Professional Documents
Culture Documents
Application Book
Chromatography Volume 2
Fast GC/GCMS
Application Book
Copyright:
Shimadzu Deutschland GmbH, Duisburg.
Reprint, in whole or in part, is subject to the
permission of the editorial office.
Editorial Team:
Prof. Luigi Mondello, University of Messina, Italy
Dr. Hans-Ulrich Baier, Shimadzu Deutschland GmbH,
Germany
Publisher:
Shimadzu Deutschland GmbH
Albert-Hahn-Str. 6 -10 47269 Duisburg, Germany
Telephone: + 49 (0) 203 7687-0
+ 49 (0) 203 766625
Telefax:
Email:
shimadzu@shimadzu.de
Internet: www.shimadzu.de
15
19
23
31
32
37
39
7
11
Overview
I.
Content
I. OVERVIEW
Chromatography Volume 2
x 104
x 106
0.25
6.0
3
4
0.50
7.0
Chromatography Volume 2
8.0
0.75
9.0
Minutes
1.00
Minutes
10.0
11.0
1.25
12.0
1.50
13.0
14.0
1.75
FWHM = 0.48 s
15.0
FWHM = 3 s
Peak identification:
1) n-Decane
2) n-Octanole
3) n-Undecane
4) 2.6-Dimethylphenole
5) 2.6-Dimethylaniline
6) Decane acid methyl ester
7) Undecane acid methyl ester
8) Dicyclohexylamine
9) Dodecane acid methyl ester
Figure I.1:
I. OVERVIEW
12
sample capacity, which is considerably lower than with conventional capillaries (this aspect will
be discussed later).
Dt
R EL
Wb
L
N = L = column length
HETP
Wa
tR
k2
tR 2
k=
, a =
=
tM
k1
tR 1
k2
EN a
R =
4 a 1 k2 + 1
it
R =
1_ [w + w ]
b
2 a
tR
N = 16
wb
Chromatography Volume 2
KD = k b
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0
100
150
50
200
isothermal (150 C)
HETPmin prop dI
ure II.2 for 2 columns of differing inner diameter [10]. The plate
height is characterized by a minimum value (HETPmin) at the
optimum linear velocity [9].
Both columns have a b value of
approximately 250. For columns
with such a high phase ratio value, the resistance to mass transfer
in the stationary phase can be
neglected and HETPmin can
therefore be approximated to the
column ID [10]:
13
Figure II.2: Van Deemter curves [10] for 0.25 mm and 0.1 mm ID columns.
The phase ratio is 250 in both cases.
where:
dI,df = inner diameter/film
thickness of the column
KD = distribution constant
b
= phase ratio
dI
b
4df
Chromatography Volume 2
HETP (mm)
20
40
14
temperature program
35
35
GC instrument requirements
The aforementioned issues have direct consequences on GC instrumentation requirements such as injection system, carrier gas pneumatics, column oven heating/cooling and detection. These aspects are
summarized as follows:
fast injection
60
[u] cm/s
N2
80
H2
He
This is achieved by the application of a pressure program automatically calculated by the GC software, and leads to a final pressure
of 660 kPa at 280 C. The cooling time for this analysis is below
2 minutes and the cycle time is under 4 minutes.
In the example illustrated in Figure I.1 (see page 9), a 120 cm/s average linear velocity was applied. In order to obtain this velocity an
initial pressure of 502 kPa was required at the initial temperature of
140 C. The gas chromatograph maintains the average linear velocity
constant over the temperature program (60 C/min up to 280 C).
