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Validation of a multi-residue method for the analysis of off-flavour compounds in wine by SBSE-GC-MS-SIM : a
rapid off-flavour profile
Cécile Franc, Gilles de Revel
To cite this version:
Cécile Franc, Gilles de Revel. Validation of a multi-residue method for the analysis of off-flavour
compounds in wine by SBSE-GC-MS-SIM : a rapid off-flavour profile. 8. Symposium International
d’Œnologie ”Œno 2007”, Jun 2007, Talence, France. 1 p., 2007. �hal-02815500�
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VALIDATION OF A MULTI-RESIDUE METHOD FOR THE ANALYSIS OF OFF-FLAVOUR COMPOUNDS IN WINE BY SBSE-GC-MS-SIM :
A RAPID OFF-FLAVOUR PROFILE
Céline Franc and Gilles de Revel
UMR 1219 œnologie - Université Victor Segalen Bordeaux 2 - INRA – ISVV
Faculté d’Œnologie, 351 cours de la Libération, F-33405 Talence Cedex - revel@u-bordeaux2.fr
Introduction
Validation of the multi-residue SBSE-GC-MS-SIM method Methodology
Applications : off-flavour profile of wine
Conclusion
References
24.00 25.00 26.00 27.00
0 1000000 2000000 2500000
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Abundance
EP 126 µg/L
24.5024.70 24.90
000
5000 8500 Abundance
IBMP-d3 IBMP 22.3 ng/L
31.00 33.00 35.00 37.00 39.00
EG-d5
EG
56 µg/L 33.40 34.00 34.60
2500 5500 Abundance
TCA-d5 TCA 5.4 ng/L
38.00 38.40 38.80 39.20 39.60 15000 30000 Abundance
Geo-d5
Geosmin 46.4 ng/L
44.00 45.00 46.00 47.0048.00 44.00 45.00 46.00 47.00 48.00 5000
10000 12000 Abundance
TBA 9.9 ng/L TeCA 10.3 ng/L
PCA 29.0 ng/L
24.00 25.00 26.00 27.00
0 1000000 2000000 2500000
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Abundance
EP 126 µg/L
24.00 25.00 26.00 27.00
0 1000000 2000000 2500000
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Abundance
24.00 25.00 26.00 27.00
0 1000000 2000000 2500000
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Abundance
EP 126 µg/L
24.5024.70 24.90
000
5000 8500 Abundance
IBMP-d3 IBMP 22.3 ng/L
24.5024.70 24.90
000
5000 8500 Abundance
24.5024.70 24.90
000
24.5024.70 24.90
000
5000 8500 Abundance
IBMP-d3 IBMP 22.3 ng/L
31.00 33.00 35.00 37.00 39.00
EG-d5
EG 56 µg/L
31.00 33.00 35.00 37.00 39.00
31.00 33.00 35.00 37.00 39.00
EG-d5
EG
56 µg/L 33.40 34.00 34.60
2500 5500 Abundance
TCA-d5 TCA 5.4 ng/L
33.40 34.00 34.60 2500 5500 Abundance
33.40 34.00 34.60 2500 5500 Abundance
TCA-d5 TCA 5.4 ng/L
38.00 38.40 38.80 39.20 39.60 15000 30000 Abundance
Geo-d5
Geosmin 46.4 ng/L
38.00 38.40 38.80 39.20 39.60 15000 30000 Abundance
38.00 38.40 38.80 39.20 39.60 15000 30000 Abundance
Geo-d5
Geosmin 46.4 ng/L
44.00 45.00 46.00 47.0048.00 44.00 45.00 46.00 47.00 48.00 5000
10000 12000 Abundance
TBA 9.9 ng/L TeCA 10.3 ng/L
PCA 29.0 ng/L
44.00 45.00 46.00 47.0048.00 44.00 45.00 46.00 47.0048.00 44.00 45.00 46.00 47.0048.00 44.00 45.00 46.00 47.00 48.00 5000
10000 12000 Abundance
TBA 9.9 ng/L TeCA 10.3 ng/L
PCA 29.0 ng/L
44.00 45.00 46.00 47.00 48.00 5000
10000 12000 Abundance
44.00 45.00 46.00 47.00 48.00 44.00 45.00 46.00 47.00 48.00 5000
10000 12000 Abundance
TBA 9.9 ng/L TeCA 10.3 ng/L
PCA 29.0 ng/L
9Comparison with the measurements by other validated analysis methods used routinely (extraction-enrichment by HS-SPME or liquid-liquid extraction). The averages of triplicate measurements are presented along with standard deviations.
