Analysis of Pine Needles

Essential Oils by GCGC-MS

and GCGC-FTIR
Y.
Y. BADJAH-HADJ-AHMED,
BADJAH-HADJ-AHMED, F.
F. TAZEROUTI,
TAZEROUTI, B.Y.
B.Y. MEKLATI
MEKLATI11
U.S.T.H.B.,
U.S.T.H.B., Faculty
Faculty of
of Chemistry,
Chemistry, B.P.
B.P. 32,
32, El
El
Alia,
Bab
Ezzouar,
16111
Algiers,
ALGERIA
Alia, Bab Ezzouar, 16111 Algiers, ALGERIA
11 C.R.A.P.C., B.P. 248, 16004 Algiers,
C.R.A.P.C., B.P. 248, 16004 Algiers,
ALGERIA
ALGERIA
E-mail:
E-mail: ybadjah@hotmail.com
ybadjah@hotmail.com

Pinus halepensis Mill.

It is also called the Aleppo pine, which grows up to
20 meters. It is the largest variety of many fir
trees that grow all around the Mediterranean region.

This tree has a silver-colored bark that is quite
smooth

The resin harvested from various species of Pinus
is undoubtedly the oldest and most important of the
non-wood products from conifers

Resins of pines were well known in ancient times;
an essential oil or turpentine was used by ancient
Greeks

Pine extracts are largely used in various fields:
perfumery, cosmetics, pharmaceuticals, synthesis

Many studies show the dependance of infesting
insects such as processionary moth and caterpillar on
the chemical composition of the pine tree host

These results indicated that the essential oils
from pine species were effective against insects and
their larvae

It is therefore feasible to use these essential oils
as environment-friendly insecticides for the control
of insect infestion in large forests

Aleppo pine essential oil

Aleppo pine is the main tree species in the large
forests covering the northern regions of Algeria

This work aims to investigate the chemical
composition of essential oil extracted from pine
needles in collaboration with the Algerian Forestry
Institute

Two vegetal samples were collected in the forests
of Tissemsilt and Djelfa

Essential oils were extracted by water distillation
at laboratory scale, using a Clevenger device during
three hours

After characterization of the obtained essential
oils by determination of their physical and chemical
properties, they were analysed by:
 gas chromatography on capillary column in
order to optimize the separation of their
components
 gas chromatography coupled to mass
spectrometry in electron impact and positive
chemical ionisation modes
 gas chromatography hyphenated to Fourier
transform infrared spectrometry

GC-MS chromatogram of the Pinus halepensis

needles essential oil (sample 1, Tissemsilt)
separated on a FFAP capillary column (EI mode)


 Fused
Fused silica
silica capillary
capillary column
column FFAP,
FFAP, 50m
50m xx 0.2mm
0.2mm

.mn-1-1,, split
split ratio:
ratio: 1/40
1/40
 Carrier
Carrier gas:
gas: helium,
helium, flowrate:
flowrate: 1.25cm
1.25cm33.mn

 Temperature
Temperature program:
program: from
from 60C
60C to
to 220C
220C (2.mn
(2.mn-1-1))

 VG
VG Micromass
Micromass with
with magnetic
magnetic separator
separator operating
operating at
at 70eV
70eV

 mass
mass range:
range: 20
20 to
to 320
320
-6 Torr

 Source
Source pressure:
pressure: 10
10-6
Torr

GC-MS chromatogram of the Pinus halepensis

needles essential oil (sample 2, Djelfa)
separated on a FFAP capillary column (EI mode)


 Fused
Fused silica
silica capillary
capillary column
column FFAP,
FFAP, 50m
50m xx 0.2mm
0.2mm

 Carrier
Carrier gas:
gas: helium,
helium, flowrate:
flowrate: 1.25cm
1.25cm33.mn
.mn-1-1,, split
split ratio:
ratio: 1/40
1/40

 Temperature
Temperature program:
program: from
from 60C
60C to
to 220C
220C (2.mn
(2.mn-1-1))

 VG
VG Micromass
Micromass with
with magnetic
magnetic separator
separator operating
operating at
at 70eV
70eV

 mass
mass range:
range: 20
20 to
to 320
320
-6 Torr

 Source
Source pressure:
pressure: 10
10-6
Torr

Constituents identified in Pine needles

essential oils by GC-MS (EI mode)
P eak N
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49

