytical techniques. Results obtained concerning various steps where the
Keywords:
CO2 molecule plays a role (from its ingestion in the liquid phase during the fermentation process to its
Champagne
Sparkling wines
progressive release in the headspace above the tasting glass) are gathered and synthesized to propose a
CO2 self-consistent and global overview of how gaseous and dissolved CO2 impact champagne and sparkling
Effervescence wine science.
Glass shape 2011 Elsevier B.V. All rights reserved.
Tasting
Grard Liger-Belair received his PhD in physical sci- Guillaume Polidori received his PhD in uid mechan-
ences in 2001 from the University of Reims, in France. ics in 1994 from the University of Poitiers in France,
He received an associate professor position at the Uni- and became an associate professor in 1994 in the
versity of Reims in 2002, and a full professor position, University of Reims. He then became a full profes-
in 2007, in the same University. He has been research- sor in 2004 in the same University. His main current
ing the physics and chemistry behind the bubbling interests include theoretical modeling in thermal con-
properties of champagne and sparkling wines for sev- vection and ow visualization applied to various
eral years. His current interests include the science scientic elds, such as free convection, underwater
of bubbles, foams and thin lms, and their broad swimming in sport science, or mixing phenomena in
interdisciplinary applications. He is the author of sev- champagne and sparkling wine tasting.
eral academic and popular science books. His rst
book, Uncorked: the science of champagne, published
by Princeton University Press, won the 2004 award for
the Best Professional/Scholarly Book in Physics from the Association of American
Publishers.
Corresponding author at: Equipe Effervescence, Groupe de Spectromtrie Molculaire et Atmosphrique (GSMA), UMR CNRS 6089, UFR Sciences Exactes et Naturelles,
BP 1039, 51687 Reims Cedex 2, France. Tel.: +33 3 26 91 86 14; fax: +33 3 26 91 86 14.
E-mail address: gerard.liger-belair@univ-reims.fr (G. Liger-Belair).
0003-2670/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2011.10.007
2 G. Liger-Belair et al. / Analytica Chimica Acta 732 (2012) 115
Table 1
Henrys law constant of dissolved CO2 in champagne (in g L1 bar1 ), as a function
of temperature, for a typical champagne with 12.5% (v/v) of ethanol and 10 g L1 of
sugars.
0 2.98
1 2.88
2 2.78
3 2.68
4 2.59
5 2.49
6 2.41
7 2.32
8 2.23
Fig. 1. A cellar master (here Thierry Gasco, from Champagne Pommery) will blend 9 2.16
several different still wines from various grape varieties, vineyards and vintages to 10 2.07
produce one champagne. 11 2.00
Alain Cornu/Collection CIVC. 12 1.93
13 1.86
14 1.79
actually reduced by its presence. The amount of ethanol generated 15 1.73
16 1.67
by this rst alcoholic fermentation is about 11%. At this step, cham-
17 1.60
pagne is still actually a non-effervescent white wine, because the 18 1.54
huge amount of gaseous carbon dioxide produced during the rst 19 1.48
alcoholic fermentation (close to 50 L of gaseous CO2 per liter of 20 1.44
21 1.40
must) is allowed to escape into the atmosphere.
22 1.34
23 1.29
2.2. The art of blending 24 1.25
25 1.21
Because it is rare that a single wine of a single vintage from a Compiled from the data by Agabaliantz [29].
single vineyard and grape variety will provide the perfect balance
of avor, sugar level, and acidity necessary for making a ne cham-
pagne, wine makers will often mix several different still wines. This above a solution is proportional to the concentration of the gas
is called the assemblage (or blending) step, and it is carried out dissolved into the solution, as expressed by the following relation:
directly after the rst alcoholic fermentation is complete. Blend- c = kH PCO2 (2)
ing is considered a key step in the art of champagne-making (see
Fig. 1). A cellar master will sometimes blend up to 80 different wines where c is the concentration of dissolved CO2 molecules, PCO2 is
from various grape varieties, vineyards and vintages to produce one the partial pressure of CO2 molecules in the vapor phase, and kH is
champagne. The blending of still wines originally made from the its Henrys law constant (i.e., its solubility into the wine). Since the
three grape cultivars forms a base wine, which will then undergo present work specically deals with the dissolved CO2 concentra-
a second fermentation the key step in producing the sparkle in tion found in champagne samples, and to facilitate the reading of
champagne and other sparkling wines. the article, the subscript CO2 found in the formulas will be omitted
in the following.
