Investigation and sensory characterisation of 1,4-cineole:
A potential marker of Australian Cabernet Sauvignon wine aroma
Guillaume ANTALICKa , Sophie TEMPEREc,d, Katja ŠUKLJEa, John W. BLACKMANa,b,
Alain DELOIREa, Gilles DE REVELc,d, Leigh M. SCHMIDTKEa,b
a National
Wine and Grape Industry Centre, Charles Sturt University, Locked Bag 588, Wagga Wagga, NSW 2678, Australia.
b School of Agricultural and Wine Sciences, Charles Sturt University, Locked Bag 588, Wagga Wagga, NSW 2678, Australia.
Université de Bordeaux, EA 4577, ISVV, Unité de recherche Œnologie, Villenave d’Ornon, France
dINRA, ISVV, USC 1366 Oenologie, Villenave d’Ornon, France
c
Introduction
Identification and method development
Australian Cabernet Sauvignon wines aromas
have been
described using specific attributes such as “eucalyptus” and
“dried herbs” [1-2]. It has been established that 1,8-cineole plays
an important role in the occurrence of “eucalyptus” character in
Australian red wines [3]. The relationship between the presence
of eucalyptus trees in the vicinity of vineyards and the presence of
1,8-cineole in corresponding wines has also been reported [4].
In parallel, other studies have
suggested that the 1,8-cineole found
CH3
CH3
in Australian Cabernet Sauvignon
wines could also be directly derived
from grapes [5]. 1,4-cineole, another
monoterpene with a similar structure
O
O
to that of 1,8-cineole, has never been
identified in red wines. In contrast 1,4cineole has been identified at low
levels in many other plants which also
contained 1,8-cineole [6]. This study
CH3 H C
CH3
H3C
investigated the occurrence and
3
potential aromatic contribution of 1,41,8-cineole
1,4-cineole
cineole to Australian red wines.
Figure 2: 1,4-cineole mass spectrum (EI, 70 eV)
Figure 1: HS-SPME-GC-MS equipment
The 1,4-cineole identification in red wines consisted of the analyses of different Australian red wines and
solutions of 1,4-cineole in water and wine by HS-SPME-GC-MS. Peaks that displayed the identical mass
spectrum of 1,4-cineole were found in all the chromatograms at the same retention time that matched the
1,4-cineole retention index. A method for quantifying 1,4-cineole and 1,8-cineole by HS-SPME-GC-MS was
developed in combination of previously published method for wine volatiles [3,7]. The method was validated
with a limit of quantification for 1,4-cineole and 1,8-cineole calculated at 4 and 10 ng/L respectively using
octan-2-ol as internal standard.
Preliminary Investigation of 1,4-cineole occurrence in red wines
WINE AGE INFLUENCE ON 1,4-CINEOLE
EXPERIMENT
Concentration of
1,4-cineole (μg/L)
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
A range of commercial Australian red wines (104 in total), comprising of 51 Cabernet Sauvignon (mean age 3.5 years), 4
Cabernet Sauvignon/Merlot blends (mean age 7 years), 27 Shiraz (mean age 3.5 years) and 22 Pinot Noir wines (mean age
2 years) were purchased. The wines originated from different Australian regions, including important regions for Cabernet
Sauvignon wine production: Barossa, Coonawarra, McLaren Vale and the Margaret River. Twelve commercial French wines,
predominantly Cabernet Sauvignon-Merlot blends (mean age 6.5 years) from the Bordeaux region, were also analysed.
CULTIVAR EFFECT ON CINEOLES CONCENTRATION
French Cabernet
Sauvigon/Merlot
Australian Cabernet
Sauvignon
1995 2000 2004 2005 2008 2010 2011 2012 2013
Table 1: Mean concentrations ± SD (μg/L) of 1,4-cineole and 1,8-cineole in Australian Cabernet Sauvignon,
Shiraz, Pinot Noir. One way ANOVA was used to compare data. Means followed by different letters in a row
are significant at p ≤ 0.05 (Fischer’s LSD).
Compounds
Years
Figure 2: Effect of wine age on 1,4-cineole in Australian and French red wines.
Wines
Cab. Sauv.
(n = 52)
Shiraz
(n = 27)
Pinot Noir
(n = 22)
1,4-cineole
0.59 ± 0.33a
0.07 ± 0.04c
0.22 ± 0.2b
1,8-cineole
2.82 ± 3.26 a
1.75± 1.42a
0.99 ± 0.33b
The analysis of different vintages of a unique Australian and French wine label from different vintages showed that
the concentration of 1,4-cineole increased with wine age (Figure 2). 1,4-cineole has been previously reported in an
aged Riesling wine [8], suggesting that 1,4-cineole might be chemically synthesised during wine ageing.
Sensory characterisation of 1,4-cineole in red wines
1,4-cineole was detected in all the wines analysed, with concentrations ranging from 0.023 to 1.6
μg/L. An important varietal effect was observed, with an average concentration 8.4 and 2.7 fold
higher in Cabernet Sauvignon wines than in Shiraz and Pinot Noir wines respectively (Table 1).
