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

Importance of the topic

Per‑ and polyfluoroalkyl substances (PFAS) are widely used in textiles for water and stain repellency but are persistent, bioaccumulative and of increasing regulatory concern. The EU POPs framework sets specific limits (e.g. 0.025 mg/kg = 25 ppb for certain PFAS), creating a need for robust, sensitive analytical workflows able to detect both ionic and neutral PFAS species in textile matrices. Standardized, reproducible methods are essential for regulatory compliance, product safety screening and environmental risk management.

Objectives and overview of the study

This work demonstrates combined LC/MS/MS and GC/MS/MS workflows that implement the EN 17681 family of European standards to quantify a broad panel of PFAS in textiles. Key aims were to: (1) apply the updated EN 17681‑1:2025 alkaline extraction to improve recovery of polymer‑derived PFAS; (2) cover volatile/semi‑volatile neutral PFAS by EN 17681‑2 (GC/MS(/MS)); (3) validate method performance at or below the EU POPs threshold using spike recovery tests; and (4) analyze real consumer textile samples to illustrate practical outcomes.

Methodology and sample preparation

The study followed the sample‑preparation workflows prescribed by EN 17681‑1 and EN 17681‑2 with these principal steps:

• Sample: 1 g textile pieces (cut to roughly 0.3–1 cm squares depending on protocol).
• EN 17681‑1:2025 (LC/MS/MS): alkaline hydrolysis extraction by adding NaOH to methanol, ultrasonic extraction at 60 ±5 °C for 60 ±5 min, neutralization/pH adjustment, dilution to 20 mL, filtration, and dilution prior to analysis as required. Internal standards MPFOA and MPFOS were added to assess matrix effects (no surrogate required by the standard).
• EN 17681‑2 (GC/MS(/MS)): methanolic ultrasonic extraction (60 ±5 °C for 120 ±5 min) with surrogate PFDodiAOMe, centrifugation, and direct analysis of the supernatant; optional nitrogen concentration (omitted in this work).
• Careful anti‑contamination measures: PFAS‑grade reagents, delay column between mixer and autosampler to reduce system background.

Instrumental conditions

LC/MS/MS and GC/MS/MS platforms and principal analytical settings used in the study are summarized below:

• LC system: Nexera‑X3 UHPLC with Shim‑pack Scepter C18‑120 column (100 × 3.0 mm, 1.9 µm). Mobile phases: 5 mM ammonium acetate in water (A) and 5 mM ammonium acetate in acetonitrile (B). Gradient program with runtime ≈25 min, flow 0.30–0.40 mL/min, column 40 °C. Delay column installed to limit PFAS bleed.
• LCMS: LCMS‑8050RX (triple‑quadrupole) operated in negative ESI, MRM acquisition. Source and gas settings optimized for sensitivity; probe and interface temperatures controlled to reduce background.
• GC system: Nexis GC‑2030 with AOC‑30i autosampler; splitless high‑pressure injection (240 kPa). Column: SH‑I‑624Sil MS (60 m × 0.32 mm, 1.8 µm) with a short guard column. Temperature program tailored to separate volatile/semi‑volatile PFAS.
• GCMS: GCMS‑TQ8050 NX triple‑quadrupole with a boosted efficiency ion source (BEIS) for improved electron‑impact ionization efficiency at low analyte levels. MRM acquisition was used for targeted quantitation.

Used Instrumentation

• LCMS‑8050RX / LCMS‑TQ8050RX triple‑quadrupole mass spectrometer (Shimadzu).
• GCMS‑TQ8050 NX triple‑quadrupole mass spectrometer with BEIS source (Shimadzu).
• Nexera‑X3 UHPLC and Nexis GC‑2030 systems; AOC‑30i autosampler.
• Shim‑pack Scepter C18‑120 analytical column; GL Science delay column for PFAS background suppression; SH‑I‑624Sil MS GC column and guard column.

