Sie sind auf Seite 1von 8

Determination of Aroma Compounds from

Alcoholic Beverages in Spiked Blood Samples


by Means of Dynamic Headspace GCMS

2007, 66, 879886

Katja Schulz1,&, R. Klaus Mueller2, Werner Engewald3, Adelgunde Graefe4, Jan Dreler1
1
Institute of Legal Medicine, Medical Faculty Carl Gustav Carus of Dresden Technical University,
Fetscherstr. 74, 01307 Dresden, Germany; E-Mail: Katja.Schulz@tu-dresden.de
2
Institute of Doping Analysis and Sports Biochemistry, Dresdner Str. 12, 01731 Kreischa, Germany
3
Institute of Analytical Chemistry, University of Leipzig, Linnestr. 3, 04103 Leipzig, Germany
4
Institute of Legal Medicine, University of Leipzig, Johannisallee 28, 04103 Leipzig, Germany

Received: 11 May 2007 / Revised: 20 July 2007 / Accepted: 27 August 2007


Online publication: 5 October 2007

Introduction
Abstract The analysis of congener substances is
used in forensic toxicological analysis to
Some aroma compounds found in alcoholic beverages are characteristic of a certain beverage examine claims relating to drinking.
(i.e. 2,4-decadienoic acid ethyl ester is characteristic of pear spirit and 5-butyltetrahydro-4- The analysis of congeners in alcoholic
methylfuran-2-on whiskey lactone is characteristic of aged spirits like whiskey). These sub- beverages was introduced by Machata and
stances were detectable in beverages but not in blood samples. The aim of this investigation was Prokop in 1971 [1]. On this basis, Bonte
to find a sensitive sampling technique for aroma compounds in whole blood samples. This developed the current standard of analysis:
technique may be used in forensic toxicology for examination of drinking claims. The method static headspace sampling in combination
comprises dynamic headspace sampling using a purge and trap concentrator, followed by with cryofocussing gas chromatography
quantitative gas chromatographymass spectrometry (dynamic HSGCMS). The influence of and ame ionisation detection (static
sample preparation, trap adsorbents and sample temperature as well as desorption time and HSGCFID). Before headspace analysis,
purge time on the quality of the analytical results were investigated. The following optimal the alcohol-glucuronides in blood samples
parameters were determined: stirred and diluted whole blood sample without salt addition, use were hydrolysed and then subjected to
of Carbotrap C as trap material, sample temperature at 80 C, desorption time 20 min and ultracentrifugation [25]. Besides ethanol,
purge time 30 min. These optimal parameters were used for the determination of detection the analyses also comprised the detection
limits (LOD). The LOD of aroma compounds by means of dynamic headspace sampling were of methanol, 1-propanol, 2-butanol,
compared with the results of conventional sampling: the static headspace technique. Limits of isobutanol, 1-butanol, 2- and 3-methyl-
detection for the aroma compounds with conventional static headspace GC are in the range 1-butanol, acetone and 2-butanone, the
40010,000 lg L 1. Dynamic headspaceGC was found to be a more sensitive sampling so-called congener substances. The con-
technique for most of the aroma compounds investigated (e.g. C4C8 ethyl esters, benzoic acid centrations of congeners analytically
ethyl ester, linalool oxide and 4-ethylguaiacol) with detection limits between 1 and 50 lg L 1, determined in blood samples are compared
but there were also limits to the sampling of substances with lower volatility like decanoic acid with the theoretically expected concentra-
ethyl ester, 2,4-decadienoic acid ethyl ester, eugenol and whiskey lactone with detection limits tions based on the information given by the
of about 1,000 lg L 1. defendant regarding the type and quantity
of the beverage consumed as well as the
drinking time. If the concentrations of the
Keywords congeners do not correspond to the defen-
dants claims, the post-oence drinking
Gas chromatographymass spectrometry claim is considered to be disproved.
Congener substances in alcoholic beverages For the calculation of the theoretically
Aroma compounds in blood samples expected concentrations, the concentra-
tions of congener substances in beverages
are required. A large database exists for