2.3. The prise de mousse: a second alcoholic fermentation in a Generally speaking, the solubility of a given gas into a solution
sealed bottle is strongly temperature-dependent (the lower the temperature of
the solution, the higher the gas solubility). In champagne and other
Once the base wine is created, sugar (about 24 g L1 ) and yeast sparkling wines, Agabaliantz thoroughly examined the solubility
are added. The entire concoction is put into thick-walled glass bot- of dissolved CO2 molecules as a function of both temperature and
tles, and sealed with caps. The bottles are then placed in a cool cellar wine parameters [29]. His empirical relationships are still in use
(1012 C), and the wine is allowed to slowly ferment for a second nowadays by champagne and other sparkling winemakers. For a
time, producing alcohol and carbon dioxide again. Following Eq. typical sparkling wine elaborated according to the mthode tradi-
(1), 24 g L1 of sugar added in closed bottles to promote the second tionnelle, Agabaliantz established the temperature dependence of
alcoholic fermentation produce approximately 11.8 g of CO2 per the Henrys law constant, which is displayed in Table 1.
liter of wine. The concentration of dissolved CO2 in champagne (in Thermodynamically speaking, the behavior of Henrys law con-
g L1 ) is therefore roughly equivalent to half of the concentration stant as a function of temperature can be conveniently expressed
of sugar (in g L1 ) added into the base wine in order to promote the with a Vant Hoff like equation as follows:
prise de mousse. Finally, a standard 75 cl champagne bottle holds H 1 1
diss
close to 9 g of dissolved CO2 molecules. By use of the molar mass kH (T ) = k298 K exp (3)
R T 298
of CO2 (44 g mol1 ), and the molar volume of an ideal gas (close to
24 L mol1 at 12 C), it can be deduced that about 5 L of gaseous CO2 where k298 K is the Henrys law constant of dissolved CO2 at
are trapped into a single bottle of champagne (i.e., six times its own 298 K (1.21 g L1 bar1 ), Hdiss is the dissolution enthalpy of CO2
volume!). molecules in the liquid medium (in J mol1 ), R is the ideal gas con-
Actually, during this second fermentation process which occurs stant (8.31 J K1 mol1 ), and T is the absolute temperature (in K). By
in cool cellars, the bottles are sealed, so that the CO2 molecules tting Agabaliantz data with the latter equation, it is worth noting
cannot escape and progressively dissolve into the wine. Therefore, that the dissolution enthalpy of CO2 molecules in champagne may
CO2 molecules dissolved into the wine and gaseous CO2 molecules be evaluated [30]. The best t to Agabaliantz data was found with
under the cork progressively establish equilibrium an application Hdiss 24 800 J mol1 . In comparison, the dissolution enthalpy of
of Henrys law which states that the partial pressure of a given gas CO2 molecules in pure water is about 19 900 J mol1 [31].
4 G. Liger-Belair et al. / Analytica Chimica Acta 732 (2012) 115
12
Standard Bottle
Magnum Bottle
10 Half Bottle
P (bars)
6
2
0 5 10 15 20 25 30
T (C)
Fig. 3. Temperature dependence of the pressure P under the cork, within the three
most common champagne bottle types, namely, the standard bottle, the magnum
bottle, and the half bottle, respectively.
C (g L )
-1
12
11
Standard Bottle
Magnum Bottle
Half Bottle
10
0 5 10 15 20 25 30
T (C)
Fig. 4. Temperature dependence of the dissolved CO2 concentration within cham- Fig. 5. Scheme of the bottle neck, and compilation of the various cork, bottle, and
pagne, within the three most common champagne bottle types. wine parameters.
