Quantitative Analysis of Two Perfluorooctane Sulfonamides (FOSEs) and Four Fluorotelomer Alcohols (FTOHs) in Textiles using LC/MS/MS

Importance of the topic

The widespread use of perfluoroalkyl substances (PFAS) in textiles brings strong oil‐ and water‐repellent properties but also raises environmental and health concerns. Among these, fluorotelomer alcohols (FTOHs) and perfluorooctane sulfonamides (FOSEs) may degrade into more persistent and regulated species. Sensitive and robust analytical methods are essential for monitoring these precursors at trace levels in textile products to ensure compliance with regulations and to assess human and environmental exposure.

Objectives and overview of the study

This work aims to develop and validate a liquid chromatography–tandem mass spectrometry (LC/MS/MS) method for simultaneous quantitation of four FTOHs (4:2, 6:2, 8:2, 10:2) and two FOSEs (N-MeFOSE, N-EtFOSE) in textile samples. Key performance parameters—including calibration linearity, limits of detection and quantitation, repeatability, matrix effects and recovery—were evaluated using mixed standard solutions and spiked textile extracts.

Methodology

Sample preparation involves cutting textile into small pieces, extracting 1 g with methanol by sonication at room temperature, centrifuging, filtering and evaporating under nitrogen. Extracts are reconstituted in 50/50 acetonitrile–water prior to analysis. Chromatographic separation is performed on a C18 column with a water/ammonium acetate–acetonitrile gradient. Mass spectrometric detection uses negative‐mode electrospray ionization targeting acetate adduct transitions in multiple reaction monitoring (MRM) mode.

Instrumentation used

Shimadzu LCMS-8050 triple quadrupole system with heated ESI source
Shim-Pack GIST C18 column (2.1 mm × 100 mm, 2 µm)
Mobile phase: 5 mM ammonium acetate in water (A) and acetonitrile (B)
Flow rate: 0.3 mL/min; column temp: 40 °C; injection volume: 20 µL
MRM transitions optimized via LabSolutions automated program

Key results and discussion

Calibration curves for all six compounds exhibited excellent linearity (R2 ≥ 0.999) over the chosen ranges. Limits of quantitation (LOQs) and detection (LODs) reflect high sensitivity for FOSEs compared to FTOHs. Precision and matrix effects underscore the need for careful cleanup in complex textile extracts.

• Calibration ranges: 1–50 ng/mL for FTOHs; 0.02–1 ng/mL for FOSEs
• LOQs: 0.5–3.7 ng/mL (FTOHs); 0.002–0.005 ng/mL (FOSEs)
• LODs: 0.2–1.2 ng/mL (FTOHs); 0.001–0.002 ng/mL (FOSEs)
• Repeatability: RSD < 10% at low and mid spiking levels
• Matrix effects: 30–96% suppression; recoveries: 63–143%

Significant ion suppression was observed in textile extracts, especially for 10:2 FTOH (30–56% matrix effect), indicating the potential need for additional cleanup steps to achieve trace‐level quantitation.

Benefits and practical applications

This LC/MS/MS protocol provides:

• High sensitivity and selectivity for six low‐polar PFAS precursors
• Fast analysis suitable for routine screening and QA/QC in textile manufacturing
• Compliance support for regulatory limits on PFAS in consumer products

Future trends and possibilities

Further optimization may include advanced sample cleanup (e.g., solid‐phase extraction) to reduce matrix interferences, extension to additional PFAS classes, integration of high‐resolution mass spectrometry for non‐target screening, and automation for high‐throughput monitoring in industrial and environmental laboratories.

Conclusion

A robust MRM‐based LC/MS/MS method on the Shimadzu LCMS-8050 enables reliable quantitation of four FTOHs and two FOSEs in textiles with excellent linearity, low detection limits and acceptable precision. Addressing matrix suppression via enhanced cleanup will further improve trace‐level performance for PFAS precursor analysis.

References

1. Renner R. Perfluorinated Sources Outside and Inside. Environ. Sci. Technol., 2004, 38(5), 80A.
2. Jun Xiang Lee, Zhe Sun, Jie Xing, Jia Yi Tan, Zhaoqi Zhan. A Fast LC/MS/MS Method for High Sensitivity Determination of Twenty-Six Perfluorocompounds in Textiles, ASMS poster session, TP 585.
3. Lahey CM, Ting GWE, Yeong HXC, et al. Fast and Accurate Analysis of Fluorotelomer Alcohols and Acrylates using Triple Quadrupole GC-MS/MS. ASMS poster session, 2016, ThP156.
4. Yeong HX, Olivia S, Lahey CM, Ting GWE, Loo LC. Fast Screening and Quantitation of Perfluorinated Sources from Textiles using Chemical Ionization GC-MS. ASMS poster session, 2017, TP295.