Constituent

M ain fragm ents

tricyclene
-pinene
camphene
-pinene
sabinene
-3-carene
myrcene
-terpinene
limonene
-phellandrene
cis- -ocimene
-terpinene
trans- -ocimene
p-cymene
-terpinolene
cis-3-hexen-1-ol
3,5-dimethylstyrene
-cubebene
-ylangene
-elemene
C 15H24 + C 10H16O
-pinene oxide
-copaene
Z-3-hexenyl-isovalerate
camphor
linalool
C 10H18O
bornyl acetate
-elemene
trans- -caryophyllene
terpinene-4-ol
C 10H16O
cis-caran-2-ol
-elemene
-humulene
trans- -farnesene
C 15H24
-muurolene
-terpineol
D germacrene
-selinene
C 15H24O
-muurolene
bicycloelemene

93, 121, 136, 92, 91, 79

93, 92, 91, 77, 41, 79
93, 121, 79, 107, 67, 41
93, 41, 69, 79, 77, 91
93, 77, 91, 41, 79, 94
93, 91, 77, 79, 92, 136
93, 41, 69, 39, 79, 77
121, 93, 136, 91, 77, 79
68, 93, 67, 136, 79, 94
93, 77, 91, 136, 79, 94
93, 92, 79, 91, 77, 41, 121
93, 136, 121, 91, 77, 43
93, 80, 79, 91, 41, 77
119, 134, 91, 120, 117, 41
121, 93, 136, 91, 79, 77
41, 67, 82, 55, 69, 42
132, 117, 115, 91, 131, 92
161, 105, 119, 93, 43, 41
81, 95, 161, 41, 79, 119
121, 136, 93, 161, 91, 41
95, 41, 204, 81, 161, 105
95, 91, 108, 81, 41, 136
161, 119, 105, 93, 41, 81
82, 41, 67, 95, 57, 83, 85
95, 81, 41, 108, 152, 69
71, 93, 41, 55, 43, 69
43, 139, 41, 94, 111, 69
95, 43, 41, 121, 136, 69
81, 93, 41, 69, 80, 133
41, 133, 93, 69, 91, 79
71, 93, 111, 43, 86, 69
71, 82, 43, 67, 41, 55
43, 93, 139, 69, 41, 136
161, 105, 119, 204, 91, 81
93, 80, 121, 41, 147, 92
99, 41, 93, 113, 79, 161
81, 93, 41, 121, 107, 67
161, 93, 119, 105, 104
59, 93, 136, 121, 81, 43
161, 105, 91, 81, 119, 41
204, 93, 41, 91, 105, 161
41, 93, 161, 44, 91, 105
105, 161, 204, 94, 93, 119
121, 93, 43, 136, 107

% (P1) % (P 2)
1.60
0.04
6.66
17.56
0.17
0.33
2.04
1.56
6.95
2.59
1.88
0.13
8.65
3.22
0.65
0.04
0.80
0.14
0.97
0.66
0.11
0.07
1.18
0.02
2.05
0.04
0.27
3.07
0.19
Tr
tr
0.09
tr
tr
tr
tr
0.24
0.21
020
tr
tr
tr
tr
tr
0.03
tr
tr
tr
0.05
0.39
2.01
tr
tr
tr
0.16
tr
0.20
7.07
2.69
0.59
tr
tr
tr
0.54
tr
0.58
2.77
1.38
tr
0.03
tr
tr
tr
tr
0.29
1.48
0.21
0.03
tr
tr
tr
tr
0.29
0.19
tr
tr

50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95

cis-piperitol
C 15H24
-cadinene
geranyl acetate
levomenol
nerol
phenylethyl acetate
calamenene
p-cymene-8-ol
geraniol
ethyl laurate
terpenyl n-butyrate
phenylethyl isobutyrate
C 15H26O
C 15H26O
C 15H26O
C 15H26O
phenylethyl butyrate
phenylethyl 2-methylbutyrate
phenylethyl isovalerate
methyl eugenol
humulene epoxide
nerolidol
cubenol
cadinenol
elemol
guaiol
methyl isoeugenol-1
phenylethyl n-hexanoate
C 20H32
C 15H16O3
C 15H16O3
C 20H32
trans-cadinol
methyl isoeugenol-2
C 20H32
Z-phenylethyl tiglate
torreyol
E-phenylethyl tiglate
C 20H32
-eudesmol
-cadinol
C 20H32
C 20H32
C 20H32
C 15H24O

