FLAVOUR AND FRAGRANCE JOURNAL, VOL.

2, 13-16 (1987)

On the Genuineness of Citrus Essential Oils. Part XV. Detection

of Added Orange Oil Terpenes in Lemon Essential Oils
Antonella Verzera, Antonella Cotroneo and Giovanni Dugo*
Dipartimento Farmaco-Chimico, Facoltd di Farmacia, Universitd, 98 I00 Messina, Italy

Franco Salvo
Dipartimento di Chimica organica e biologica, Facoltd di Scienze. Universitd, 98 I00 Messina, Iialy

Sicilian lemon essential oil is a very high quality product which is offered to the international market at prices that
are higher than those of the lemon essential oils produced in other citrus-growing countries.
Market competition sometimes leads producers to ‘blend’ genuine essential oil with less expensive products,
which are generally ‘citral’ and orange terpenes.
These terpenes, which are usually obtained from orange essential oil produced abroad, possess characteristics
which modify the composition of lemon essential oil, even if added in only moderate quantities.
In particular, the percentage of A3-carene and the ratios of A3-carene/a-terpinene and A3-carene/camphene can
provide a good indication of the possible addition of orange essential oil or vf by-products obtained’therefrom to
genuine lemon essential oil.
After a study made on a great number of genuine lemon essential oils, on several samples of sweet orange
terpenes, and on a large number of lemon oil and orange terpene blends we propose a gas chromatographic
method which allows the detection of the addition of even 5% of sweet orange oil terpenes to genuine lemon
essential oils.

K E Y WORDS Lemon essential oil Genuineness determination

INTRODUCTION products, without trying to meet its competitors at

Genuine Sicilian lemon essential oil, for several
reasons, among which is basically, the lack of
efficient coordination between the citrus-
processing industry and the nation’s citrus grow-
ers, is offered on the international market at
prices which are considerably higher than those of
lemon essential oils produced in other citrus-
growing countries.
However, despite the disadvantage of a cost
which is at least double that of essential oil pro-
duced in Argentina or in California, cold-pressed
Sicilian lemon essential oil is highly valued and is
able to find an outlet on the international market
owing to the superior quality of its odour.
It has always been our opinion that, in order to
defend its position on the international market,
the Italian citrus-processing industry must have its
basis on the genuineness and high quality of its
‘Author to whom correspondence should be addressed.
their price levels. Bringing the price of Italian
products such as, for example, lemon essential oil
down to the price levels of essential oils produced
abroad necessarily implies the addition of a less
valuable product to the genuine oil, because it is
impossible to count upon a reduction in costs.
In fact, market competition, in addition to the
low degree of interest on the part of some buyers
in the quality of the product, sometimes induces
some producers to blend cold-pressed essential oil
with other, less costly products.
One of the most common ‘dilutions’,which also
requires the separate addition of extraneous
‘citral’ (the commercial fraction) ,is accomplished
by using terpenes obtained from orange essential
oil produced abroad, as this is economically more
convenient than the analogous product obtained
from Italian produced oil, even though the latter
is more readily available and has highly suitable
odour characteristics. However, the composition
of oil produced abroad does not show substantial

