R.
Guba,
Essential Therapeutics Pty Ltd., 100
Dight Street, Collingwood, Vic.
3066, Australia.
E-mail: esstherapeutics@ozemail.
com.au
W
e must thank the practi-
tioners of the ancient
hermetic art of alchemy
for what we know as essential oils
today. The famous physician and al-
chemist Ibn Sina or Avicenna (AD
980–1037) is credited with perfecting
the process of steam distillation to
produce pure essential oils. This ex-
traction method was only part of the
process for creating an alchemical
‘spagyric’ preparation (from the
Greek spagyria – spao- to draw out or
divide and ageiro – to gather bind or
join: hence to ‘dissolve and bind’).
As in the treatises of the ‘father’
of western alchemy, Paraecelsus (AD
1493–1541), the creation of aspagyric
plant remedy was based on the lib-
eration and joining together of the
‘three philosophical principles’ of
the plant.
First, the volatile sulphur would be
liberated via steam distillation. This is
the essential oil that represents the
very ‘soul’ or consciousness of the
plant. Sulphur is fiery, radiant and a
masculine or active yang principle.
Then, the plant residues would
be fermented with yeast to produce
ethanol – or grain alcohol. This was
distilled to create the pure mercury,
which represents the principle of life;
the vital power or ‘life force’, prana
Qi, etc. It represents the feminine or
passive Yin principle.
0962-4562/02/$ - See Front Matter