84, 93, 139, 83, 41, 77

107, 121, 123, 41, 93, 91
161, 204, 134, 119, 105, 162
69, 41, 43, 68, 93, 136
93, 204, 121, 119, 109, 80
69, 41, 93, 68, 84, 39
104, 43, 44, 36, 41, 91
159, 81, 69, 95, 41, 82
43, 135, 91, 150, 136, 39
69, 41, 68, 93, 39, 123
88, 101, 43, 41, 55, 73
121, 108, 136, 93, 43, 41
71, 104, 43, 41, 105, 243
161, 104, 207, 105, 44, 119
41, 79, 93, 96, 44, 69, 83
161, 105, 207, 119, 204, 41
138, 41, 96, 79, 83, 82
104, 71, 41, 44, 43, 105
104, 57, 105, 42, 91, 79
104, 105, 57, 85, 41, 91
178, 163, 147, 91, 103, 179
138, 109, 43, 96, 67, 41
69, 41, 93, 81, 43, 71
161, 179, 119, 204, 105, 41
119, 161, 204, 105, 41, 82
59, 93, 161, 107, 41, 81
161, 59, 107, 105, 163, 93
178, 163, 107, 91, 103, 179
104, 105, 44, 43, 71, 41
121, 105, 229, 119, 107, 41
244, 204, 81, 43, 161, 159
189, 204, 244, 161, 133, 91
161, 105, 41, 257, 204, 121
161, 109, 95, 204, 81, 41
178, 163, 91, 107, 41, 105
93, 81, 107, 105, 119, 121
104, 55, 83, 105, 44, 91
161, 119, 105, 204, 43, 95
104, 83, 105, 55, 204, 161
161, 81, 93, 91, 41, 79, 105
59, 149, 164, 41, 109, 95
81, 95, 121, 93, 43, 41
41, 257, 69, 71, 93, 95
68, 93, 81, 107, 121, 67
121, 136, 93, 44, 41, 272
136, 41, 69, 67, 79, 91

tr
tr
0.87
tr
tr
tr
tr
tr
tr
tr
tr
tr
tr
tr
tr
1.05
0.97
7.37
tr
0.17
tr
tr
tr
tr
0.20
0.17
tr
tr
tr
tr
0.27
tr
tr
tr
tr
tr
0.18
tr
tr
tr
tr

tr
0.47
0.29
0.03
0.04
0.12
0.18
0.14
tr
tr
1.48
tr
tr
tr
tr
tr
1.87
10.29
8.38
tr
0.17
0.42
0.17
tr
tr
tr
tr
tr
0.17
tr
tr
tr
tr
tr
tr
tr
0.15
tr
tr
-

Identification
Identification of
of the
the constituents
constituents of
of Pine
Pine needles
needles
essential
essential oils
oils by
by GC-MS
GC-MS in
in electron
electron impact
impact mode
mode



Constituents
Constituents identified
identified by
by comparison
comparison of
of

 their
their retention
retention indices
indices to
to those
those of
of reference
reference pure
pure compounds
compounds

 their
their mass
mass spectra
spectra to
to those
those of
of standard
standard spectral
spectral libraries
libraries



sample
sample 1:
1: interpretation
interpretation of
of 90
90 mass
mass spectra
spectra,, 68
68 components
components
identified
identified



sample
sample 2:
2: interpretation
interpretation of
of 98
98 mass
mass spectra
spectra,, 64
64 components
components
identified
identified



54
54 constituents
constituents are
are simultaneously
simultaneously characterized
characterized in
in both
both samples
samples



the
the main
main components
components in
in P1
P1 and
and P2
P2 are
are respectively:
respectively:

 monoterpenic
monoterpenic hydrocarbons:
hydrocarbons:

-pinene

-pinene ((6.7%
6.7% and
and 17.6%
17.6%))

 sabinene
sabinene (6.9%
(6.9% and
and 2.6%
2.6%))

