ELSEVIER Journal of Supercritical Fluids 12 (1998) 59-67

Supercritical carbon dioxide extraction of

Angelica archangelica L. root oil
Catalin Doneanu a, Gheorghe Anitescu b,*
a Department of Organic Chemistry, Faculty of Pharmacy, 6 Traian Vuia Str., Bucharest, Romania
b Department of Chemical Engineering and Materials Science, Syracuse University, Syracuse, NY 13244, USA

Received 5 May 1997; received in revised form 19 August 1997; accepted 26 August 1997

Abstract

Angelica (var. Angelica archangelica L.) oil was isolated from grated fresh roots of the plant by supercritical fluid
extraction using carbon dioxide and a two-stage fractional separation system. Throughout the extraction process the
pressure and temperature were maintained at 120 bar and 40°C respectively. A 1 h static extraction step was followed
by a 2 h dynamic extraction conducted at a flow rate of 0.5 kg h-‘. The extracted material was characterized by
capillary gas chromatography-mass spectrometry using three different mass spectra libraries. More than 200
compounds were found in the extracted oil, of which 118 compounds were positively identified and four other
compounds tentatively identified. 0 1998 Elsevier Science B.V.

Keywords: Angelica archangelica L.; Carbon dioxide; Capillary GC-MS; Essential oil; Supercritical fluid extraction

1. Introduction because of the partial loss of the most volatile

compounds. Further, by drying, some terpenes
Angelica (var. Angelica archangelica L.) is a (especially a-phelandrene) become resinous.
herbaceous biennial or perennial plant of the Therefore, the top fragrance notes of the oil,
umbel family, with tall stalks and large divided usually fresh and gently pungent, may be altered.
leaves. The roots and fruits are used in flavoring, Essential oil obtained from rhizomes and roots of
perfumes, medicine, etc. It is specific to European angelica is a yellow liquid having a fresh, herba-
flora, and it is cultivated mostly in France, ceous, and gently pungent aroma on an earthly
Germany, Belgium, and the Netherlands. and woody background.
Essential oil of angelica is usually obtained from There are many studies on the extraction and
the rhizomes and roots by steam distillation. This composition of angelica root oil [l-9]. In the early
method yields O.l-1.0% of essential oil related to investigations, reviewed by Gildemeister and
the angelica root material. A preliminary drying Hoffmann [ 11, only a small number of constituents
of the rhizomes and roots is not recommended were identified. The essential oil composition of
angelica roots has been investigated by Klouwen
* Corresponding author. Tel.: (+ 1) 315 443 191; and ter Heide [ 21, Taskinen and Nyktinen [ 31,
fax: (+ 1) 315 443 1243; e-mail: ganitesc@mailbox.syr.edu For& [4], Srinivas [ 51, Kallio et al. [ 61, Nykgnen

0896-8446/98/$19.00 0 1998 Elsevier Science B.V. All rights reserved.

