Analysis of PFAS in Textiles Based on EN 17681-1 and EN 17681-2

Significance of the topic

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative chemicals widely used for water- and stain-repellent textile treatments. Regulatory limits such as the EU POPs threshold (0.025 mg/kg, 25 ppb) require reliable analytical methods to detect PFAS in finished textiles. Accurate, sensitive analysis protects consumers, supports compliance, and informs source-reduction strategies.

Aims and study overview

This application study evaluates analytical workflows aligned with European standard EN 17681 parts 1 and 2 for PFAS determination in textiles. The goals were to: demonstrate combined LC-MS/MS and GC-MS(/MS) measurement of ionic and neutral PFAS at or below 25 ppb, validate method performance (calibration linearity, repeatability, spike recovery), and compare the updated EN 17681-1:2025 alkaline extraction to the earlier methanol-only procedure using real textile samples.

Methodology and sample preparation

EN 17681-1:2025 (LC-MS/MS) — Updated extraction:

• Sample: 1 g textile cut into small pieces (≤ ~1 cm square).
• Extraction: NaOH added to methanol followed by ultrasonic extraction at ~60 °C for 60 minutes to perform alkaline hydrolysis and release PFAS including transformation products and side-chain fluorinated polymer residues.
• Post-extraction: volume made to 20 mL, pH adjustment, filtration/centrifugation, dilution as needed. No surrogates per the standard; matrix effects monitored by adding isotopically labeled internal standards (MPFOA, MPFOS) prior to analysis.

EN 17681-2:2022 (GC-MS/MS) — Neutral PFAS and volatile/semi-volatile analytes:

• Sample: 1 g textile cut into ~1 cm pieces.
• Extraction: methanol with addition of surrogate (PFDodiAOMe), ultrasonic extraction at 60 °C for 120 minutes.
• Post-extraction: centrifugation and analysis by GC-MS/MS; optional concentration by nitrogen purge (omitted in this study).

Instrumental setup

Both LC and GC triple-quadrupole MS platforms were used to cover complementary analyte classes:

• LC-MS/MS: Shimadzu LCMS-8050RX (triple quadrupole) with Nexera-X3 UHPLC. Column: Shim-pack Scepter C18-120 (100 mm × 3.0 mm, 1.9 µm). A PFAS delay column was installed between mixer and autosampler to reduce system background. Mobile phases: 5 mM ammonium acetate in water (A) and acetonitrile (B). ESI negative mode, MRM acquisition. Typical run: 25 min, 5 µL injection, column 40 °C.
• GC-MS/MS: Shimadzu GCMS-TQ8050 NX with BEIS (boosted efficiency ion source) for enhanced ionization and sensitivity. GC: Nexis GC-2030, SH-I-624Sil MS column (60 m × 0.32 mm, 1.8 µm), splitless injection, helium carrier, MRM acquisition. Ion source ~200 °C, interface ~250 °C.
• Software: LabSolutions for integrated control of both systems and data processing.

Calibration, sensitivity and QA/QC

Calibration and linearity:

• EN 17681-1 (LC-MS/MS) external calibration ranges typically 0.1–10 µg/L (10–1000 µg/L for FTOHs). Correlation coefficients R > 0.998 for all analytes, indicating excellent linearity.
• EN 17681-2 (GC-MS/MS) internal or surrogate-based calibration ranges 1–100 µg/L (some FTOHs measured at higher ranges). All calibration curves showed R > 0.998.

Precision and detection:

• Repeatability at lowest calibration levels showed area %RSD generally <20% (many compounds <<10%).
• Instrument and method contamination control: use of PFAS-grade reagents and a delay column to mitigate background PFAS leaching from the LC system.

Main results and discussion

Calibration and instrument performance:

• Both platforms provided robust linear calibration with low %RSD at the lowest concentrations, supporting reliable quantitation near regulatory limits.

