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On the Genuineness of
Essential Oils. Part XXX.
Detection of Distilled Essential
Oils Added to Cold-pressed
Mandarin Essential Oils
a a
Antonella Verzera & Antonella Cotroneo
a
Ildefonsa Stagno d'Alcontres and Maria Grazia
Donato Dipartimento Farmaco-chimico, Facoltà di
Farmacia , Università di Messina , Messina, Italy
Published online: 28 Nov 2011.

To cite this article: Antonella Verzera & Antonella Cotroneo (1992) On the
Genuineness of Essential Oils. Part XXX. Detection of Distilled Essential Oils Added to
Cold-pressed Mandarin Essential Oils, Journal of Essential Oil Research, 4:3, 273-280,
DOI: 10.1080/10412905.1992.9698061

To link to this article: http://dx.doi.org/10.1080/10412905.1992.9698061

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 RESEARCH REPORT J. Essent. Oil Res., 4,273-280 (Maygun 1992)

On the Genuineness of Essential Oils.

Part XXX. Detection of Distilled
Essential Oils Added to
Cold-pressed Mandarin Essential Oils

Antonella Verzera, Antonella Cotroneo,”

Downloaded by [New York University] at 10:31 05 May 2015

Ildefonsa Stagno dAlcontres and Maria Grazia Donato

Dipartimento Farmaco-chimico, Facoltk di Farmacia
Universitk di Messina, Messina, Italy

Received: February 1991

Revised: June 1991

ABSTRACT: The oil obtained by distillation of the liquid of the screw-pressed residues
of the cold-extraction of mandarin oil, and the cold-pressed mandarin oil have been
examined using capillary GC. Thirty-six components were characterized in both oils. The
results of 266 analyses of cold-pressed mandarin oil, 29 analyses of distilled mandarin oil
and 26 analyses of mixtures of 5-20% of distilled oil mixed with cold-pressed oil are
presented. Component ratios of terpinen-4-01 with cis-sabinene hydrate, trans-sabinene
hydrate, citronella1and decanal have been used to detect the additions of the less valued
distilled oil in the cold-pressed oil. In most cases the component ratios found in mixtures
of 10% distilled oil in cold-pressed oil can be used to infer that such a mixture has taken
place. Nevertheless, because of wide component value ranges found in both the cold-
pressed and distilled oils it remains difficult to determine the lower limits of adulteration
detection.

KEY WORD INDEX: Citrus reticulata, mandarin, Rutaceae, cold-pressed mandarin oil,
distilled mandarin oil, adulteration.

INTRODUCTION: “Peratoner” is the essential oil obtained by distillation from the

liquids of the screw-pressed residues of cold-extraction of citrus oils and from other waste
liquors. These products, which are less valuable than the cold-pressed oils, are usually
obtained by batch distillation and seldom in continuous distillation.

The distilled products, which were banned until some years ago, are now permitted to be
traded. The Italian law (1)allows their production and trade now and the technology of

‘Senior author
Originally presented at 1 Congress0 Nazionde di Chimica degli Alimenti, Messina e Giardini-
Naxos, 9-13 October 1990.

1041-2905/92/0003-0273$04.00/0-01992 Allured Publishing Corp. 273

 274 JOURNAL O F ESSENTIAL OIL RESEARCH

producing thein has advanced to a point where tlie recovery of good quality products call
be achieved.

As previously noted for lemon oil ( 2 ) ,and also for tlie mandarin oil, tlie two products show
notable differences in composition. For example, citronellal and cis- and trans-sabinene
hydrate are present in smaller proportions in tlie distilled oils than in the cold-pressed oils.
The distilled products possess unusual component percentages, resulting in higher levels
of some alcohols (such as tei-pinen-4-01, a-terpineol and octanol) than normally found in
tlie cold-pressed oils. The formation ofthese alcohols is thought to be due to tlie conversion
of some of the essential oil components during distillation. These differences between tlie
two products make it easy to distinguish a cold-pressed oil from a distilled oil, even so it is
difficult to detect small additions of one to the other.