2002 Published by
Elsevier Science Ltd
The modern
alchemy of
carbon dioxide
extraction
Ron Guba
Lastly, the remaining plant resi-
due or fixed sulphur would be com-
pletely burnt or calcined, the ash
would be washed with water and the
water evaporated, to liberate the wa-
ter soluble mineral salts or the sal
(which represents the ‘body’ or ve-
hicle of the first two principles).
The three ‘principles’ were then
joined together to create a finished
preparation. In the view of alchem-
ists, ordinary plant tinctures only
utilise part of the curative powers of
the plant. Spagyric preparation
‘opens’ the plant, and liberates
stronger curative powers. As in Ho-
meopathy and other forms of vibra-
tional medicine, spagyric
preparations are based on their syn-
ergistic and ‘energetic’ effects, in-
stead of simply looking at
pharmacologically active compo-
nents (Junius, 1985).
In Aromatherapy then, we have
an entire therapeutic approach
based on the volatile sulphur of the
alchemists. We can see where the
term ‘essential oil’ derived from –
‘essence’ meaning the ‘soul’ or deeper
‘personality’ of the individual plant
(and with mercury, we can still go to
the liquor store and purchase a bot-
tle of ‘spirits’).
Traditionally, Aromatherapy has
employed the use of essential oils
created primarily through steam dis-
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120 The International Journal of Aromatherapy 2002
tillation, and less commonly,
through solvent extraction (the
flower absolutes, generally extracted
using the petrochemical, hexane).
I would like to consider another
form of the preparation of volatile
sulphur, using the modern alchemy
of dense carbon dioxide extraction.
Cagniard de la Tour first dis-
covered the phenomenon of a su-
percritical fluid back in 1822. In 1879
and 1880, the first research was
published detailing that various gases
under high pressure were found to
exhibit excellent solvent qualities for
lipophilic compounds (i.e., com-
pounds that dissolve in non-polar
solvents such as vegetable oil, etha-
nol, benzene, etc.).
Due to the lack of technology in
developing the key high pressure
equipment required, supercritical
fluid extraction was not commercia-
lised for over 50 years. Eventually, in
the 1980s, a number of supercritical
carbon dioxide extraction plants
came into operation (Supercritical
Technology Consultants, 2002).
A number of gases have been
trailed for supercritical extraction,
including trifluromethane, ethane,
dinitrogen monoxide, sulphur hexa-
fluoride and propane. However, car-
bon dioxide has been accepted as the
extraction medium of choice, for the
extraction of volatile compounds for
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 flavour, fragrance and therapeutic
use, for decaffeinating coffee beans,
for extraction of cocoa butter and
other vegetable oils and on (Stahl et
al., 1988; Phasex Corporation, 2002).
Carbon dioxide
We generally know of carbon dioxide
(CO2 Þ in two forms: solid, dry ice,
and as a gas. A liquid form does not
exist at normal atmospheric pressure
(see Fig. 1).
However, as pressure increases
we can create a liquid form of CO2
(liquid CO2 plants often operate at
50–60 bar pressure at around 10 C
(1 bar ¼ 1 atm (normal atmospheric
pressure) ¼ 10 kPa ¼ 76 mm Hg ¼ ap-
proximately 14–15 lb/in:2 pressure).
As we take the pressure and
temperature beyond the ‘critical
point’ (T c and P c ), carbon dioxide
becomes supercritical, this being the
boundary where the difference be-
tween being a gas and a liquid dis-
solve. Hence, we have an extremely
dense ‘fluid’ with the properties of a
gas – it diffuses easily throughout the
plant material being extracted and it
has low viscosity and surface tension.
Fig. 1 Solid–liquid–gas – supercritical fluid diagram. Pc , critical pressure; Tc , critical termperature. The critical pressure and temperature for
carbon dioxide is 73.79 bar and 31.04 C, respectively. The triple point is where the solid, liquid, and gas phase co-exist in equilibrium.
The International Journal of Aromatherapy 2002
Yet, this ‘fluid’ also shares the prop-
erties of a liquid, with its high density
and excellent solvating power. As the
pressure is increased, the dissolving
power of the supercritical carbon di-
oxide increases. In Fig. 2, we see the
solubility of a variety of aromatic
compounds found in essential oils, in
carbon dioxide. At pressure levels
below the supercritical state, these
compounds will only dissolve to a
small degree, but as the supercritical
state is reached the solubility in-
creases to quite high levels as the
pressure is increased further.
The solubility of typical essential
oil components in dense carbon di-
oxide at 40 C is shown in Fig. 3.
What can be extracted with
carbon dioxide?
1. The compounds that are most
easily extractable (up to 300 bar
pressure) are lipophilic (‘oil-lov-
ing’), compounds that have a
high vapour pressure (volatility)
and a low molecular weight (up
to 400 Da). This includes most
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d121
importantly compounds found
in essential oils: ethers, esters, ter-
pene hydrocarbons, alcohols, ke-
tones, etc.
2. At higher pressure and tempera-
ture, triglycerides (vegetable oils
and animal fats), wax esters (as
in Jojoba oil) and other higher
weight non-polar compounds
can be extracted.
3. As in the above two statements,
compounds that are predomi-
nantly non-polar are best ex-
tracted in carbon dioxide, which
functions as a non-polar solvent.
Hence, the presence of po-
lar functional groups will
lower the extraction to varying
degrees.
4. Not extractable are polar com-
pounds such as sugars, glycosides,
amino acids, and lecithins;
alkaloids are extracted at varying
levels. Hence, carbon dioxide is
not suitable for the extraction
of all medicinal plants – it is
dependent on the solubility of
the most active compounds
desired.
5. More polar modifying com-
pounds, such as water, can be
Fig. 2 The solubility of naphthalene in carbon dioxide increases greatly as the supercritical state is reached, and with further increase of
pressure.

Fig. 3 The solubility of typical essential oil components in dense carbon dioxide at 40 C (Franchomme, 1984).

added to the extraction process used to create extracts from aromatic

to increase the extraction of
more polar compounds. This in-
cludes the extraction of the alka-
loids caffeine from coffee beans
and nicotine from tobacco as
prime examples (Stahl et al.,
1988; Amajuoyi, 2001).
Varieties of carbon dioxide
extraction
Supercritical CO2 plants generally
operate from 80 to 500 bar pressure
from 40 to 60 C. This supercritical
extraction is of most interest in Aro-
matherapy and herbal medicine, as
plants and for the extraction of veg-
etable oils, antioxidant compounds,
and other therapeutically active
compounds that cannot be extracted
via steam distillation.
Liquid CO2 extraction is the
other major variant. As a prime