Spike recovery (matrix recovery) at regulatory-relevant concentrations:

• EN 17681-2 (GC-MS/MS): 1 g cotton glove spiked to 25 ppb; mean recoveries for all target compounds ranged from 70 to 130% with %RSD ≤10% (n = 3), meeting common analytical acceptance criteria.
• EN 17681-1:2025 (LC-MS/MS): 1 g cotton glove spiked to 20 ppb (FTOHs at higher spike levels); internal standards (MPFOA, MPFOS) used to assess matrix effects. After a 2-fold dilution of final extracts, internal standard recoveries met the reference criterion and target analyte recoveries were 70–130% with %RSD ≤11% (n = 3).

Comparison of extraction methods and real sample analysis:

• Analysis of aged ski wear demonstrated that the EN 17681-1:2025 alkaline hydrolysis markedly increased measured concentrations of several fluorotelomer alcohols (FTOHs) and N-alkyl FOSE/FOA derivatives relative to the 2022 methanol-only extraction. Several FTOHs exceeded calibration ranges after the updated extraction, indicating previously bound or polymer-linked sources were liberated by alkaline hydrolysis.
• Combining LC-MS/MS and GC-MS/MS allowed detection of complementary sets of PFAS: ionic, semi-volatile and volatile neutral analytes. In the tested ski wear, LC-MS/MS detected 20 of 33 targeted ionic analytes, and GC-MS/MS detected 8 of 12 targeted neutral compounds, with several analytes above the calibration upper limits.

Benefits and practical applications

• Regulatory compliance: The combined EN 17681-1/EN 17681-2 workflow supports monitoring to the EU POPs threshold (25 ppb) for both ionic and neutral PFAS classes.
• Improved extraction: Inclusion of alkaline hydrolysis (EN 17681-1:2025) enhances release and detection of FTOHs and degradation products from side-chain fluorinated polymers, reducing false negatives.
• Robust QA/QC: Use of isotopic internal standards, surrogate in GC workflow, delay columns, PFAS-grade solvents, and validated calibration demonstrates fit-for-purpose performance for laboratory testing and compliance screening.
• Laboratory efficiency: Integrated instrument control and data processing (LabSolutions) streamline combined LC/GC workflows.

Future trends and applications

• Standard evolution: Continued updates to EN standards and harmonization across jurisdictions will refine extraction protocols and analyte lists, especially for polymeric and precursor PFAS.
• Non-target and high-resolution screening: Complementing targeted MRM methods with HRMS workflows can identify unknown PFAS relatives and transformation products liberated by alkaline hydrolysis.
• Improved sensitivity and contamination control: Advances in ion source design (e.g., BEIS), hardware to reduce background, and certified PFAS-free consumables will lower method detection limits and reduce false positives.
• Automation and high-throughput testing: Automated sample-prep and instrument coupling will support larger-scale compliance testing for textiles in regulatory and commercial settings.
• Field and near real-time screening: Development of portable or rapid screening tools for textile PFAS could support supply-chain surveillance and pre-screening before laboratory confirmation.

Conclusion

The combined LC-MS/MS (EN 17681-1:2025) and GC-MS(/MS) (EN 17681-2) workflow provides comprehensive, sensitive, and reproducible measurement of a wide spectrum of PFAS in textiles at or below EU regulatory thresholds. The 2025 update to EN 17681-1 introducing alkaline hydrolysis substantially improves extraction and detection of FTOHs and polymer-related precursors. Method validation metrics (linearity, repeatability, spike recoveries) demonstrate the approach is suitable for regulatory testing and quality assurance in textile analysis.

References

1. EUR-Lex - Regulation (EU) 2019/1021 on persistent organic pollutants (POPs) (reference to consolidated text through 2025).
2. EN 17681-1:2025 Textiles and textile products - Per- and polyfluoroalkyl substances (PFAS) - Part 1: Analysis of an alkaline extract using liquid chromatography and tandem mass spectrometry.
3. EN 17681-2:2022 Textiles and textile products - Organic fluorine - Part 2: Determination of volatile compounds by extraction method using gas chromatography.