 -3-carene
-3-carene ((1.9%
1.9% and
and 0.13%
0.13%))

 -terpinene
-terpinene ((1.18%
1.18% and
and 0.02%
0.02%))

-ocimene
 trans-
trans-
-ocimene ((2.1%
2.1% and
and 0.04%
0.04%))

 sesquiterpenic
sesquiterpenic hydrocarbons:
hydrocarbons:

-caryophyllene
 trans-
trans-
-caryophyllene ((7.1%
7.1% and
and 6.7%
6.7%))

2.8% and
and 1.4%
1.4%))
 -humulene
-humulene ((2.8%

 oxygenated
oxygenated compounds
compounds (esters
(esters and
and alcohols):
alcohols):

 phenylethyl
phenylethyl isovalerate
isovalerate ((7.4%
7.4% and
and 8.4%
8.4%))

 phenylethyl-2-methylbutyrate
phenylethyl-2-methylbutyrate ((1.0%
1.0% and
and 10.3%
10.3%))

2.0% and
and 0.4%
0.4%))
 linalool
linalool ((2.0%

 -terpineol
-terpineol ((0.3%
0.3% and
and 1.5%
1.5%))

Mass spectrum of peak # 7

corresponding to -pinene

Mass spectrum of peak # 35

corresponding to trans-
-caryophyllene

Mass spectrum of peak # 24

corresponding to -ylangene

Mass spectrum of peak # 76

corresponding to guaiol

GC-MS chromatogram of the Pinus halepensis

needles essential oil (sample 1, Tissemsilt)
separated on a FFAP capillary column (PCI mode)


 Fused
Fused silica
silica capillary
capillary column
column FFAP,
FFAP, 50m
50m xx 0.2mm
0.2mm

 Carrier
Carrier gas:
gas: helium,
helium, flowrate:
flowrate: 1.25cm
1.25cm33.mn
.mn-1-1,, split
split ratio:
ratio: 1/40
1/40

 Temperature
Temperature program:
program: from
from 60C
60C to
to 220C
220C (2.mn
(2.mn-1-1))

 VG
VG Micromass
Micromass with
with magnetic
magnetic separator
separator operating
operating at
at 50eV
50eV

 mass
mass range:
range: 20
20 to
to 350,
350, reacting
reacting gas
gas :: isobutane
isobutane iC
iC44
-5 Torr

 Source
Source pressure:
pressure: 3.10
3.10-5
Torr

Constituents identified in Pine needles

essential oil (sample 1) by GC-MS (PCI mode)
Peak
N
7
8
8a
9
10
11
12
13
14
15
16
17
18
19
20
20a
20b
20c
22
28
31
32
33
35
36

Constituent

Main fragments

-pinene
camphene
hexanal

93, 92, 81, 137, 79, 136

137, 121, 93, 136, 81, 67
69, 67, 83, 101, 71, 81
93, 81, 137, 136, 69, 67
93, 137, 81, 136, 67, 69
93, 137, 136, 81, 67, 69
93, 69, 81, 137, 67, 95
136, 137, 121, 93, 81, 135
81, 137, 67, 93, 69, 136
137, 93, 136, 81, 69, 67

trans-
-caryophyllene
terpinene-4-ol

37
38
38a

C10H16O
cis-caran-2-ol
C10H20O

-pinene
sabinene
-3-carene
myrcene
-terpinene
limonene
-phellandrene
cis-
-ocimene
-terpinene
trans-
-ocimene
p-cymene
-terpinolene
m-diethylbenzene
p-diethylbenzene
o-diethylbenzene
3,5-dimethylstyrene
-copaene
linalool
C10H18O
bornyl acetate

69, 67, 81, 93, 79, 71

93, 137, 136, 69, 67, 81
81, 93, 137, 69, 80, 92
119, 135, 134, 69, 67, 93
136, 137, 135, 121, 93, 81
69, 67, 83, 74, 81, 71
69, 67, 81, 79, 85, 71
69, 67, 85, 79, 71, 81
69, 67, 71, 85, 79, 133
69, 67, 83, 161, 81, 79
81, 137, 69, 93, 71, 67
137, 69, 67, 81, 79, 71
137, 69, 67, 81, 85, 71
109, 95, 149, 81, 133, 205
137, 81, 69, 95, 93, 109,
111
137, 69, 81, 79, 85, 93
69, 67, 85, 81, 79, 71, 155
69, 67, 85, 81, 71, 79

