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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 material-solvent ratio, the method of feeding the
et al. [9]. However, the detailed effects of both the solvent, conditions of extraction (pressure, temper-
plant’s environmental conditions and extraction ature, time, flow rate), preparation of raw material
parameters on the yield and composition of the and separation conditions, etc. Analysis of the oils’
extract of angelica flavor have not yet been eluci- composition revealed that oils extracted under
dated. A large variability in the relative amounts different SFE conditions possessed widely different
of the compounds was found to depend on the percentage compositions. Qualitative aroma tests
stage of plant development and the kind of strains showed that the oil obtained at optimum SFE
and freshness of the roots at the time of extrac- conditions had a fragrance that better resembled
tion [9]. the flavor profile of the starting material.
Throughout the investigations, angelica root oil Angelica root oil has been isolated by SFE
was found to have a very complex composition. (12 MPa/SO”C) into three fractions with distinctly
The bouquet aroma of this oil is the result of the different compositions by three successive extrac-
combination of the aromas of a very large number tion steps and by using a single separator [9].
of components. Thus, it is very important that the Obviously, each of the fractions was found to
native natural proportion of the components is present a composition which did not resemble that
maintained during any extraction procedure. of the natural aroma composition. To perform
Unfortunately, the traditional extraction tech- that requirement, the fractions must be mixed after
niques based on liquid solvents or steam distilla- completing the extraction process and the removal
tion were found to present some disadvantages. of undesired compounds.
For example, the steam distillation procedure The aims of this study were to use an appropriate
cannot recover the pungent compounds because extraction procedure to obtain a more detailed
these are thermally degraded to produce volatile knowledge of the proportion of fragrant constitu-
aldehydes or ketones. Some of the aromatic com- ents of angelica roots and to elucidate the actual
pounds are also known to be affected by heat. The aroma composition of a fresh root extract.
essential oil when extracted with liquid solvents Therefore, this study reports an SFE technique to
lacks a strong aroma due to the loss of volatile isolate the volatile oil, consisting of two successive
compounds during the evaporation process of the extraction stages (static and dynamic), and a two-
solvents. Further, the alcohol extraction of the stage separation process. Approximately 200 com-
flavors was found to produce artifacts by esterifi- pounds were separated from extracted oil by a gas
cation, etherification, and/or acetal formation [ 31. chromatography-mass spectrometry (GC-MS)
Supercritical fluid extraction (SFE), mainly by analytical method, and more than half have been
supercritical carbon dioxide (SC-C02), can be used identified. Throughout the extraction process, nei-
to extract volatile oils from natural products and ther coumarins nor psoralens were detected in the
does not produce substantial thermal degradation GC traces of the extracted material, except for a
or solvent pollution/alteration of the extracts [lo]. small amount of osthol. Also, neither waxes, nor
Nevertheless, a high density of supercritical fluid large amounts of long-chain fatty acid esters, nor
(SCF) and one-stage subcritical separation is ethers were found. Furthermore, extracts with a
unsuitable due to the simultaneous extraction of high resemblance to the native aroma of angelica
many undesired compounds, such as fatty acids roots were obtained.
and their esters, cuticular waxes, coumarins, etc.
[ 111. SFE performed in multiple steps by increasing
the SCF density and a multistage separation tech- 2. Experimental section
nique give superior quality products compared
with those obtained by the traditional techniques 2.1. Materials
[ 12,131. However, there are many parameters that
must be considered in the SFE procedure. These Fresh angelica roots of var. Angelica archangel-
include the type of solvent/cosolvent, raw ica L. cultivated in Romania were used 1 day after
C. Doneanu, G. Anitescu / Journal of Supercritical Fluids 12 (1998) 59-67 61