SENSORY IMPACT LEVEL
Level of sensory impact of 1,4-cineole
in Cabernet Sauvignon wines
* p = 0.03
1.4
p = 0.08
Concentration of
1,4-cineole (μg/L)
1.2
1
0.8
0.6
0.4
0.2
0
MR
Cwarra
Bar/McLV
Significant
variations
in
1,4-cineole
concentrations were observed between
Cabernet Sauvignon wines from different
Australian regions, despite similar vintages
being analysed. The wines that originated
from Margaret River exhibited higher
concentrations of 1,4-cineole than wines
from Barossa, McLaren Vale and to a lesser
extent Coonawarra regions.
Proportion of wines (%)
GEOGRAPHIC ORIGIN INFLUENCE ON 1,4-CINEOLE
100
90
80
70
60
50
40
30
20
10
0
Shiraz
Pinot Noir
Cab. Sauv.
<0.2
0.2-0.5 0.5-0.8 0.8-1.0 1.0-1.6
The sensory impact level of 1,4-cineole was assessed in a
French Cabernet Sauvignon wine using a series of triangle
tests. An addition of 0.54 μg/L of 1,4-cineole in a French
Cabernet Sauvignon wine, to produce a
final
concentration of 0.63 μg/L, was required before it was
detected by the panel (n = 18). 60% of Australian Cabernet
Sauvignon wines exhibited higher concentrations of 1,4cineole than its sensory impact level. This proportion was
only 9% for Pinot Noir wines whereas Shiraz wines were
all below 1,4-cineole impact level (Figure 5).
Concentration of 1,4-cineole (μg/L)
Figure 5: Sensory impact level of 1,4-cineole in Australian red wines
DESCRIPTIVE ANALYSIS
Figure 3: Effect of geographic origin on 1,4-cineole
concentration in Australian Cabernet Sauvignon wines.
One way ANOVA was used to compare data. All quoted
uncertainty is the standard deviation of each group of
wines.
a
0.3
***
0.25
0.2
0.15
0.1
0.05
0
Australia
France
a
0.6
The average concentration of 1,4-cineole
was 2.4 fold lower in the French wines in
comparison
to
Australian
Cabernet
Sauvignon wines (single variety wines and
blends) despite the greater age of French
wines. This regional difference increases
considering wine age (Figure 4).
0.4
0.2
a
ab
b
0
-0.2
-0.4
0.8
Normalized score
Barossa Valley
McLaren Vale
Coonawarra
Normalized score
Ratio Concentration of 1,4cineole: Wine age (μg/L/year)
Margaret River
bay leaf
hay
0.6
0.4
CS+1,4c
CS+1,8c
CS+1,4c+1,8c
b
b
CS
CS+1,4c
CS+1,8c
0
-0.2
-0.4
-0.6
CS
b
0.2
-0.6
CS+1,4c+1,8c
-0.8
Figure 6: Evaluation of the contribution of 1,4-cineole and 1,8-cineole to hay and bay leaf aromas in Cabernet Sauvignon wines using the deviation
from reference method [9], and expressed in normalized score (33 panelists).
Figure 4: Comparison of 1,4-cineole concentration:wine age ratio between Australian and French Cabernet Sauvignon
wines (single variety and blended wines included).
[1] Robinson et al., 2011, Aust. J. Grape Wine Res., 17, 327-340
[2] Halliday, 2011, Australian Wine companion.
[3] Capone et al., 2011, J. Agric. Food Chem., 59, 953-959
[4] Capone et al., 2012, J. Agric. Food Chem., 60, 2281-2287
[5] Kalua and Boss, 2010, Aust. J. Grape Wine Res. 16, 337-348.
[6] Romagni et al. 2000, J. Chem. Ecol. 26, 303-313.
[7] Antalick G.,et al., 2015, J. Agric. Food Chem., DOI 10.1021/acs.jafc.5b00966.
[8] Simpson R F. and Miller G. C., 1983, Vitis, 22, 51-63.
[9] Larson-Powers N., and Pangborn R.M., 1978, J. Food Sci., 43, 47-51.
This project was partly funded by Australia’s grapegrowers and winemakers through their investment body, the Australian Grape and Wine Authority,
with matching funding from the Australian federal Government, NWGIC/Charles Sturt University and ISVV/Bordeaux University. The collaboration
between NWGIC and ISVV has been performed through Oenoviti network.
www.csu.edu.au/nwgic
The tests were performed by comparing the aromatic perception of the hay and bay leaf reference standards to the same
base wine (CS) that had been spiked with 1,4-cineole (1.6 μg/L) and/or 1,8-cineole (2.5 μg/L). For each test, the panel
assessed the olfactory similarity of the samples compared to the standard presented. The ANOVA and Duncan post-hoc
test showed the addition of 1,4-cineole, both independently and in combination with 1,8-cineole, enhanced hay aromas in
comparison to the control wine (p<0.05) (Figure 6). The intensity of bay leaf notes were significantly enhanced by the
association of 1,4-cineole and 1,8-cineole (p<0.05) (Figure 6).
These findings highlight that 1,4-cineole may contribute to the hay and dried herb aromas that have been reported in
Australian Cabernet Sauvignon wines.
The National Wine and Grape Industry Centre is a research centre within Charles Sturt University in alliance with the Department of Primary Industries NSW and the NSW Wine Industry Association