Main results and discussion

Calibration and linearity:

• EN 17681‑1 (LC/MS/MS) external calibration ranges were typically 0.1–10 µg/L (FTOHs measured at higher ranges up to 1000 µg/L as required). Correlation coefficients R > 0.998 for all LC targets and repeatability at the lowest calibration points yielded area %RSD generally <20 %.
• EN 17681‑2 (GC/MS/MS) used internal standard calibration from 1–100 µg/L (PFDodiAOMe as IS). R > 0.998 and %RSD at low concentrations were also acceptable.

Spike recovery and precision:

• Spike experiments used 1 g cotton glove fragments spiked to 25 ppb (EN 17681‑2) or 20 ppb (EN 17681‑1; FTOH spiked at 2000 ppb). Both methods achieved mean recoveries between 70–130 % for all targeted compounds and repeatability (%RSD, n = 3) generally ≤11 % (EN 17681‑1) or ≤10 % (EN 17681‑2), meeting performance expectations at or below the EU POPs threshold.

Effect of EN 17681‑1:2025 alkaline hydrolysis:

• Introducing NaOH in the extraction (2025 revision) markedly increased measured amounts of several analytes associated with side‑chain fluorinated polymer degradation—notably NMeFOSE and multiple FTOHs (6:2, 8:2, 10:2 FTOH)—compared with pure‑methanol extraction (EN 17681‑1:2022). This indicates that alkaline hydrolysis releases polymer‑bound or precursor PFAS, improving the detection of otherwise underestimated species.

Real sample (ski wear) findings:

• LC/MS/MS analysis detected 20 of 33 targeted ionic PFAS in the tested garment; several FTOHs and related compounds were present above calibration ranges after alkaline treatment. GC/MS/MS detected 8 of 12 targeted neutral PFAS, with some FTOHs above calibration limits. These results demonstrate the complementary role of LC and GC methods to cover the complete target list.

Benefits and practical applications

• Combining EN 17681‑1 (LC/MS/MS) and EN 17681‑2 (GC/MS(/MS)) provides comprehensive coverage of ionic and neutral PFAS classes in textiles, enabling measurement at or below regulatory thresholds (25 ppb).
• The updated EN 17681‑1:2025 alkaline extraction improves recovery of polymer‑derived precursors and FTOHs, reducing false negatives.
• Validated spike recoveries and acceptable precision support implementation for quality control, regulatory compliance testing, and manufacturer screening.
• Integrated software control (LabSolutions) for LC and GC platforms streamlines data acquisition and reporting for routine laboratory workflows.

Future trends and potential uses

• Expand target analyte lists and adopt complementary non‑target and suspect screening (high‑resolution MS) to identify emerging PFAS and transformation products not captured by current lists.
• Improve quantitation of oxy‑ and ether‑containing PFAS and low‑level volatile species through enhanced sample cleanup, automation, and lower background analytical hardware.
• Standardize calibration/quality criteria across laboratories and develop certified matrix reference materials for textiles to improve interlaboratory comparability.
• Integrate alkaline hydrolysis or other release steps selectively to reveal bound precursors while validating potential artefacts from harsh extraction.
• Broaden surveillance programs for consumer textiles to inform product stewardship, circular‑economy recycling policies and supply‑chain controls.

Conclusion

The combined LC/MS/MS (EN 17681‑1:2025) and GC/MS/MS (EN 17681‑2) approach provides a robust, complementary analytical solution for comprehensive PFAS profiling in textiles. The 2025 update to EN 17681‑1 (alkaline hydrolysis) substantially improves extraction of polymer‑derived precursors and FTOHs, while validated calibration, spike recoveries and repeatability demonstrate fitness for regulatory screening at the EU POPs threshold. Together, these methods support regulatory compliance, product safety testing and broader monitoring efforts.

References

1. European Union. Regulation (EU) 2019/1021 on persistent organic pollutants (POPs). EUR‑Lex reference 02019R1021‑20251203.
2. CEN. 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. CEN. EN 17681‑2:2022. Textiles and textile products — Organic fluorine — Part 2: Determination of volatile compounds by extraction method using gas chromatography.