Essential oil quality and standards, with
special reference to Mentha oils.
Copyright
©Alexandrov A.N. & Zinchenko A.A. October 2003.
Ukraine,
Kharkov.
(English language modifications carried out
by T. Burfield & D. Archer).
Essential oils are widely used in medicine, the food industry
and perfumery. >From a modern point of view, they are produced from natural
raw materials by a number of possible extraction processes [1]. The basic
components of essential oils (EO) are hydrocarbons, aromatic derivatives,
terpenes and their oxygenated derivatives (mono- and sesqui-terpenoids, alcohols
and esters); less often in EO's we find the presence of diterpenes, paraffins,
furocoumarins etc. Contrastingly, in EO and absolutes not derived from
distillation, we find some virtually nonvolatile components (such as
furanocoumarins in cold-pressed citrus oils, waxes and triterpenes in extracted
oils, etc).
There is no universal standard for a concept of "EO
quality", or yet an easily definable characteristic. Traditionally EO's have
been assessed on the basis of individual requirements. A general approach to a
formulation of normative requirements for EO's is absent - the way that EO's are
assessed is dependent by virtue of its intended use. Physical characteristics of
EO's - such, as density, optical rotation, solubility in ethanol-water mixes,
boiling temperature, odour, color etc. - are easily measured. From our point of
view the EO's have auxiliary, technological characteristics, which help
manufacturers & perfumers to estimate the quality of EO's. However some
maunufacturers do not provide the full identification of the components of the
EO and consequently do not give a guarantee of authenticity, or estimate the
influence of individual components on properties of the EO. Even considered with
the data from the chemical analysis of the "basic" components, these are
insufficient to characterize the quality of the EO.
EO quality is
determined by a complex of technological and agrobiological factors, weather and
geographical conditions of cultivation, duration of storage & the conditions
thereof. There are some traditional ways of EO extraction to produce natural
fragrant products (preferably water or steam distillation, but also extraction,
enfleurage, mechanical pressing, etc.). The chemotype of the plant and the
equipment used for oil extraction can determine the ratio of components in EO
and also the proportion of undesirable impurities (furocoumarins, pesticides,
etc.). Changes in density, optical rotation, etc. especially occur rapidly in
the first few weeks after distillation/extraction of an EO. Some components
(especially terpenoids) are very prone to isomerisation; esters may also be
hydrolyzed during distillation and storage. Some components can oxidise in the
presence of air.
Comparison of the published literature [2,3] with our
own measurements (in Table 1. below), indicates that many samples of a given EO,
range widely in composition, and frequently do not meet the standards declared
in the certificate. At the same time, formal checks using the some of the older
test methodology described in these standards, quite often successfully give the
same results. But the demand for meaningful EO standards has increased, because
reproducibility of pharmacological effects is essentially determined by a parity
{ratio} of concentration of EO components. Thus, the recorded anti-microbial
effects of a given EO (determined by different researchers for a particular
microorganism), quite often differs by a magnitude of 2-5 times - simply because
the researchers often have not taken the EO composition into account.
On
the other hand, nowadays it is often a requirement to provide a chromatogram of
an EO with 5-10 components identified with their appropriate concentrations,
which should fall within given limits, and also to include the component ratios
of certain specified items [4]. Differences in EO composition, usually not
controllable at manufacture, can appear rather important at organoleptical
control or, for example, in storage. The presence of traces of oxygen and water
are also important as they can accelerate chain processes of polymerization
and/or condensation of terpenoid components of the EO. In the presence of
considerable amounts of oxygen, especially in conjunction with light or at
increased temperatures, the tendency for peroxidation is amplified. Overall,
within the EO, concentrations of aldehydes, acids, peroxides and oxides can
accrue, resulting in the accelerated resinification of EO components. Under such
conditions the physical, and more particularly, the biological properties of
EO's are therefore changed [5]. This does not necessarily imply "deterioration"
of the EO, - since in certain situations some modification of the properties can
give positive pharmacological effect. But from the perfumer's point of view, or
from the viewpoint of experts in the food-processing industry, "old" oils are
inferior to fresh ones. It is obvious therefore, that the estimation of the
quality of EO samples will vary, depending on the end use of the oil.