Original Chromatographia 2007, 66, December (No. 11/12) 879


DOI: 10.1365/s10337-007-0414-4
0009-5893/07/12  2007 Friedr. Vieweg & Sohn Verlag/GWV Fachverlage GmbH
these congeners in alcoholic beverages [6]. ducted in parallel with the development Sample Preparation
The disadvantage of this test is that the of United States Environmental Protec-
congener substances mentioned above are tion Agency (USEPA) methods of envi- The sample (750 lL deionised water for
present in most alcoholic beverages. They ronmental analysis, such as those used optimisation tests and 500 lL deionised
dier only in their concentration pattern for drinking water, wastewater, soils and water plus 250 lL whole blood for
in the individual beveragesthe relative solid waste. This technique is also used determination of detection limits) was
concentration of congeners one to an- for many other applications: polymer spiked with aroma compounds (1 lg
otherand hence also in blood samples analysis, pharmaceuticals and food and mL 1 each substance) and 50 lL internal
after consumption. beverage analysis. standard (1-heptanol, 10 lg mL 1). The
The congener substances mentioned Conventional congener analysis sample was stirred at 500 rpm.
above are not the only substances con- investigates nine substances (methanol, The sample preparation was opti-
tained in alcoholic beverages. There are 1-propanol, 2-butanol, isobutanol, mised in a preliminary study, and the
several 100 substances, i.e. the avour or 1-butanol, 2- and 3-methyl-1-butanol, nal conditions were as follows: stirring
aroma compounds. About 600 volatile acetone and 2-butanone) in concentra- (500 rpm) and heating (80 C) the whole
compounds have been identied in wine tions between 100 and 2,000 lg L 1 and blood samples without addition of salt.
[7] and about 200 [8] in beer, with about above 50 mg L 1 for methanol in special
the same number being found in spirits cases. The static HSGC is the best-suited
[9]. Therefore, it would be useful to ex- method for detection of these clear de- Headspace Conditions
tend the spectrum of substances detect- nite substances in the expected concen-
able in blood samples after consumption tration range. The ame ionisation The static headspace conditions for
of alcoholic beverages, such as aliphatic detector and the mass selective detector comparing both methods, static and dy-
and aromatic alcohols and esters, lac- can be used likewise. The method namic HS, are listed in the literature [25].
tones and terpenes [1015]. However, the parameters used for routine congener The headspace system used for anal-
detection of these aroma compounds in analysis in Germany are listed in the ysis was a Hewlett Packard 7695 purge
blood samples is not yet possible. literature [29]. and trap concentrator (Agilent). The trap
Determination is much more dicult in The intention of this paper is to was self-lled with 1.06 g Carbotrap C
biological material than in alcoholic broaden the spectrum of substances (s = 10 m2 g 1; particle size = 20/40
beverages because of their very low investigated by congener analysis. Some mesh). The trap pressure was 55 kPa. The
concentrations. It can be assumed that representative substances from alcoholic volume of the purge vessel was 44 mL
aroma compoundslike congener sub- beverages (Table 1), which occur in very and the needle position was 10 mm above
stancesare diluted by a factor of about low expected concentrations in blood, the sample (dynamic headspace mode).
1,000 in blood samples after consump- were investigated in spiked blood samples The sample was heated to 80 C1, the
tion of alcoholic beverages. The degree by means of dynamic HSGCMS. transfer line temperature was 200 C and
depends on the metabolism and kinetics In later studies, the method presented the desorption temperature 340 C. A
of the individual substance and the time here will need to be tested through anal- purge time of 30 min1, a dry purge time
after drinking. ysis of blood samples from drinking tests of 0.5 min1 and desorption time of
For preparing samples of beverages, with volunteers and road users. 20 min1 were used.
direct injection [16], liquidliquid
extraction [1719], static [2022] and
dynamic [23, 24] headspace, static head- Experimental GCMS Method
space trap analysis [25] or solid-phase-
micro-extraction (SPME) [2628] are Reagents and Materials The GCMS system used for analysis was
suitable. For the latter techniques, only a a Hewlett Packard G1800A GCD with a
few microlitres of the beverage are nee- All the aroma compounds listed in mass selective detector (Agilent). Data
ded in order to detect substances in the Table 1, as well as 1-heptanol as the acquisition and analysis were performed
range of lg L 1. internal standard, were purchased from using standard software supplied by the
Headspace sampling techniques (static Sigma-Aldrich (Taufkirchen, Germany). manufacturer. Substances were separated
and dynamic) oer many advantages for Ethanol, Na2SO4 and HClO4 for on a fused silica capillary column
sample preparation in the GC analysis of optimisation tests were obtained from HP-VOC, 90 m 0.32 mm i.d., lm
volatile and semi-volatile organic com- Merck (Darmstadt, Germany). Water thickness = 1.8 lm (Agilent). Tempera-
pounds. Volatile analytes are separated was deionised. Blank blood samples for ture program: 40 C hold for 5 min,
from the sample matrix (i.e. blood) prior spiking with aroma compounds were 10 C min 1 up to 220 C, hold for
to their introduction to the gas chro- obtained from the authors. The trap 20 min.
matograph without solvent extraction. material (Carbotrap C) was purchased The temperatures for the injection
Only minimal sample handling is re- from Sigma-Aldrich. The trap was self- port, ion source, quadrupole and inter-
quired. The dynamic headspace tech- lled by the authors. The adsorbent traps face were set at 220, 230, 150, 250 C,
nique also makes it possible to extract Tenax TA and VocarbTM 3000 for the respectively. Split injection mode (split
and concentrate volatile analytes from a 7695 purge and trap concentrator were ratio 4:1) and helium with a ow rate of
large volume of sample in combination obtained from Agilent Technologies 1.7 mL min 1 as carrier gas was used.
with high sensitivity. The development of (Waldbronn, Germany). All solvents and
1
purge and trap samplers has been con- reagents were of analytical reagent grade. Optimised parameters.