PII SO896-8446(97)00040-5
60 C. Doneanu, G. Anitescu / Journal of Supercritical Fluids I2 (1998) 59-67
et al. [7], Kerrola and Kallio [8], and Kerrola
et al. [9]. However, the detailed effects of both the
plant’s environmental conditions and extraction
parameters on the yield and composition of the
extract of angelica flavor have not yet been eluci-
dated. A large variability in the relative amounts
of the compounds was found to depend on the
stage of plant development and the kind of strains
and freshness of the roots at the time of extrac-
tion [9].
Throughout the investigations, angelica root oil
was found to have a very complex composition.
The bouquet aroma of this oil is the result of the
combination of the aromas of a very large number
of components. Thus, it is very important that the
native natural proportion of the components is
maintained during any extraction procedure.
Unfortunately, the traditional extraction tech-
niques based on liquid solvents or steam distilla-
tion were found to present some disadvantages.
For example, the steam distillation procedure
cannot recover the pungent compounds because
these are thermally degraded to produce volatile
aldehydes or ketones. Some of the aromatic com-
pounds are also known to be affected by heat. The
essential oil when extracted with liquid solvents
lacks a strong aroma due to the loss of volatile
compounds during the evaporation process of the
solvents. Further, the alcohol extraction of the
flavors was found to produce artifacts by esterifi-
cation, etherification, and/or acetal formation [ 31.
Supercritical fluid extraction (SFE), mainly by
supercritical carbon dioxide (SC-C02), can be used
to extract volatile oils from natural products and
does not produce substantial thermal degradation
or solvent pollution/alteration of the extracts [lo].
Nevertheless, a high density of supercritical fluid
(SCF) and one-stage subcritical separation is
unsuitable due to the simultaneous extraction of
many undesired compounds, such as fatty acids
and their esters, cuticular waxes, coumarins, etc.
[ 111. SFE performed in multiple steps by increasing
the SCF density and a multistage separation tech-
nique give superior quality products compared
with those obtained by the traditional techniques
[ 12,131. However, there are many parameters that
must be considered in the SFE procedure. These
include the type of solvent/cosolvent, raw
material-solvent ratio, the method of feeding the
solvent, conditions of extraction (pressure, temper-
ature, time, flow rate), preparation of raw material
and separation conditions, etc. Analysis of the oils’
composition revealed that oils extracted under
different SFE conditions possessed widely different
percentage compositions. Qualitative aroma tests
showed that the oil obtained at optimum SFE
conditions had a fragrance that better resembled
the flavor profile of the starting material.
Angelica root oil has been isolated by SFE
(12 MPa/SO”C) into three fractions with distinctly
different compositions by three successive extrac-
tion steps and by using a single separator [9].
Obviously, each of the fractions was found to
present a composition which did not resemble that
of the natural aroma composition. To perform
that requirement, the fractions must be mixed after
completing the extraction process and the removal
of undesired compounds.
The aims of this study were to use an appropriate
extraction procedure to obtain a more detailed
knowledge of the proportion of fragrant constitu-
ents of angelica roots and to elucidate the actual
aroma composition of a fresh root extract.
Therefore, this study reports an SFE technique to
isolate the volatile oil, consisting of two successive
extraction stages (static and dynamic), and a two-
stage separation process. Approximately 200 com-
pounds were separated from extracted oil by a gas
chromatography-mass spectrometry (GC-MS)
analytical method, and more than half have been
identified. Throughout the extraction process, nei-
ther coumarins nor psoralens were detected in the
GC traces of the extracted material, except for a
small amount of osthol. Also, neither waxes, nor
large amounts of long-chain fatty acid esters, nor
ethers were found. Furthermore, extracts with a
high resemblance to the native aroma of angelica
roots were obtained.
2. Experimental section
2.1. Materials
Fresh angelica roots of var. Angelica archangel-
ica L. cultivated in Romania were used 1 day after