Unfortunately the specifications provided by the various bodies that
regulate the quality of EO's, do not only serve technological aspects. They can,
for example, indirectly influence the character of an export-import policy
{politics} of nation-states, thus limiting competitive access to home market
EO's into some regions. For example, the American standard on Mint EO's (MEO)
contains rigid restrictions favouring high menthofuran contents. Manufacturers
from Europe and Asia cannot meet these standards because of distinctions in
cultivated peppermint chemotypes which have low menthofuran levels. According to
our data, menthofuran concentrations in Ukrainian peppermint EO, as well as in
other samples from European MEO, are almost always below the level required by
the US standard; nevertheless this peppermint EO can be of good perfumery
quality and possess standard pharmaceutical properties. We can therefore regard
such standards as part of a complex of protectionist measures! By the American
rules, products such as dementholised EO of Japanese mint Mentha arvensis should
have the inscription "Cornmint", since these are considered as low grade goods
[6]. Among identified components of a complex of volatile organic compounds
(VOC) of MEO (see picture) the basic is l (-) menthol. Various grades of
extraction of menthol receive the most types of MEO, and so requires target
selection of Mentha plants strains. The menthol content in some samples of our
mint oils that we have analysed (see Table 1, and [3]) varied between 25 up to
90 %. Mint EO contains about 15 basic components, not considering additional
trace substances.
Table 1. The contents of some compounds in the
peppermint oils
|
compounds
|
GDR* |
Sophia* |
Krasnosarskaja-2* |
Kubanskaja* |
Prilukskaja
* |
Prilukskaja
** (66%) |
Prilukskaja
** (40%) |
Krimskaja
** |
European
Pharm/ [4] |
ISO
Standard [6] |
1. |
Menrhol |
33,6 |
34,8 |
36,0 |
38,4 |
37,5 |
66,0 |
40,2 |
61,2 |
30,0-55,0 |
32-49 |
2. |
Neomenrhol
|
2,5 |
4,5 |
2,7 |
1,6 |
4,5 |
|
|
|
|
2-6 |
3. |
Isomenthol |
0,2 |
0,5 |
0,4 |
0,3 |
0,1 |
|
|
|
|
|
4. |
Neoisomenrhol |
0,7 |
1,2 |
0,9 |
1,6 |
0,8 |
|
|
|
|
|
5. |
Menthol |
23,5 |
28,5 |
23,4 |
5,9 |
14,9
. |
15,0 |
20,9 |
20,0 |
14,0-32,0 |
2-8 |
6. |
Isomenthone |
3,9 |
5,1 |
4,0 |
15,5 |
1,4 |
1,5 |
10,1 |
3,3 |
1,5-10,0 |
2-8 |
7. |
Menthofuran |
3,2 |
2,0 |
1,1 |
|
0,4 |
0,1 |
0,8 |
0,1 |
1,0-9,0 |
1-8 |
8. |
Menthyl
acetate |
5,1 |
4,5 |
5,5 |
20,2 |
9,7 |
5,9 |
3,5 |
3,1 |
2,8-10,0 |
2-8 |
9. |
Neomenthyl
acetate |
0,6 |
0,5 |
0,4 |
1,6 |
|
4,9 |
1,6 |
2,0 |
|
|
10. |
Pulegone |
0,7 |
0,9 |
0,6 |
0,1 |
|
0,03 |
1,4 |
0,55 |
<
4,0 |
0-3,5 |
11. |
Piperitone |
1,8 |
1,5 |
1,1 |
1,4 |
1,2 |
|
|
|
|
|
12. |
Carvone |
0,4 |
0,5 |
1,1 |
0,3 |
1,5 |
0,26 |
1,3 |
1,7 |
<1,0 |
|
13. |
1,8-Cineol |
4,1 |
3,0 |
3,6 |
0,1 |
4,7 |
0,2 |
0,2 |
0,1 |
3,5-14,0 |
3-8 |
14. |
Terpinen
-4-ol |
1,1 |
0,3 |
0,2 |
|
0,1 |
|
|
|
|
|
15. |
Octan-3-ol |
0,2 |
0,2 |
0,1 |
0,2 |
0,2 |
|
|
|
|
0,1-2 |
16 |
Limonene |
|
|
|
|
|
2,6 |
0,8 |
3,1 |
1,0-5,0 |
1-3 |
17 |
a-Pinene |
|
|
|
|
|
0,3 |
0,5 |
0,6 |
|
|
*)
W. Schmidt, etc., Miltitzer Ber. 1979, 20-25,
**) Our data – (Shimadzu
GC-14B, a quartz capillary column 60м x 0,32mm, HP Innowax 0,5mm,
Temp start 60º - 10mins, ramped at speed of 2ºC/min, Temp end
210º, period at the maximal temperature – 15min).
