Determination of 20 PAEs in Alcoholic Drinks by Using Ultra High Performance Liquid Chromatography-Tandem Mass Spectrometry

Significance of the Topic

Phthalate esters are plasticizers widely used to impart flexibility to polymers and are known reproductive and developmental toxins. As alcoholic beverages often contact plastic during production and storage, monitoring phthalate migration is essential for consumer safety and regulatory compliance.

Objectives and Study Overview

This work aimed to develop and validate a rapid, sensitive UHPLC-ESI-MS/MS method to quantify 20 phthalate esters in alcoholic drinks. The method was assessed for linearity, precision, accuracy, and detection limits to support routine quality control and regulatory testing.

Methodology and Instrumentation

Sample Preparation:
Accurately weigh 5 g of alcoholic beverage, centrifuge at 6000 rpm for 20 minutes, and directly analyze the supernatant.

• Chromatography: Shim-pack XR-ODS III column (150×2.0 mm, 2.2 μm) with Inertsil ODS-4 guard (50×3.0 mm, 2 μm); mobile phases—5 mM ammonium acetate (A) and methanol (B); flow 0.35 mL/min; column at 45 °C; injection volume 10 µL.
• Mass Spectrometry: Shimadzu LCMS-8040 triple quadrupole with ESI positive mode at +4.5 kV; nebulizing gas 3.0 L/min; drying gas 15 L/min; DL 250 °C; heat block 450 °C; MRM scan with 15 ms dwell and 3 ms pause times.
• Instrumentation: Shimadzu Nexera UHPLC system (LC-30AD pump, CTO-30A oven, DGU-30A3 degasser, SIL-30AC autosampler) coupled to LCMS-8040.

Results and Discussion

• Separation: All 20 phthalates were resolved within a 14-minute run, confirmed by MRM chromatograms.
• Linearity: Calibration curves over 5–200 μg/L yielded correlation coefficients greater than 0.999 for each analyte.
• Precision: Retention time RSDs ≤0.26% and peak area RSDs ≤4.79% across low, medium, and high concentrations.
• Accuracy: Recoveries ranged from 78% to 127% at spiking levels of 50 and 100 μg/kg, meeting acceptance criteria.
• Sensitivity: Limits of detection and quantification based on signal-to-noise ratios satisfied requirements for beverage analysis.

Benefits and Practical Applications

The validated UHPLC-MS/MS method delivers high throughput and reliable results for routine screening of phthalate contamination in alcoholic products. Its simplicity and robustness make it suitable for industrial QA/QC labs, regulatory bodies, and research institutions focused on food safety.

Future Trends and Potential Applications

Future work may explore automated sample preparation, integration of high-resolution mass spectrometry for improved selectivity, and expansion to other food matrices. Development of portable screening devices and real-time monitoring techniques could further enhance on-site compliance testing.

Conclusion

A rapid and robust UHPLC-ESI-MS/MS protocol was established and validated for the quantification of 20 phthalate esters in alcoholic beverages. The method demonstrates excellent linearity, precision, accuracy, and sensitivity, supporting its deployment in routine safety and regulatory analyses.

References

• Dong H, Yao J, Huang T, Tian F, Zhou L, Kawano S, Hashi Y. Determination of 20 PAEs in Alcoholic Drinks by UHPLC-MS/MS. Shimadzu Application Note PO-CON1516E, Pittcon 2015.