 C. Doneanu, G. Anitescu / Journal of Supercritical Fluids 12 (1998) 59-67
harvesting. Grated samples of 500 g each were
placed in a stainless steel sieve basket to prevent
carryover of particulates. Particle size was non-
uniform because of the particular procedure of
grating a fresh root material. Although grated
material was passed through 1 mm diameter grater
holes, the length of the plant fibers was variable
(N l-4 mm). Carbon dioxide of 99.5% purity was
used by passing through a filter filled with ZSM-20
molecular sieves for a further purification. The
molecular sieves were conditioned before using a
new cylinder with carbon dioxide by heating in an
oven at 200°C for 7 h.
2.2. Apparatus andprocedure
SFE experiments were performed on an appara-
tus mainly consisting of a thermostatic extractor
(1 1 internal volume) and two separators operated
in series (100 ml and 300 ml). More details on the
SFE apparatus were provided in a previous paper
[ 131. No pump or compressor was used to deliver
SC-CO,. The system is essentially maintenance-
free, with virtually no moving parts.
In the experimental runs, the extractor was
charged with 500 g of grated roots of angelica
plant, and carbon dioxide was delivered into the
extractor by controlled heating of a siphon-type
cylinder. In the first step, the extractor was loaded
with carbon dioxide up to a desired pressure and
thermostatically controlled at a given temperature
during a 1 h period of time (a static period). In
the second step, a carbon dioxide flow rate of
0.5 kg h-’ (measured at the outlet of the appara-
tus) was used during all the tests in a downflow
mode. Downflow of SCF through the fixed bed of
plant material is more effective than upflow,
because in this mode any condensate is simply
pushed out of the bottom of the extraction vessel,
and the resultant oil content recovered [ 141. The
pressure control valve at the outlet of the extractor
is moderately warmed by heating tape to prevent
plugging by freezing due to the Joule-Thomson
effect produced by flowing carbon dioxide.
Extracted fractions from the extractor were
precipitated/condensed in two separators oper-
ated in series at pressures/temperatures of
6.0 MPa/lO”C and 3.0 MPa/O”C. Extractions
61
performed at various densities of carbon dioxide
showed that an extraction at 12.0 MPa and 40°C
(1 h static process followed by 2 h dynamic pro-
cess) was optimum in order to have an acceptable
yield and a composition containing a minimum of
unwanted co-extracted compounds. Using these
conditions, the undesired compounds, co-extracted
during the designated extraction time, were precipi-
tated selectively in the first separator, and the
essential oil was recovered in the second separator.
The water collected in the second separator was
removed by addition of sodium sulfate.
2.3. GC-MS
The GC-MS apparatus was a Fisons
Instruments MD 800 gas chromatograph-mass
spectrometer equipped with a split/splitless injector
(maintained at 250°C) and with a fused silica
SPB-5 column (50 m x 0.32 mm i.d. x 0.25 urn film
thickness, Supelco, Bellefonte, PA, USA). Helium
was used as the carrier gas, with an inlet pressure
of 70 kPa, and the septum purge was 4 ml mini.
The split ratio was 1:lOO and the volume of each
of the injected samples was 0.1 ~1. The GC oven
was programmed to operate from 60 to 240°C
(20 min) at 3°C min- ‘. The ion source temperature
was 200°C and the interface temperature was
250°C. Data acquisition was performed with
MassLab software for the mass range from 35 to
480 a.m.u. with a scan rate of one scan per second.
The ionization energy of electrons was 70 eV. The
identification of compounds was based on a com-
parison of experimentally obtained mass spectra
with NIST, WILEY-6 and TERPENE mass
spectra libraries, using relative retention indices
already established [ 151. In a second run, the oil
was injected into the same column, using a flame
ionization detector. The percentage composition
was computed from peak areas without correction
factors. Finally, by using the same temperature
program, a mixture of n-alkanes from Ca to C&
was analyzed. The retention times were then
used for assigning Kovats retention indices of
identified compounds in the angelica root oil
extracts [ 16,171. In order to determine the ratio
of the co-eluted compounds, limonene and
P-phellandrene, the oil was solved in hexane
62 C. Doneanu, G. Anitescu /Journal of Supercritical Fluids 12 (1998) 59-67