Constituents identified in Pine needles

essential oil (sample 1) by GC-MS (PCI mode)
P eak N

7
8
8a
9
10
11
12
13
14
15
16
17
18
19
20
20a
20b
20c
22
28
31
32
33
35
36
37
38
38a
39
40
41

C o n s titu e n t
-p in e n e
ca m p h e n e
h ex a n a l
-p in e n e
sa b in e n e
-3 -ca re n e
m y rce n e
-te rp in e n e
lim o n e n e
-p h e lla n d re n e
cis-
-o cim e n e
-te rp in e n e
tra n s-
-o cim e n e
p -cy m e n e
-te rp in o le n e
m -d ieth y lben z en e
p -d ieth y lb en z en e
o -d ieth y lb en z en e
3 ,5 -d im e th y lsty re n e
-co p a e n e
lin a lo o l
C 10H 18O
b o rn y l a ce ta te
tra n s-
-ca ry o p h y lle n e
te rp in e n e -4 -o l
C 10H 16O
cis-ca ra n -2 -o l
C 10H 20O
-e le m e n e
-h u m u le n e
tra n s-
-fa rn e se n e

M a in fr a g m e n ts
93, 92, 81, 137, 79, 136
137, 121, 93, 136, 81, 67
69, 67, 83, 101, 71, 81
93, 81, 137, 136, 69, 67
93, 137, 81, 136, 67, 69
93, 137, 136, 81, 67, 69
93, 69, 81, 137, 67, 95
1 3 6 , 1 3 7 , 1 2 1 , 9 3 , 8 1 , 1 35
81, 137, 67, 93, 69, 136
137, 93, 136, 81, 69, 67
69, 67, 81, 93, 79, 71
93, 137, 136, 69, 67, 81
81, 93, 137, 69, 80, 92
119, 135, 134, 69, 67, 93
1 3 6 , 1 3 7 , 1 3 5 , 1 2 1 , 9 3 , 81
69, 67, 83, 74, 81, 71
69, 67, 81, 79, 85, 71
69, 67, 85, 79, 71, 81
69, 67, 71, 85, 79, 133
69, 67, 83, 161, 81, 79
81, 137, 69, 93, 71, 67
137, 69, 67, 81, 79, 71
137, 69, 67, 81, 85, 71
1 0 9 , 9 5 , 1 4 9 , 8 1 , 1 3 3 , 2 05
137, 81, 69, 95, 93, 109,
111
137, 69, 81, 79, 85, 93
69, 67, 85, 81, 79, 71, 155
69, 67, 85, 81, 71, 79
69, 67, 85, 71, 79, 81, 204
93, 147, 205, 109, 69, 95
69, 67, 81, 79, 95, 109

44
45
46
48

-te rp in e o l
D g e rm a cre n e

137, 81, 136, 69, 67, 93

161, 204, 205, 81, 69, 67

-se lin e n e
-m u u ro le n e

49
51
52
54
59
60
62
68
68a
69
70
71
72
76

b icy clo e le m e n e
C 15 H 24
-ca d in e n e
le v o m e n o l
g e ra n io l
e th y l la u ra te
p h e n y le th y l iso b u ty ra te
p h e n y le th y l-2 -m e th y lb u ty ra te
C 15 H 24 O
p h e n y le th y l iso v a le ra te
m e th y l e u g e n o l
h u m u le n e e p o x id e
n e ro lid o l
g u a io l

69, 67, 137, 81, 71, 79

205, 204, 203, 161, 105,
69
69, 81, 67, 137, 79, 121
69, 67, 81, 71, 79, 85
2 0 4 , 2 0 5 , 8 1 , 6 9 , 1 3 7 , 1 61

77

m e th y l iso e u g e n o l-1

78
79
83
84
85
88
89
92
93
98
101
102

p h e n y le th y l n -h e x a n o a te
C 20 H 32
tra n s-ca d in o l
m e th y l iso e u g e n o l-2
C 20 H 32
E -p h e n y le th y l tig la te
C 20 H 32
C 20 H 32
C 20 H 32
m a n o y l o x id e
C 20 H 32
C 20 H 32

