Ultra-fast LC-MS/MS Analysis of PFAS in Environmental Samples

Importance of the Topic

Per- and polyfluoroalkyl substances (PFAS) are highly persistent environmental pollutants with demonstrated toxicity and global distribution in water sources. Their resistance to degradation and widespread use in consumer and industrial products has raised significant public health and regulatory concerns. Continuous monitoring of PFAS in surface water, groundwater, wastewater, and drinking water is essential to enforce guideline levels and limit human exposure.

Objectives and Overview of the Study

This study reviews state-of-the-art LC-MS/MS methods for PFAS analysis and demonstrates the performance of Shimadzu’s Ultra-fast Mass Spectrometry (UFMS™) platform. The primary goal is to validate a simple direct-injection workflow in compliance with ASTM D7979 for the rapid separation and quantitation of a broad PFAS panel in environmental waters.

Methodology and Instrumentation

• Sample Preparation: 5 mL environmental water diluted 1:1 with methanol, spiked with isotopically labeled surrogate PFAS, vortexed, filtered and acidified for direct injection.
• Calibration Strategy: Nine-point external calibration curves (5–200 ng/L) for 44 PFAS, and 100–4000 ng/L for fluorotelomer acids (FHEA, FOEA, FDEA), prepared in 50:50 methanol/water with 0.1% acetic acid.
• Contamination Control: Use of PFAS-free consumables, high-purity solvents and a solvent delay column to trap background PFAS from glassware and HPLC plumbing.
• Data Acquisition: Multiple reaction monitoring at 555 transitions per second with fast polarity switching, ensuring at least ten data points per chromatographic peak.

Instrumentation

• Shimadzu LCMS-8060 triple quadrupole mass spectrometer with UFMS™ technology.
• Shim-pack GIST Phenyl-Hexyl column (2.1×100 mm, 3 μm) for isomeric separation.
• Shim-pack XR-ODS solvent delay column (3×50 mm, 2.2 μm) to minimize background.
• Electrospray ionization source (ESI) with optimized interface temperatures and gas flows.

Main Results and Discussion

• Chromatographic separation of 49 PFAS compounds achieved within 13 minutes, including linear chain isomers.
• Method detection limits of 0.6–5.4 ng/L for 44 PFAS; higher ranges for selected fluorotelomer acids due to matrix effects.
• Recoveries of 84–113% and precision (RSD) below 13% for the majority of analytes at mid-level spikes.
• Solvent stability tests confirmed that formulations with at least 50% methanol maintain PFAS solubility; thorough vortexing prevented adsorption losses.

Benefits and Practical Applications

The direct injection UFMS™ method offers high throughput, minimal sample handling and robust performance for routine PFAS surveillance. Fast cycle times and sensitivity support compliance with stringent regulatory limits, including those below 10 ng/L in drinking water.

Future Trends and Possibilities

Emerging PFAS alternatives such as GenX and novel fluorotelomer derivatives require expanded analytical panels. The UFMS™ platform’s capability for large-scale MRM scheduling positions it well for future method extensions and high-volume monitoring, aiding evolving regulatory and environmental health assessments.

Conclusion

Shimadzu’s UFMS™-enabled LCMS-8060 facilitates rapid, sensitive and reproducible analysis of a diverse PFAS suite in environmental waters via a streamlined direct-injection workflow. This approach meets ASTM validation criteria and supports routine monitoring under increasingly stringent guidelines.

References

• U.S. EPA (2009) Method 537: Determination of Selected Perfluorinated Alkyl Acids in Drinking Water by SPE and LC-MS/MS.
• ASTM International (2017) ASTM D7979-17: Standard Test Method for Determination of Perfluorinated Compounds in Water by LC-MS/MS.
• ASTM International (2017) ASTM D7968-17a: Standard Test Method for Determination of Perfluorinated Compounds in Soil by LC-MS/MS.
• U.S. EPA (2018) Method 537.1: Determination of Selected Per- and Polyfluoroalkyl Substances in Drinking Water by SPE and LC-MS/MS.
• Prakash B, Lee C, Byrne G, Ogura T (2019) Ultra-fast LC-MS/MS Analysis of PFAS in Environmental Samples. Shimadzu White Paper C10G-E074.