Fast and Accurate Analysis of Fluorotelomer Alcohols and Acrylates using Triple Quadrupole GC-MS/MS

Importance of the Topic

Fluorotelomer-based polymers are widely used as oil and water repellents in textiles and consumer goods. Residual fluorotelomer alcohols (FTOHs) and acrylates (FTAs) from these products can degrade into toxic perfluorocarboxylic acids, posing environmental and health concerns. Rapid, sensitive and accurate methods for their detection are essential for quality control, environmental monitoring, and regulatory compliance.

Objectives and Study Overview

This study aimed to develop and validate a fast gas chromatography–tandem mass spectrometry (GC-MS/MS) method in electron ionization (EI) mode for simultaneous quantification of four FTOHs and three FTAs in textile matrices. Key goals included achieving low detection limits, high linearity, good repeatability, and assessing matrix effects.

Methods and Instrumentation

• Sample Preparation: Calibration standards (1–200 ng/mL) were prepared in ethyl acetate with 2-Perfluorobutyl-[1,1,2,2-2H4]-ethanol (MFBET) as internal standard. Textile samples (1 g) were cut into small pieces, extracted with ethyl acetate at 60 °C for 2 h, filtered (0.22 μm) and concentrated tenfold.
• Instrumentation: Shimadzu GCMS-TQ8040 triple quadrupole GC-MS/MS in EI mode with MRM acquisition. Shimadzu AOC-20i/s autosampler. Column: SH-Stabilwax (30 m × 0.25 mm, 0.25 μm).
• GC Conditions: Splitless injection (1 μL) at 240 °C; helium carrier at 43.4 cm/s; oven: 40 °C (1 min) → 20 °C/min → 150 °C → 30 °C/min → 240 °C (2 min).
• MS/MS Parameters: Ion source 200 °C; interface 240 °C; MRM transitions optimized for each analyte with collision energies between 3 and 18 V.

Main Results and Discussion

• Calibration: Excellent linearity (R² > 0.999) for all analytes over their respective concentration ranges. FTOH 4:2 required a higher lower limit due to poor peak shape at low levels.
• Detection Limits: Instrument detection limits (S/N ≥ 3) ranged from 0.1 to 0.5 ng/mL, except FTOH 4:2 at 2 ng/mL.
• Precision: Repeatability tests (n=7) at low (1 ng/mL; 5 ng/mL for FTOH 4:2) and mid (20 ng/mL) levels yielded RSDs below 10% for all compounds.
• Matrix Effects: Significant enhancement observed in textile extracts (100–400% for 1 ng/mL spikes). This indicates the need for matrix-matched calibration or appropriate sample cleanup.
• Column Protection: Injection of matrix extracts led to retention time shifts and peak distortion. The addition of a 5 m guard column improved peak stability over extended sequences.

Benefits and Practical Applications

• Rapid Analysis: Total runtime under 7 minutes enables high sample throughput.
• High Sensitivity and Reproducibility: Suitable for trace-level monitoring in environmental and textile quality control.
• Comprehensive Approach: EI-MRM offers robust detection without complicated CI maintenance.

Future Trends and Opportunities

• Matrix-Matched Calibration: To correct for significant matrix effects in complex samples.
• Advanced Sample Cleanup: Techniques such as solid-phase extraction to reduce potential column fouling.
• Broader Compound Scope: Extension to other per- and polyfluoroalkyl substances in various matrices.
• Automation and Miniaturization: Integration with online extraction and smaller-scale GC columns for lower solvent use.

Conclusion

The developed triple quadrupole GC-MS/MS method in EI mode delivers fast, accurate, and reproducible quantification of FTOHs and FTAs in textiles. Excellent linearity, low detection limits, and satisfactory precision were demonstrated. Attention to matrix effects and column protection with a guard column is essential for routine analysis. Further improvements may include matrix-matched calibration and enhanced sample cleanup to extend column life and ensure quantification accuracy.

Reference

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