35
35
high concentration range
35
Chromatography Volume 2
Figure II.3: Van Deemter curves measured using different carrier gases
(Shimadzu Corporation, Kyoto, Japan)
0.4
0.8
HETP (mm)
6. GC hardware requirements
16
Fl
Column flow
Splitting point
Fs
1.0
1.5
Minutes
2.0
2.5
3.0
3.5
4.0
1. Glass insert
0.5
n-Decane
Glass insert
Dimethylaniline
Split
n-Octanole
n-Undecane
Dimethylphenole
Purge
Carrier
Dicyclohexylamine
Fc
Chromatography Volume 2
Chromatography Volume 2
10.0
1.0
100.0
1,000.0
17
Figure III.3: Number of theoretical plates as a function of sample amount for two
different columns
60
70
80
90
100
Filter time t
Time
20
0.030
0.031
0.032
Minutes
0.033
0.034
0.036
100 ms
0.035
50 ms
20 ms
4 ms
200 ms
Figure IV.2: FID signal of chlorodecane. The filter time constant t was changed
from 4 to 200 ms. The sampling frequency was 250 Hz in all cases.
0.0
0.5
1.0
1.5
2.0
uV (x 10,000)
1. Conventional detectors
Signal
Chromatography Volume 2
2s
Time constant
Figure IV.4: Signal-to-noise ratio as a function of the filter time constant and for different peak widths
(source: GC-2010 operation manual)
04 ms
5 ms
0.2
Half width 1 s
0.6
The most common mass spectrometric detector used in gas chromatography is the quadrupole
MS. With regard to fast GC/MS
analysis, the MS detector obviously needs to be fast enough for
the rapid eluting analyte bands.
For identification purposes,
GC/MS applications are carried
Half width 10 s
0.4
Minutes
Minutes
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 0.2 0.4 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
21
0.8
1.2
Chromatography Volume 2
Normalized SN ratio
22
120
160
80
120
160
40
m/z
m/z
3.89
40
3.88
200
200
3.90
240
240
3.91
280
280
3.92
Minutes
3.922
20
min.
Linalool
2.4
60
61,307,110
m/z
100
140
Wiley
SI = 97
180
TIC
2.5
20
min.
60
2.4
61,307,110
m/z
100
Scan N +1
3.97
140
Wiley
SI = 98
180
TIC
2.5
20
min.
60
2.4
61,307,110
m/z
100
140
Wiley
SI = 97
RF setup
3.96
Inter-scan time
3.95
Scan N
3.94
Intervall I:
m1
m2
3.93
180
TIC
TIC*1.00
2.5
3.98
Chromatography Volume 2
Figure IV.5: Definition of scan speed, inter-scan delay and sampling frequency for a quadrupole MS
100
100
3.87
6,086,271
uV (x 1,000.000)
Trichlorphon
10
11
Minutes
10
Minutes
12
Phosphamidon (Z)
Fenthion
15
Tolclophos - Me
Ethion
Methidathion
Disulfoton
Profenophos
Dioxathion Phosphamidon (E)
20
13
Azinphos - Me
Carbophenothion
24
Peak identification: 1. Dichlorphos, 2. Trichlorphon, 3. Dioxathion, 4. Phosphamidon (E), 5. Disulfoton, 6. Phosphamidon (Z),
7. Tolclophos methyl, 8. Fenthion, 9. Methidathion, 10. Profenophos, 11. Ethion, 12. Carbophenothion, 13. Azinophos methyl
Figure V.1: Top: conventional GC chromatogram of organophosphorous pesticide standards in a tomato extract.
Concentrations vary beween 125 and 1,000 pg. Bottom: fast GC organophosphorous pesticide analysis carried out with a
RTX-5 : 10 m, 0.1 mm, 0.4 m column.
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
2.25
2.50
2.75
3.00
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
3.00
Chromatography Volume 2
A chromatogram relative to an
OPP-spiked (amount range
between 125 and 1,000 pg) tomato matrix is shown in Figure V.1.