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 example, the prime flavouring
compounds from pelletised Hops
for use in beer, are extracted
by liquid carbon dioxide as in
my hometown, Melbourne, Aus-
tralia at the Carlton United
Breweries.
Supercritical extraction is the
basis of the remainder of the manu-
script (see Fig. 4).
Solubility isotherms of typical
essential oil components in dense
carbon dioxide.
Supercritical carbon dioxide ex-
traction demonstrates a number of
advantages over the traditional
methods of obtaining essential oils
and absolutes.
Carbon dioxide vs. steam
distillation
Steam distillation is the oldest and
most common method of obtaining
essential oils. In fact, we can define
an essential oil as the volatile com-
pounds that will be removed via
steam distillation.
Volatile aromatic compounds,
with a boiling point of 150–200 C,
are selectively separated out from
other plant constituents via the heat
Fig. 4 Diagram of a supercritical carbon doxide extraction plant.
The International Journal of Aromatherapy 2002
of steam, and condense upon cool-
ing.
Generally, steam distillation is
carried out at a temperature of
100 C, the boiling point of water. At
this temperature, in the presence of
oxygen, water, and elevated temper-
ature, various changes can occur in
the structure of aromatic com-
pounds. Certain compounds are heat
sensitive, or thermo labile.
In other cases, various proteins
present will decompose, creating what
are known as artefacts. These can be
various types of decomposition prod-
ucts such as hydrogen sulphide, am-
monia, acetaldehyde, and others.
Linalyl acetate will decompose back to
linalool and acetic acid in lavender
oil; the sesquiterpene lactone, matri-
cin (above 80 C) will decompose to
the intensely blue sesquiterpene hy-
drocarbon, chamazulene in German
Chamomile. This is why the very ex-
pensive Bulgarian Damask Rose oil
does not quite smell like a Rose – it has
been changed to some degree during
steam distillation.
As well, steam distillation favours
only the most volatile compounds,
starting with monoterpenes (10 car-
bon atoms) and lastly diterpenes (20
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carbon atoms). The ‘heavier’ the
compound, the higher its boiling
point and vapour pressure, and
hence heavier compounds remain
behind in the still.
Depending on the plant and
whether active ingredients can pass
over with steam, a more complete
extract can be of higher therapeutic
value.
Solvent extraction
A variety of organic non-polar sol-
vents can be used for extracting
lipophilic (oil loving) compounds,
such as ethanol (in herbal tinctures,
etc.), benzene, and trichloroethyl-
ene.
In Aromatherapy, we see are the
floral absolutes, obtained using the
petrochemical solvents hexane and
pentane.
The traditional fat-extraction
method, or enfleurage is hardly used
these days, due to the very high la-
bour costs involved. Almost all ‘ab-
solutes’ are produced via hexane/
pentane extraction, as well as a few
other novel hydrocarbon solvents
(butane, for example).
Solvent extraction is generally
employed for the finest floral fra-
grances, as the process creates less
‘re-arrangement’ of compounds than
steam distillation (hence truer to the
fragrance of the original flower) and
will also extract heavier lipophilic
components.
Although this is valuable for the
perfume and flavour industry (and
hexane extraction is also the domi-
nant method for the extraction of
commercial vegetable oils), we find
problems with the use of solvent
extracted absolutes in Aroma-
therapy.
Firstly, hexane, being simply
high-vapour-pressure petrol, is very
volatile, flammable and explosive.
Numerous hexane extraction plants
have exploded and burned over the
past 50 years, often with the loss of
multiple lives (PNP Inc., 2002). It
has also been suggested that pro-
longed exposure to hexane amongst
workers in extraction plants leads to
a variety of illnesses (Franchomme,
1984).
A severe environmental prob-
lem exists with the inevitable loss of
hexane to the atmosphere during
manufacturing and processing. Even
a state-of-the-art, medium sized soy-
bean oil producing plant is esti-
mated to leak approximately