The SBSE multi-residue results essentially agree with the data from the more conventional method.
Limits
• 10 mL of wine at pH 9–10 (sodium carbonate)
• 20 µL of a solution of IBMP-d3, EG-d5, TCA-d5and geosmin-d5(ISTD)
• stirring with a Twister™ (magnetic stir bar coated with PDMS)
• at 900 rpm for 1 hour at room temperature
The chromatographic conditions as well as the main sorption and desorption parameters were optimised for the simultaneous analysis of the 8 compounds.
Linearity Repeatability Reproducibilty
Perception
threshold LOD LOQ Concentration range r2 Average
concentration Standard deviation Variation
coefficient Standard deviation Variation coefficient IBMP 15 ng/L 0.8 ng/L 2.5 ng/L 5 - 60 ng/L 0.9796 34.3 ng/L 2.2 ng/L 6.3 % 7.0 ng/L 23.7 %
EP 430 µg/L 0.3 µg/L 1.1 µg/L 20 - 1471 µg/L 0.9997 429.1 µg/L 13.2 µg/L 3.1 % 23.9 µg/L 5.9 % EG 33 µg/L 0.3 µg/L 0.9 µg/L 4 - 150 µg/L 0.9999 49.1 µg/L 0.4 µg/L 0.8 % 1.4 µg/L 2.8 % TCA 3 ng/L 0.2 ng/L 0.6 ng/L 1.5 - 16 ng/L 0.9959 4.3 ng/L 0.2 ng/L 4.0 % 0.5 ng/L 10.4 % TeCA 35 ng/L 0.1 ng/L 0.4 ng/L 4 - 109 ng/L 0.9957 15.0 ng/L 0.3 ng/L 1.8 % 2.2 ng/L 14.5 % PCA 100 ng/L 0.2 ng/L 0.7 ng/L 12 - 189 ng/L 0.9933 33.5 ng/L 0.7 ng/L 1.9 % 3.6 ng/L 10.2 % TBA 3 ng/L 0.3 ng/L 0.9 ng/L 1 – 19 ng/L 0.9965 7.0 ng/L 0.2 ng/L 2.6 % 0.4 ng/L 5.2 % Geo 50 ng/L 3 ng/L 6 ng/L 8 - 116 ng/L 0.9993 67.0 ng/L 1.7 ng/L 2.5 % 5.8 ng/L 9.4 %
IBMP (ng/L) Geosmin (ng/L) TCA (ng/L) EP (µg/L) EG (µg/L)
SBSE HS-SPME SBSE Liquid-liquid
extraction SBSE HS-SPME SBSE HS-SPME SBSE HS-SPME
6.8 ± 1.06 6.7 ± 0.19 57 ± 1.3 49 ± 3.0 3.2 ± 0.05 3.6 ± 0.78 54 ± 1.0 39 ± 1.0 6 ± 0.1 7 ± 0.2 8.5 ± 0.70 9.1 ± 0.11 60 ± 0.8 64 ± 2.4 6.5 ± 0.06 4.9 ± 0.06 242 ± 10.4 268 ± 1.1 38 ± 0.1 27 ± 0.1
10 ± 0.9 10 ± 0.2 70 ± 1.0 90 ± 2.9 9.4 ± 0.50 12.3 ± 0.45 707 ± 20.5 641 ± 12.6 86 ± 1.1 84 ± 1.9 17 ± 1.5 17 ± 0.7 90 ± 1.4 89 ± 1.1 20.6 ± 0.77 20.0 ± 0.76 1342 ± 17.5 1229 ± 8.3 197 ± 0.9 202 ± 2.6 23 ± 0.4 21 ± 0.2 117 ± 1.3 109 ± 1.5 298 ± 6.4 375 ± 12.5 2917 ± 126.4 3273 ± 73.7 290 ± 6.6 205 ± 8.3