The column used was a RTX-35
30 m, 0.25 mm, 0.5 m. The figure also shows the result
obtained with a RTX-5 (5 %
phenyl), 10 m, 0.1 mm, 0.4 m
column under fast GC conditions [14] (temperature program
from 100 C (1 min) at 80 C/
min to 220 C at 10 C/min to
240 C at 50 C/min to 320 C;
carrier gas: H2 (120 cm/s). The
injection volume was 2 L in the
splitless mode. In order to
increase the sample transfer
speed (see above) a 600 kPa high
pressure injection was applied
for 1 minute. The peak widths
(FWHM) are approximately 3 s
in the standard analysis and,
below, 0.5 s in the chromatogram
obtained with the narrow-bore
column. As the area in general is
determined by the sample
amount which was not changed
(both runs were carried out in
the splitless mode) the signal-tonoise ratio was higher in the fast
GC experiment. The retention
time of azinophos methyl was 22
minutes in the standard analysis
and 9 minutes in the fast result.
the procedure for the determination of organochlorine, nitrogencontaining and other types of pesticides. The procedure steps are
mainly: 1. extraction and partition,
2. gel permeation chromatography,
3. mini silicagel chromatography
and 4. analysis with GC-FTD,
GC-FPD or GC/MS.
2.0
3.0
Dichlorphos
Dioxathion
Phosphamidon (E)
Disulfoton
uV (x 1,000,000)
Phosphamidon (Z)
4.0
5.0
Ethion
6.0
Minutes
7.0
He 50 cm/sec
4.0
5.0
6.0
Endosulfan sulfate
Captan
Chlorpyrophos
8.0
9.0
7.0
0.0
2.5
5.0
0.0
2.5
5.0
7.5
GC/MS data:
Minutes
125.0
115
150.0
150.0
145 158
NCI
125.0
237
200.0
225.0
200.0
225.0
175.0
311
325.0
375.0
379
400.0
390
395
337
350.0
350
375.0
400.0
386
371 388
392
350.0
341349 357
386
387
169
313, 315, 212, 214
150, 149
97, 386
328, 192
Table V.1: EI and NCI dominant peaks observed with the organophosphorous
pesticides
Methamidophos
Methomyl
Diazinon
Chlorpyriphos-OEt
Captan
Endosulfan sulfate
Piperonyl butoxide
Potasan
325.0
EI Peaks (Da)
300.0
Substance
275.0
254 270
250.0
301
300.0
276
279 289
275.0
270
272
263
250.0
242
193 206
217 226
231
229
175.0
170
121 133 143 157
169
EI
NCI 50 pg Splitless
100.0
99
97
(x 1,000,000)
100.0
102
(x 10,000)
25
Figure V.3: Fast GC chromatogram of an olive oil sample. For the quantitative
determination of ethylparathion, bromophos methyl was added as internal standard; concentration ethylparathion: 3 ppb.
95,000
90,000
85,000
80,000
75,000
70,000
65,000
60,000
55,000
50,000
45,000
40,000
35,000
30,000
25,000
20,000
15,000
10,000
5,000
0
- 5,000
Figure V.4: Total ion chromatograms (TIC) of an OPP standard mixture analysis carried in the EI and NCI modes
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
(x 10,000,000)
Diazinon
1.3
Piperonyl butoxide
0.00
0.25
0.50
0.75
1.00
1.25
1.50
Chromatography Volume 2
Azinophos methyl
Potasan
Ethylparathion
Bromophos methyl (i.s.)
