Comprehensive PFAS Analysis in Textiles Using Triple Quadrupole GC/MS and LC/MS Workflows

Significance of the topic

Per- and polyfluoroalkyl substances (PFAS) are widely applied to textiles for water-, oil- and stain-repellence but have become a focus of regulatory and industry scrutiny because of persistence, bioaccumulation and potential human-health effects. Textile supply-chain initiatives (ZDHC, OEKO-TEX®, AFIRM, Bluesign) and regulatory frameworks (REACH/POPs, EN 17681-1:2025) require sensitive, reliable and standardized analytical approaches able to quantify both volatile and non-volatile PFAS across diverse textile matrices. This work addresses that need by presenting a dual-platform, end-to-end workflow optimized for rapid, trace-level PFAS analysis in typical garments.

Objectives and study overview

The study aimed to demonstrate a comprehensive analytical workflow, compliant with EN 17681-1:2025, for quantifying a broad PFAS panel in textiles. Key goals were to: quantify >100 PFAS across 14 chemical classes in real textile products (T-shirts, waterproof shorts, socks); validate extraction and instrument workflows for volatile and non-volatile PFAS; establish method sensitivity (LOQs), linearity and reproducibility; and provide a simplified, productivity-enhancing protocol suitable for routine laboratory use.

Methodology

Sample set and general approach:

• Representative textile samples (e.g., T-shirts, waterproof shorts, socks) were analyzed using a dual-platform strategy to cover both volatile and non-volatile PFAS.

Extraction and sample preparation (aligned with Annex E of EN 17681-1:2025):

• Approximately 1.0 g of textile was weighed into 50 mL tubes.
• Target analytes and surrogate/internal standards were spiked into samples as required.
• Two parallel extractions were performed: methanol extraction for volatile PFAS and alkalized methanol extraction for non-volatile PFAS.
• Both extraction workflows applied heat- and ultrasound-assisted (HUA) treatment: sonication at 60 °C for 1 hour.
• Post-sonication, samples were shaken at 1500 rpm for 10 minutes, centrifuged at 4200 rpm for 5 minutes, and the supernatant processed by filtration (nylon syringe filters).
• For GC samples, filtrates were diluted with ethyl acetate and adjusted (pH 6–7 with acetic acid where specified) prior to adding ISTDs and injection. For LC samples, extracts were diluted, internal standards added, mixed and injected.

Calibration and QC design:

• Volatile PFAS calibration: eight levels from 0.5–100 ng/mL with 5 ppb ISTD.
• Non-volatile PFAS calibration: twelve levels from 0.001–50 ppb with 1 ppb surrogates.
• Method performance assessed by matrix-spiked QCs at low/medium/high concentrations—recoveries, RSD, linearity and LOQs were evaluated.

Instrumentation used

The dual-platform instrumentation deployed in this study was:

• Gas chromatography triple quadrupole: Agilent 8890 GC coupled to a 7010D triple quadrupole mass spectrometer, using a DB-624 column for analysis of volatile PFAS (>30 compounds, e.g., FTOHs).
• Liquid chromatography triple quadrupole: Agilent 1290 Infinity III UHPLC coupled with a 6475A LC/TQ and a ZORBAX RRHD Eclipse Plus C18 column for non-volatile PFAS analysis (over 70 compounds).
• All standards and consumables were sourced from Agilent and pre-verified for PFAS suitability on both LC and GC platforms.

Main results and discussion

Scope and quantitative capability:

• The workflow quantified over 100 PFAS from 14 chemical classes by combining GC/TQ and LC/TQ platforms to capture volatile and non-volatile species respectively.

Extraction efficiency and recoveries:

• More than 80% of analytes showed recoveries within the acceptable 60–140% range across QC levels on both platforms.
• Typical volatile PFAS such as FTOHs showed recoveries of 70–120%. PFAS mandated by EN 17681 and ZDHC exhibited tight recoveries (96–109%), indicating effective extraction across classes.

Linearity and sensitivity:

• Calibration linearity was excellent for all analytes (R2 > 0.99 across at least five points).
• LOQs were established from matrix-spiked QCs while satisfying identification criteria. For volatile FTOHs (4:2, 6:2, 8:2, 10:2), LOQs down to 10 µg/kg were achieved—well below common formulation limits (e.g., ZDHC 1000 µg/kg).
• On the LC/TQ platform, 58 of 74 non-volatile PFAS reached LOQs of 10 µg/kg, meeting EN 17681-1:2025 and ZDHC sensitivity targets.

Reproducibility and robustness:

• Within-batch precision (n = 6) produced %RSD values below 20% for all analytes, confirming good reproducibility for routine testing.
• MRM chromatogram overlays (e.g., PFOA and PFNA) showed consistent peak shapes and retention times across technical preparations.

Operational advantages:

• The simplified protocol eliminated time-consuming evaporation/reconstitution steps, improving throughput and reducing potential contamination or analyte loss.
• Using verified consumables and dedicated workflows for volatile vs. non-volatile PFAS enhanced data integrity and method transferability.

Benefits and practical applications

The validated dual-platform workflow supports laboratory and industry needs by delivering:

• Comprehensive PFAS coverage across volatile and non-volatile classes, enabling manufacturers and test labs to meet evolving regulatory and certification requirements.
• Trace-level sensitivity (many analytes at or below 10 µg/kg), suitable for conformity checks against EN 17681-1:2025, ZDHC and similar restrictions.
• Robust QC performance and good throughput that facilitate routine monitoring of textile batches, supplier audits and compliance testing.

Future trends and potential applications

Anticipated developments and opportunities include:

• Broader adoption of complementary high-resolution mass spectrometry (HRMS) workflows for non-targeted screening and identification of unknown/novel PFAS in complex textile formulations.
• Further lowering of LOQs as regulatory thresholds tighten and instruments/consumables improve, especially for short-chain or substitution chemistries.
• Increased automation of extraction and clean-up to improve sample throughput and reduce analyst variability, plus development of certified textile reference materials for PFAS to strengthen inter-lab comparability.
• Expanded method validation across a wider range of textile fibers, coatings and matrix treatments to ensure transferability across industry-relevant sample types.

Conclusion

This study demonstrates a practical, EN 17681-1:2025-aligned dual-platform approach using GC/TQ and LC/TQ systems to deliver sensitive, reproducible and comprehensive PFAS analysis in textiles. The HUA extraction workflows combined with targeted MRM quantitation achieved strong recoveries, excellent linearity and LOQs meeting industry and regulatory expectations. The streamlined protocol improves laboratory productivity and provides a robust basis for routine compliance monitoring and supply-chain screening.

References

1. Agilent Technologies. Quantitative Volatile PFAS Analysis in Textiles. Publication No. 5994-8966 EN.
2. European Committee for Standardization (CEN). EN 17681-1:2025, Textiles — Determination of PFAS in textiles — Part 1: (method alignment for extraction and analysis).