Because of tlie veiywide range of tlie values found for the components ofcold-pressed oils
and distilled oils, only an investigation of a large nuniber of samples of cold-pressed oils,
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distilled oils and their niixtures can provide enough information to detect tlie additions.

Considering the results previously obtained on tlie cold-pressed mandarin oils produced
over four productive seasons (3,4),we suggest a survey of the value of the ratios between
teq%nen-4-o1(which is present in high percentage in tlie distilled oils) and citronellal, cis-
and trans-sabinene hydrate (which are present in lower amounts in distilled oils than in tlie
cold-pressed ones). Another useful ratio is te1~~inen-4-o~decana1, the decanal showing a
similar value both in the cold-pressed oils and in the distilled oils.

EXPERIMENTAL: The investigation was carried out analyzing:

266 saniples of cold-pressed Sicilian and Calabrian mandarin essential oils, absolutely
genuine, produced in industiy by "pelatrice" (peel machine) or "torchi" (screw-
press), over the 1982-1983, 1983-1984, 1984-1985 and 1985-1986 productive sea
sons, the features of which have been previously described (3,4);
29 samples of distilled mandarin essential oils; and
26 mixtures obtained by adding 5 2 0 % of distilled to cold-pressed essential oils.

The mixtures have been prepared using eight oils of the 1988-1989productive season and
five distilled oils. Four oils were representative of tlie first part of the productive season,
obtained from green mandarins and tlie other four were representative of the second part
of tlie season, obtained from ripe red mandarins. Their coinpositions fell within tlie range
of the 266 oils considered a s reference; tlie content of teq1inen-4-ol being lower for five
of them and scarcely higher than the average content for three of them.

We chose tlie five distilled oils at random after having discarded those showing tlie highest
content of terpinen-4-01.

Each saniple \vas analyzed by GC using a Carlo Erba chroinatograph 5160 Mega Series,
equipped with a Sliiinadzu data processor C-R3A using the follo\Ying experimental
conditions previously used for lemon (5)and inandarin (6)oils: glass capillary column, 25
m x 0.32 nini i.d. coated with SE 52; column temperature, 60°C (8 minutes) to 100°C at
3°C/niin, to 130°C at 2.S°C/min, to 180°C at SoC/min;injector and detector temperatures:
280°C; carrier gas: hydrogen, 0.4 kglcin'; injection mode, split; detector, FID.

The compounds were identified by retention times and by GUMS using a Finnigan Model
4021 system, with a 25 in x 0.35 inin i d . fused silica capillary column coated with D131,
column temperature 50°C (3 inin) to 200°C at 5"C/min; ionizing voltage, 70 eV. Quanti-
tative coinposition of each sample was obtained from normalized peak areas.
 JOURNAL OF ESSENTIAL OIL RESEARCH 275

C D L M L S S E O M O A R I N ESSENTUL O I L
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OlSTlLLEO M O A R l N E S S E N T I U 011

f O N
- d
- O I
,, D
<* c
*, ”
0,
-
e
m
-
. m
f
-
n

Figure 1. Chromatograins of cold-pressed and distilled inandarin oil

RESULTS: Table I shows the average percentage composition, expressed as single

components and as classes of compounds, of the 266 samples of mandarin oil. Table I1
shows the average percentage composition, expressed as single components and as classes
of compounds, of the 29 samples of distilled oil of mandarin.

The tables also show the minimum and rnaxiinuin values observed for each parameter.
Figure 1 shows the chromatograms of a cold-pressed mandarin oil and of a distilled oil.

The data presented in these tables and figure clearly shows that alcohols are the most
important constituents for differentiation between the two products because in the
distilled oils the relative alcohol percentage is 0.69-1.52% while in cold-pressed oils it is
only found in amounts of 0.45%. The greatest differences are found in the following
compounds: linalool, octanol, a-terpineol and terpinen-4-01, In particular terpinen-4-01
has an average value (0.~ 0 . 4 8 %which
) is three times higher in the distilled oils than the
maxiinuin content (0.08%) found in the cold-pressed oils. This high concentration of
alcohols, which is typical of the essential oils obtained by distillation, especially in acid
medium, is due to addition of water molecules to double bonds of some monoterpenes.