Dicofol Bunkaibutu
Malathion
Parathion
Dimethylvinphos
Pyrifenox-Z
Parathion methyl
Kresoxim methyl
Folpet
Cyanazine
Cadusafos
Tolclofos methyl
Pretilachlor
Malathion
Captafol
Flutolanil
2 - 10 times
Dichlofluanid
Fenalimol
Pendimethalin
Dieldrin
Edifenphos
Tefluthrin
Cypermethrin
Thifluzamide
Acetamiprid
PAP, Phenthoate
Pyrethrin-1
Endrin
Deltamethrin
b-BHC
a-BHC
3.0
4.0
(x 1,000,000)
5.0
6.0
7.0
26
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
2.25
2.50
2.75
3.00
3.25
Chlorpyrofos
p,p'-DDT
Dimethoate
d-Lindane
Cafenstrole
Fluvalinate-1
Pyrifenox-E
Diflufenican
Hexaconazole
Thiometon
Diazinon
Prothiofos
Difenoconazole
Pyridaben
Teraconazole
Chinomethionate
Bifenthrin
Inabenfide
Myclobutanil
8.0
9.0
Mix 0.5 pg
Black Tea
Table V.2: Classification of sensitivities with EI and NCI modes for pesticides
Bifenox
Fenvalerate
Chlorfenapyr
Cyfluthrin
Pyrethrin-2
MEP
EPN
Fenpropathrin
Acrinthrin
Trifluralin
Phosalone
Cyhalothrin
b-CVP
Flucythrinate
Butamifos
g-BHC
Captan
Imibenconazole
> 10 times
Chromatography Volume 2
Fosthiazate
Acephate
Terbacil
Pyraclofos
Penconazol
Uniconazolep
Fensulfothion
Cyhalofop buthyl
Butachlor
Aldin
Thiobencarb
Permethrin
Pyributicarb
p,p'-DDD
Chlorpyrofos
Bitertanol
Isofenphos
Quinalphos
p,p'-DDE
Pirimiphos methyl
p,p'-DDT
Halfenprox
Ethoprophos
Dichloros
2 - 10 times
Equality
Mepronil
Propiconazol
Lenacil
Tebucanzole
Etoxazole
Tebufenpyrad
Pyriproxyfen
Pyrimidifen
Mefenacet
Triadimenol
Etrimfos
Chlorobenzilate
Esprocarb
Thenylchlor
Tricyclazole
Isoprocarb
In conclusion, a combination of
EI and NCI as well as mass spectra library search for both modes
is a powerful tool for pesticide
analysis.
Chlorfentezinedeg
Metamidophos
EPTC
Propamocarb
Chlorpropham
Terbufos
Benfuresate
Dimethenamid
Alachlor
Metolachlor
Diethofencarb
Fenthion
Fludioxonil
Methoprene
Paclobutrazol
Flusilazole
Cyproconazole
> 10 times
Endosulfan sulfate
In conventional GC analysis
using standard columns of about
30 m length with a 0.25 mm inner
diameter and 0.25 m film, the
typical run time for an OCP standard solution containing 23 compounds is about 30 minutes (Figure V.6; for quantitative results
refer to Table V.3). The retention
time of p,p-DDD is about 21.5
minutes. The column used in this
application was a 5 % phenyl; the
temperature program was as follows: from 100 C (1 min) to 170
C, at 50 C/min (1 min), then to
220 C at 5 C/min, then to 260
C at 10 C/min, then to 280 C
(10 min) at 20 C/min using N2 as
carrier gas with an initial pressure
of 77 kPa corresponding to an
average linear velocity of 23 cm/s.
The injection was carried out in
the splitless mode (1 L).
Pentachlorbenzene
10.0
12.5
delta-HCH
15.0
17.5
Heptachlor
Tecnazene
uV (x 10,000)
Pentachlorbenzene
2.25
Pentachloranisole
alpha-HCH
Benfluraline
beta-HCH
HCB
Pentachloranisole
Lindane
epsilon-HCH
2.50
Pentachloraniline
2.75
Pentachloraniline
Benfluraline
Tecnazene
Minutes
20.0
22.5
25.0
3.00
Minutes
3.25
3.50
3.75
27.5
Mirex
4.00
27
Figure V.7: Fast analysis of the OCP standard mixture containing 23 compounds with a CP SIL 8 9 m, 0.1 mm, 0.1 m column.
For retention times and concentrations see Table V.3.