harvesting. Grated samples of 500 g each were performed at various densities of carbon dioxide
placed in a stainless steel sieve basket to prevent showed that an extraction at 12.0 MPa and 40°C
carryover of particulates. Particle size was non- (1 h static process followed by 2 h dynamic pro-
uniform because of the particular procedure of cess) was optimum in order to have an acceptable
grating a fresh root material. Although grated yield and a composition containing a minimum of
material was passed through 1 mm diameter grater unwanted co-extracted compounds. Using these
holes, the length of the plant fibers was variable conditions, the undesired compounds, co-extracted
(N l-4 mm). Carbon dioxide of 99.5% purity was during the designated extraction time, were precipi-
used by passing through a filter filled with ZSM-20 tated selectively in the first separator, and the
molecular sieves for a further purification. The essential oil was recovered in the second separator.
molecular sieves were conditioned before using a The water collected in the second separator was
new cylinder with carbon dioxide by heating in an removed by addition of sodium sulfate.
oven at 200°C for 7 h.
2.3. GC-MS
2.2. Apparatus andprocedure
The GC-MS apparatus was a Fisons
SFE experiments were performed on an appara- Instruments MD 800 gas chromatograph-mass
tus mainly consisting of a thermostatic extractor spectrometer equipped with a split/splitless injector
(1 1 internal volume) and two separators operated (maintained at 250°C) and with a fused silica
in series (100 ml and 300 ml). More details on the SPB-5 column (50 m x 0.32 mm i.d. x 0.25 urn film
SFE apparatus were provided in a previous paper thickness, Supelco, Bellefonte, PA, USA). Helium
[ 131. No pump or compressor was used to deliver was used as the carrier gas, with an inlet pressure
SC-CO,. The system is essentially maintenance- of 70 kPa, and the septum purge was 4 ml mini.
free, with virtually no moving parts. The split ratio was 1:lOO and the volume of each
In the experimental runs, the extractor was of the injected samples was 0.1 ~1. The GC oven
charged with 500 g of grated roots of angelica was programmed to operate from 60 to 240°C
plant, and carbon dioxide was delivered into the (20 min) at 3°C min- ‘. The ion source temperature
extractor by controlled heating of a siphon-type was 200°C and the interface temperature was
cylinder. In the first step, the extractor was loaded 250°C. Data acquisition was performed with
with carbon dioxide up to a desired pressure and MassLab software for the mass range from 35 to
thermostatically controlled at a given temperature 480 a.m.u. with a scan rate of one scan per second.
during a 1 h period of time (a static period). In The ionization energy of electrons was 70 eV. The
the second step, a carbon dioxide flow rate of identification of compounds was based on a com-
0.5 kg h-’ (measured at the outlet of the appara- parison of experimentally obtained mass spectra
tus) was used during all the tests in a downflow with NIST, WILEY-6 and TERPENE mass
mode. Downflow of SCF through the fixed bed of spectra libraries, using relative retention indices
plant material is more effective than upflow, already established [ 151. In a second run, the oil
because in this mode any condensate is simply was injected into the same column, using a flame
pushed out of the bottom of the extraction vessel, ionization detector. The percentage composition
and the resultant oil content recovered [ 141. The was computed from peak areas without correction
pressure control valve at the outlet of the extractor factors. Finally, by using the same temperature
is moderately warmed by heating tape to prevent program, a mixture of n-alkanes from Ca to C&
plugging by freezing due to the Joule-Thomson was analyzed. The retention times were then
effect produced by flowing carbon dioxide. used for assigning Kovats retention indices of
Extracted fractions from the extractor were identified compounds in the angelica root oil
precipitated/condensed in two separators oper- extracts [ 16,171. In order to determine the ratio
ated in series at pressures/temperatures of of the co-eluted compounds, limonene and
6.0 MPa/lO”C and 3.0 MPa/O”C. Extractions 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 These conditions precluded contamination of the
by a rate of 25”Cmin’ to 240°C (20min) was liquid extract collected in the second separator. A
performed. 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
3. Experimental results and discussion charged in the extractor. When only a dynamic
procedure was used, carbon dioxide left the extrac-
The main goal of this study was to obtain the tor unsaturated with biocompounds in the first
best quality and the maximum yield of the angelica step of the extraction process. Therefore, a 1 h
oil by an optimal selection of SFE parameters. static step was completed before the dynamic step.
As expected, fresh root angelica oil was found The identification of the compounds constituting
to have a very complex composition. Its GC trace angelica root oil and their GC area percentages
is shown in Fig. 1, with compound identifications were reported in the first column of data in Table 1.
reported in Table 1. A series of runs was performed In the next columns of data are reported the
to assess the optimal extraction conditions: compositions of angelica oil extracted from dried
12.0 MPa and 40°C for the extractor (1 h static roots by different techniques: Soxhlet extraction
period of time and 2 h dynamic process) and performed by Kerrola et al. [9]; SFE method
6.0 MPa/lO”C and 3.0 MPa/O”C for the separators. (1.20 MPa/SO”C) performed by the same authors;
C. Doneanu, G. Anitescu / Journal of Supercritical Fluids 12 (1998) 59-67 65

18 23-34 82 93
lO(

Fig. 1. GC trace of the angelica (var. Angelica archnngelica) root oil (numbering of the peaks corresponds with the compounds
in Table 1).