Besides, distilled oils show very low content of citronella1 and cis- and trans-sabinene
hydrate; the latter two alcohols are sometimes not found in the oils.
 276 JOURNAL OF ESSENTIAL OIL RESEARCH

Table 1. Composition of cold-pressed mandarin oils

~

X S Min Max
a-thujene 0.89 0.058 0.73 1.06
a-pinene 2.36 0.119 2.03 2.74
camphene 0.02 0.002 0.01 0.02
sabinene 0.26 0.016 0.23 0.34
P-P'inene 1.68 0.104 1.39 2.10
myrcene 1.70 0.052 1.57 1.84
octanal 0.16 0.033 0.06 0.20
a-phellandrene 0.05 0.012 0.02 0.09
a-terpinene 0.44 0.038 0.26 0.52
p-cymene 0.33 0.155 0.1 0 1.38
limonene 69.51 1.689 65.30 74.26
(Z)-p-ocimene t t 0.01
(E)-P-ocimene 0.02 0.004 0.01 0.04
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y-terpinene 19.85 1.160 16.40 22.75

cis-sabinene hydrate 0.03 0.011 t 0.07
octanol t t 0.01
terpinolene 0.87 0.051 0.72 1.01
trans-sabinene hydrate 0.04 0.022 0.01 0.10
linalool 0.1 1 0.033 0.04 0.19
nonanaI 0.03 0.006 0.01 0.04
citronella1 0.03 0.005 0.02 0.05
terpinen-4-01 0.04 0.014 0.01 0.08
a-terpineol 0.14 0.050 0.03 0.27
decanal 0.09 0.01 1 0.05 0.12
nerol + citronellol 0.02 0.005 t 0.05
neral 0.01 0.007 t 0.05
geraniol t t 0.01
geranial 0.04 0.01 1 0.01 0.10
alcohol 1 0.01 0.003 t 0.02
alcohol 2 0.01 0.003 t 0.02
thymol 0.05 0.020 t 0.11
undecanal 0.01 0.002 t 0.02
methyl N-methyl anthranilate 0.45 0.090 0.26 0.66
carbonyl compound 0.02 0.003 t 0.03
P-caryophyllene 0.10 0.012 0.07 0.14
a-humulene 0.01 0.002 t 0.02
oxygenated compound 0.02 0.004 0.01 0.03
sesquiterpene 0.04 0.006 0.03 0.06
a farnesene 0.15 0.046 0.06 0.32
a-sinensal 0.29 0.059 0.12 0.53

monoterpenes 97.98 0.378 96.79 98.81

sesquiterpenes 0.33 0.056 0.18 0.54
hydrocarbons 98.31 0.346 97.04 99.12
carbonyl compounds 0.67 0.102 0.36 0.97
alcohols 0.45 0.146 0.13 0.81
esters 0.45 0.090 0.26 0.66
oxygenated compounds 1.56 0.287 0.88 2.17
oxygenatedlhydrocarbons 0.02 0.003 0.01 0.02

t =trace
 JOURNAL OF ESSENTIAL OIL RESEARCH 277

Table II. Composition of distilled mandarin oils

~

X S Min Max
a-thujene 0.77 0.258 0.47 1.86
a-pinene 2.04 0.646 1.41 4.87
camphene 0.02 0.005 0.01 0.04
sabinene 0.22 0.055 0.09 0.33
P-pinene 1.70 0.289 1.17 2.60
myrcene 1.66 0.096 1.56 2.01
octanal 0.1 9 0.054 0.09 0.29
a-phellandrene 0.06 0.018 0.03 0.10
a-terpinene 0.48 0.072 0.25 0.60
p-cymene 0.38 0.1 87 0.20 0.94
limonene 69.92 1.773 66.28 73.33
(Z)-p-ocimene t t 0.01
(E)-p-ocimene
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0.02 0.003 0.01 0.03