880 Chromatographia 2007, 66, December (No. 11/12) Original


To determine the retention times and Table 1. Structures and boiling points of the aroma compounds tested in blood samples
characteristic mass fragments, electron
No. Compound Boiling Structure
impact (EI) mass spectra of the analytes point (C)
were recorded by total ion monitoring.
All analytes were baseline separated. For 1 Butanoic acid 121 H3C O CH3
investigation of optimal analysis, the ethyl ester
parameters were monitored in full scan O
mode with a scan range 33270 m/z. For
investigation of detection limits, the 2 Acetic acid 126 H3C O CH3
chosen diagnostic mass fragments (see butyl ester
Table 2) were monitored in the selected O
ion monitoring (SIM) mode. O
3 Furfural 162 O

Validation H

Specicity was evaluated by analysing


blank whole blood samples from three
dierent persons. The mass spectra of 4 1-Hexanol 157 HO CH3
any peaks eluting at the same time as
aroma compounds were examined.
Linearity was tested by preparing 5 Acetic acid 3-methyl- 142 H3C O O
spiked whole blood samples of aroma 1-butyl ester
compounds at 0.54,000 lg L 1, The CH3 CH3
least squares method was used to calcu-
late the linear regression equation and the
correlation coecient (R2). 6 Hexanoic acid 166 H3C O CH3
ethyl ester
Intra- and interday precision were
evaluated by analysing ve samples of all O
the aroma compounds at 1,000 lg L 1
each on the same day and on dierent 7 Acetic acid 169 H3 C O CH3
days. hexyl ester
The detection limits of the investi- O
gated aroma compounds with static and
dynamic headspaceGC in spiked whole 8 1-Octanol 195
blood samples are summarised in HO CH 3
Table 2. They were determined by spik-
ing blood samples with dened dilutions 9 cis/trans-Linalool 188 HO
CH3
of aroma compounds. oxide O
Limit of detection (LOD) and limit of
H3C CH2
quantication (LOQ) were considered to CH3
be the concentration where the signal-to-
noise ratios were of 3 and 10, respec- 10 Butanedioic acid 216 O
tively. diethyl ester H3C O
The determination of detection limits O CH3
started with a relatively high concentra- O
tion of 4 lg mL 1 of each substance in
11 Octanoic acid 208 O
whole blood. Even higher concentrations
ethyl ester
of aroma compounds are irrelevant for
analysis because of their low concentra- H3C O CH3
tions in alcoholic beverages. The con-
centration was then successively reduced O
12 Benzoic acid 214
through bisection of the concentration by ethyl ester CH 3
dilution with blank blood samples. O