5.50
5.25
5.00
4.75
4.50
4.25
4.00
3.75
3.50
3.25
3.00
2.75
2.50
2.25
2.00
1.75
1.50
1.25
1.00
0.75
0.50
0.25
0.00
- 0.25
Heptachlor
Figure V.6: Conventional GC analysis of an OCP standard mixture (23 compounds) using a RTX-5 30 m, 0.25 mm ID,
0.25 m column. For operational conditions refer to text.
- 0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
Isobenzane
O
HCB
alpha-HCH
uV (x 1,000)
Lindane
beta-HCH
8.0
Aldrine
Isobenzane
Bromophos methyl
Isodrine
cis-Heptachloroepoxide
trans-Heptachloroepoxide
Bromophos ethyl
trans-Chlordane
cis-Chlordane
Aldrine
Bromophos methyl
Isodrine
cis-Heptachloroepoxide
trans-Heptachloroepoxide
Bromophos ethyl
trans-Chlordane
rganochlorine (OCP)
pesticides are commonly
measured using ECD or
MS (NCI mode) detectors.
p,p-DDD
cis-Chlordane
p,p-DDD
Chromatography Volume 2
Mirex
1.5
2.0
2.5
Minutes
3.0
3.5
4.0
4.5
Cypermethrin
28
cypermethrin at a concentration
of 0.55 ng/mL (corresponding to
0.5 ng/kg) were found.
1.25
1.50
uV (x 100,000)
1.75
2.00
Tecnazene
2.25
2.50
2.75
Minutes
3.00
3.25
3.50
RT
2.23
2.37
2.58
2.548
2.613
2.631
2.598
2.662
2.818
2.683
2.842
2.96
3.109
3.065
3.139
3.163
3.196
3.206
3.291
3.325
3.469
3.508
3.961
Conc (ppb)
21.3
22.5
52.8
22.1
24.1
20.6
20.4
28.8
23.2
1
26
30.4
21.7
5
22.6
22.04
25
25
50.36
5
5
22.4
21.84
3.75
4.00
4.25
4.50
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Chromatography Volume 2
Figure V.9: Fast GC chromatogram relative to an OCP standard mixture. Injection volume: 1 L, in the splitless mode,
high pressure pulse 400 kPa. Column: RTX-5 10 m, 0.18 mm, 0.4 m.
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
Figure V.8: Fast GC-ECD result for a grape sample: chlorpyrofos 0.53 ng/mL
(corresponds to 0.48 mg/kg grapes) and cypermethrin 0.55 ng/mL (corresponds
to 0.5 mg/kg)
- 0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
Chlorpyrofos
Benfluraline
6.5
Pentachloranisole
alpha-HCH
HCB
6.0
Lindane
beta-HCH
Lindane
7.0
Pentachloroaniline
8.0
delta-HCH
epsilon-HCH
7.5
Heptachlor
9.0
Pentachlorobenzene
Tecnazene
Benfluraline
a-HCH
HCB
Pentachloroanisole
b-HCH
Lindane
D-HCH
e-HCH
Pentachloroaniline
Heptachlor
Aldrine
Isobenzane
Bromophosmethyl
Isodrine
cis-Heptachloroepoxide
trans-Heptachloroepoxide
Bromophosethyl
trans-Chlordane
cis-Chlordane
p,p-DDD
Mirex
Aldrine
Isobenzane Bromophosmethyl
Isodrine
cis-Heptachloroepoxide
trans-Heptachloroepoxide
Bromophosethyl
8.5
Pentachlorobenzene
01
02
03
04
05
06
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
trans-Chlordane
uV (x 10,000)
p,p-DDD
9.5
cis-Chlordane
Mirex
5.0
5.6
5.1
5.4
316
237
5.2
5.3
5.0
5.1
346
5.7
344
237
5.2
5.4
406
244
242
280
282
71
5.0
0.0
2.0
0.0
5.9
6.6
Mass: 71.00
2.0
Name: t-Heptachloroepoxide
ID#:2
Calibration
[*10 ^ 4]
5.6
R.T.: 6.597
Name: p,p-DDE
ID#:7
11,109
5.8
R.T.: 6.011
Name: Endrin
ID#:6
54,371
5.8
5.0
5.9
6.7
6.8
6.0
6.0
6.9
308
272
6.1
6.1
ppb
7.0
70
310
308
5.0
6.1
274
6.1
406
404
242
Figure V.10: NCI (methane) GCMS data recorded in SIM mode (figures on the graphs refer to the selected mass traces) with an organochlorine standard containing
oxychlordane, t-heptachloroepoxide, endosulfan I, dieldrin, endosulfan II, endrin and p,p-DDE. Concentration of each compound is 0.4 to 0.6 ppb.