c of CO2 dissolved molecules found in champagne expresses as of c 11.5 g L1 [3740]. Recently, the concentration of dissolved
follows: CO2 was measured in various samples of an older champagne wine
elaborated in the late 1990s (also with 24 g L1 of sugar added in
kH mRT the base wine to promote the prise de mousse), disgorged, and aged
c = kH P (5)
4.4 103 v + (kH RT )V in a cool cellar ever since. Approximately ten years after having
been disgorged and corked, this old champagne was found
The temperature dependence of the dissolved CO2 concen-
to hold a much lower level of dissolved CO2 of only c 8 g L1
tration within champagne, for the three above-mentioned bottle
[44,45]. As expected, the old champagne contains substantially less
types, is displayed in Fig. 4. It can be seen from Fig. 4 that the smaller
dissolved CO2 than the young one, undoubtedly due to the slow
the bottle volume, the lower the concentration of dissolved CO2 . It
but continuous diffusion of gaseous CO2 through the cork, all along
is also worth noting from Fig. 4 that the concentration of dissolved
the aging period. Actually, deeper investigations about the way
CO2 is rather slightly temperature-dependent (despite a pressure
cork stoppers alter with time in a bottle neck are needed to better
within the bottle which is highly temperature-dependent, as seen
understand how their porosity and permeability are affected
in Fig. 3).
with regards to gas transfers during champagne aging. Such
Concentrations of CO2 molecules dissolved into champagne are
experiments are to be conducted along that line in a near future.
indeed easily accessible by use of carbonic anhydrase, which is the
ofcial method recommended by the OIV (namely the International
2.6. Uncorking the bottle
Ofce of Vine and Wine) for measuring the CO2 content in cham-
pagne and sparkling wines [36]. This method is thoroughly detailed In order to visualize the cloud of gaseous CO2 escaping and
in two papers [37,38]. Numerous experiments with early disgorged expanding when the cork pops out of a bottle (invisible in the visible
champagne samples were done recently [3840]. The characteris- light spectrum), a technique based on the infrared (IR) thermogra-
tic concentration of dissolved CO2 measured inside freshly opened phy principle has been used [46]. The CO2 absorptions observable
standard bottles was found to be of order of 11.5 g L1 , and therefore by the IR camera are quite weak because this gas molecule has only
in very good accordance with Eq. (5). a strong absorption peak in the detector bandwidth at 4.245 m.
Consequently, the best way to visualize the ow of gaseous CO2 des-
2.5. The impact of champagne aging orbing from champagne is to t the camera with a band-pass lter
(centered on the CO2 emission peak), as shown in a recent article
The cork of a wine bottle is far from being completely hermetic [47]. The time sequence displayed in Fig. 6 illustrates the uncorking
with regard to gas exchanges. Cork is a porous material [4145]. of a champagne bottle as seen through high-speed infrared imag-
Gas species are therefore able to slowly diffuse through the cork ing. As seen from Fig. 6, the gaseous volume of CO2 under pressure
along their respective inverse partial pressure gradients (see Fig. 5) in the headspace under the cork, suddenly expands and gushes out
[44,45]. In case of a corked champagne bottle, the huge difference of the bottleneck. The shock wave of the gushing gaseous CO2 can
in CO2 partial pressure between the headspace (close to 6 bar at even be evidenced.
12 C) and the ambient air (of order of only 0.0004 bar) forces CO2 After the uncorking of the bottle, the pressure of gaseous CO2
molecules to slowly diffuse through the cork. Therefore, during its experienced by the champagne inside the bottle suddenly falls.
aging period of time, a corked champagne bottle progressively loses Consequently, the thermodynamic equilibrium of CO2 is broken,
its gaseous CO2 content, as well as its dissolved CO2 content (which and the dissolved CO2 content found in champagne must inevitably
both experience equilibrium through the so-called Henrys law). escape to recover equilibrium, and fulll Henrys law, as stipulated
As seen in the preceding paragraph, early disgorged champagne by Eq. (2).
wines (elaborated with 24 g L1 of sugar added in the base wine to After having been uncorked by the taster, the bottle is then gen-
promote the prise de mousse) hold a concentration of dissolved CO2 erally inclined to pour champagne into a ute or a coupe. The aim
6 G. Liger-Belair et al. / Analytica Chimica Acta 732 (2012) 115
Fig. 6. Time sequence illustrating the uncorking of a champagne bottle as seen through infrared thermography; the time interval between successive frames is 100 ms.
of the following paragraphs is to closely examine how dissolved the bottle to the tasting glass, into the form of a liquid tongue,
CO2 progressively escapes from the liquid medium to progressively which presents a very large interface with regard to its own volume
invade the headspace above glasses, thus progressively modifying [48]. Moreover, the pouring step is a hugely turbulent phase, with
the gaseous chemical space perceived by the consumer. possible entrapment of air bubbles inside champagne, which also
contribute to the diffusion of dissolved CO2 from the liquid phase
3. Evidence for losses of dissolved CO2 during champagne to the ambient air. Besides, champagne is strongly mixed during
serving the pouring step, with formation of eddies of various sizes in the
liquid matrix, which also undoubtedly contribute to signicant
The impact of the pouring step on the loss of dissolved CO2 losses of dissolved CO2 .
