Analysis of Volatile PFAS in Textiles Using GCMS-TQ8040 RX with MMI

Analysis of Volatile PFAS in Textiles Using GCMS-TQ8040 RX with MMI — Summary

Significance of the topic

Per- and polyfluoroalkyl substances (PFAS) are widely used in textiles for water and heat repellency but are persistent, bioaccumulative, and increasingly regulated. Reliable, sensitive methods for quantifying volatile PFAS in textile articles are required to enforce limits such as the EU POPs threshold (0.025 mg/kg, 25 ppb) and to support industry quality control and regulatory compliance. This study demonstrates a gas chromatography–tandem mass spectrometry (GC-MS/MS) workflow optimized to quantify multiple volatile PFAS at trace levels in textiles without solvent concentration steps.

Objectives and study overview

• Evaluate the GCMS-TQ8040 RX triple-quadrupole GC-MS combined with a Multi-Mode Injection Unit (MMI) for trace analysis of 12 volatile PFAS in textiles, including compounds referenced in EN 17681-2.
• Optimize injection conditions to improve sensitivity and peak shape, enabling analysis at the ppb level without preconcentration.
• Validate performance via calibration, repeatability, and spike-recovery tests at the EU POPs regulatory limit (25 ppb), and apply the method to a real textile sample (ski glove).

Used instrumentation

• GCMS-TQ8040 RX triple-quadrupole mass spectrometer (Shimadzu).
• Multi-Mode Injection Unit (MMI) enabling split/splitless, programmable temperature vaporization (PTV), large-volume injection (LVI), direct injection and thermal desorption/extraction modes.
• AOC-30i autosampler supporting co-injection.
• GC column: SH-I-624Sil MS (60 m × 0.32 mm, 1.8 µm) with 5 m guard column.

Methodology and experimental workflow

• Target list: 12 volatile PFAS including Me-PFOA, a set of FTOHs (4:2, 6:2, 8:2, 10:2 FTOH), FTAs, FTMAs and N-alkyl FOSEs. Four FTOH compounds are not covered by EN 17681-2 but were included because GC/MS is commonly used for these analytes.
• Sample preparation (EN 17681-2 based): cut 1 g textile into ≤1 cm squares, add surrogate (10 ppm, 0.05 mL) and 10 mL methanol, ultrasonic extraction at 60 ±5 °C for 120 ±5 min, centrifuge and analyze supernatant. Nitrogen concentration step optional and omitted in this work.
• Injection strategy: MMI operated in programmed temperature vaporization (PTV) / pulsed splitless mode with a threefold increase in practical injection volume (from ~2 µL typical to 6 µL sample + co-injected ethyl acetate) to enhance sensitivity while preserving peak shape.
• Co-injection optimization: Me-PFOA suffered peak broadening when injected with methanol alone; co-injecting 2 µL ethyl acetate into 6 µL sample improved vaporization and chromatographic shape.
• Chromatography: linear velocity ~40 cm/s; column temperature program from 40 °C initial ramp to 280 °C final hold. MS operated in MRM mode; quantifier transitions established for each analyte (see method table in original text).
• Calibration: internal standard calibration curves prepared over 1–100 µg/L (except Me-PFOA); internal standards: 9Me 8:2 FTOH and D7-N-MeFOSE. Lowest-level repeatability tested at 1 µg/L (n = 5).

Key analytical performance and results

• Linearity: all calibration curves showed excellent linearity (correlation coefficients R ≥ 0.998).
• Precision: repeatability at the lowest calibration level (n = 5) yielded %RSD values below ~12% for all compounds.
• Sensitivity: increasing injection volume using MMI improved peak intensity across targets, enabling detection at and below the EU POPs threshold (25 ppb) without concentration steps.
• Spike recovery at regulatory limit: 1 g cotton glove samples spiked to 25 ppb (n = 3) produced mean recoveries between 80 and 120% for all measured compounds, with %RSD ≤ 10%.
• Real sample application: analysis of a ski glove (100% cotton) detected 8 of 12 targeted volatile PFAS. Two FTOHs (8:2 and 10:2 FTOH) were present above the upper calibration range, indicating higher contamination for those analytes.

Discussion and practical implications

• The MMI’s programmable vaporization and ability to accept larger injection volumes (with co-injection solvent management) substantially increases sensitivity for volatile PFAS compared with conventional split/splitless injectors where vaporization chamber volume limits injection size.
• Omitting solvent concentration (nitrogen purge) simplifies workflow and reduces potential analyte loss or bias introduced by additional handling, while still meeting regulatory detection requirements owing to the enhanced injection strategy.
• Good linearity and repeatability indicate the method is robust for quantification over the evaluated range; however, compounds exceeding calibration range in real samples require extended calibration or dilution/secondary analysis to obtain accurate concentrations.
• Inclusion of GC-amenable FTOHs not covered by EN 17681-2 highlights the complementary role of GC/MS/MS to LC/MS/MS in comprehensive PFAS monitoring programs for textiles.

Benefits and applications of the method

• Regulatory compliance testing for textiles under EU POPs limits and EN 17681-2 framework without a concentration step, reducing turnaround time and sample handling.
• Quality control in textile manufacturing and incoming-material screening to detect volatile PFAS contamination at ppb levels.
• Screening and targeted quantification of a multi-component PFAS panel within a single GC-MS/MS run, improving laboratory throughput.

Future trends and potential uses

• Broader target lists and isotope-labeled internal standards: expanding analyte panels and using labeled analogues will improve quantitation and account for matrix effects.
• Lower detection limits and automated workflows: combining thermal desorption or on-line preconcentration with advanced injection strategies could support sub-ppb monitoring as regulatory demands tighten.
• Method harmonization: inter-laboratory validations and standardized certified reference materials for textile matrices will increase comparability of results across labs and jurisdictions.
• Integrated monitoring: pairing GC-MS/MS volatile PFAS analysis with LC-MS/MS for nonvolatile PFAS in a tiered workflow will offer comprehensive assessment of total PFAS burden in articles.
• High-throughput screening: adoption of advanced autosamplers and software for Analytical Intelligence can support routine large-scale surveillance programs in industry and regulatory labs.

Conclusion

The GCMS-TQ8040 RX combined with an MMI and optimized co-injection strategy enables reliable, ppb-level analysis of a panel of volatile PFAS in textiles following EN 17681-2 style sample preparation without solvent concentration. The approach delivers strong linearity, acceptable precision, and spike recoveries within regulatory acceptance criteria at 25 ppb. Increased injection volume and controlled vaporization are key to achieving sufficient sensitivity for regulatory and QC applications. For samples exceeding calibration ranges, extended calibration or alternative dilution/analysis is recommended.

References

1. EU POPs Regulation (2019/1021) — restriction limits for certain PFAS (permitted threshold for selected PFAS: 0.025 mg/kg, 25 ppb).
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.

Acknowledgements

The original study acknowledges contributions from KOTITI Testing & Research Institute personnel (Mr. Na and Dr. Kim) for experimental support.