88,000 kg of hexane into the
atmosphere each week (PNP Inc.,
2002).
Lastly, no matter how efficient
the final extraction of hexane is
from the finished absolute, some
hexane residues do remain in the
final product. The current Euro-
pean Union standards are for less
than 10 parts per million solvent
residues in a finished absolute. This
permitted level is small (0.001% or
less), nevertheless, from a thera-
peutic perspective, a solvent-free
extract for topical application, cer-
tainly for ingestion, would be pre-
ferred.
Carbon dioxide extraction, on
the other hand, bypasses the above
problems.
• CO2 extraction uses relatively low
temperature; in the absence of ox-
ygen and water. Hence, no decom-
position products or artefacts are
formed. The final extract contains
what originally was in the plant.
• As in hexane solvent extraction, all
the heavier, less volatile compo-
nents will be extracted, without
the problem, however, of any sol-
vent residues. At the end of extrac-
tion, the pressure is reduced to
normal and the CO2 simply evapo-
rates.
• CO2 extracts do not require fur-
ther processing, as hexane ex-
tracted concretes do. More highly
volatile ‘top notes’ are retained.
• CO2 extraction is non-toxic, non-
flammable and is environmentally
safe without harmful emissions or
toxic by-products. In the case of
one large manufacturer, Flavex Na-
turextrakte, natural carbon dioxide
is collected from areas of volcanic
activity. Hence, no additional CO2
is added to the atmosphere.
Supercritical CO2 extraction also has
the unique capacity to selectively ex-
tract different components. At 80–
100 bar pressure at 40–60 C, super-
critical CO2 will extract primarily
the volatile aromatic compounds,
termed a ‘select’ extract. This is
somewhat comparable to a hexane
extracted absolute.
By increasing the pressure from
200 to 500 bar with a longer extrac-
tion cycle, heavier lipophilic compo-
nents are removed, including waxes,
triglycerides (vegetable oils), wax es-
ters (as in Jojoba), carotenoids, etc.
These are termed total extracts and
are somewhat comparable with a
hexane extracted concrete.
Disadvantages of carbon dioxide
extraction
• The first limitation is that of cost. As
compared to the set-up costs of a
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124 The International Journal of Aromatherapy 2002
bush still, CO2 extraction plants
are very expensive, in the range
of millions of US dollars. This is
a major reason why there are but
a handful of CO2 plants in opera-
tion. This, however, does not
translate to extraordinary prices
for the extracts. Some extracts
are comparable in cost to a corre-
sponding, high quality essential
oil. Other extracts, depending on
yield and other factors, are signifi-
cantly more expensive.
• Pesticide residues. As compared to
the amount of pesticide residues
in spices that can be extracted by
conventional liquid solvent extrac-
tion, carbon dioxide extraction
has been demonstrated to concen-
trate from seven to 53 times more
pesticide residues in the final ex-
tract. This can be addressed, of
course, by only extracting plant
material from certified organic
growing practices, or shown to be
pesticide-free by analysis. Varying
different parameters of the extrac-
tion process will also reduce the
extraction of pesticides (Amajuoyi,
2001).
Carbon dioxide extracts for
therapeutic use
The major market for CO2 extracts is
their application in flavours and fra-
grances. Additionally, there are a
number of extracts available that
have definite applications in herbal
and aromatic medicine. A selected
list of such extracts includes: Calen-
dula, German Chamomile, Frankin-
cense, Ginger, Kava Kava, Marjoram,
Melissa, and Rosemary; primarily
vegetable oil extracts of Borage,
Evening Primrose, Neem, Rose Hip,
and Sea Buckthorn.
Let us consider three extracts
with outstanding therapeutic prop-
erties.
Calendula CO2 total extract
(Calendula officinalis) contains the
active triterpene monools, diols, and
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 Anti-inflammatory activity of Calendula officinalis extracts in
Table 1 reducing croton oil-induced oedema of mouse ear (Della Loggia
et al., 1990a,b)