69, 67, 81, 79, 85, 71

69, 67, 81, 71, 85, 79, 83
229, 69, 67, 85, 71, 79
105, 69, 67, 104, 71, 85
1 0 5 , 1 0 4 , 6 9 , 2 0 7 , 6 7 , 1 47
69, 203, 67, 81, 79, 95
105, 104, 69, 67, 207, 85
179, 178, 69, 67, 79, 85
69, 67, 81, 109, 85, 79
69, 67, 81, 79, 85, 71, 83
205, 69, 67, 204, 81, 79,
71
179, 178, 69, 67, 79, 71,
85
69, 67, 85, 71, 81, 79, 105
69, 67, 85, 71, 81, 79, 83
205, 69, 67, 81, 85, 71
1 7 9 , 1 7 8 , 6 9 , 6 7 , 1 8 0 , 1 51
273, 272, 81, 69, 149, 67
105, 69, 104, 67, 205, 85
69, 67, 161, 81, 79, 109
67, 69, 81, 95, 68, 109
69, 67, 71, 85, 79, 81
69, 67, 273, 81, 85, 79
69, 67, 71, 85, 79, 81
69, 67, 85, 71, 81, 79

Identification
Identification of
of the
the constituents
constituents of
of Pine
Pine needles
needles
essential
essential oils
oils by
by GC-MS
GC-MS in
in positive
positive chemical
chemical
ionization
ionization mode
mode (with
(with isobutane
isobutane as
as reactant
reactant gas)
gas)

Constituents
Constituents identified
identified by
by comparison
comparison of
of

 their
their retention
retention indices
indices to
to those
those of
of reference
reference pure
pure
compounds
compounds

 interpretation
interpretation of
of their
their PCI
PCI mass
mass spectrum
spectrum (due
(due to
to the
the
lack
lack of
of reference
reference data
data in
in CI-MS)
CI-MS)



Confirmation
Confirmation of
of 51
51 components
components identified
identified in
in sample
sample 11 (among
(among
which
which 44 were
were not
not detected
detected in
in EI-MS)
EI-MS)



Chemical
Chemical ionization
ionization is
is aa softer
softer technique
technique than
than electron
electron impact
impact
thus,
less fragments
fragments are
are observed
observed in
in PCI
PCI mass
mass spectra
spectra
thus, less



Proton
Proton transfer
transfer often
often occurs
occurs leading
leading to
to an
an adduct
adduct protonated
protonated
ion
observed in
in most
most spectra
spectra
ion MH
MH++ observed



Fragmentation
Fragmentation of
of this
this protonated
protonated adduct
adduct ion
ion gives
gives the
the
observed
observed fragment
fragment ions
ions


odd mass
mass and
and an
an even
even

Most
Most fragments
fragments correspond
correspond to
to an
an odd
number
(very few
few ion-radical
ion-radical fragments)
fragments)
number of
of electrons
electrons (very



The
The differentiation
differentiation between
between stereoisomers
stereoisomers is
is easier
easier with
with CI
CI
than
than EI
EI mass
mass spectra,
spectra, the
the identification
identification is
is more
more accurate
accurate with
with
the
the former
former mode
mode

Mass spectrum in PCI mode of bicycloelemene

Mass spectrum in PCI mode of -cadinene

Comparison of cis and trans-

-ocimene
mass spectra in EI and PCI modes
EI

CI

EI

CI

GC-FTIR chromatogram of the Pinus

halepensis needles essential oil (sample P1)
separated on a BP1 capillary column

GC-FTIR chromatogram of the Pinus halepensis

needles essential oil (sample P1) separated on
a BP20 capillary column

Constituents identified in Pine needles

essential oil (sample 1) by GC-FTIR
pe a k N a nd
re te ntio n inde x
BP1
BP20

Com ponent

Ch a ra c te ris tic b a n d s

4 -m e th y l-2 -p e n ta n o n e

2965, 1732, 1364, 2895, 1164

tr ic y c le n e

2967, 2910, 3056, 778, 1446, 1380

5(928)

-p in e n e
cam phene

2925, 2892, 2993, 1456, 1380, 3027, 759

3(1032)

6(942)

