PFAS Analysis: Application Notebook

Importance of Topic

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative industrial chemicals of growing environmental and public health concern. Widely used in materials and products for their oil- and water-repellent properties, PFAS are now ubiquitous in environmental waters, food, and consumer goods. Ultra-trace analysis of PFAS is essential for monitoring regulatory compliance, assessing human exposure via drinking water and food, and guiding remediation efforts.

Study Objectives and Overview

This compilation of application studies illustrates the use and performance of Shimadzu ultra-fast and high-resolution LC-MS/MS platforms for PFAS analysis under diverse protocols, including:

• Ultra-fast direct injection LC-MS/MS of 49 PFAS in environmental waters (ASTM D7979; UFMS-8060).
• Targeted quantitation of 27 PFAS (EPA 537, 537.1) by triple quadrupole LCMS-8045 and 8050.
• Emerging EPA Method 8327 for 24 PFAS in groundwater, surface water, and wastewater using LCMS-8050.
• Offline supercritical fluid extraction (SFE) of PFAS from fish tissue followed by LCMS-8050 quantitation.
• Screening of PFAS in bottled water by direct injection on LCMS-8050.
• High-resolution accurate mass (HRAM) quantitation of EPA 537.1 targets on QTOF LCMS-9030 with untargeted PFAS discovery.

Methodology and Instrumentation

All studies employ Shimadzu LC-MS/MS systems (LCMS-8045/8050/8060 UFMS or QTOF-9030) coupled to UHPLC with phenyl-hexyl or C18 columns. Key methodological features include:

• Delay columns (ODS) to trap background PFAS before analytical separation.
• Simple sample prep: methanol dilution and direct LC injection for water; SPE (WAX) for drinking water methods; SFE for fish tissue.
• Use of stable-isotope surrogates and internal standards for quantitation.
• Multiple Reaction Monitoring (MRM) on triple quadrupoles at >500 transitions/sec.
• High-resolution TOF acquisition for accurate mass screening and formula prediction of unknown PFAS.

Key Results and Discussion

Ultra-fast LCMS-8060 UFMS enabled separation of 49 PFAS in 13 min with MDLs of 0.6–5.4 ng/L and recoveries of 84–113%. For EPA 537 (27 PFAS) on LCMS-8050 and 8045, MDLs of 0.6–3.3 ng/L, recoveries 86–106%, and ≤15% RSD satisfied method criteria. Method 8327 on LCMS-8050 achieved MDLs of 0.7–1.7 ng/L for 24 PFAS in non-potable waters. SFE-LCMS-8050 of fish tissue yielded 95–110% recoveries for 18 PFAS with LOQs down to 0.5 ng/g and ≤15% RSD. Bottled water screening on LCMS-8050 detected short-chain PFBA and fluorotelomer sulfonate at <100 ppt; plastic bottles (especially recycled) showed higher PFAS compared to glass or cardboard. HRAM QTOF quantitation of EPA 537.1 targets achieved LOQs of 1–16 ng/L, linearity r2>0.99, and provided accurate mass data and software-driven workflows to tentatively identify unknown PFAS formulas.

Benefits and Practical Applications

• Rapid direct-injection protocols for routine monitoring of drinking and environmental waters.
• Method compliance across EPA, ASTM, and ISO guidelines with high sensitivity and throughput.
• Minimal sample preparation reduces labor and risk of contamination.
• Ultra-fast scanning capacity of UFMS systems supports large PFAS panels in a single run.
• HRAM QTOF systems enable both targeted quantitation and untargeted discovery of new PFAS species.
• SFE offers efficient extraction of PFAS from complex matrices like fish tissue.

Future Trends and Opportunities

• Expansion of PFAS target lists to include shorter-chain and emerging fluorochemical replacements.
• Integration of high-resolution methods with suspect and non-target screening for comprehensive PFAS profiling.
• Automation of sample prep (SPE, SFE) for high-throughput laboratories.
• Standardization of multi-method platforms to harmonize data across regulatory and research applications.
• Continued development of software tools for rapid formula prediction and structure elucidation of unknown PFAS.

Conclusion

Shimadzu’s suite of LC-MS/MS platforms, from ultra-fast triple quadrupole to high-resolution QTOF, offers robust, sensitive, and versatile workflows for PFAS analysis across environmental, food, and consumer product matrices. These methodologies meet or exceed regulatory requirements while enabling high throughput, reliable quantitation, and discovery of emerging PFAS contaminants.

References

1. EPA Method 537.1, November 2018.
2. EPA Method 8327 (draft), 2018.
3. ASTM D7979-17 and D7968-17a, 2017.
4. UCMR3 Monitoring (EPA), 2018.
5. FDA PFAS food testing method, 2020.
6. Lindstrom et al., Environ. Sci. Technol. Lett., 2016.