Detection of Plasticizers and Flame Retardants in Polymers by Pyrolysis GC-APCI QTOF MS

Importance of the Topic

The presence of plasticizers and flame retardants in polymeric materials used in textiles and protective gear poses significant health risks due to toxicity and potential endocrine disruption. Rapid and reliable detection methods are essential to ensure safety of consumer and industrial products, especially those in close contact with skin.

Objectives and Study Overview

This study aimed to develop a targeted screening approach for 85 common plasticizers and flame retardants in various fabrics using pyrolysis gas chromatography coupled with atmospheric pressure chemical ionization quadrupole time-of-flight mass spectrometry (pyrolysis GC-APCI QTOF MS). Five fabric types were analyzed, including natural cotton and engineered protective materials containing Kevlar®, Nomex®, and PBI®.

Methodology and Instrumentation

A small fabric fragment (100–200 µg) was pyrolyzed at 750 °C and the resulting volatile fragments were separated by GC and ionized by APCI. Accurate mass analysis and isotopic pattern matching were performed using a compact UHR-QTOF MS.

• Pyrolyzer: CDS 6200 Pyroprobe
• Gas Chromatograph: Bruker 456 GC with RXI-5Sil MS column
• Mass Spectrometer: Bruker compact UHR-QTOF MS with APCI interface
• Data Analysis: TASQ software with Suspect Finder workflow for targeted screening

Key Results and Discussion

Only two of the five fabrics contained target additives. Melamine was detected in the cotton T-shirt, while ethyl terephthalate and four additional compounds were identified in the moisture barrier fabric. The TASQ Suspect Finder enabled extraction of ion chromatograms (±3 mDa) and automatic isotopic pattern validation (mSigma scoring), facilitating confident identification even at low abundance. Positional isomers were noted where retention times overlapped.

Benefits and Practical Applications

• No extensive sample preparation is required, making the method fast and adaptable to diverse polymer matrices.
• High mass accuracy (<2 ppm) and isotope ratio fidelity (<2 % error) support reliable elemental composition determination.
• Turnkey TASQ software streamlines screening and quantitation of large target lists for QA/QC and regulatory compliance.

Future Trends and Applications

Advances could include expanding suspect libraries to novel additives, integrating real-time monitoring for manufacturing processes, and coupling pyrolysis screening with quantitative MS/MS workflows. Machine-learning-driven data mining may further enhance detection sensitivity and specificity.

Conclusion

Pyrolysis GC-APCI QTOF MS combined with targeted data analysis provides a robust platform for rapid detection of hazardous additives in polymeric textiles. The approach addresses challenges posed by complex sample forms and supports safety screening in industrial and consumer applications.

References

• Shaw S, et al. Halogenated flame retardants: Do the fire safety benefits justify the risks? Rev Environ Health. 2010;25(4):261–306.
• National Institute of Environmental Health Sciences. Flame Retardants [online]. Reviewed October 12, 2018.
• Kind T, Fiehn O. Metabolomic database annotations via query of elemental compositions: Mass accuracy is insufficient even at less than 1 ppm. BMC Bioinformatics. 2006;7:234.