Results and Discussion

The principle of the dynamic headspace passes the volatile analytes over or by passing the carrier gas through the
technique is as follows: the trap is loaded through the heated sample at the cooled cold trap to remove moisture from the
by an inert gas ow (carrier gas) that adsorbent trap. Then the trap can be dried system. Finally, the analytes are thermally

Original Chromatographia 2007, 66, December (No. 11/12) 881


Table 1. continued blood volumina in this magnitude were
not available.
No.Compound Boiling Structure
point (C) All analytes (Table 1) were tested, but
only the analytes with the highest boiling
13 Acetic acid 2-phenyl 232 O CH 3 points and the lowest volatility are shown
ethyl ester in the gures. All other analytes were
O easily detectable in the concentration
range and under the conditions tested.
Whiskey lactone and eugenol could
14 4-Ethylguaiacol 234236 OH
only be detected in aqueous samples.
O
CH3

Sample Preparation

Initially, spiked aqueous samples were


H3C investigated to optimise the chromato-
graphic conditions in order to obtain a
15 Decanoic acid 245 O good separation of all the aroma com-
ethyl ester pounds under investigation.
O CH3 For optimisation, the spiked whole
H3 C
blood samples were investigated using
dierent procedures: stirring (500 rpm),
16 trans-2, cis-4- 7072 O heating (80 C), salting out by addition of
Decadienoic acid (0.05 mm) Na2SO4 (0.5 g) and protein precipitating
ethyl ester
O CH3 by addition of HClO4 (0.5 mL).
Furthermore, serum and ultraltrates of
blood samples were investigated.
The best results were achieved by
stirring and heating whole blood samples
simultaneously (Fig. 1). Whiskey lactone
and eugenol could only be detected in
CH3
aqueous samples.

17 Eugenol 254 OH
Choice of Trap Adsorbents
O
CH3
Three dierent sorbents were evaluated
on the trap: Tenax TA (s = 35 m2 g 1),
Vocarb 3000 (specic surface see below)
and Carbotrap C (s = 10 m2 g 1). The
manufacturers recommended tempera-
tures were used as desorption tempera-
CH2 tures. The trap Vocarb 3000known as a
sandwich-trapconsists of the materials
Carbopack B (s = 100 m2 g 1), Carbo-
18 cis/trans 9394 O
5-Butyltetrahydro- (5 mm)
O xen 1000 (s = 1,200 m2 g 1) and
4-methylfuran-2-on CH3 Carboxen 1001 (s = 500 m2 g 1) and is a
(Whiskey lactone) universal trap for very small molecules.
CH3 This trap material is preferred for use
with air pollutants. With these materials
the retention of 6 out of the 18 aroma
compounds was too strong. Butanedioic
acid diethyl ester, 4-ethylguaiacol, deca-
noic acid ethyl ester, 2,4-decadienoic acid
desorbed from the trap and injected into choice of trap adsorbents, sample tem- ethyl ester, eugenol and whiskey lactone
the GC. For adsorption dierent packing perature, purge time and desorption time. could not be desorbed from the trap
materials are available; in this study the For optimisation tests, only spiked material.
Carbotrap C material was used. aqueous samples were investigated be- The Tenax trap is a resin-based porous
For the investigation of optimal con- cause of the sample volume (250 lL), the polymer of 2,6-diphenylene oxide. It is
ditions, the following parameters were multitude of optimised parameters and also a universal trap and has been de-
tested: sample preparation, purge mode, the need for three replicates in each case; signed for the trapping of volatiles and

