The Comparison of HS-SPME and SPME Arrow Sampling Techniques Utilized to Characterize Volatiles in the Headspace of Wine over an Extended Period of Time

Significance of the Topic

Profiling volatile compounds in wine headspace is essential for quality control and product differentiation. Understanding how aroma constituents evolve during storage helps producers maintain flavor consistency and comply with regulatory standards. Analytical methods that monitor these compounds support product development and sensory evaluation programs.

Study Objectives and Overview

The study compared two headspace microextraction techniques over a four month period: classical fiber based headspace solid phase microextraction and a sorptive phase arrow design. The aim was to evaluate extraction efficiency, sensitivity and compound stability in wine headspace samples stored under ambient conditions.

Methodology

Sample preparation and extraction parameters were kept consistent for both techniques. Key steps included salt addition to promote volatile release, temperature controlled incubation and agitation, and defined extraction and desorption times. A consistent chromatographic gradient and mass spectrometric scan range enabled direct comparison of volatile profiles.

Instrumentation Used

• Autosampler AOC 6000 implementing fiber and arrow sampling
• DVB CAR PDMS sorptive fibers with 0.6 microliter phase and SPME Arrow with 15.3 microliter sorption volume
• GC 2010 Plus equipped with Rxi 5 MS column (30 m x 0.25 mm x 0.25 micron)
• GCMS QP2020 detector operating in full scan electron ionization mode (50 to 350 m/z)

Main Results and Discussion

Extraction with the classical fiber immediately after bottle opening yielded 48 distinct volatile peaks. After four months, fiber sampling detected 26 peaks while the arrow design recovered 25 peaks. The mechanized arrow device offered up to tenfold greater sensitivity for key volatiles and identified additional compounds absent in fiber data. Increased sorption volume and mechanical resilience minimized analyte loss and sampling variation over time.

Benefits and Practical Applications

• Enhanced sensitivity and detection limits support trace level analysis
• Extended device lifetime reduces sample preparation downtime and costs
• Robust performance over prolonged storage periods aids shelf life and aging studies
• Potential to standardize aroma fingerprinting for quality assurance

Future Trends and Opportunities

Advances may include integration of automated arrow sampling in production lines, coupling with high resolution mass spectrometry for definitive compound identification, and expansion to other food and beverage matrices. Correlation of instrumental data with sensory outcomes will drive comprehensive flavor optimization strategies.

Conclusion

The SPME Arrow technique demonstrates superior sensitivity and reproducibility compared to classical fiber extraction for long term monitoring of wine headspace volatiles. Its larger sorptive phase and mechanical durability make it a valuable tool for quality control, research and product development in the wine industry.

References

1. Khio SW Cheong MW Zhou W Curran P Yu B Characterization of flavor compound volatility in beverages by headspace SPME and modeling Journal of Food Science 2011 77 C61 C70
2. Kremser A Jochmann MA Schmidt TC Extended phase SPME Arrow performance and validation Anal Bioanal Chem 2016 408 943