Table 1
Identification and quantification of compounds contained in the Angelica archangelica L. root oil compared with literature data

No. Compound Kovats index Percentage composition

C” Cb CC Cd

1 Isobutyraldehyde 591 0.01

2 2-Methyl-3-buten-2-01 611 0.01
3 2-Methyl furane 615 trace
4 Isovaleraldehyde 649 0.02
5 2-Methyl 2-butanol 659 0.03
6 Hexanal 798 0.02 0.60 0.90
7 Isovaleric acid 819 trace
8 2-Vinyl-5-methyl furane 826 trace
9 2-Methyl butyric acid 830 trace
10 2-Pentenoic acid 873 0.01
11 2-Heptanone 886 trace
12 Tricyclene 925 0.02
13 a-Thujene 928 0.43 0.55 0.05 24.0’
14 2-Methyl-5-isopropyl furane 933 0.01
15 a-Pinene 936 16.66 6.50 17.10 24.0’
16 2,CThujadiene 945 0.01
17 a-Fenchene 949 trace
18 Camphene 951 1.09 0.38 0.45 1.30
19 Verbenene 956 0.57
20 Hexanoic acid 969 0.02
21 o-Cymene 972 0.04
22 Sabinene 975 0.62 6.98 20.20 0.76
23 /+Pinene 980 1.12 0.73 1.30 1.25
24 Myrcene 990 3.91 1.83 5.35 7.6”
25 2-Carene 1006 0.13
26 a-Phellandrene 1008 11.27 0.50 1.35 7.6”
27 3-Carene 1013 8.69 3.28 7.80 10.1
28 a-Terpinene 1018 0.31 0.07
29 m-Cymene 1022 0.09
30 p-Cymene 1026 5.56 0.86 0.65 9.8
31 Limonene 1030 13.12 2.85 4.40 13.2
32 p-Phellandrene 1030 8.92 8.45 6.75 10.0
33 cis+Ocimene 1036 2.05 1.25
34 trm+Ocimene 1043 5.43 0.43 3.10 2.68
35 y-Terpinene 1059 0.64 0.75 0.55 0.11
36 Benzyl formate 1076 0.02
37 Dimethyl styrene (isomer) 1082 0.07
38 a-Terpinolene 1090 0.78 0.30 0.55 0.16
39 a-p-Dimethyl styrene 1090 0.78’
40 Camphen-6-one 1098 0.05
41 Linalool 1099 0.09 0.01
42 Perillene 1101 0.03
43 1,3,8-p-Menthatriene 1113 0.01
44 cis-allo-Ocimene 1129 0.07
45 trans-Verbenol 1146 0.22 0.64
46 n-Amy1 benzene 1158 0.02
47 6-Butyl- 1,4-cyclopentadiene 1160 0.19
48 a-Phellandren-8-01 1167 0.20 0.40
49 (E,Z) 1,3,5-Undecatriene 1173 0.10
50 Terpinen-4-01 1179 0.14 trace
51 p-Cymen-7-ol(cuminylalcoho1) 1181 0.12 0.50 0.45 0.02
 C. Doneanu, G. Anitescu 1 Journal of Supercritical Fluids 12 (1998) 59-67 63

Table 1 (continued)
Identification and quantification of compounds contained in the Angelica archangelica L. root oil compared with literature data

No. Compound Kovats index Percentage composition

C” Cb CC Cd

52 p-Cymen-8-01 1184 0.10 1.28 0.25 0.31

53 Sabina ketone 1187 0.18
54 a-Terpineol 1192 0.22
55 Tyrtenal 1198 0.41
56 Sabinol 1203 0.23
51 Thujol 1206 0.02
58 trans-Piperitol 1209 0.10 trace
59 Verbenone 1211 trace
60 Carve01 1219 0.03 0.11
61 Chrysanthenyl acetate 1223 0.01 1.96 1.73
62 cis-3-Hexenyl isovalerate 1230 trace
63 u-Phellandrene epoxide 1238 0.05
64 Cuminyl aldehyde 1241 0.04 0.02
65 Carvone 1245 0.03
66 Carvotanacetone 1249 0.19
67 Piperitone 1255 0.07
68 Isoascaridol (?) 1266 0.02
69 Phellandral 1217 0.27 0.40
70 Bornyl acetate 1288 0.98 2.36 2.10 0.73
71 Thymol 1289 trace
12 trans-Verbenyl acetate 1293 0.16 0.46
13 Carvacrol 1299 0.34
14 cis-Pinocarvyl acetate 1301 0.02 0.17
15 trans-Carvyl acetate 1337 0.06 0.03
16 trans-Piperitol acetate 1341 0.14
II Terpenyl acetate 1351 1.23
78 a-Cubebene 1355 0.03 0.38 0.20
19 Eucarvone 1358 0.01
80 cis-Carvyl acetate 1363 0.01 0.05
81 Longicyclene 1376 0.11
82 a-Copaene 1383 1.16 0.63 1.10 1.91
83 B-Elemene 1397 0.21 0.38 3.55 0.9
84 n-Tetradecane 1400 0.01
85 Sativene 1404 0.02
86 Piper&one oxide (?) 1414 0.07
87 l3-Cedrene 1424 0.11 0.25 0.20
88 8Caryophyllene 1428 0.14 1.15 trace 0.40
89 Octyl isovalerate 1434 0.01 trace
90 Thujopsene (widdrene) 1441 0.05 0.23
91 a-Elemene (?) 1446 0.01
92 P-Famesene 1458 0.16 1.08 0.15
93 a-Humulene 1463 1.20 0.50
94 y-Muurolene 1484 0.05 0.50 0.04
95 Germacrene-D 1491 1.13 1.93 0.26
96 g-Selinene 1496 0.03 0.33 0.10
97 a-Zingiberene 1499 0.16
98 cl-Muurolene 1507 0.59 1.2
99 8-Bisabolene 1513 1.13 1.28 0.72
100 &Cadinene 1530 0.31 0.98 0.51
101 cc-Copaen-l l-ol 1549 0.45 4.08 0.46
102 Elemol 1555 0.17 1.35 0.30 0.18
64 C. Doneanu, G. Anitescu / Journal of Supercritical Fluids I2 (1998) 59-67