0882-5374/87/010013-04$05.00 Received I7 February 1987

0 1987 by John Wiley & Sons, Ltd. Amended version 29 May 1987; Accepted 29 May I987
14 A. VERZERA E T A L.
differences when compared to the Italian product.
Following our researches which aim at the safe-
guarding of genuine lemon essential oil,’-’ we
have perfected a method based upon direct gas
chromatographic analysis, which allows the detec-
tion of possible additions of sweet orange ter-
penes to genuine lemon essential oil, and which
forms the basis of the report contained in this
paper.
EXPERIMENTAL
The research was carried out upon:
- 831 samples of lemon essential oil, which
were undoubtedly genuine, produced with the
usual industrial techniques (‘pelatrice’,
‘sfumatrice’, ‘torchi’ and FMC) during the
1982-83, 1983-84, 1984-85 citrus seasons,
and which had been analysed during previous
researches on lemon essential oils;
- 7 samples of terpenes obtained from sweet
orange essential oil, of which 6 were produced
abroad and 1 was produced in Sicily and
which were representative of commercially
obtainable products;
- numerous laboratory-prepared blends,
obtained by the addition to genuine lemon
essential oil of the seven samples of orange
terpenes, in percentages varying from 5% to
20%.
All the samples were analysed by gas
chromatography using Carlo Erba instruments on
SE 52 capillary columns, under the same condi-
tions described previously.’
RESULTS AND DISCUSSION
Figure 1 shows the chromatograms of a genuine
lemon essential oil and of sample of orange ter-
penes; the components which determine the
fundamental differences between the two pro-
ducts are indicated on the chromatograms.
The samples of orange terpenes are completely
lacking in carbonyl compounds (‘citral’), esters
and sesquiterpenes. When compared to lemon
essential oil, they also show much smaller quan-
tities of a-thujene, P-pinene, y-terpinene and
terpinolene.
Orange terpenes, as well as the orange essential
oil from which they are derived, are characterized
by the presence of about 0.10%of A3-carene,which
is practically absent in lemon essential oil, and by
the almost complete absence of a-terpinene and
of camphene which in lemon essential oil are
found in percentages of about 0.20% and 0.06%
respectively.
It can be expected, therefore, that the addition
of orange oil terpenes to a lemon essential oil will,
in consequence, lower the ‘citral’ content and the
percentage of a-thujene, P-pinene, y-terpinene,
camphene and a-terpinene, and increase the per-
centage of A3-carene.
It is fairly simple, in general, to correct the
composition of a product by the addition, if avail-
able, of suitable amounts of certain components;
while it is decidedly more complicated, and at
times practically impossible, to select and elimi-
nate a single component out of a blend in which
other components having very similar chemical or
physical properties are also present. Therefore,
we consider that the A3-carene content, and the
percentage ratios of the latter in regard to cam-
phene and a-terpinene, are particularly suited to
indicate the possible presence of orange terpenes
in lemon essential oil.
We have calculated, for the samples of genuine
lemon essential oil, the average percentage of
A3-carene and the ratios between A3-carene and
a-terpinene and between A3-carene and cam-
phene. We have also calculated, for these three
parameters, the standard deviation and the 99%
confidence interval calculated by the Poisson
distribution method (I(= X & 2.75s).
The above values are reported in Table 1.
Table 2 indicates the frequency with which the
values of the three parameters considered were
registered for the 831 samples of lemon essential
oil tested.
We can observe, from the results reported in
Table 2, that in about 90% of the cases, genuine
lemon essential oil shows A’-carene values below
0.006%; the A3-carene/a-terpinene ratio shows
Table 1. Values for the A’-carene content and the
A3-carene/a-terpinene and As-carene/camphene ratios in
genuine lemon essential oils
x s 99%1confidence limits
A3-carene (%) 0.004 0.0016 0.000-0.008
A3-carene/a-terpinene 0.021 0.0090 0.000-0.044
A’-carene/camphene 0.067 0.0240 0.005-0.129
 ORANGE OIL TERPENES IN LEMON ESSENTIAL OIL
LEMON OIL
!
ORANGE
TERPENES
l
I I
m
m
r- ro r-
a 0 2 P
Fig. 1 . Chromatograms of a lemon essential oil and of sweet orange oil terpenes
values below 0.040, and the A3-carene/camphene
ratio is below 0.100.
The seven samples of orange terpenes used
showed a A3-carenecontent between 0.070% and
0.140%; and the values for the ratios between
A3-carene, camphene and a-terpinene were very
high owing to the presence of the latter two
components in traces only.
Table 3 reports the 99% confidence limits for
the three parameters investigated calculated on
the basis of the average values and the standard
deviations for genuine lemon essential oils, and
the results obtained for groups of blends of lemon
essential oils and orange oil terpenes.
As can be observed from the results reported in
Table 3, blends containing 10% and 20% of the
orange oil terpenes showed considerably 'higher
values for the three Darameters considered than
15
I I I
ro
m 0
Ir)
ro
r- 0
ID
O
N N m m m e
those registered for the genuine lemon essential
oils-which left no doubt as to the presence of
orange terpenes. The results for the 5% blends
are valid enough to indicate additions even if
some of the parameters registered values which
were only slightly higher than the maximum val-
ues recorded for the genuine oils.
Even though a minimum quantity of orange
terpene can always be detected, its amount can-
not be determined with precision, for much
depends upon the composition both of the essen-
tial oil and of the orange oil terpenes utilized in
the blend. However, considering that the orange
oil terpenes tested were representative of the
products found on the market, and considering
the standard used in the choice of the essential
oils (low A3-carene content), we believe that the
detection of a 5% addition of orange terDenes to a
16 A. VERZERA ET A L .