882 Chromatographia 2007, 66, December (No. 11/12) Original


Table 2. Results of method validation comparing static and dynamic headspaceGC of blood samples

Static Dynamic Dynamic HSGC SIMMS


HSGC HSGC
FID TIC-MS
LOD LOD Characteristic Linear R2 LOD LOQ Precision Precision
(lg L 1) (lg L 1) ionsa range (lg L 1) (lg L 1) intradayb interdayb
(lg L 1) (%) (%)

Butanoic acid ethyl ester 400 10 71/88/101 14,000 0.997 1 3 9.8 11.9
Acetic acid butyl ester 200 5 56/61/73 14,000 0.996 1 3 11.6 13.9
Furfural 400 20 67/95/96 24,000 0.999 2 7 6.0 6.9
1-Hexanol 20,000 10 56/69/84 14,000 0.999 1 3 10.4 12.9
Acetic acid 3-methyl-1-butyl ester 200 10 55/70/87 14,000 0.998 1 3 11.2 13.4
Hexanoic acid ethyl ester 200 10 88/99/101 24,000 0.999 2 7 8.9 10.4
Acetic acid hexyl ester 400 10 56/69/84 104,000 0.999 10 35 8.8 10.2
1-Octanol NP 50 70/84/112 504,000 0.997 50 150 6.6 8.7
cis/trans Linalool oxide 400/400 100/200 94/111/155 504,000/ 0.999/ 50/100 150/300 7.1/6.0 7.7/6.7
1004,000 0.993
Butanedioic acid diethyl ester 400 500 101/129 504,000 0.994 50 150 9.7 11.0
Octanoic acid ethyl ester 400 10 88/101/127 24,000 0.997 2 7 9.0 10.3
Benzoic acid ethyl ester 200 10 77/105/122 14,000 0.999 1 3 8.6 9.9
Acetic acid 2-phenyl ethyl ester 400 50 91/104/105 204,000 0.999 20 70 8.5 10.1
4-Ethylguaiacol 10,000 500 122/137/152 204,000 0.993 20 70 5.9 7.0
Decanoic acid ethyl ester 1,000 500 88/101/155 2004,000 0.997 200 700 11.1 13.2
2, 4-Decadienoic acid ethyl ester 2,000 2,000 97/125/196 5004,000 0.974 1,000 3,000 8.9 10.8
Eugenol 4,000 NP 131/149/164 ND ND NP NP ND ND
Whiskey lactone 2,000 NP 87/99/114 ND ND NP NP ND ND

All measurements were made in three replicate


NP Not present, ND not determined
a
Target ion underlined
b
Precisions are expressed as RSD (%), intra- and interday (n = 5)

semi-volatiles. Tenax TA did not work 500


Acetic acid 2-phenyl ethyl ester
4-Ethylguaiacol
well for eugenol and whiskey lactone.
Decanoic acid ethyl ester
Eugenol could not be detected with Tenax 400
2,4-Decadienoic acid ethyl ester
Peak area * 1000