5.5
R.T.: 5.585
Name: Dieldrin
ID#:4
7,135
R.T.: 5.350
Name: Endosulfan II
ID#:3
66,700
4.9
R.T.: 5.062
Name: t-Heptachloroepoxide
ID#:2
30,396
4.9
318
Name: Endosulfan I
R.T.: 5.888
R.T.: 5.008
ID#:5
ID#:1
Name: Oxychlordane
45,640
25,424
Chromatography Volume 2
29
30
A conventional GC application
carried out with butter FAMEs is
illustrated in Figure V.11 [18].
The separation may be considered
to be quite complex and with the
column type used (Carbowax
30 m, 0.25 mm ID, 0.25 m film),
the total analysis time exceeds
30 minutes.
0.2
1) C4 : 0
2) C5 : 0
3) C6 : 0
4) C7 : 0
5) C8 : 0
6) C9 : 0
7) C10
8) C10 : 1
9) C11 : 0
10) C12 : 0
11) C12 : 1
12) C12 : 1 isomer
13) C13 : 0
14) C14 : 0 iso
15) C14 : 0
16) C14 : 1
17) C15 : 0 anteiso
18) C15 : 0 iso
5.0
10.0
15.0
Minutes
10
20.0
1112 13 14
15
16
18
19
25.0
21
22
23
25 2628
0.6
19) C15 : 0
20) C15 : 1
21) C16 : 0 iso
22) C16 : 0
23) C16 : 1
24) C17 : 0 anteiso
25) C17 : 0 iso
26) C17 : 0
27) C17 : 1
28) C18 : 0 iso
29) C18 : 0
30) C18 : 1 v9
31) C18 : 1 v7
32) C18 : 2 v?
33) C18 : 2 v6
34) C18 : 2 v?
35) C18 : 3 v3
36) C18 : 2 con.
C4 : 0
C6 : 0
C8 : 0
C10 : 0
C10 : 1
C12 : 0
C14 : 0
C14 : 1
C15 : 0
C16 : 0
C16 : 1
C17 : 0
C17 : 1
C18 : 0
C18 : 1
C18 : 2
C18 : 3
9
1.0
Minutes
10
1112 13 14
16
1819 21
1.4
15
1.4
1.4
1.1
2.7
0.2
3.5
11.6
1.0
1.3
32.0
1.8
0.7
0.3
10.7
24.2
3.0
0.5
Conventional
(run time: 33.0 minutes)
23
22
33
30
30.0
29
25
1.8
28
26
29
30
33
35 36
1.6
1.3
1.1
2.8
0.2
3.5
11.8
0.9
1.1
32.0
1.8
0.6
0.3
10.1
24.2
2.7
0.6
Ultra-fast
(run time: 2.0 minutes)
36
35
Chromatography Volume 2
0 e3
50 e3
100 e3
150 e3
200 e3
250 e3
300 e3
350 e3
uV
Figure V.12: Fast GC chromatogram of butter FAMEs using a wax column: 10 m, 0.1 mm, 0.1 m.
For experimental conditions refer to text.
0e3
10 e 3
20 e 3
30 e 3
40 e 3
50 e 3
60 e 3
70 e 3
80 e 3
90 e 3
100 e 3
110 e 3
uV
Table V.4:
Comparison of relative peak areas
for conventional and fast GC.