Table 1 (continued)
Identification and quantification of compounds contained in the Angelica archangelica L. root oil compared with literature data

No. Compound Kovats index Percentage composition

C” Cb CC Cd

103 Germacrene-B 1568 0.10 1.15

104 Spathulenol 1587 0.03 1.10 trace
105 June01 1591 0.14
106 Caryophyllene oxide 1594 0.02
107 n-Hexadecane 1600 0.03
108 a-Copaen-S-01 1605 0.01 0.20 0.10
109 Cedrol 1615 0.01 0.25 0.10
110 Humulene epoxide III 1620 0.11
111 Dehydroaromadendrene 1625 0.01
112 Isomethyl-a-damascone 1629 0.01
113 y-Eudesmol 1631 0.02
114 13-Tridecanolide 1636 0.82 2.25 1.50 0.45
115 cc-Muurolol 1650 0.02
116 B-Eudesmol 1661 0.17 0.50 trace 0.21
117 3-Butylidene phthalide 1678 0.04
118 12-Methyl-13-tridecanolide 1692 0.33 0.50 0.65
119 Pentadecanolide 1844 0.49 4.30 2.90 0.37
120 Dimyrcene 1958 0.02
121 Heptadecanolide 2051 0.06 trace
122 Osthol 2144 0.23 7.60 1.60
Unidentified compounds (%) 2.17

(?) Compounds tentatively identified.

’ This work, SFE method (12.0 MPa/40”C).
b Kerrola et al. [9], Soxhlet extaction.
c Kerrola et al. [9], SFE method (12.0 MPa/SO”C).
d Taskinen and Nykanen [3]: extraction with ether-pentane followed by steam distillation.
’ The percentage represents the sum of two co-eluting peaks.