TA and the peak area was signicantly Eugenol

lower (two times) for whiskey lactone. 300 Whiskey lactone

For all other analytes the recoveries (peak


areas) for Tenax TA were in the same 200
range as for Carbotrap C.
Carbotrap C is a graphitised carbon
100
black that is an ideal adsorbent resin for
the trapping of a wide range of organic
0
analytes from C4/C5 through to the 2 3 4 5 6 7
1
medium boilers [30, 31]. Sample preparation
The results of the investigation
showed that all three trap-types are Fig. 1. Eect of sample preparation (1 = blood stirring, heating, salt, HClO4; 2 = blood stirring,
equally suitable for the lighter volatile heating, HClO4; 3 = blood stirring, heating, salt; 4 = blood stirring, heating; 5 = serum stirring,
heating, salt, HClO4; 6 = ultraltrate stirring, heating, salt; 7 = water stirring, heating, salt,
substances (details not given). For the HClO4)
low-volatility substances the afore-men-
tioned restrictions are observable.
Therefore, Carbotrap C is the most suit-
able material for the tested aroma com- ethyl ester, whiskey lactone and eugenol increasing temperatures the sensitivity
pounds and was therefore used for the (Fig. 3), which need a minimal desorp- increases, but also a greater amount of
following optimisation (Fig. 2). tion time of 10 min. Because of the water is retained on the trap. It must be
strong retention, a desorption time of pointed out that the separation and peak
20 min was used. shapes of the aroma compound were not
Desorption Time
inuenced. The high boiling-point and
The desorption time was tested in the low-volatility aroma compounds 2,4-
Sample Temperature
range of 0.520 min with Carbotrap C decadienoic acid ethyl ester, whiskey
at the recommended temperature of The sample temperature was tested in the lactone and eugenol are only detectable
340 C. For most compounds desorption range 2580 C (Carbotrap C). The at sample temperatures above 70 C
time of 5 min is sucient, except for sample temperature has an essential eect (Fig. 4). The best results were achieved at
4-ethylguaiacol, 2,4-decadienoic acid on the sensitivity, as expected. With a temperature of 80 C.

Original Chromatographia 2007, 66, December (No. 11/12) 883


600
Carbotrap C
break through the trap together with
Tenax ethanol (Ethanol is used to dissolve the
500
Vocarb 3000 aroma compounds with a relatively low
degree of water solubility). The peak
Peak area * 1000

400
areas of the semi-volatile substances
300 4-ethylguaiacol and eugenol further in-
crease after 30 min purge time (Fig. 5).
200 They need a longer time to accumulate
than the lighter volatile compounds.
100
Therefore, a compromise purge time of
30 min was used.
0
Acetic acid 2- 4-Ethylguaiacol Decanoic acid 2,4-Decadienoic Eugenol Whiskey lactone The optimal conditions for the deter-
phenyl ethyl ethyl ester acid ethyl ester mination of detection limits were se-
ester
lected, namely: a stirred and diluted
Fig. 2. Choice of trap adsorbents, aqueous sample, purge temperature 80 C, purge time 30 min, whole blood sample (250 lL blood and
desorption time 10 min, n = 3 500 lL deionised water), the use of
Carbotrap C as a trap, a desorption time
of 20 min, a sample temperature of 80 C
and a purge time of 30 min. The GCMS
600 Acetic acid 2-phenyl ethyl ester chromatogram of separated substances in
4-Ethylguaiacol a spiked blood sample is shown in Fig 6.
500 Decanoic acid ethyl ester
2,4-Decadienoic acid ethyl ester
Eugenol
Peak area * 1000

400 Whiskey lactone

300 Validation

200 No interfering peaks were found in whole


blood samples with the same retention
100
time as the aroma compounds investi-
0 gated. Statistical data for the calibration
0 5 10 15 20 functions are summarised in Table 2. The
Desorption time (min) relative standard deviations (RSD), both
intra- and interday, indicate good repro-
Fig. 3. Eect of desorption time, aqueous sample, sample temperature 80 C, purge time 30 min,
ducibility of the method. The correlation
desorption temperature 340 C, Carbotrap C, n = 3
coecients (R2) of the calibration graphs
emphasise a good linearity in the con-
centration range investigated. LOD for
the majority of compounds in the range of
500
Acetic acid 2-phenyl ethyl ester 150 lg L 1 (SIM) with trap enrichment
4-Ethylguaiacol
450
Decanoic acid ethyl ester
are signicantly better than in classical
400 2,4-Decadienoic acid ethyl ester static headspace mode (LOD 200
350 Eugenol 10,000 lg L 1). Limits of detection for
Peak area * 1000