from champagne has remained completely unexplored until very The impact of the pouring step on the loss of dissolved CO2
recently. During the pouring step, the free air/champagne interface from champagne was examined, depending on the way cham-
indeed considerably increases. Actually, champagne ows from pagne is served into the ute [48]. Two ways of serving champagne
G. Liger-Belair et al. / Analytica Chimica Acta 732 (2012) 115 7
Fig. 7. Time-sequences illustrating both ways of serving 100 mL of champagne into the ute; the champagne-like way of serving (this way is the traditional way of serving
champagne and sparkling wines in bars, clubs, and restaurants) (a); the beer-like way of serving, traditionally reserved for beer serving (to prevent an excessive formation
of foam) (b).
Grard Liger-Belair.
were examined, i.e., (i) a standard champagne-like way and (ii) usually providing a thick head of foam, which quickly vertically
and a standard beer-like way of serving, respectively. More- extends, and then progressively collapses during serving). This
over, impacts on losses of dissolved CO2 of three champagne way is the traditional way of serving champagne and sparkling
service temperatures were also examined (i.e., 4 C, 12 C, and 18 C, wines in bars, clubs, and restaurants.
respectively). (ii) During the beer-like way of serving, champagne ows along
the inclined ute wall and progressively lls the ute. The axis
3.1. Impact of the way champagne is served, and the role of of symmetry of the ute inevitably and progressively recovers
temperature its vertical position during serving. This beer-like way of serv-
ing champagne is less turbulent, with usually much less foam
After uncorking a bottle, two ways of serving 100 mL of cham- generation.
pagne into the ute were examined with regard to their respective
impacts on losses of dissolved CO2 : (i) a standard champagne-like Impacts on losses of dissolved CO2 in champagne were inves-
and (ii) a standard beer-like way of serving. Photographs displayed tigated for three sets of champagne temperatures, i.e., 4 C, 12 C,
in Fig. 7 illustrate both ways of serving champagne into the ute. and 18 C, respectively, and for both ways of serving champagne.
A volume of 100 4 mL of champagne was carefully poured into
(i) During the standard champagne-like way of serving, cham- the ute. It is worth noting that the heat capacity of the glass
pagne vertically falls and hits the bottom of the ute (thus (0.8 kJ kg1 K1 ) being much lower than that of champagne
8 G. Liger-Belair et al. / Analytica Chimica Acta 732 (2012) 115
Table 2
Losses of dissolved CO2 concentrations in champagne during the pouring step (in
g L1 ), and corresponding volumes of gaseous CO2 discharged from champagne
(converted in cm3 ), for both ways of serving, and at three champagne temperatures.
Fig. 9. Snapshots illustrating both ways of serving champagne, as seen through the objective of the IR video camera for a bottle stored at 4 C (a) and (b), and for a bottle
stored at 18 C (c) and (d).
G. Liger-Belair et al. / Analytica Chimica Acta 732 (2012) 115 9
Fig. 10. Laser tomography reveals the ow patterns found inside a ute poured with champagne; within a ute thoroughly washed and therefore showing no effervescence
at all, a few tens of seconds after pouring, champagne is completely at rest (a), whereas in a ute showing effervescence, ascending bubbles drive characteristic ow patterns
(b); detail in (c).
camera recordings, that the higher the champagne temperature is, rst 10 min following pouring, as shown in two papers [38,39]. To
the more easily dissolved CO2 escapes during the pouring process, prolong the drinks chill and to help champagne retain its CO2 con-
thus conrming the tendency underscored by chemical measure- tent (and therefore its effervescence), the champagne-like way of
ments (for both ways of serving champagne). It is also worth noting serving is certainly not the most appropriate.