(l/100) and a GC run at 80°C (20 min) followed
by a rate of 25”Cmin’ to 240°C (20min) was
performed.
3. Experimental results and discussion
The main goal of this study was to obtain the
best quality and the maximum yield of the angelica
oil by an optimal selection of SFE parameters.
As expected, fresh root angelica oil was found
to have a very complex composition. Its GC trace
is shown in Fig. 1, with compound identifications
reported in Table 1. A series of runs was performed
to assess the optimal extraction conditions:
12.0 MPa and 40°C for the extractor (1 h static
period of time and 2 h dynamic process) and
6.0 MPa/lO”C and 3.0 MPa/O”C for the separators.
These conditions precluded contamination of the
liquid extract collected in the second separator. A
yield of 0.18% was measured by weighing this
fraction after water removal by anhydrous sodium
sulfate and by weight of the fresh root sample
charged in the extractor. When only a dynamic
procedure was used, carbon dioxide left the extrac-
tor unsaturated with biocompounds in the first
step of the extraction process. Therefore, a 1 h
static step was completed before the dynamic step.
The identification of the compounds constituting
angelica root oil and their GC area percentages
were reported in the first column of data in Table 1.
In the next columns of data are reported the
compositions of angelica oil extracted from dried
roots by different techniques: Soxhlet extraction
performed by Kerrola et al. [9]; SFE method
(1.20 MPa/SO”C) performed by the same authors;
 C. Doneanu, G. Anitescu / Journal of Supercritical Fluids 12 (1998) 59-67
18 23-34
lO(
Fig. 1. GC trace of the angelica (var. Angelica archnngelica) root
in Table 1).
extraction with ether-pentane followed by steam
distillation, performed by Taskinen and Nykanen
[ 31. The second column of data shows averaged
results reported for four various origins of angel-
ica, while in the next column, results for the first
two SFE fractions out of three were averaged.
The results reveal a large variability in the
relative amounts of the compounds, particularly
between our results and those reported by Kerrola
et al. The percentage composition for commonly
identified compounds reported by Taskinen and
Nykanen appears to be in a reasonable concor-
dance with ours. The results also show a strong
dependence of the oil composition on a number
of parameters, such as variety of wild or cultivated
angelica strains, stage of the plant development,
freshness of the roots at the time of the extraction,
environmental conditions during the plant devel-
opment, extraction methods, analytical pro-
cedure, etc.
The oil obtained from fresh roots of var.
Angelica archangelica L. was examined in this
study by capillary GC-MS using three mass
spectra libraries: NIST, WILEY-6 and TERPENE.
A total of approximately 200 compounds were
65
82 93
oil (numbering of the peaks corresponds with the compounds
separated, of which 118 compounds were positively
identified and another four were tentatively iden-
tified. To allow a comparison, the main families
of compounds identified from Table 1 are summa-
rized in Table 2. Besides the hydrocarbons (monot-
erpenes and sesquiterpenes) and their oxygenated
compounds, Table 2 also presents the specific
angelica macrocyclic lactones and total undesired
coumarins co-extracted with the oils. Compounds
collected in the first separator were identified quali-
tatively, but only a rough estimation of the percen-
tage composition was made. The SFE process was
optimized by quantification of the desired and
undesired compounds in the second separator to
obtain maximum and minimum percentages
respectively. These data indicate reasonably good
agreement between our results and those reported
by Taskinen and Nykanen.
Monoterpene hydrocarbons represent the larger
fraction of the angelica root oil constituents
(- 80%). It was previously reported that the main
proportion of angelica root oil consists of monoter-
pene hydrocarbons (up to 88%) [4]. Considerably
smaller proportions of monoterpenes were detected
in the Soxhlet extracts of angelica roots by Kerrola
66 C. Doneanu, G. Anitescu / Journal ojSupercritical Fluids 12 (1998) 59-67
Table 2
Percentage comparison of main families of compounds extracted by different methods (as shown in Table 1)
Compound family Percentage composition
C”
Monoterpene hydrocarbons 81.57
Sesquiterpene hydrocarbons 6.13
Oxygenated compounds 6.91
Lactones 1.70
Others 2.99
(Coumarins) (0.23)