Whiskey lactone
300 the lower volatility compounds, decanoic
250 acid ethyl ester, 2,4-decadienoic acid ethyl
200 ester, eugenol and whiskey lactone were in
150
the same range as with classical static
headspace analysis. These substances
100
have boiling points above 240 C or are
50
distillable only under vacuum conditions.
0
They seem to be insuciently volatile for
1 30 40 50 60 70 80
Sample temperature (C)
headspace techniques.
Finally, the very low concentrations
Fig. 4. Eect of sample temperature, aqueous sample, purge time 30 min, desorption time 20 min, require an enrichment technique like
desorption temperature 340 C, Carbotrap C, n = 3 dynamic headspace (purge & trap).
Because of the large number of sub-
stances contained in blood samples
Purge Time 10 min the peak area of lighter volatile (from the biological matrix and nutri-
compoundsbutanoic acid ethyl ester, tional elements), a very long capillary
The purge time was tested in the range 2 acetic acid butyl ester and acetic acid 3- column is required for adequate separa-
60 min (Carbotrap C). Two contrasting methyl-1-butyl esterdoes not increase, tion and a mass selective detector (MSD)
eects can be seen: after a purge time of but rather decreases. These substances is needed.

884 Chromatographia 2007, 66, December (No. 11/12) Original


500
Acetic acid 2-phenyl ethyl ester
be detected in the expected concentration
4-Ethylguaiacol ranges of about 150 lg L 1 in whole
500 Decadienoic acid ethyl ester
blood. The detection limits established by
2,4-Decadienoic acid ethyl ester ester
Eugenol
dynamic headspace should be suitable for
400
Peak area*1000

Whiskey lactone the investigation of congeners in blood


300
samples of road users who have been
found to be under the inuence of alcohol.
200 Therefore a better verication of post-
oence drinking claims may be possible.
100 Further investigations of original
blood samples from drinking tests with
0
0 10 20 30 40 50 60
volunteers and road users are required
Purge time (min) before this method can be implemented in
practice.
Fig. 5. Eect of purge time aqueous sample, sample temperature 80 C, desorption time 20 min,
desorption temperature 340 C, Carbotrap C, n = 3

