Analysis Method of Polybrominated Diphenyl Ethers Using GC-MS and GC-MS/MS Coupled With an Automated Identification and Quantitation System with a Database

Significance of the topic

Polybrominated diphenyl ethers (PBDEs) comprise 209 congeners that persist in the environment and exhibit varying toxicity and occurrence. Accurate, cost-effective analysis in complex matrices such as sediment is critical for environmental monitoring and risk assessment.

Objectives and study overview

This work presents a hybrid analytical strategy combining an automated identification and quantitation database (AIQS-DB) with single-quadruple GC-MS and triple-quadruple GC-MS/MS. The aim was to minimize the use of expensive 13C-labeled standards while ensuring precise quantitation of high-priority PBDE congeners.

Methodology and instrumentation

Sample preparation involved Soxhlet extraction of dried sediment with toluene, acid cleanup, florisil column purification, concentrated acid wash, activated copper treatment, and solvent exchange to nonane or hexane.
Used instrumentation:

• Shimadzu GCMS-TQ8030 with Rtx-1614 column (15 m × 0.25 mm i.d., 0.10 µm)
• Splitless injection (1 µL at 320 °C), helium carrier gas, SIM mode for GC-MS and MRM mode for GC-MS/MS
• AIQS-DB containing retention indices, predicted retention times, mass spectra, and calibration curves for 1,000 pollutants

Main results and discussion

Retention time predictions across three GC-MS systems and real samples deviated by less than ±0.14 min. Semi-quantitative analysis of spiked sediment yielded recoveries from 53.7 to 68.5 ng/mL for most congeners; one co-eluting hepta-BDE could not be quantified accurately. GC-MS/MS achieved repeatability (%RSD <6%) and linearity (R >0.9996) across a wide concentration range. Comparative quantitation in sediment using GC-MS, GC-MS/MS and GC-HRMS showed excellent agreement within analytical uncertainty.

Benefits and practical applications

• Substantial reduction in the requirement for costly isotope-labeled standards through AIQS-DB automation
• High selectivity and sensitivity in complex sample matrices via GC-MS/MS
• Streamlined workflow suitable for routine environmental laboratories in both developed and developing regions

Future trends and possibilities

• Expansion of AIQS-DB coverage to emerging flame retardants and other micropollutants
• Integration with high-resolution mass spectrometry platforms for enhanced specificity
• Development of on-site or real-time screening systems using portable instrumentation
• Advancement of machine learning algorithms for rapid data interpretation and anomaly detection

Conclusion

The combined AIQS-DB, GC-MS and GC-MS/MS approach delivers reliable, high-throughput analysis of PBDEs in sediment, reducing cost and complexity while maintaining accuracy and reproducibility.

Reference

• Kadokami K, Tanada K, Taneda K, Nakagawa K. Novel gas chromatography-mass spectrometry database for automatic identification and quantification of micropollutants. J Chromatogr A. 2005;1089:219–226.