Volatile phenols
0 1000 2000 3000 1995
1996
1997
1998 1999 2000 2001
2002
IBMP
0 5 10 15 20 25 1995
1996
1997
1998 1999 2000 2001
2002
Geosmin
0 25 50 75 1995
1996
1997
1998 1999 2000 2001
2002
TCA
0 1 2 3 4 5 1995
1996
1997
1998 1999 2000 2001
2002
1. E. Baltussen, P. Sandra, F. David, C. A. Cramers, J. Microcol. Sep. 11 (1999) 737.
2. P. Popp, C. Bauer, B. Hauser, P. Kell, L. Wennrich, J. Sep. Sci. 26 (2003) 961.
3. C. Franc, G. de Revel, J. Chromatogr. A. in preparation.
This SBSE-GC-MS-SIM multi-residue method allows the simultaneous quantification of eight major off-flavour compounds in wine.
This validated method detects these compounds to limits lower than the perception thresholds in wines.
This technique can be applied to the simultaneous analysis of many other analytes in the future and will help to diagnose off-flavours in wine and anticipate defects during wine making.
9Limit of detection and quantification: far below the perception threshold in the wine for each compound
9Linear in the concentration range generally found in wines 9Excellent repeatability (10 preparations - injections) maximum variation 6.3%
9Reproducibility acceptable (15 injections over 4 months)
A rapid analytical method (with rapid sample preparation) was needed for the simultaneous quantification of the maximum number of off-flavour compounds in order to guarantee the quality of the wines.
We chose to use SBSE1as it is a multi-residue, solventless sample preparation technique that provides higher extraction capacity and increased sensitivity compared to SPME2.
SBSE coupled with GC-MS-SIM allows the quantification in a single run of the following compounds : 2-isobutyl-3- methoxypyrazine (IBMP), 4-ethylphenol (EP), 4-ethyl- guaiacol (EG), 2,4,6-trichloroanisole (TCA), 2,3,5,6-tetra- chloroanisole (TeCA), 2,3,4,5,6-pentachloroanisole (PCA), 2,4,6-tribromoanisole (TBA) and geosmin (geo)3. This list is not exhaustive and methods are being developed in our laboratory.
0 1 2 3 4
IBMP EP + EG Geosmin TCA
0 1 2 3 4
IBMP EP + EG Geosmin TCA
0 2 4 6 8 10
1994 1995 1996 1997 1998 1999 2000 2001 2002 2003
Vintage
Concentration (ng/L) TeCA
PCA
The authors thank CIVB (Conseil Interprofessionnel des Vins de Bordeaux) for support. They also thank the Research Institute for Chromatography (RIC – Belgium) and Agilent Technologies for their collaboration.
Comparison of 2 bottles of the same 1999 wine
Cork taint
Comparison between the concentration of the main molecules responsible for off-flavour and the perception threshold (red line) for eight vintages of a Bordeaux wine
Evolution of the concentration in TeCA and PCA over eight vintages of a Bordeaux wine
Comparison of 13 bottles of 2003 vintage Bordeaux wines
Threshold
Threshold
Fruity, spicy, woody
0 0.5 1 1.5 2 2.5 3 3.5 4
1 2 3 4 5 6 7 8 9 10 11 12 13
IBMP EP + EG Geosmin TCA