that the ow of gaseous CO2 seems to ow down from the opening
of the ute, by licking the glass walls, rather than by diffusing
isotropically all around it. This observation betrays the fact that 4. On the losses of dissolved CO2 within the glass, after the
gaseous CO2 is approximately 1.5 times denser (CO2 = 1.87 g L1 pouring step
at 20 C) than dry air is (air = 1.20 g L1 at 20 C), and therefore
tends to naturally ow down. Once champagne is poured into a ute, there are indeed two
Ambient air being considered as a huge thermal tank, it quickly pathways for progressive CO2 and potentially aromatic volatile
thermalizes the volume of gaseous CO2 outgassing from cham- organic compounds (VOC) losses. CO2 and VOC escape (i) into the
pagne during the pouring step. Therefore, by considering the ux of form of heterogeneously nucleated bubbles, the so-called efferves-
gaseous CO2 discharging from champagne as an ideal gas, the vol- cence and (ii) by invisible diffusion through the free surface of
ume of gaseous CO2 discharging during the pouring step, denoted the glass [16]. Glass-shape is therefore also suspected to play an
V20 C (expressed in cm3 ), expresses as follows, important role as concerns the kinetics of CO2 and avor release
during champagne tasting.
c vf RT From the consumer point of view, the role of bubbling is
V20 C = 106 (6)
MCO2 P0 indeed essential in champagne, in sparkling wines and even in any
other carbonated beverage. Without bubbles, champagne would be
with c being the loss of dissolved-CO2 concentration during the unrecognizable, beers and sodas would be at. However, the role
pouring step (i.e., c = ci cL , expressed in g L1 ), vf being the vol- of effervescence is suspected to go far beyond the solely aesthetical
ume of champagne poured into the ute (in L, namely 0.1 L in the point of view. It was indeed recently demonstrated that the contin-
present case), T being the ambient temperature (namely 293 K in uous ow of ascending bubbles strongly modies the mixing and
the present case), MCO2 being the molar mass of CO2 (44 g mol1 ), convection conditions of the liquid medium [5052]. In turn, the
and P0 being the atmospheric pressure (close to 105 Pa). CO2 discharge by diffusion through the free air/champagne inter-
Besides, Table 2 compiles losses of dissolved CO2 concentra- face may be considerably accelerated, as well as the release of the
tions (with regard to the initial concentration ci before pouring of numerous VOC, which both strongly depend on the mixing ow
ci 11.5 g L1 ) as well as the corresponding volume of gaseous CO2 conditions of the liquid medium [53]. The photographs displayed
escaping during the pouring step. It is worth noting that during in Fig. 10, done with the laser tomography technique, shows the
the few seconds of the champagne-like way of serving, cham- ow patterns driven by ascending bubbles, and which consider-
pagne loses approximately as much dissolved CO2 as during the ably increase the release of gaseous CO2 and VOC [5052]. Sufce
10 G. Liger-Belair et al. / Analytica Chimica Acta 732 (2012) 115
Table 3
Geometrical parameters linked with each type of drinking vessel lled with 100 mL of champagne, and concentration of dissolved CO2 found in champagne after pouring it
in each type of drinking vessel.
Type of vessel Liquid level after Surface area offered to gas Initial concentration of dissolved CO2
pouring, h (in cm) discharge, A (in cm2 ) in the glass, after pouring (in g L1 )
to say that a strong coupling therefore nally exists between rising 4.1.1. The progressive loss of dissolved CO2 with time
bubbles, glass shape, CO2 discharge and avor release. From the For each type of drinking vessel, the corresponding loss of dis-
tasters point of view indeed, the perception of wine avors was solved CO2 concentration with time, all along the rst 10 min
also clearly found to be inuenced by glass shape [54,55]. following pouring, is displayed in Fig. 11. Despite signicant stan-
Quite recently, glassmakers showed interest in proposing to dard deviations (mainly attributed to the difcult repeatability of
consumers, a new generation of champagne tasting glasses, espe- the manual pouring process between the six successive pouring
cially designed, with a well controlled CO2 release all along tasting. and time series data records conducted for each type of drinking
This is the reason why, in recent years, much interest has been vessel), it is clear from Fig. 11 that the progressive loss of dis-
devoted to depict each and every parameter involved in the release solved CO2 concentration with time is signicantly higher when
of gaseous CO2 from glasses poured with champagne or sparkling champagne is served in the coupe than in the ute. From the taster
wine. point of view, this observation is of importance for both the visual
aspect of champagne tasting and its mouth feel sensation. Actu-
ally, it was shown that the higher the concentration of dissolved
4.1. Flute versus coupe CO2 in champagne, the higher the kinetics of bubble nucleation, the
larger the average bubbles size, and nally the more effervescence
In case of champagne and other sparkling wine tasting, two quite in the glass [5,6]. Moreover, it is also well known in champagne,
emblematic types of drinking vessels have coexisted for decades: and in other sparkling beverage tasting, that the higher the con-
(i) the classical ute, namely a long-stemmed glass with a deep centration of dissolved CO2 , the higher the zzy sensation when
tapered bowl and a narrow aperture and (ii) the classical coupe, bubbles burst over the tongue [710]. To the best of our knowledge,
namely a shallower glass with a much wider aperture. Advantages this is the rst set of analytical results concerning the inuence of
and disadvantages of both glass shapes have long been debated in glass shape on its progressive loss of dissolved CO2 concentrations
popular wine magazines, nevertheless without bringing any ana- with time in tasting conditions, and therefore the rst analytical
lytical data corresponding to each type of drinking vessel. proof that a long-stemmed glass with a deep tapered bowl and a
Due to their very different geometrical properties, the rate at narrow aperture prolongs the drinks chill and helps to retain its
which gaseous CO2 escapes was therefore supposed to signi- effervescence, by contrast with a shallower coupe of much wider
cantly differ from these two types of drinking vessel. Recently, aperture.