References
1. Machata G, Prokop O (1971) Blutalkohol
TIC: SIM1A.D 8:349353
Abundance 2. Bonte W, Busse J (1980) Blutalkohol
17:4957
3500000 3. Bonte W, Sprung R, Jurgens H, Manigold
IS J, Olbrich P, Pahl W (1983) Zbl Rechtsmed
3000000 25:368
4. Bonte W, Stoppelmann G, Rudell E,
2500000 3 Sprung R (1981) Blutalkohol 18:303310
6 5. Kuhnholz B, Bonte W (1983) Blutalkohol
4 12
2000000 20:399410
5 11 13 6. Bonte W (1987) In: Weinig E, Berg S (eds)
1500000 1 2 7 Begleitstoe alkoholischer Getranke,
10 Verlag Max Schmidt-Romhild, Lubeck,
1000000 pp 205341
8
9 14 15 7. Belitz HD, Grosch W (1992) Alkoholische
500000 Getranke. In: Belitz HD, Grosch W (eds)
Lehrbuch der Lebensmittelchemie,
Springer, Berlin, pp 805848
16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 8. Rompp Chemielexikon (1989) Georg
Time (min) Thieme Verlag, Stuttgart, New York,
pp 110112
Fig. 6. GCMSSIM chromatogram of spiked blood sample by dynamic headspace, 1 mg L 1 9. Strohmer G, Fauth R (2004) Extraktfreie
each compound (1 = butanoic acid ethyl ester, 2 = acetic acid butyl ester, 3 = furfural, und extraktarme Spirituosen. In: Kolb E
4 = 1-hexanol, 5 = acetic acid 3-methyl-1-butyl ester, 6 = hexanoic acid ethyl ester, 7 = acetic (ed) Spirituosentechnologie B. Behrs
acid hexyl ester, 8 = 1-octanol, 9 = cis/trans linalool oxide, 10 = butanedioic acid diethyl ester, Verlag, Hamburg, pp 43147
11 = octanoic acid ethyl ester, 12 = benzoic acid ethyl ester, 13 = acetic acid 2-phenyl ethyl 10. Lachenmeier DW, Emmert J, Kuballa T,
ester, 14 = 4-ethylguaiacol, 15 = decanoic acid ethyl ester) Sartor T (2006) Forensic Sci Int 158:18
11. Postel W, Adam L (1982) Alkohol-
Industrie 95:339341
12. Postel W, Adam L (1982) Alkohol-
Industrie 95:360363
Conclusions for these substances are 200 lg L 1 and 13. Postel W, Adam L (1982) Alkohol-
Industrie 95:287289
higher. 14. Postel W, Adam L (1982) Alkohol-
A new quantitative method for the For congener analysis, static head- Industrie 95:304306
determination of aroma compounds in space is the standard method. The 15. Lachenmeier K, Mussho F, Madea B,
congener substances like methanol, Sohnius EM, Frank W, Lachenmeier DW
blood samples has been developed. (2005) Dtsch Lebensm Rundsch 101:187
Optimal dynamic headspace conditions 1-propanol, 2-butanone, 2-butanol, iso- 192
were determined for sensitive detection. butanol, 1-butanol and 2- and 3-methyl- 16. European Commission (2000) O J Eur
Most aroma compounds, especially 1-butanol can be detected well in con- Commun L333:20
17. Heide R ter (1984) Found Biotech Ind
volatile and semi-volatile substances, can centrations of about 1002,000 lg L 1 Ferment Res 3:149165
be detected with a higher degree of whole blood. In static headspace mode, 18. Hildenbrand K, Christoph N, Bernreuther
sensitivity than by means of static the aroma compounds investigated here A (1990) Dtsch Lebensm Rdsch 86:3944
could not be detected satisfactorily (LOD 19. Guntert M, Rapp A, Takeoka GR,
headspaceGC. For the substances with
Jennings W (1986) Z Lebensm Unters
lower volatility, decanoic acid ethyl ester, above 200 lg L 1) because of their low Forsch 182:200204
trans-2, cis-4-decadienoic acid ethyl ester, vapour pressure and the resulting poor 20. Kolb B (1980) GIT Fachz Lab 24:1134
eugenol and whiskey lactone, a more transition in the gas phase. Only by 1139
21. Kolb B (1989) InCom instrumentalized
sensitive method for determination in enrichment of aroma compounds in the
analytical chemistry and computer tech-
blood samples must be found. The LOD gas phase the majority of substances can nology, pp 159170

Original Chromatographia 2007, 66, December (No. 11/12) 885


22. Diedericks W, Diedericks WJ (1996) 25. Schulz K, Dreler J, Sohnius EM, Lach- 29. Schulz K, Teske J, Gilg T, Aderjan R,
Hewlett-Packard PEAK 3:24 enmeier DW (2007) J Chromatogr A Herbold M (2006) Blutalkohol 43:269276
23. Salinas MR, Alonso GL, Esteban-Infantes 1145:204209 30. Dettmer K, Engewald W (2002) Anal
FJ (1994) J Agric Food Chem 42:1328 26. Ng LK, Hupe M, Harnois J, Moccia D Bioanal Chem 373:490500
1331 (1996) J Sci Food Agric 70:380388 31. Dettmer K, Engewald W (2003) Chroma-
24. Kaufmann AJ (1997) High Resolut Chro- 27. Vas G (1996) Supelco Report 15(5):67 tographia 57:339347
matogr 20:1016 28. Vas G (1997) Supelco Report 16(4):7

886 Chromatographia 2007, 66, December (No. 11/12) Original

Das könnte Ihnen auch gefallen