Area reproducibility over 5 successive
runs was below 1 % RSD.
C analysis of kerosene
may be considered to be
a very common quality
control procedure in the petrochemical field.
Chromatography Volume 2
10
Chromatogram
20
30
40
Minutes
50
60
0.25
0.5
0.75
1.0
Minutes
1.25
1.5
1.75
2.0
750 e 3
700 e 3
650 e 3
600 e 3
550 e 3
500 e 3
450 e 3
400 e 3
350 e 3
300 e 3
250 e 3
200 e 3
150 e 3
100 e 3
50 e 3
0e3
uV
2.25
1400 e 3
1300 e 3
1200 e 3
1100 e 3
1000 e 3
900 e 3
800 e 3
700 e 3
600 e 3
500 e 3
400 e 3
300 e 3
200 e 3
100 e 3
0e3
uV
31
2.0
(x 10,000,000)
3.0
4.0
5.0
6.0
[temperature program: 50 C
(1 min) to 210 C at 2 C/min, to
280 C at 10 C/min (10 min).
Carrier gas: He; average linear
velocity 34.4 cm/s; split ratio
300 : 1]. As the analysis time is
more than 75 minutes, the aim is
to decrease this extensive GC run
time in order to increase the sample throughput.
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
50.0
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.20
2.25
2.50
2.75
3.00
(x 1,000,000)
75.0
Coumarin
Iso-eugenol
Methyl gamma ionone
Lilial
Amyl cinnamic aldehyde
Lyral
Amyl cinnamic alcohol
Farnesol 1
Farnesol 2
Hexyl cinnamic aldehyde
Benzyl benzoate
Benzyl salycilate
Benzyl cinnamate
14
15
16
17
18
19
20
21
22
23
24
25
26
33
01
02
03
04
05
06
07
08
09
10
11
12
13
Chromatography Volume 2
27.5
(x1,000,000)
TIC
30.0
35.0
12 / Cinnamyl Alcohol
Minutes
5 / Citronellol
6 / Citral (Neral)
7 / Cinnamic Aldehyde
8 / Geraniol
9 / Citral (Geranial)
10 / Anisyl Alcohol
11 / Hydroxy Citronellal
32.5
37.5
13 / Eugenol
40.0
34
100
R = 0.9995
Limonene
Area (x 1,000,000)
200
300
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
(x10,000)
TIC
con. (ppm)
3.00
0.0
1.0
2.0
3.0
4.0
5.0
3.25
9 / Citral (Geranial)
6 / Citral (Neral)
8 / Geraniol
0
R = 0.9995
Lyral
Area (x 100,000)
5 / Citronellol
3.0
Eau de Toilette
4.0
Minutes
16
5.0
17
19
3.75
6.0
25
200
4.00
7.6
7.6
con. (ppm)
2.0
TIC
100
Minutes
3.50
7 / Cinnamic Aldehyde
Figure VII.4: Calibration curves determined with fast GC/MS for limonene and lyral
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Figure VII.3: Chromatographic expansions relative to Figure VII.1 and Figure VII.2
4.00
3.75
3.50
3.25
3.00
2.75
2.50
2.25
2.00
1.75
1.50
1.25
1.00
0.75
0.50
0.25
10 / Anisyl Alcohol
11 / Hydroxy Citronellal
Segment S1
Chromatography Volume 2
12 / Cinnamyl Alcohol
13 / Eugenol
Linalool
4.0
5.0
6.0
Citronellol
Geraniol
0.5
Chromatogram
uV (x 10,000)
Limonene
1.0
1.5
Rose Oxide
Rose Oxide
2.5
Myrcene + alpha-Phaellandrene
Limonene
cis-beta-Ocimene
gamma-Terpinene
trans-beta-Ocimene
Paracymene
Terpinolene
2.0
3.0
0.5
Chromatogram
Ethanol
alpha-Pinene
1.0
Camphene
1.5
Myrcene + alpha-Phaellandrene
alpha-Terpinene
Limonene
beta-Phellandrene Cineol 1,8
cis-beta-Ocimene gamma-Terpinene
Paracymene
Terpinolene trans-beta-Ocimene
2.0
3.0
Octanal
Sabinene
beta-Pinene
alpha-Pinene
7.0
8.0
3.5
4.0
4.5
3.5
4.0
4.5
Figure VII.8: Fast GC/MS chromatogram (DB wax 10 m, 0.1 mm, 0.2 m) of a limette essential oil (5 % in ethanol)
- 0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
uV (x 10,000)
Nonanal
Figure VII.7: Fast GC/MS chromatogram (DB wax 10 m, 0.1 mm, 0.2 m) of a geranium essential oil (5 % in ethanol)
- 0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
were identified with a high similarity using the aforementioned commercial library.
