Streamlined EMR LC-MS/MS Approach for Sensitive PFAS Determination in Alcoholic Beverages

Streamlined EMR LC-MS/MS Approach for Sensitive PFAS Determination in Alcoholic Beverages — Summary

Significance of the topic

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative contaminants increasingly found across the food chain. Alcoholic beverages (e.g., wine, beer, cocktails) can become contaminated via raw agricultural materials, processing water, and contact with PFAS-impacted environments. Despite this risk, alcoholic drinks have been less frequently monitored than other food matrices. A sensitive, robust, and high-throughput analytical workflow tailored to high-organic matrices such as alcoholic beverages is therefore important for routine food-safety testing and regulatory compliance.

Objectives and study overview

The study presents a streamlined sample-preparation and LC–MS/MS workflow for quantifying 43 PFAS in alcoholic beverages. Goals were to (1) overcome matrix effects associated with high organic content, (2) achieve low limits of quantitation (LOQs) compatible with food-safety targets, (3) maintain accuracy and precision in line with AOAC SMPR criteria, and (4) reduce processing time while improving chromatographic performance via a feed-injection strategy.

Methodology

Sample preparation:

• Sample aliquot: 2 g of beverage used as starting material.
• Protein/organic removal: Samples extracted with acetonitrile (ACN) containing 1% acetic acid; vortexed and centrifuged to separate phases.
• EMR cleanup: Supernatant passed through Captiva EMR PFAS Food I passthrough cartridges (680 mg, P/N 5994-2231) that were pre-washed and equilibrated. Elution conducted by gravity; cartridges dried with a brief 10 psi gas push to remove residual solvent.
• Internal standards: Isotopically labeled internal standards (EIS and NIS) were spiked to monitor recoveries and matrix effects.
• Final handling: Aliquots of the eluate were taken directly for LC–MS/MS analysis.

Chromatography and injection:

• Column: RRHD Eclipse Plus C18, 1.8 µm, 2.1 × 100 mm with an Eclipse Plus guard (2.1 × 5 mm) and an Agilent InfinityLab PFC delay column (4.6 × 30 mm).
• Mobile phase: A—5 mM ammonium acetate in water; B—acetonitrile. Flow set at 0.4 mL/min with a multi-step gradient to 100% B by ~13.25 min and total run stop at 15.5 min.
• Injector: Agilent 1290 Infinity III Hybrid Multisampler operated in feed-injection mode (feed injection volume 12.5 µL; adaptive feed speed at 10% of pump flow). Cleaning and wash cycles optimized to minimize carryover.

Mass spectrometry:

• System: Agilent 6495D triple quadrupole operated in negative polarity with dynamic MRM (dMRM).
• Gas/settings: Drying gas 200 °C, 18 L/min; sheath gas 300 °C, 11 L/min; nebulizer 15 psi; capillary voltage ~2500 V. Nozzle voltage set at 0 V in this configuration.

Instrumention used

• Agilent 1290 Infinity II / Infinity III LC systems (multisampler with feed-injection capability).
• RRHD Eclipse Plus C18 analytical column and Eclipse Plus guard column.
• Agilent InfinityLab PFC delay column for PFAS background separation.
• Captiva EMR PFAS Food I passthrough cartridges (680 mg, P/N 5994-2231) for matrix removal.
• Agilent 6495D triple quadrupole mass spectrometer operated in dMRM negative mode.

Main results and discussion

Sensitivity and LOQ:

• Method achieved low LOQs suitable for trace PFAS monitoring in alcoholic matrices; an example LOQ of 0.01 ng/mL was demonstrated for red wine with high signal-to-noise ratios (e.g., PFOA S/N ≈ 288; PFNA S/N ≈ 241; PFOS S/N ≈ 124; PFHxS S/N ≈ 85).

Accuracy, precision and reproducibility:

• Recoveries of isotopically labeled internal standards (EIS and NIS) were within predefined acceptance criteria across matrices (red wine, beer, cocktail mix), indicating effective cleanup and compensated matrix effects.
• Intra- and inter-batch precision (RSDs and RSDR%) met method validation targets consistent with AOAC SMPR guidance for PFAS in food.

Chromatography and feed injection:

• Feed-injection mode improved peak shape and chromatographic integrity compared with conventional and sandwiched injection approaches, reducing dispersion and preserving narrow peaks for PFAS analytes in high-organic matrices.

Throughput and workflow efficiency:

• Streamlined EMR passthrough cleanup and reduced handling lowered processing time by up to 50% versus more elaborate SPE protocols, enabling higher sample throughput in routine labs.

Benefits and practical applications

• Method suitability for routine monitoring of PFAS in alcoholic beverages (wine, beer, mixed drinks) within food-safety laboratories and quality-control settings.
• High sensitivity and robust internal-standard performance enable reliable quantitation at trace concentrations relevant to regulatory and exposure assessments.
• Reduced sample-preparation time and a passthrough EMR format simplify workflow, lower labor, and minimize solvent use relative to multi-step SPE workflows.
• Feed-injection capability enhances chromatographic reproducibility and reduces injection-related artefacts in high-organic matrices.

Future trends and potential applications

• Broader matrix extension: Adapting the EMR passthrough and feed-injection workflow to additional food and environmental matrices (dairy, juices, bottled water) to provide harmonized PFAS monitoring across the food chain.
• Method sensitivity: Continued optimization to lower LOQs for highly regulated PFAS and to detect newly emerging PFAS at sub-ppt levels using high-resolution or enhanced ionization strategies.
• Automation and throughput: Integration with 96-well passthrough formats, robotic liquid handling, and automated sample tracking to scale laboratory capacity.
• Non-target and suspect screening: Complementing targeted TQ analyses with high-resolution MS for broader PFAS suspect screening and discovery of transformation products.
• Green analytical trends: Reducing solvent volumes and adopting greener extraction chemistries while maintaining cleanup efficiency for PFAS analyses.

Conclusion

The described EMR passthrough plus LC–MS/MS feed-injection workflow delivers a sensitive, accurate, and efficient method for quantifying 43 PFAS in alcoholic beverages. It meets AOAC SMPR-aligned performance criteria, substantially reduces sample-preparation time, and benefits from feed-injection–driven chromatographic improvements. The protocol is well suited for routine laboratory monitoring and can be extended and optimized for broader food-safety applications.

Reference

• Zhao L., De Leoz M. L. Streamlined EMR LC-MS/MS Approach for Sensitive PFAS Determination in Alcoholic Beverages. ASMS 2026 Poster ThP 227. Agilent Technologies, Wilmington, DE (2026).
• Agilent Technologies. Determination of 43 PFAS in Beer and Wine Using the Agilent Captiva EMR PFAS Food I passthrough cleanup and LC/MS/MS detection. Application Note 5994-8813EN.
• Agilent Technologies. Captiva EMR PFAS Food cartridges — Sample Preparation for Food Analysis. Agilent application literature.