y-terpinene 19.48 1.296 16.37 21.79
cis-sabinene hydrate 0.01 0.005 t 0.02
octanol 0.02 0.018 t 0.09
terpinolene 0.90 0.080 0.69 1.02
trans-sabinenehydrate 0.02 0.013 t 0.04
linalool 0.24 0.052 0.15 0.34
nonanal 0.03 0.009 0.02 0.06
citronella1 0.01 0.009 t 0.04
terpinen-4-01 0.32 0.082 0.18 0.48
a-terpineol 0.34 0.083 0.20 0.49
decanal 0.09 0.020 0.05 0.12
nerol + citronellol 0.04 0.010 0.02 0.06
neral 0.02 0.012 0.01 0.05
geraniol t t 0.01
geranial 0.06 0.020 0.03 0.1 1
alcohol 1 0.02 0.005 0.01 0.03
alcohol 2 0.01 0.004 t 0.02
thymol 0.06 0.031 0.01 0.13
undecanal 0.01 0.003 t 0.01
methyl N-methyl anthranilate 0.48 0.195 0.14 0.79
carbonyl compound 0.01 0.007 0.01 0.03
P-caryophyllene 0.06 0.017 0.03 0.09
a-humulene 0.01 0.002 t 0.01
oxygenated compound 0.01 0.005 t 0.02
sesquiterpene 0.02 0.007 0.01 0.03
a farnesene 0.08 0.035 0.02 0.16
a-sinensal 0.08 0.059 0.01 0.21

monoterpenes 97.60 0.582 96.62 98.57

sesquiterpenes 0.17 0.058 0.06 0.29
hydrocarbons 97.77 0.548 96.92 98.74
carbonyl compounds 0.52 0.120 0.25 0.71
alcohols 1.05 0.241 0.69 1.52
esters 0.48 0.195 0.14 0.79
oxygenated compounds 2.07 0.510 1.21 2.94
oxygenatedthydrocarbons 0.02 0.005 0.01 0.03

t = trace
 278 JOURNAL OF ESSENTIAL OIL RESEARCH

Table 111. Values of some ratios between areas of the peaks of the cold-
pressed mandarin essential oils and those of the mixtures of them with 5% of
oil obtained by distillation
I
95% confidence limits of the
cold-pressed essential oils Mixtures
~

X s Min Max 1* 2* 3** 4**

terpinen-4-oV
cis-sabinene hydrate 1.61 0.44 0.74 2.48 1.91 2.16 1.78 2.16
terpinen-4-oll
trans-sabinene hydrate 0.96 0.31 0.35 1.57 1.50 1.06 1.08 1.37
terpinen-4-ol/citronellal 1.26 0.44 0.40 2.12 2.25 2.30 1.20 2.03
terpinen-4-oVdecanaI 0.44 0.14 0.17 0.72 0.68 0.80 0.49 0.68
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* Essential oil from green mandarins + distilled oil

** Essential oil from red mandarins + distilled oil

Because of all these considerations, it is evident that any addition of distilled oils into cold-
pressed oils can be detected by examining the concentrations of the above mentioned
components. What seems important for the detection of distilled oils mixed in cold-
pressed oils is the determination of the following component ratios: terpinen-4-oVcis-
sabinene hydrate, terpinen-4-ol/trans-sabinene hydrate and terpinen-4-oVdecana1. The
last ratio mentioned is of particular use because as the two compounds are found close
together on the chromatogram possessing a similar relative percentage in the cold-pressed
oils, any modification, even a slight change in the ratio of the areas, will result in the easy
detection.

The average value, standard deviation and 95% confidence intervals of the ratios consid-
ered have been calculated from the values of the ratios obtained for each sample of
mandarin oil. For our research purposes we found that only the upper value of this interval
is important, the values of the ratios always increased and never decreased, when a distillate
was added to the cold-pressed oil. The results are reported in Table 111.

We calculated the ratios for each mixture of cold-pressed oiVdistilled oils analyzed.

Tables 111to V show the 95% confidence limits of the cold-pressed essential oils compared
with the values of the mixtures containing 5, 10 and 20% of distilled oil respectively.

What is immediately evident is that the ratio of terpinen-4-01 to citronella1 and to decanal
vary greatly when the amount of added distilled oil increases. For example the quantity of
terpinen-4-01which is approximately half the value of decanal in cold-pressed oils (Xof the
ratio terpinen-4-oVdecanal = 0.44), is almost equal to or higher than that of decanal in
mixtures with 20% distilled oil (terpinen-4-oVdecana1ratio = 0.80:1.51).