measurements of CO2 volume uxes outgassing from champagne
were done, during the rst 10 min following pouring [39]. In order
to avoid the randomly located bubbling environment inevitably
provided in glasses showing natural effervescence, single standard
utes and coupes identically etched on their bottoms were used for 8
this set of experiments thus providing a standardized and arti- Flute
cial effervescence [38,39]. Between the successive pouring and Coupe
time series data recordings, the ute and the coupe were systemat- 7
ically thoroughly washed in a dilute aqueous formic acid solution,
rinsed using distilled water, and then compressed air dried. This
drastic treatment limits the potential formation of calcium car- 6
bonate crystals on the ute wall, as well as the adsorption of any
CL (g L )
-1
2,0 70
Coupe Flute
1,8 Flute
60 Coupe
Total CO2 volume flux (cm s )
-1
1,6
3
1,4 0,4 50
FUS (mm3 s cm )
-2
1,2 0,3
40
-1
1,0 0,2
0,8 30
0,1
0,6 0,0
20
200
300
400
500
600
0,4
10
0,2
0,0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
t (s) t (s)
Fig. 12. Total CO2 volume uxes recordings (in cm3 s1 ) desorbing from a ute and Fig. 13. CO2 volume uxes per unit surface (in mm3 s1 cm2 ) as determined with
coupe respectively lled with 100 mL of champagne, all along the rst 10 min fol- Eq. (7), desorbing from a ute and a coupe respectively lled with 100 mL of cham-
lowing the pouring process; each datum of each time series is the arithmetic average pagne, all along the rst 10 min following the pouring process.
of six successive values recorded from six successive pouring.
uxes outgassing from the ute become higher than those out-
gassing from the coupe (see the inset in Fig. 12). However, it is
4.1.2. Kinetics of CO2 uxes outgassing from both the ute and worth noting that, from the point of view of champagne and other
the coupe sparkling wine tasting, the pertinent parameter which character-
In champagne and other sparkling wine tasting, in addition to izes a given type of drinking vessel with regard to its progressive
the visual aspect of effervescence and mouth feel both depending CO2 release with time is not really the total CO2 volume ux out-
(among many other parameters) on the dissolved CO2 concentra- gassing from it. Actually, the open aperture of tasters nostrils being
tion cL (t) an other important aspect is the smell or nose of the obviously much smaller than the surface area of the drinking vessel
wine, the so-called bouquet [11,12]. Effervescence of champagne offered to total gas discharge, we proposed a more adapted ana-
and other sparkling wines is strongly suspected to promote the lytical parameter in order to compare the progressive CO2 release
development of aromas in the headspace above the glass. The myr- from various glasses, namely the CO2 volume ux per unit surface
iad of bubbles nucleating on the utes wall and travelling through area, denoted FUS , and deduced as follows for each type of drinking
the wines bulk is expected to enhance the release of volatile organic vessel:
compounds by considerably enhancing exchange surfaces between
FT
the wine and the atmosphere. It is worth noting that, in a typi- FUS = (7)
cal ute poured with champagne or sparkling wine, approximately A
50 000 bubbles would have already nucleated, rose and nally with FT being the total CO2 volume ux outgassing from each type
exploded during the rst 3 min following pouring [5]. Each bubble of drinking vessel (given in Fig. 12), and A being the free surface
having a diameter close to 1 mm, this cloud of 50 000 bubbles total- area of the given type of drinking vessel (given in Table 3). CO2
izes a global exchange surface of approximately 1500 cm2 during volume uxes per unit surface area outgassing from each type of
the rst 3 min following pouring. This is huge compared with the drinking vessel poured with 100 mL of champagne, are presented
area of the air/wine interface which rarely exceeds 20 cm2 in a clas- in Fig. 13. Fig. 13 shows that CO2 volume uxes outgassing per unit
