A Fast LC/MS/MS Method for High Sensitivity Determination of Twenty-Six Perfluorocompounds in Textiles

Importance of the Topic

Perfluorinated compounds (PFCs) are widely applied as oil- and water-repellent coatings on textiles.
They persist in the environment and bioaccumulate, raising health and regulatory concerns.
European and other regulations set stringent limits (e.g., 1 µg/m² for PFOS/PFOA) in consumer products, driving the need for highly sensitive analytical methods.

Study Objectives and Overview

This work aimed to establish a rapid, robust LC-MS/MS method for screening and quantifying 26 perfluorinated analytes in textile materials.
The method targets extractable PFCs, including PFOA and PFOS, using a Shimadzu LCMS-8050 triple quadrupole system coupled to a Nexera UHPLC.

Methodology and Instrumentation

Sample Preparation:

• Cut 1 g textile into pieces and transfer to a 50 mL tube.
• Add 20 mL methanol, sonicate at 50 °C for 2 h, centrifuge at 10 000 rpm for 5 min.
• Filter supernatant (0.22 µm nylon), spike with 13C-PFOA internal standard.

Chromatographic Conditions and Mass Spectrometry:

• Column: Kinetex C18 (100 × 2.1 mm, 1.7 µm), 0.4 mL/min flow rate, 40 °C.
• Mobile phases: 5 mM ammonium formate in water (A), acetonitrile (B); gradient 20 %→80 % B over 12 min.
• Injection volume: 5 µL; total run: 13.5 min.
• ESI negative mode; interface 300 °C; DL 250 °C; block 400 °C; CID gas Ar 270 kPa.
• Gas flows: nebulizing N₂ 1.5 L/min; drying N₂ 10 L/min; heating air 10 L/min.

Main Results and Discussion

MRM Optimization:

• Two transitions per analyte (quantifier and qualifier) were established for 26 PFCs plus M-PFOA IS.
• Calibration in blank textile matrix showed linearity r² > 0.997 across relevant ranges.

Sensitivity and Repeatability:

• Limit of quantitation (LOQ): 4.1–50.2 pg/mL for 22 compounds; PFOA and PFOS LOQs at 17.7 pg/mL and 16.1 pg/mL.
• Limit of detection (LOD): 1.4–16.6 pg/mL.
• Intra-day precision (%RSD) < 15 % at 50 and 1 000 pg/mL.

Matrix Effects and Recovery:

• Matrix suppression/enhancement ranged from 60 % to 144 % at low spiking; two compounds (FOSA, N-MeFOSA) showed > 190 % enhancement.
• Recoveries for most PFCs were 96 %–130 % at low and high levels.

Application to Real Samples:

• Five commercial textiles were analyzed; only one sample contained PFOA at 650 pg/g.

Benefits and Practical Applications

This method provides:

• High sensitivity for regulatory compliance testing of PFOA, PFOS and other PFCs in textiles.
• Rapid throughput (13.5 min per run) suitable for QC/QA labs.
• Reliable quantitation over a broad concentration range with isotope-labelled internal standard.

Future Trends and Potential Applications

Emerging directions include:

• Expanding analyte scope to new and shorter-chain fluorochemicals.
• Integration with high-resolution MS for non-targeted screening.
• Automation and on-site or direct surface analysis techniques.

Conclusion

A fast LC-MS/MS protocol on the Shimadzu LCMS-8050 provides robust, sensitive quantitation of 26 perfluorinated compounds in textiles.
It meets stringent LOQ/LOD requirements for regulatory monitoring and offers reliable performance in real-world samples.

References

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• Wellington Laboratories. Quick Reference Guide for Perfluoroalkyl Compounds. 2016.