The ratios of the aforementioned compounds calculated from data obtained from mixing
10%and 20% distilled oil in cold-pressed oil can be seen in Tables IV and V. It is evident
that from these results the existence of distilled oil in cold-pressed oil can be readily
determined.
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Table IV. Values of some ratios between areas of the peaks of the cold-pressed mandarin essential oils and those of the mixtures of
them with 10% of oil obtained by distillation

95% confidence limits

of the CP essential oils Mixtures

Min Max 1* 2* 3* 4* 5* 6** 7** 8** 9** lo** 11** 12**

terpinen-4-011
cis-sabinene hydrate 0.74 2.48 2.20 1.94 1.81 2.50 2.06 2.36 2.95 2.22 3.67 2.46 2.15 2.15
terpinen-4-011
trans-sabinene hydrate 0.35 1.57 1.79 1.21 1.12 1.92 1.69 1.37 1.55 1.11 2.22 2.19 1.93 2.07
terpinen-4-ollcitronellal 0.40 2.12 3.12 3.79 3.27 2.78 2.54 1.73 2.32 2.29 2.11 2.27 2.00 2.15
terpinen-4-olldecanal 0.17 0.72 1.07 1.28 1.13 0.87 0.81 0.63 0.72 0.82 0.62 0.60 0.55 0.60

* Essential oil from green mandarins + distilled oil

**Essential oil from red mandarins + distilled oil; CP = cold pressed

Table V. Values of some ratios between areas of the peaks of the cold-pressed mandarin essential oils and those of the mixtures of
them with 20% of oil obtained by distillation

95% confidence limits

of the CP essential oils Mixtures

Min Max 1* 2* 3*
4* 5* 6** 7** 8** 9** lo**

terpinen-4-011
cis-sabinene hydrate 0.74 2.48 2.40 2.54 3.38 3.96 3.76 3.27 2.78 6.29 6.15 6.54
terpinen-4-011
trans-sabinene hydrate 0.35 1.57 1.85 1.56 2.97 2.75 2.13 1.57 3.00 3.38 2.96 3.27
terpinen-4-ol/citronellal 0.40 2.12 3.43 4.48 3.92 4.71 3.16 3.15 3.39 3.52 3.33 3.86
terpinen-4-olldecanal 0.17 0.72 1.01 1.51 1.08 1.18 0.82 0.91 0.80 0.94 0.83 0.90
~~

See Table IV for legends

 280 JOURNAL OF ESSENTIAL OIL RESEARCH

Additions of 5% distilled oil to cold-pressed oil can force the values of the ratios to exceed
the expected maximum levels for the cold-pressed oils, while on the contrary, the addition
of 10% is rarely not detected using the ratios mentioned. This is due to the wide range of
the component values found in both types of mandarin oils.

In case of the additions of 5%, as shown in Table 111, only sometimes do the values of the
ratios considered exceed the upper limits for the cold-pressed oils. In particular, for
mixtures made up byadding5% distilled to cold-pressed oils from red mandarins, thevalue
of all the ratios is lower than these limits whereas, in mixtures obtained from cold-pressed
oils from green mandarins, the value of the terpinen-4-ovdecanal ratio exceeds the upper
limit in one of the two examples reported, and the value of the terpinen-4-ol/citronellal
ratio exceeds it in both cases. Thus the addition of distilled oil to cold-pressed mandarin
oil at a level of 5% is not always detectable.

Finally it should be noted that oils, which possess a low content of alcohols and are usually
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obtained from ripe mandarins, are more easily mixed with distilled oils without detection
than those obtained from mandarins harvested during the first part of the productive
season. This means that “ideal” mixtures of cold-pressed oils/distilled oils cannot be
detected using the methodproposed; however, if even one ofthe ratios goes over the range
expected for the genuine oils, it is indicative of something being not correct and could be
used to infer that a distilled oil has been added to a cold-pressed oil.

ACKNOWLEDGMENTS:This research was supported by National Research Council

of Italy, Special Project RAISA, Sub-project No. 4, Paper No. 139.

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