Substances Dose (lg per ear) Milligrams of crude druga Inhibition of edema (%)
Hydro alcoholic extract 300 1.04 9.3
600 2.08 12
1200 4.16 20

Carbon dioxide extract 75 1.79 14.5

150 3.58 30.6
300 7.16 44
600 14.3 58.7
1200 28.6 70.7

Indomethacin 30 – 37.3
120 – 73.3
a
Milligrams of dried calendula flowers.

their esters, with the faradiol mono-
esters being the most important
(about 20% of the total extract).
Such compounds could not be
extracted by steam distillation; they
are found in low concentration in
both hydro alcoholic (tinctures)
and vegetable oil extracts (infused
oils).
As compared to a typical infused
oil, the concentration of ‘actives’ in
the CO2 extract is approximately 180
times greater. Calendula CO2 is an
excellent anti-inflammatory and
healing extract. It is suited for con-
ditions such as acne, eczema, allergic
dermatitis and the healing of burns,
wounds, and ulcers. It is also quite
non-toxic and non-sensitising; up to
a 10% concentration can be applied
even on young infant (Quirin and
Gerard, 1999).
One study demonstrated the
superior anti-inflammatory activity of
Calendula CO2 extract versus a hydro
alcoholic tincture. As well, the CO2
extract was as active in reducing in-
flammation as the potent anti-in-
flammatory drug, indomethacin (see
Table 1).
German Chamomile (Matricaria
recutita) yields an essential oil that is
substantially altered during steam
distillation. The dark blue colour of
German Chamomile is due to the
sesquiterpene hydrocarbon, cham-
azulene, which is formed from the
decomposition of the sesquiterpene
lactone, matricin during distillation.
The CO2 extract of German Chamo-
mile maintains the matricin content.
It has a fine, characteristic chamo-
mile odour, yellow–green in colour.
As well, the extract of choice is de-
rived from the a-bisabolol type Ger-
man Chamomile; a-bisabolol having
demonstrated anti-inflammatory and
wound healing activity (Jakovlev and
von Schlichtegroll, 1969).
In terms of anti-inflammatory
power, there is research demonstrat-
ing that matricin has significantly
stronger (10 times more active) anti-
inflammatory properties than cham-
azulene.
Hence, in the treatment of in-
flammatory disorders – dermatitis,
oral mucositis, and the like — the
CO2 extract stands superior (Della
Loggia et al., 1990a,b).
Most of the therapeutic applica-
tions of steam distilled Ginger
(Zingiber officinale) essential oil listed
in numerous books on Aromather-
apy, are extrapolated from the use of
the whole rhizome. However, the es-
sential oil lacks the active, less vola-
tile pungent phenyl propanoid
compounds.
The total Ginger CO2 extract
contains from 25 to 33% of these
pungent actives – gingerols, shogaols,
and zingerone. Therefore Ginger
CO2 extract is therapeutically more
active than the essential oil, making it
more suitable for treating nausea,
travel sickness, muscular pain,
cramping, arthritis, etc., as outlined in
both Eastern and Western herbal
medicine (Flavex Naturextrakte,
2002).
In summary, we can see that es-
sential oils have progressed beyond
the stills of the ancient alchemists.
Although traditional steam distilled
oils will remain the most popular and
accessible plant extracts used in
Aromatherapy, we can see some def-
inite advantages in a variety of car-
bon dioxide extracts. As the interest
in Aromatherapy and botanical
medicine continues to increase, we
can look forward to adding more of
these products of ‘modern alchemy’
to our working collection of health
serving extracts.

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d125
 inflammatory activity of Fluids 2000. Available from:
Acknowledgments
chamomile preparations. Planta <http://www.phasex4scf.com/scf.
With thanks to Flavex Naturetrakte Med. 56: 657–658. htm>.
of Rehlingen, Germany for their as- Flavex Naturextrakte (2002). Producers Natural Processing
sistance (www.flavex.com). Specification – ginger–ginger Inc. (2002). Edible oil
CO2 total extract. Available from: extraction: severe limitations
<http://www.flavex.com>. of hexane (solvent extrac-
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