sical ute. However, each bubble collapsing at the wines surface surface area are much higher in the ute than in the coupe, during
inevitably frees its tiny CO2 volume. Consequently, the inevitable the 10 min following the pouring process. From the point of view
counter party of the exhausting aromas effect attributed to bub- of champagne tasting, it means that the ute should nally enable
bles exchange surfaces, is to progressively bring gaseous CO2 in the higher concentrations of gaseous CO2 above the champagne free
headspace above the wines surface. It is indeed well-known that a surface during tasting (due to its narrower open aperture compared
sudden and abundant quantity of CO2 may irritate the nose during to that of the coupe), despite lower total CO2 volume uxes in the
the evaluation of aromas [1319]. rst 3 min following pouring [39].
The analytical parameter which characterizes the progressive Further determination of the gaseous CO2 concentration in the
release of gaseous CO2 desorbed from a glass poured with cham- headspace above the champagne free surface, a parameter use-
pagne is the total volume ux of CO2 escaping from the wine/air ful for champagne tasting, will be achieved by use of micro gas
interface. The total CO2 volume uxes outgassing from each type chromatography (GC) in a near future.
of drinking vessel poured with 100 mL of champagne, are presented
in the graph displayed in Fig. 12, during the rst 10 min following 4.2. The impact of champagne temperature
the pouring process. Experimentally, during approximately the rst
3 min following the pouring process, it is clear that total CO2 vol- In order to test the inuence of champagne temperature on the
ume uxes are signicantly higher when champagne is served in kinetics of CO2 release from a ute, experiments were performed at
the coupe than in the ute. Nevertheless, this tendency reverses three sets of champagne temperature, namely 4 C, 12 C, and 20 C,
from about 3 min until 10 min after pouring, and total CO2 volume respectively, in a temperature-controlled room [38]. The total CO2
12 G. Liger-Belair et al. / Analytica Chimica Acta 732 (2012) 115
1,2
T = 4 C 1,2 T = 4 C
T = 12 C T = 12 C
1,0
T = 20 C T = 20 C
1,0
CO2 volume flux (cm s )
-1
0,8
3
0,8
0,6
0,6
0,4
0,4
0,2
0,2
0,0
0 100 200 300 400 500 600
0,0
t (s) 4 5 6 7 8
-1
Fig. 14. Total CO2 volume uxes recordings (in cm3 s1 ) desorbing from a 100 mL
CL (g L )
ute poured with champagne, all along the rst 10 min following the pouring pro-
cess, and at three different champagne temperature; each datum of each time series Fig. 16. Total CO2 volume uxes recordings (in cm3 s1 ) desorbing from a ute lled
is the arithmetic average of six successive values recorded from six successive with 100 mL of champagne as a function of its dissolved CO2 concentration, and at
pouring; standard deviations correspond to the root-mean-square deviations of the three champagne temperatures.
values provided by the six successive data recordings.
Table 4
Viscosity and concentration of dissolved CO2 found in both champagne types (in the bottle, and after pouring 100 mL of champagne).
Champagne type Dynamic viscosity, Initial concentration of dissolved CO2 Initial concentration of dissolved CO2
(at 20 C, and in mPa s) in the bottle, before pouring (in g L1 ) in the ute, after pouring (in g L1 )
4.4. Development of a CO2 sensor based on near infrared atmospheric CO2 measurements. Concentrations of gaseous CO2
technology are in very good agreement with the standard atmospheric CO2
concentrations (approximately 380400 ppm), thus validating our
In champagne tasting, since a sudden and abundant quantity of experimental set-up. After the pouring process, signicant dif-
CO2 is known to irritate the nose during the evaluation of aromas, ferences in CO2 concentrations above the glass were evidenced
it seemed pertinent to us to develop a non destructive and non depending on whether it was poured with champagne or beer.
