Development of Automated Screening and Quantitation Approach on Novel On-Line SFE-SFC-MS/MS Platform – (I) For 23 Restricted Perflurocompounds in Textiles

Significance of the Topic

Perfluorinated compounds (PFCs) are persistent environmental contaminants regulated in many consumer goods, including textiles. Their widespread use and potential health risks demand sensitive, high-throughput analytical methods.

Objectives and Study Overview

This study aims to develop and validate an automated on-line screening and quantitation workflow for 23 restricted PFCs in textile matrices. The approach integrates supercritical fluid extraction (SFE) with supercritical fluid chromatography–tandem mass spectrometry (SFC-MS/MS) on the Shimadzu Nexera UC platform, enabling direct analysis of un-pretreated samples.

Methodology and Instrumental Setup

A two-step SFE-SFC-MS/MS protocol was established:

• Static extraction: 4 minutes at 40 °C with pure supercritical CO₂
• Dynamic extraction: 2 minutes with CO₂-methanol modifier

SFC separation employed a 250 mm × 2.1 mm, 3 µm silanol-functionalized column under a 7-minute gradient (0–50% methanol with 5 mM ammonium formate). Electrospray ionization in negative mode and multiple reaction monitoring ensured selectivity.

Main Results and Discussion

• Calibration for all 23 PFCs exhibited linearity (r² > 0.97) over 2.5–125 pg injected, with limits of quantitation between 0.03 and 1 ng/mL.
• Method repeatability ranged from 6% to 60% RSD at 5 pg and improved at higher levels.
• On-line SFE-SFC-MS/MS introduced slight retention time shifts (~0.2 min) and peak broadening due to system volume.
• System recoveries averaged 90% at 25 pg and 74% at 50 pg spike levels, with RSDs of 12%–14%.
• Direct analysis of un-spiked textile samples showed no detectable PFCs, while spiked textiles at 0.42 ng/g yielded clear detection of all target analytes.

Benefits and Practical Applications

The fully automated workflow offers:

• Minimal sample preparation and solvent use
• Rapid throughput with 7-minute chromatographic runs
• Trace-level sensitivity suitable for RSL compliance
• Versatility to screen multiple PFCs in diverse textile products

Future Trends and Opportunities

Further optimization may focus on improving extraction recovery for complex textiles and expanding the methodology to other restricted substances and consumer matrices. Integration with data-processing software and advanced ionization sources may enhance throughput and robustness.

Conclusion

The novel on-line SFE-SFC-MS/MS platform demonstrates promising performance for automated screening and quantitation of 23 regulated PFCs in textiles, achieving sub-ng/g sensitivity without offline sample preparation. Continued method refinement and broader application will support regulatory monitoring and quality control in industrial laboratories.

Reference

1. Shimadzu Application News No. LAAN-A-LC-E273, Analysis of Residual Pesticides Using Nexera UC Online SFE-SFC-MS System, 2015.
2. van der Veen I., Weiss J.M., Hanning A.C., de Boer J., Leonards P.E., Talanta 147 (2016) 8–15.
3. Wellington Laboratories, Quick Reference Guide for Perfluoroalkyl Compounds.
4. Lee J.X., Sun Z., Xing J., Tan J.Y., Zhan Z., ASMS 2016, Poster TP 485.