Table 2. Values for the percentage of A3-carene, the A3-carene/a-terpinene and

A3-carene/camphene ratios, and the number of samples of genuine lemon essential oils for which
they were registered

A3-carene Number of A3-carene/ Number of A3-carene/ Number of

(%I samples a-terpinene samples camphene samples

0.002 16 0.009-0.010 14 0.029-0.040 22

0.003 325 0.011-0.020 480 0.041-0.060 355
0.004 27 1 0.021-0.030 218 0.G61-0.080 282
0.005 66 0.031-0.040 71 0.081-0.100 83
0.006 56 0.041-0.050 31 0.101-0.120 39
0.007 46 0.051-0.060 17 0.12 1-0.140 50
0.008 32
0.009 19

Table 3. Values for the A3-carene content, the A3-carene/a-terpinene and A3-carene/camphene ratios
for genuine lemon essential oils, and 6 out of 30 random examples of the values registered for the same
components in samples of lemon oils with 5%, 10%. and 20% additions of orange terpenes

Lemon oils Lemon oils with orange terpenes added

99% confidence limits

Min. Max. 5% 10% -20% 5% 10% 20%

A3-carene (%) 0.000 0.008 0.014 0.022 0.032 0.010 0.016 0.024
A’-carene/a-terpinene 0.000 0.044 0.086 0.146 0.254 0.056 0.093 0.170
A3-carene/camphene 0.005 0.129 0.274 0.468 0.744 0.182 0.320 0.510

5% 10% 20% 5% 10% 20%

A’-carene (96) 0.008 0.012 0.021 0.009 0.014 0.020

A3-carene/a-terpinene 0.046 0.069 0.191 0.044 0.070 0.104
A3-carenelcamphene 0.163 0.226 0.467 0.145 0.241 0.328

5% 10% 20% 5% 10% 20%

A3-carene (%) 0.010 0.016 0.025 0.010 0.016 0.027

A’-carene/a-terpinene 0.050 0.088 0.153 0.051 0.088 0.166
A’--carene/camphene 0.160 0.286 0.510 0.164 0.296 0.574

genuine lemon essential oil is a concrete possi-
bility.
This limit confirms the validity of the method
proposed, considering that additions of less than
5% are of little commercial interest.
Acknowledgernenr-Research accomplished with a CNR con-
tribution as part of a research project on ‘Chimica fine e
secondaria’. Work Group Director: Professor Guglielmo
Stagno d’ Alcontres.
REFERENCES
2. A. Cotroneo, Giacomo Dugo. G. Licandro and G. Dugo,
Essenze Derivati Agrumari, 53, 291 (1983).
3. G. Dugo, A. Cotroneo, G. Licandro, Giacomo Dugo and
A. Verzera, Rivista Italiana Sostanze Grasse, 61, 441
(1984).
4. G. Dugo, G. Licandro, A. Cotroneo and A. Verzera, Arti I
Conferenza Nationale sugli Aromdzzanti, Salsomaggiore
Terme, 2-3 April 1984.
5. G. Licandro, G. Dugo, G. Lamonica and A. Cotroneo,
Essenze Derivari Agrumari, 54. 22 (1984).
6. A. Cotroneo, A. Verzera, F. Salvo and G. Dugo, Essenze
Derivati Agrumari, 54, 49 (1984).
7. A. Cotroneo, A. Verzera, G . Lamonica, G. Dugo and G.
Licandro, Nav. Fragr. J . , 1, 69 (1986).

1. G . Dugo, G. Licandro, A. Cotroneo and Giacomo Dugo,

Essenze Derivari Agrumari, 53, 173 (1983); 53, 218
(1983); 53, 258 (1983).