SPME-GC/MS of 2,4,6-Trichloroanisole using an Agilent DVB/PDMS SPME Fiber

Importance of the Topic

The aroma profile of wine critically influences its sensory quality and market acceptance. Cork taint, predominantly caused by 2,4,6-trichloroanisole (TCA) and related chloroanisoles, can impart an undesirable musty off-flavor even at nanogram per liter levels. Reliable detection and control of these compounds is essential to safeguard product quality and avoid economic losses.

Objectives and Scope of the Study

This application note aimed to:

• Quantify trace levels of 2,4,6-TCA and 2,4-DCA in red wine using headspace SPME coupled to GC/MS.
• Evaluate reproducibility of an Agilent 65 µm DVB/PDMS SPME fiber across multiple injections and fibers.
• Demonstrate method sensitivity, repeatability, and practical suitability for routine quality control.

Methodology

Ten milliliters of red wine were placed into a 20 mL headspace vial containing approximately 4 g of NaCl to enhance analyte transfer into the gas phase. A 25 µL aliquot of a 10 ppm methylated haloacetic acids mixture served as an internal standard. Equilibration and extraction were performed at 30 °C for 30 minutes with stirring at 1,000 rpm. After extraction, analytes were desorbed in the GC inlet for 3 minutes prior to separation and detection.

Used Instrumentation

• PAL RTC autosampler with headspace SPME capability
• Agilent 65 µm DVB/PDMS SPME fiber (p/n 5191-5873)
• Agilent 7890B gas chromatograph equipped with HP-5ms Ultra Inert column (15 m×0.25 mm×0.25 µm)
• Agilent 5977B High Efficiency Source GC/MSD operated in scan mode

Main Results and Discussion

Eight replicate analyses were performed on three different SPME fibers. The average %RSD for 2,4-DCA was 12.5% and for 2,4,6-TCA 16.9%, demonstrating acceptable fiber-to-fiber and injection-to-injection repeatability (<30% RSD). Chromatograms of blank and spiked wine samples confirmed clear separation and no significant matrix interferences.

Benefits and Practical Applications

The HS-SPME-GC/MS method offers:

• High sensitivity for sub-ng/L detection of chloroanisoles.
• A rapid, solvent-free sample preparation workflow.
• Good repeatability suitable for routine quality control in wineries and testing laboratories.

Future Trends and Opportunities

Emerging developments may include novel fiber coatings for even lower detection limits, automation of headspace extraction, coupling with high-resolution mass spectrometry for enhanced selectivity, and expansion to other aroma fault compounds in diverse beverage and food matrices.

Conclusion

This study demonstrates that Agilent’s 65 µm DVB/PDMS SPME fiber combined with GC/MS provides a reliable, repeatable, and sensitive approach to detect cork taint markers in wine. Implementation of this protocol can help producers and laboratories maintain high quality standards and protect consumer experience.

Reference

1. Özhan, D. et al. Determination of Chloroanisoles and Chlorophenols in Cork and Wine using HS-SPME and GC-ECD Detection. J. Inst. Brew. 2009, 115, 71–77.
2. Riu, M. et al. Determination of 2,4,6-Trichloroanisole in Wines by Headspace Solid-Phase Microextraction and GC–ECD. J. Chromatogr. A 2002, 977(1), 1–8.
3. Azzi-Achkouty, S. et al. Headspace SPME for Wine Volatile Analysis. Crit. Rev. Food Sci. Nutr. 2017, 57(10), 2009–2020.