’ This work, SFE method (12.0 MPa/40”C).
b Kerrola et al. [9], Soxhlet extaction.
’ Kerrola et al. [9], SFE method (12.0 MPa/SO”C).
d Taskinen and NykZnen [3]: extraction with ether-pentane
et al. [9]: 24 to 46%. Nykanen et al. [7] reported
28% monoterpenes in an angelica root commercial
oil. The main component in our fresh root angelica
oil isolated by SFE is a-pinene (16.66%). Its
isomer, S-pinene, is present at a lower percentage
( 1.12%). As pinene and limonene oxidize to pro-
duce citronellol, carvone, piperitone, and carvacrol
[ lo], their high percentages in our oil compos-
ition show the lack of oxidation phenomenon.
Note that a-phellandrene is also present in a
high amount (11.27%), whereas its isomer,
(3-phellandrene, was estimated quantitatively in a
first step because of the co-elution with limonene
(together they represent 22.04%). From a later GC
analysis, limonene and B-phellandrene were found
to represent 13.12% and 8.92% respectively. Other
monoterpene hydrocarbons identified in a large
amount were: 3-carene (8.69%), p-cymene (5.56%),
truns-p-ocimene (5.43%) and its geometric isomer,
ci,+ocimene (2.05%), myrcene (3.91%), and cam-
phene (1.09%). The difference in odor of the
angelica root oils can be attributed to the composi-
tional differences of the volatiles, especially in the
relative amounts of various monoterpene hydro-
carbons [4]. It can be assumed that a high number
of different monoterpene compounds indicates a
high quality of the oil aroma [9].
Sesquiterpene hydrocarbons represented 6.73%
of the angelica oil composition, in very good
concordance with the percentage reported by
Taskinen and Nykiinen (6.75%). The main
compounds identified are: a-humulene (1.23%),
Cb c” Cd
34.39 69.60 82.28
15.01 10.45 6.75
20.43 6.15 4.98
7.05 5.05 0.82
23.12 8.75 5.17
(8.40) (2.05)
followed by steam distillation.
a-copaene ( 1.16%), germacrene-D ( 1.13%), and
B-bisabolene (1.13%).
Oxygenated compounds of terpene hydro-
carbons confer special characteristics to the angel-
ica root oil, such as particular odor notes and
stability of the oil against alteration. The com-
pounds extracted by SFE in significant amounts
are: terpenyl acetate (1.23%), bornyl acetate
(0.98%), a-copaen- 1l-01 (0.45%)) carvacrol
(0.34%), and phellandral (0.27%).
Macrocyclic lactones were found in a relatively
low percentage (1.70%), but they are very impor-
tant compounds in angelica root oil. The musk-
like odor of this oil is generally attributed to the
lactone of 15-hydroxypentadecanoic acid. Besides
pentadecanolide (0.49%), three other macrocyclic
lactones were found in the oil isolated by SFE
from fresh roots of angelica var. archangelica
L.: 13-tridecanolide (0.82%), 12-methyl-13-tride-
canolide (0.33%) and heptadecanolide (0.06%).
Coumarins as undesired compounds were found
in a very low concentration in our SFE oil (only
osthol, 0.23%) compared with those found in the
oils extracted by Kerrola et al. [9]: 2.05% in SFE
oils and 8.40% in the oils extracted by the
Soxhlet method.
A qualitative sensory analysis of a number of
fractions extracted at different SFE conditions
showed that the fraction extracted under the
above-mentioned conditions had the best quality
compared with the other fractions and a commer-
cially available sample of the essential oil.
 C. Doneanu, G. Anitescu / Journal ofSupercritica1 Fluids 12 (1998) 59-67
4. Conclusions
A two-step SFE process (1 h static period at
12.0 MPa/40”C followed by 2 h dynamic period at
12.0 MPa/40”C and 0.5 kg CO2 h-‘) coupled with
a two-stage separation process (6.0 MPa/lO”C and
3.0 MPa/O”C) was selected as an optimum pro-
cedure to extract a very complex oil from the fresh
roots of Angelica archangelica L. By this pro-
cedure, approximately 200 compounds were sepa-
rated by capillary GC-MS, of which 118 were
conclusively identified and four were tentatively
identified. The aroma provided by this composition
was found to have the highest quality when com-
pared with other fractions extracted under different
conditions.
The advantages of SC-CO, extraction over
steam distillation or liquid solvent extraction
include: no thermal degradation of most of the
labile compounds; a minimum coextracted amount
of undesired compounds; no production of arti-
facts; and no solvent contamination.
References
[l] E. Gildemeister, Fr. Hoffmann, Die .&the&hen Gle,
vol. VI, Akademie, Berlin, 1961, p. 479.
[2] M.H. Klouwen, R. ter Heide, Quantitative determinations
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