intrusive instrument able to monitor and quantify the concentra- Immediately after pouring, the level of gaseous CO2 above the glass
tion of gaseous CO2 , in tasting conditions. Laser diode spectrometry poured with champagne is approximately twice the one reached
proved to be an effective tool to provide accurate gaseous CO2 above the glass poured with beer (around 2.5% for champagne
concentration measurements, by infrared absorption spectroscopy against only 1.3% for beer). Then, the decrease of the gaseous CO2
[56]. In particular, a new generation of laser diodes emitting at concentration above the ute which ensues is faster for champagne
room-temperature near 2.7 m appear promising for the future than for beer. About 15 min after pouring, gaseous CO2 concentra-
development of highly compact laser sensors [57]. Based on this tions above the ute superimpose [58,59].
near-infrared laser technology, a compact CO2 sensor was therefore We were logically tempted to wonder why such differences
recently developed in order to quantify accurately the concentra- appear between champagne and beer. In order to depict our experi-
tion of gaseous CO2 found above glasses poured with champagne mental observations, the contribution of effervescence to the global
or sparkling beverages [58]. The spectrometer developed for the kinetics of CO2 release was discussed, and modeled by use of results
CO2 sensing above champagne glasses is shown in Fig. 18. A lot of developed over recent years on the bubble rise, growth, and col-
preliminary experiments have been necessary to develop a com- lapse at the liquid surface.
plete protocol for measurements, such as isolation of the set-up
and cleaning procedure of the glass before it was lled [59]. 4.5. The contribution of collapsing bubbles to CO2 volume uxes
Standard commercial champagne wine and beer were used for outgassing from a glass: a multi-parameter modeling
this set of preliminary experiments. In order to avoid the randomly
located bubbling environment inevitably provided in glasses The contribution of rising bubbles to the global kinetics of CO2
showing natural effervescence, a single standard ute etched at released from a sparkling beverage is quite easily accessible by tak-
its bottom was used, thus providing a standardized and arti- ing into account the whole number of nucleation sites in the glass,
cial effervescence. Gaseous CO2 concentrations were monitored the average frequency of bubble production from a nucleation site,
above the ute poured with champagne or beer, all along the rst and the average size of a bubble as it reaches the liquid surface (to
25 min following pouring. It is worth noting that, in order to cal- nally collapse and release its CO2 content above the liquid surface).
ibrate our instrument, the rst 5 min of each data processing on The frequency of bubble formation from a single bubble nucleation
champagne or beer (before pouring), systematically correspond to site, denoted f, was modeled in previous works and found to obey
the following scaling law [6]:
DT (cL kH P)
f (8)
1,4 P
YC
OC
1,2
CO2 volume flux (cm s )
-1
1,0
3
0,8
0,6
F
0,4
0,2
0,0
0 100 200 300 400 500 600
t (s)
Fig. 17. Total CO2 volume uxes recordings (in cm3 s1 ) desorbing from a 100 mL Fig. 18. A three-dimensional view of the infrared diode laser spectrometer designed
ute poured with YC and OC samples, respectively. to monitor gaseous CO2 concentrations above glasses poured with carbonated bev-
Reprinted with permission from Ref. [45]. erages.
14 G. Liger-Belair et al. / Analytica Chimica Acta 732 (2012) 115
with T being the liquid temperature, cL being the bulk concentra- Acknowledgments
tion of dissolved CO2 , kH being the Henrys law constant, P being
the ambient pressure, and D being the diffusion coefcient of CO2 Many thanks to Marielle Bourget and Herv Pron, for their
molecules dissolved into the liquid medium. constant and precious help with the high-speed infrared imaging
The diameter of a bubble reaching the liquid surface, denoted d, device. Thanks are due to the EuroplAgro institute and to the Asso-
was also found to depend on various parameters as follows [5,30]: ciation Recherche Oenologie Champagne Universit for nancial
support, and to Thierry Gasco, chef de cave of Champagne Pom-
2/9 c k P 1/3
L H mery, for regularly supplying us with various champagne samples.
d T 1/3 D2/9 h1/3 (9)
g P Authors are also indebted to the Rgion Champagne-Ardenne, the
Ville de Reims, and the Conseil Gnral de la Marne for supporting
with being the liquid density, g being the acceleration due to our research.
gravity, and h being the distance travelled by the bubble from its
nucleation site.
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