APWC: Determination of tetrabromobisphenol A/S and their main derivatives in water samples by HPLC-ICP-MS/MS

Significance of the topic

Brominated flame retardants such as tetrabromobisphenol A (TBBPA) and its sulphonic analogue TBBPS are among the most widely used additives to reduce fire risk in consumer products. Their persistence, bioaccumulation and potential health hazards have raised environmental concerns worldwide. Sensitive and selective analytical methods are therefore essential to monitor these compounds and their novel derivatives in aquatic environments.

Aims and overview of the study

This work aimed to develop and validate a high-performance liquid chromatography coupled with inductively coupled plasma tandem mass spectrometry (HPLC-ICP-MS/MS) method for the simultaneous determination of seven TBBPA/S derivatives in water samples. The study evaluated collision/reaction cell (CRC) modes to eliminate spectral interferences and optimized chromatographic separation and detection conditions for trace-level quantification.

Used instrumentation

• Agilent 1200 HPLC pump with ZORBAX Eclipse Plus C18 column (150 × 4.6 mm, 5 µm)
• HPLC mobile phase delivery and gradient control
• Agilent 8800 ICP-MS/MS equipped with octopole CRC

Methodology

Water samples were filtered and extracted by liquid–liquid extraction. The HPLC gradient employed methanol and water both acidified with 0.1% acetic acid over a 20-minute run. The ICP-MS/MS was tuned daily for bromine at m/z 79. Reaction gas H2 (4.5 mL/min) was used in mass-shift mode with a 30% optional gas mixture containing 20% O2 in Ar to improve plasma stability and suppress carbon buildup.

Main results and discussion

Use of H2 reaction gas effectively removed polyatomic interferences and lowered baselines for 79Br and 81Br signals. Seven analytes (TBBPA, TBBPA-BHEE, ‑BGE, ‑BAE, ‑BDBPE, TBBPS, TBBPS-BDBPE) were baseline-resolved. Linearity (5–200 µg/L) showed correlation coefficients >0.999. Instrumental limits of detection ranged from 0.12 to 0.19 µg/L. Intra- and inter-day RSDs were below 2.2% for peak area and 0.2% for retention time. Spiked recoveries in river, tap and seawater ranged from 67.7% to 113%, demonstrating method accuracy.

Benefits and practical applications

This HPLC-ICP-MS/MS approach offers rapid separation, high selectivity for brominated compounds and low detection limits without complex sample derivatization. It is well suited for routine monitoring of BFRs in drinking water, surface water and industrial effluents.

Future trends and opportunities

Method extensions may include analysis of sediments, biota and wastewater matrices. Integration with smaller-scale or portable ICP-MS systems could enable on-site screening. Further development might target emerging brominated species and isotopic tracer studies to track environmental fate.

Conclusion

A novel HPLC-ICP-MS/MS method has been established for seven TBBPA/S derivatives, providing high sensitivity, precision and reliability for water analysis. This technique complements existing GC-MS and LC-MS approaches and opens new avenues for environmental monitoring of brominated contaminants.

References

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• Tian Y, Liu A, Jiang G, et al. RSC Adv. 2015;5:14476–14479.