Linalooloxide
Menthone
Linalooloxide Isomenthone
Decanal
Linalool
I
n the flavor industry, routine
quality control analyses are
applied to a high number of
samples. In this field, the analysis
of essential oils is widespread and
may be considered as a complex
task. Chromatograms relative to
geranium and limette essential oil
analysis carried out on a DB
WAX 10 m, 0.1 mm, 0.2 m column are reported in Figure VII.7
and Figure VII.8.
3.0
beta-Caryophyllene
Terpin-1-en-4-ol
2. Quality control
of flavors
2.0
6-Methyl-Gamma-Ionone
Figure VII.6: Fast GC/MS TIC data relative to a perfume and obtained with a SPB-5 10 m, 0.1 mm, 0.1 m column
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
9.0
SI
93
96
99
99
98
96
91
Minutes
Minutes
Name
Ret. Time
Limonene
2,669
Linanool
3,219
Citronellol
4,18
Geraniol
4,342
6-Methyl-Gamma-Ionone
5,825
Lilial
6,201
alpha-Hexylcinnamic aldehyde 7,482
Linalool
beta-Caryophylene
Cuaiadiene + Citronellyle Formate
Geranyl Formate
Germacrene D
Geranyl Acetate
Citronellol
Nerol
Geranyl Isobutyrate
Geraniol
Geranyl Butyrate
4.5
TIC
alpha-Hexylcinnamic
aldehyde
(x 10,000,000)
Citronellyle Tiglate
alpha-Terpineol
gamma-Terpineol
Lilial
35
Phenylethyle Tiglate
Chromatography Volume 2
Geranyl Tiglate
10 gamma-epi Eudesmol
38
Table VIII.1:
List of PCBs contained
in the standard
min
Chromatogram
RT
4,537
4,746
4,953
4,957
5,011
5,065
5,138
5,161
5,219
5,238
5,255
5,42
5,437
5,555
5,577
5,601
5,648
5,676
5,703
5,734
5,745
5,816
5,869
5,987
6,072
6,105
6,122
6,197
6,223
6,339
6,36
6,426
6,488
6,548
6,681
6,839
7,004
7,165
HCB
18
31
28
53
Heptachlor
52
49
44
35
Aldrine
74
70
p,p-DDE
101
99
112
97
110
77
151
149
118
153
137
138
158
187
183
156
157
180
170
198
189
194
206
209
Chromatography Volume 2
Compound
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Target
Figure VIII.1: GC-ECD chromatogram of 38 PCBs using a SPB5 10 m, 0.1 mm, 0.1 m column.
Concentrations are about 0.1 ppb.
3,00
he reduction of analytical
cycle times in routine
applications has become
increasingly important in order
to increase productivity or to
acquire quick and correct results
in quality control processes.
39
[16]
[17]
[18]
[19]
[15]
[14]
[10]
[11]
[12]
[13]
[8]
[9]
[6]
[7]
[5]
[4]
[3]
[2]
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Literature