extraction with ether-pentane followed by steam separated, of which 118 compounds were positively
distillation, performed by Taskinen and Nykanen identified and another four were tentatively iden-
[ 31. The second column of data shows averaged tified. To allow a comparison, the main families
results reported for four various origins of angel- of compounds identified from Table 1 are summa-
ica, while in the next column, results for the first rized in Table 2. Besides the hydrocarbons (monot-
two SFE fractions out of three were averaged. erpenes and sesquiterpenes) and their oxygenated
The results reveal a large variability in the compounds, Table 2 also presents the specific
relative amounts of the compounds, particularly angelica macrocyclic lactones and total undesired
between our results and those reported by Kerrola coumarins co-extracted with the oils. Compounds
et al. The percentage composition for commonly collected in the first separator were identified quali-
identified compounds reported by Taskinen and tatively, but only a rough estimation of the percen-
Nykanen appears to be in a reasonable concor- tage composition was made. The SFE process was
dance with ours. The results also show a strong optimized by quantification of the desired and
dependence of the oil composition on a number undesired compounds in the second separator to
of parameters, such as variety of wild or cultivated obtain maximum and minimum percentages
angelica strains, stage of the plant development, respectively. These data indicate reasonably good
freshness of the roots at the time of the extraction, agreement between our results and those reported
environmental conditions during the plant devel- by Taskinen and Nykanen.
opment, extraction methods, analytical pro- Monoterpene hydrocarbons represent the larger
cedure, etc. fraction of the angelica root oil constituents
The oil obtained from fresh roots of var. (- 80%). It was previously reported that the main
Angelica archangelica L. was examined in this proportion of angelica root oil consists of monoter-
study by capillary GC-MS using three mass pene hydrocarbons (up to 88%) [4]. Considerably
spectra libraries: NIST, WILEY-6 and TERPENE. smaller proportions of monoterpenes were detected
A total of approximately 200 compounds were 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” Cb c” Cd

Monoterpene hydrocarbons 81.57 34.39 69.60 82.28


Sesquiterpene hydrocarbons 6.13 15.01 10.45 6.75
Oxygenated compounds 6.91 20.43 6.15 4.98
Lactones 1.70 7.05 5.05 0.82
Others 2.99 23.12 8.75 5.17
(Coumarins) (0.23) (8.40) (2.05)

’ 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 followed by steam distillation.

et al. [9]: 24 to 46%. Nykanen et al. [7] reported a-copaene ( 1.16%), germacrene-D ( 1.13%), and
28% monoterpenes in an angelica root commercial B-bisabolene (1.13%).
oil. The main component in our fresh root angelica Oxygenated compounds of terpene hydro-
oil isolated by SFE is a-pinene (16.66%). Its carbons confer special characteristics to the angel-
isomer, S-pinene, is present at a lower percentage ica root oil, such as particular odor notes and
( 1.12%). As pinene and limonene oxidize to pro- stability of the oil against alteration. The com-
duce citronellol, carvone, piperitone, and carvacrol pounds extracted by SFE in significant amounts
[ lo], their high percentages in our oil compos- are: terpenyl acetate (1.23%), bornyl acetate
ition show the lack of oxidation phenomenon. (0.98%), a-copaen- 1l-01 (0.45%)) carvacrol
Note that a-phellandrene is also present in a (0.34%), and phellandral (0.27%).
high amount (11.27%), whereas its isomer, Macrocyclic lactones were found in a relatively
(3-phellandrene, was estimated quantitatively in a low percentage (1.70%), but they are very impor-
first step because of the co-elution with limonene tant compounds in angelica root oil. The musk-
(together they represent 22.04%). From a later GC like odor of this oil is generally attributed to the
analysis, limonene and B-phellandrene were found lactone of 15-hydroxypentadecanoic acid. Besides
to represent 13.12% and 8.92% respectively. Other pentadecanolide (0.49%), three other macrocyclic
monoterpene hydrocarbons identified in a large lactones were found in the oil isolated by SFE
amount were: 3-carene (8.69%), p-cymene (5.56%), from fresh roots of angelica var. archangelica
truns-p-ocimene (5.43%) and its geometric isomer, L.: 13-tridecanolide (0.82%), 12-methyl-13-tride-
ci,+ocimene (2.05%), myrcene (3.91%), and cam- canolide (0.33%) and heptadecanolide (0.06%).
phene (1.09%). The difference in odor of the Coumarins as undesired compounds were found
angelica root oils can be attributed to the composi- in a very low concentration in our SFE oil (only
tional differences of the volatiles, especially in the osthol, 0.23%) compared with those found in the
relative amounts of various monoterpene hydro- oils extracted by Kerrola et al. [9]: 2.05% in SFE
carbons [4]. It can be assumed that a high number oils and 8.40% in the oils extracted by the
of different monoterpene compounds indicates a Soxhlet method.
high quality of the oil aroma [9]. A qualitative sensory analysis of a number of
Sesquiterpene hydrocarbons represented 6.73% fractions extracted at different SFE conditions
of the angelica oil composition, in very good showed that the fraction extracted under the
concordance with the percentage reported by above-mentioned conditions had the best quality
Taskinen and Nykiinen (6.75%). The main compared with the other fractions and a commer-
compounds identified are: a-humulene (1.23%), cially available sample of the essential oil.
C. Doneanu, G. Anitescu / Journal ofSupercritica1 Fluids 12 (1998) 59-67 6-l