2967, 2886, 882, 3075, 1469, 1660

7(954)

-p in e n e
s a b in e n e
-3 -c a r e n e

2929, 2989, 2898, 877, 1642, 3077, 1462, 1379

4(1123)

9(981)

2966, 2881, 873, 1655, 3077, 1463, 1385

5(1134)

8(976)

2881, 2928, 3009, 2844, 1446, 793, 1377, 1138

6(1173)

11(1001)

m yrcene

2930, 898, 2978, 2871, 3092, 1591, 990, 1448

7(1192)

10(986)

-te r p in e n e
lim o n e n e

2968, 2924, 2881, 2833, 3041, 1377, 1458

8(1210)

2926, 2969, 2877, 2850, 887, 3086, 1450, 1641

9(1220)

13(1019)

-p h e lla n d r e n e
-te r p in e n e
c is -
-o c im e n e

2945, 2885, 878, 3018, 1377, 1460, 3084, 1546

10(1237)

2969, 2876, 2928, 2719, 3095, 1464, 1153, 714

11(1251)

15(1046)

2970, 2930, 2878, 3009, 2831, 894, 1379, 3074

12(1261)

tr a n s -
-o c im e n e

2924, 2985, 2877, 899, 3084, 990, 1105, 1381

13(1279)

14(1038)

p -c y m e n e
tr a n s -a llo o c im e n e

2970, 2937, 2858, 3027, 814, 1518, 1057, 1467

14(1286)

12(1016)

2966, 2941, 2884, 1381, 1461

17(1120)

te r p in o le n e

2917, 2870, 2976, 1444, 1375, 891

15(1305)

16(1075)

-c u b e b e n e
-c o p a e n e
n o n id e n tifie d

2915, 2965, 2883, 1379, 1446, 3084

23(1381)

2928, 2972, 2887, 3009, 1375, 1453, 1111, 848

16(1519)

2926, 2970, 2891, 1371, 1446, 1107, 1202

18

c a m p h o r (m ix tu r e )
n o n id e n tifie d

2962, 2930, 2886, 1751, 3008, 832, 1173

17(1518)

2982, 2934, 3026, 1503, 1107, 1164, 1377

19

lin a lo o l

2929, 2978, 922, 2876, 1108, 1374, 1175, 999

18(1529)

-e le m e n e
b o r n y l a c e ta te

2969, 2845, 2885, 904, 726, 3074, 1073, 1382

19(1565)

2944, 1242, 2989, 1742, 2918, 2999, 2898

20(1585)

-c a r y o p h y lle n e
te r p in e n e -4 -o l
n o n id e n tifie d

2935, 2952, 2868, 891, 1454, 1379, 3076, 1627

21(1617)

24(1410)

2971, 2921, 1380, 1446, 1009, 1166, 3632, 1226

22(1628)

20(1158)

2967, 2948, 2886, 723, 1115, 1384, 3076, 1460

23

c itr o n e lly l a c e ta te

2925, 1234, 2968, 1760, 2887, 1371, 1447

24(1644)

 -muurolene
-humulene

2936, 2967, 2882, 1183, 891, 3084, 1446, 1382

27

0921, 2964, 2865, 969, 1381, 1450, 3029, 827

25(1649)

25(1459)

-terpineol
D-germacrene

2976, 2929, 2847, 1380, 1162, 924, 1451, 3645

26(1661)

21(1185)

2939, 2967, 2882, 1230, 1761, 1383, 1453, 886

27(1686)

28(1468)

-muurolene
geranyl acetate
-cadinene

2966, 2938, 2882, 1456, 1381

29(1500)

1230, 1759, 2924, 1004, 1371, 1480

29(1735)

22(1358)

2969, 2911, 2871, 2846, 1456, 1378, 773, 945

30(1761)

30(1524)

2931, 2971, 2868, 3027, 1382, 1452, 748, 1107

31(1766)

2981, 2935, 1165, 1110, 812, 3027, 1379, 1517

32(1797)

2967, 2941, 1153, 1752, 1192, 2876, 702, 912

34(1828)

1750, 1147, 1178, 2978, 2943, 1239, 1070, 1465

36(1945)

-cadinene
geraniol
terpenyl butyrate
phenylethyl-2methylbutyrate
phenylethyl isovalerate
caryophyllene oxide