There are very many chemotypes and
grades of mint plants. If all the samples were to have equal contents of
menthol, the experts in different disciplines (according to their professional
internal standards) would still prefer certain types of MEO – because of the
characterizing influence of some of the minor components. e.g. according to
German perfumery experts, the best organoleptic properties (taste) are found in
“GDR” and "Sofia" types of peppermint oil. The production of oils from breeding
hybrid grades of peppermint with high menthol contents was encouraged in the
USSR by paying premium prices with increased menthol levels and have been well
appreciated in the marketplace. Continuing on this path could lead to the
eventual displacement of peppermint strains such as Mitcham.
Crude peppermint oil is usually
subject to additional processing. The Ukrainian standard for rectified
peppermint EO has a total menthol content (free and combined) of over 50%. Other
natural components typical for Mentha species (menthone, pulegone,
menthol isomers – such as neomenthol, etc.) strongly influence the organoleptic
and pharmacological properties of mint oil. However we still have very little
objective data on quantitative distinctions in pharmacological action for
different types of MEO in animals and microorganisms.
Additionally, the authors feel that
too rigid criteria for pulegone concentrations are not justified on safety
grounds (as the pulegone LD50 value is less than that for menthol).
Thus, overemphasis on the strict adherence to concentration limits for certain
components within operating standards is not always desirable. On the other
hand, a weighed approach is necessary as is used for the so-called "peppermint
oils" from Brazil, China and India. As a matter of fact they are quite often
ersatz – as shown by tests on dementholised Japanese mint (Mentha
arvensis) EO. Some enterprises release batches of
dementholised essential oils (total menthol content 50 % or less, down as low as
25-30%). In our opinion, such EO’s should not be regarded as “inferior oils”,
but rather require additional study in order to establish a definition of an
appropriate & more effective pharmacological application; there is a
requirement for the development and introduction of special standards for
similar "nonconventional" products for a pharmaceutical industry.
1 V.P.Georgievsky, V.I Litvinenko,
J.I.Gubin, A.N.Alexandrov “Extracts as medical products - Actual problems of
creation of new medical products from the natural origin.” Pr. 3 Internat.
Congress, St Petersburg, 1999.
2 S.V.Sur (1993) “Structure of Essential oils of
plants” Plant. Resources 1, 98-117.
3 V.S.Dolja, V.I.Mozul, V.V.Karpenko
(1999) “Research of Mint Plant Essential oils” Visnik Farmacii, №
2, 1999, 158-159
4 European Pharmacopoeia,
3rd ed. suppl., 1998
5 I.V.Kovaljova,
N.M.Solodovnichenko, I.J.Holupjak, A.N.Alexandrov (1999) “The Study of Pine
Essential Oils oxygenation on its biological properties” Proced. of 5th
Ukrainian National Pharmaceutical Congress 306-307.
6 S.A.Vojtkevich (1999) Essential oils for perfumery and aromatherapy Мoscow, p 282.