4. Conclusions [5] S.R. Srinivas, Atlas of Essential Oils, S.R. Srinivas, New
York, 1986.
[6] H. Kallio, R. Huopalahti, A. Nykanen, A. Ojala, Extraction
A two-step SFE process (1 h static period at of angelica root with liquid carbon dioxide, in: M. Martens,
12.0 MPa/40”C followed by 2 h dynamic period at G.A. Dalen, H. Russwurm (Eds.), Flavor Science and
12.0 MPa/40”C and 0.5 kg CO2 h-‘) coupled with Technology, Wiley, Brisbane, Australia, 1987, p. 111.
a two-stage separation process (6.0 MPa/lO”C and [7] I. Nyklnen, L. Nykanen, M. Alkio, Composition of angel-
ica root oils obtained by supercritical CO* extraction and
3.0 MPa/O”C) was selected as an optimum pro-
steam distillation, J. Essent. Oil Res. 3 (1991) 229.
cedure to extract a very complex oil from the fresh [8] K. Kerrola, H. Kallio, Extraction of volatile compounds of
roots of Angelica archangelica L. By this pro- angelica (Angelica archangelica L.) root by liquid carbon
cedure, approximately 200 compounds were sepa- dioxide, J. Agric. Food Chem. 42 (1994) 2235.
rated by capillary GC-MS, of which 118 were [9] K. Kerrola, B. Galambosi, H. Kallio, Characterization of
volatile composition and odor of angelica (Angelica archan-
conclusively identified and four were tentatively
gelica subsp. archangelica L.) root extracts, J. Agric. Food
identified. The aroma provided by this composition Chem. 42 (1994) 1979.
was found to have the highest quality when com- [lo] D. Couchi, D. Barth, E. Reverchon, G. Della Porta,
pared with other fractions extracted under different Supercritical CO, desorption of bergamot peel oil, Ind.
conditions. Eng. Chem. Res. 34 (1995) 4508.
[ 1l] E. Reverchon, A. Ambruosi, F. Senatore, Isolation of pep-
The advantages of SC-CO, extraction over
permint oil using supercritical COz extraction, Flavour
steam distillation or liquid solvent extraction Fragr. J. 9 (1994) 19.
include: no thermal degradation of most of the [ 121 E. Reverchon, G. Della Porta, D. Gorgoglione,
labile compounds; a minimum coextracted amount Supercritical CO2 fractionation of jasmine concrete,
of undesired compounds; no production of arti- J. Supercrit. Fluids 8 (1995) 60.
[ 131 G. Anitescu, C. Doneanu, V. Radulescu, Isolation of cori-
facts; and no solvent contamination.
ander oil: comparison between steam distillation and
supercritical CO, extraction, Flavour Fragr. J. 12 (1997)
173.
[ 141 P. Barton, R.E. Hughes Jr.,, M.M. Hussein, Supercritical
References carbon dioxide extraction of peppermint and spearmint,
J. Supercrit. Fluids 5 (1992) 157.
[ 151 R.P. Adams, Identification of Essential Oils by Ion Trap
[l] E. Gildemeister, Fr. Hoffmann, Die .&the&hen Gle, Mass Spectroscopy, second edition, Academic Press,
vol. VI, Akademie, Berlin, 1961, p. 479. London, UK, 1994.
[2] M.H. Klouwen, R. ter Heide, Quantitative determinations [ 161 N.W. Davies, Gas chromatographic retention indices of
of pentadecanolide in the volatile oil of Angelica archangel- monoterpenes and sesquiterpenes on methyl silicone and
ica by gas chromatography, Perfum. Essent. Oil Rec. 56
carbowax 20M phases, J. Chromatogr. 22 (503) (1990) 1.
(1965) 156. [17] W. Jennings, T. Shibamoto, Qualitative Analysis of
[3] J. Taskinen, L. Nykanen, Chemical composition of angelica Flavour and Fragrance Volatiles by Glass Capillary
root oil, Acta Chem. Stand. Ser. B: 29 (1975) 757. Column Gas Chromatography, Academic Press, New
[4] K. For&n, Aroma constituents of Angelica archangelica. York, 1980.
variation in the composition of the essential oil of strains
of var. norvegica and var. saliva, Rep. Kevo Subarctic Res.
Stn. 15 (1979) 1.