1753, 1180, 2967, 1293, 1249, 1113, 1004

37(1955)

26(1474)

2943, 2872, 1462, 892, 1384, 3084, 872, 1750

38(1953)

34(1563)

humulene epoxide

2964, 2928, 2867, 977, 1381, 1459, 819, 3027

29(1980)

35

guaiol
phenylethyl hexanoate

2962, 2916, 1708, 2875, 1107, 1380, 1456, 921

42

37

2961, 2916, 1708, 2875, 1107, 1380, 1456, 921

43(2134)

33(1618)

non identified

2941, 2962, 2908, 2875, 1375, 1455

36

non identified
methyl isoeugenol-2

2930, 2969, 2882, 1466, 1378, 908, 1145

44

2959, 2881, 1258, 1513, 1036, 1380, 1272, 1142

45(2126)

E-phenylethyl tiglate

2962, 1146, 2881, 2848, 1221, 1383, 1731, 1459

46(2154)

31(1562)

Z-phenylethyl tiglate
non identified

2977, 2947, 1148, 1748, 1379, 2849, 2942, 2969

32(1562)

2942, 2969, 2876, 1383, 1117, 1089, 1455, 3636

47

non identified

2959, 2936, 2904, 2867, 1004, 891, 822, 3086

48

non identified
non identified

2957, 1023, 2867, 887, 1070, 3093, 1375, 1457

49

2913, 2960, 2873, 1317, 1446, 3639

38

C20H34O

2935, 2966, 2849, 1380, 975, 1450, 710, 1099

50

41

C20H34O

2934, 2964, 2886, 1382, 978, 1446

51

42

FTIR spectrum of peak # 14 (BP20)

corresponding to p-cymene

FTIR spectrum of peak # 4 (BP20)

corresponding to -pinene

FTIR spectrum of peak # 7 (BP20)

corresponding to myrcene

FTIR spectrum of peak # 24 (BP1)

corresponding to trans-
-caryophyllene

FTIR spectrum of peak # 22 (BP20)

corresponding to caryophyllene mixture

FTIR spectrum of peak # 20 (BP1)

corresponding to terpinene-4-ol

FTIR spectrum of peak # 12 (BP20)

corresponding to cis-
-ocimene

FTIR spectrum of peak # 13 (BP20)

corresponding to trans-
-ocimene

FTIR spectrum of peak # 27 (BP20)

corresponding to germacrene D mixture

FTIR spectrum of peak # 28 (BP20)

corresponding to germacrene D

FTIR reference spectrum of neryl acetate

FTIR spectrum of peak # 29 (BP1)

corresponding to -muurolene

FTIR spectrum of peak # 27 (BP1)

corresponding to muurolene

Identification of the constituents of Pine

needles essential oils by GC-FTIR



Constituents
Constituents were
were identified
identified by
by comparison
comparison of
of


 their
their retention
retention indices
indices to
to those
those of
of reference
reference pure
pure
compounds
compounds

 their
their IR
IR spectra
spectra to
to those
those of
of vapour
vapour phase
phase reference
reference
infrared
infrared spectra
spectra obtained
obtained from
from standard
standard libraries
libraries



51
51 IR
IR spectra
spectra were
were studied
studied and
and 47
47 constituents
constituents
identified
identified in
in sample
sample 11



44 components
components identified
identified by
by GC-FTIR
GC-FTIR were
were not
not detected
detected
by
by GC-MS
GC-MS (by
(by either
either EI
EI or
or PCI
PCI ionisation):
ionisation): neryl
neryl acetate,
acetate,

citronellyl
citronellyl acetate,
acetate, g-cadinene,
g-cadinene, caryophyllene
caryophyllene oxide
oxide



the
the use
use of
of two
two different
different capillary
capillary columns
columns ((polar
polar and
and nonnon-

polar
was useful
useful to
to achieve
achieve aa good
good separation
separation at
at least
least on
on
polar)) was
one
one column
column in
in order
order to
to get
get aa IR
IR spectrum
spectrum of
of the
the pure
pure
component
component



Characterization
Characterization of
of stereoisomers
stereoisomers is
is easier
easier by
by
differentiation
differentiation of
of their
their IR
IR spectra
spectra