Comprehensive PFAS Screening in Textiles Using LC-MS/MS and GC-MS/MS

Importance of the Topic

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative chemicals widely used in textiles for water- and stain-repellency. Regulatory frameworks (for example, EU POPs limits at 0.025 mg/kg for selected PFAS) demand reliable analytical screening at trace levels. Robust, validated methods that cover both ionic and neutral PFAS classes are essential for compliance testing, consumer safety, and supply-chain monitoring.

Objectives and Study Overview

This study demonstrates a combined LC-MS/MS and GC-MS/MS workflow for comprehensive PFAS screening in textiles based on the European standard EN 17681 (Part 1 for ionic PFAS; Part 2 for neutral and volatile/semi-volatile PFAS). The goals were to: validate sensitivity and repeatability for a broad PFAS panel (39 analytes); optimize injection conditions for GC-MS/MS using a Multi-Mode Injection (MMI) unit; compare extraction/pretreatment approaches (methanol extraction vs. alkaline hydrolysis) on real textile samples (used ski wear); and show practical suitability for routine regulatory screening without optional preconcentration.

Methods and Experimental Approach

• Standards and targets: 39 PFAS in total were addressed, combining ionic species (carboxylates, sulfonates, perfluoroalkyl acids) by LC-MS/MS and neutral/volatile PFAS (fluorotelomer alcohols, some neutral precursors) by GC-MS/MS.
• Pretreatment: Methods followed EN 17681-1 and -2. Two pretreatment routes were used for textiles — methanol extraction (EN 17681-1:2022) and alkaline hydrolysis (EN 17681-1:2025) — to evaluate release of precursors.
• Calibration: LC-MS/MS calibrations covered 33 targets at 0.1–10 µg/L; FTOHs were calibrated at 10–1000 µg/L. GC-MS/MS calibrations covered eight target compounds plus four FTOHs in the 1–10 µg/L range.
• Quality metrics: Linearity exceeded R>0.998 for all targets; repeatability at low levels was acceptable (%RSD <20). Recovery experiments were performed with spike levels below 0.025 mg/kg (25 µg/kg) in textile matrices.
• Method optimization: GC inlet optimization used a Multi-Mode Injection (MMI) with PTV; injection volume trials (2–6 µL, and total 8 µL including co-injected ethyl acetate) were assessed to maximize sensitivity and maintain peak shape.

Instrumentation Used

• LC-MS/MS platforms: LCMS series triple-quadrupole instruments from Shimadzu (figures reference LCMS-8050RX / LCMS-TQ8050RX).
• GC-MS/MS platform: GCMS-TQ8040 RX triple-quadrupole MS with a Multi-Mode Injection (MMI) unit capable of five injection modes; MMI-PTV mode was specifically evaluated.
• Support equipment: Standard chromatographic columns and solvent systems consistent with EN 17681 application notes; ethyl acetate used as a co-injection solvent to improve GC peak shapes for selected analytes.

Main Results and Discussion

• Analytical performance: Recovery rates across LC- and GC-based workflows were generally within 70–130% with %RSD (n = 3) below 11% for most compounds, demonstrating good accuracy and precision at regulatory-relevant concentrations.
• Linearity and sensitivity: Excellent linearity (R>0.998) and satisfactory repeatability at low calibration levels were obtained for all targets. Stable trace-level detection was possible without applying optional preconcentration in EN 17681.
• GC injection optimization: Increasing injection volume improved sensitivity; however, higher volumes broadened some peaks (e.g., Me-PFOA). Co-injection of 2 µL ethyl acetate corrected peak shape, and total injection volumes up to 8 µL enabled trace detection on the standard-performance GCMS-TQ8040 RX.
• Sample application — ski wear: LC-MS/MS detected 20 of 33 ionic/acid targets in the used textile sample. GC-MS/MS detected 8 of 12 neutral targets; several fluorotelomer alcohols (8:2 and 10:2 FTOHs) were present above calibration ranges. Alkaline hydrolysis (EN 17681-1:2025) yielded higher detected levels of certain precursors (NMeFOSE and multiple FTOHs) compared with methanol extraction, indicating that hydrolysis releases additional bound precursors.

Practical Benefits and Applications

• Comprehensive coverage: Combining LC-MS/MS and GC-MS/MS covers both ionic and neutral PFAS classes, reducing false negatives from single-technique approaches.
• Regulatory screening: Achieves detection limits and quantitative robustness compatible with EU regulatory thresholds (0.025 mg/kg) for selected PFAS, suitable for routine compliance testing of textiles.
• Operational efficiency: The MMI-enhanced GC workflow and omission of an optional preconcentration step simplify sample throughput while preserving trace sensitivity, beneficial for high-volume testing laboratories.
• Method flexibility: The MMI unit’s multiple injection modes and the choice between methanol extraction and alkaline hydrolysis allow adaption to different sample types and target analyte classes.

Future Trends and Potential Uses

• Expanded target lists and non-target screening: Adoption of high-resolution mass spectrometry (HRMS) or hybrid workflows could identify unknown PFAS precursors and transformation products beyond the targeted 39 compounds.
• Standardization and harmonization: Broader uptake and harmonization of EN 17681 revisions will support consistent regulatory compliance and interlaboratory comparability.
• Automation and throughput: Integration of automated extraction and injection workflows can further increase sample throughput for commercial and accredited testing labs.
• Improved sample preparation: Development of greener, lower-solvent extraction or selective cleanup strategies may reduce matrix effects while retaining trace-level sensitivity.
• Risk-based monitoring: Combining analytical screening with product-use and exposure data will better prioritize which textile products need detailed PFAS testing.

Conclusion

The combined LC-MS/MS and GC-MS/MS workflow presented here, aligned with EN 17681 parts 1 and 2, delivers reliable, trace-level PFAS screening in textiles without mandatory preconcentration. Method validation data show acceptable recoveries and repeatability at regulatory-relevant spike levels. Optimization of GC injection using an MMI and application of alkaline hydrolysis where appropriate enhance detection of bound precursors. Overall, the approach is practical for routine regulatory screening and adaptable to evolving analytical and regulatory demands.

References

1. European Union regulation on persistent organic pollutants relevant to PFAS (EU POPs Regulation, e.g., limits and listings concerning PFOA, PFOS, PFHxS).
2. EN 17681-1:2025 Textiles and textile products — PFAS — Part 1: Method for analysis of ionic PFAS (LC-MS/MS procedures and sample pretreatment guidance).
3. EN 17681-2:2022 Textiles and textile products — Organic fluorine — Part 2: GC-MS-based analysis for neutral, volatile and semi-volatile PFAS.