Determination of haloanisoles in wine by HS-SPME Arrow and GC-MS/MS

Significance of the Topic

Haloanisoles such as 2,4,6-trichloroanisole TCA and related compounds cause musty off aromas in wine at low ng per liter levels. Contamination originates from cork stoppers barrels and winery environment leading to economic losses and quality issues. Sensitive reliable screening methods are essential for quality control and product consistency.

Objectives and Study Overview

The aim of this study was to evaluate the performance of a TSQ 9610 triple quadrupole mass spectrometer coupled to HS-SPME Arrow sampling for the determination of TCA TeCA PCA and TBA in wine. The study demonstrates sensitivity selectivity throughput and robustness for routine analysis in winery and analytical laboratories.

Methodology

Sample preparation relied on headspace solid phase microextraction using an Arrow PDMS fiber with 100 μm coating. Wine samples were incubated at 40 °C for 5 minutes then extracted for 15 minutes with salt addition. Analytes were desorbed in a splitless inlet at 260 °C. GC separation was achieved on a 30 m × 0.25 mm × 0.25 μm TG-WaxMS column with a multistep temperature program from 40 °C to 250 °C over 15 minutes. MS/MS detection used selected reaction monitoring SRM with optimized collision energies for target transitions.

Instrumentation

• Thermo Scientific TSQ 9610 triple quadrupole MS with NeverVent Advanced Electron Ionization source
• Thermo Scientific TRACE 1610 gas chromatograph with iConnect SplitSplitless injector
• Thermo Scientific TriPlus RSH SMART autosampler configured for SPME Arrow
• Chromeleon Chromatography Data System software for full workflow control and data processing

Main Results and Discussion

Baseline chromatographic resolution of all haloanisoles was achieved within 15 minutes with Gaussian peak shapes. Method recovery in wine spiked at 0.25 2.5 and 5.0 ng/L ranged from 90 to 105 percent. Calibration was linear from 0.1 to 25 ng/L with coefficients of determination above 0.997 and calibration factor RSD below 8.2 percent. Method detection limits were 0.03 to 0.07 ng/L and limits of quantification below 0.24 ng/L. Repeatability evaluation at 0.25 ng/L yielded peak area RSD below 10 percent. No carryover was observed after 60 samples. System stability was maintained over a 36-hour unattended sequence.

Benefits and Practical Applications

HS-SPME Arrow sampling with GC-MS/MS enables minimal sample preparation fast turnaround high sensitivity and selectivity for routine QA QC of wines. The automated workflow reduces hands on time and increases sample throughput. The method supports screening of corks barrels and environmental sources to prevent contamination.

Future Trends and Applications

Further developments may include novel fiber chemistries for broader analyte coverage high resolution mass spectrometry coupling for enhanced identification and advanced data analytics for real time monitoring. Integration of automation and remote control can support in line quality testing and broader application to other complex beverage and environmental matrices.

Conclusion

The combination of HS-SPME Arrow technology and TSQ 9610 GC-MS/MS provides a fast sensitive robust and fully automated solution for trace level determination of haloanisoles in wine. The method delivers reliable quantitation low detection limits and high throughput suitable for winery quality control and analytical laboratories.

References

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