Determination of 41 Per- and Polyfluoroalkyl Substances (PFAS) in Cosmetics

Determination of 41 PFAS in Cosmetics Using QuEChERS, Captiva EMR PFAS Food II Passthrough Cleanup and LC/MS/MS

Significance of the topic

Per- and polyfluoroalkyl substances (PFAS) are persistent synthetic chemicals with strong C–F bonds that confer thermal and chemical stability and resistance to environmental degradation. Their use or unintentional presence in cosmetic formulations (e.g., water- and oil-repellent finishes, lip products, sprays) raises human exposure concerns via dermal absorption, inhalation, and oral routes. Reliable analytical workflows for trace-level PFAS in diverse cosmetic matrices are therefore essential for consumer safety monitoring and regulatory compliance.

Study objectives and overview

The study aimed to develop and validate a rapid, robust method to analyze 41 target PFAS in five types of commercial cosmetics (sunscreen, lotion, foundation, lipstick, eyeshadow). The approach combined QuEChERS extraction with a passthrough mixed-mode cleanup using Agilent Captiva EMR PFAS Food II cartridges, followed by LC/MS/MS quantitation on a triple-quadrupole system. Performance metrics included calibration linearity, analyte recoveries in different matrices, instrument method detection limits (IMDL), and demonstration of the method on real products.

Methodology and sample preparation

- Sample set: Five cosmetic categories, three commercial products per category (15 products total). Solid powders were gently pulverized; liquid/cream types were processed with minimal pretreatment to limit contamination.
- Spike level for recovery study: 20 ng/g added to matrix; due to a 20-fold dilution during sample prep the final analyzed concentration corresponded to 1 ng/mL.
- Extraction workflow (summary):

• Weigh 1 g sample into a 50 mL tube and add appropriate isotopically labeled internal standards.
• Add 10 mL acetonitrile (ACN) with 1% acetic acid, shake 5 min; ultrasonic extraction 30 min.
• Add 10 mL water, shake 1 min; add QuEChERS EN buffered salts, shake 5 min; centrifuge at 5,000 rpm, 5 min.
• Transfer 2.5 mL supernatant and dilute with ACN/1% AA and water to obtain 90:10 ACN:water crude extract.
• Cleanup: prewash Captiva EMR PFAS Food II cartridge, equilibrate, load sample (5 mL) under gravity, dry cartridge, collect eluate, filter (0.2 µm nylon) and analyze.

Instrumentation used

- LC: Agilent 1290 Infinity III (high-speed pump G7120A, multisampler G7167B, multicolumn thermostat G7116B), InfinityLab PFAS Analysis HPLC conversion kit including PFC delay column (4.6 × 30 mm). Analytical column: ZORBAX RRHD Eclipse Plus C18, 2.1 × 100 mm, 1.8 µm.
- MS: Agilent 6495D triple quadrupole LC/MS with Agilent Jet Stream ESI source; MassHunter software for acquisition and processing. PFAS MRM transitions and acquisition parameters were taken from Agilent's PFAS MRM database.
- Consumables and preparation hardware: Bond Elut QuEChERS EN extraction kit (EN 15662), Captiva EMR PFAS Food II cartridges (6 mL, 750 mg), Captiva 0.2 µm nylon filter vials, PFAS-clean verified tubes and vials.

Key LC and MS parameters (concise)

- Mobile phases: 2 mM ammonium acetate in water (A) and 2 mM ammonium acetate in methanol (B).
- Gradient: 0–18 min program ramping B from 5% to 95% and re-equilibration; stop time 18.0 min, post time 2.0 min; flow 0.3 mL/min; column temp 40 °C; injection volume 0.5 µL.
- MS: negative ionization mode (primary for PFAS), fragmentor 166 V, iFunnel standard mode. Electrospray settings: drying gas 240 °C/16 L/min; sheath gas 370 °C/11 L/min; nebulizer 25 psi; capillary ~3,200 V (negative).

Main results and discussion

- Calibration linearity: Eight-level calibration standards (0.05–10 ng/mL in ACN) for 41 PFAS produced excellent linearity with R² values ranging from 0.9940 to 0.9998 across analytes.
- Recoveries: Fortified recovery experiments (20 ng/g) across five cosmetic matrices (three products each) showed that 97.6% of the 41 analyte/matrix combinations yielded recoveries within 70–120%. Five outliers occurred in the lipstick matrix, likely due to strong matrix effects or co-eluting interferences affecting specific analytes.
- Instrument method detection limit (IMDL): Determined from seven replicate matrix blanks spiked at 0.1–0.5 ng/mL. The average IMDL in cosmetic extracts was 0.032 ng/mL, corresponding to approximately 0.64 ng/g in the original cosmetic samples.
- Real sample screening: Of 15 consumer products analyzed, one eyeshadow sample contained trace levels of PFAS (PFHeA, PFHpA, PFNA, and PFOA) at around 0.1 ng/g. Method blanks showed no corresponding peaks in the monitored windows, supporting that this detection was sample-related rather than laboratory contamination.

Benefits and practical applications of the method

- The workflow delivers a streamlined, passthrough cleanup compatible with QuEChERS extracts, reducing hands-on time and potential sample loss compared with multi-step SPE procedures.
- Captiva EMR PFAS Food II cartridges provide effective matrix removal for complex cosmetic formulations, improving quantitation accuracy and reproducibility in challenging matrices such as creams, lipsticks, and powders.
- Sensitivity and linear dynamic range are suitable for regulatory monitoring and product safety testing, with sub-ng/g limits achievable in cosmetic samples.
- The method is applicable for routine QC, surveillance testing, and targeted investigations when PFAS contamination is suspected.

Limitations and considerations

- Lipstick and other highly pigmented or oil-rich matrices may require careful evaluation for matrix effects and possible method optimization (e.g., modified dilution, alternative cartridge conditioning) for a subset of analytes.
- Strict PFAS cleanliness control of consumables and labware is essential to avoid false positives; the study verified consumables for acceptable PFAS cleanliness.

Future trends and potential applications

- Regulatory drivers will continue to demand lower reporting limits and broader PFAS panels; methods will need to expand target lists and enhance sensitivity accordingly.
- Integration of automated sample preparation (robotic QuEChERS and cartridge handling) could increase throughput for commercial testing laboratories.
- Application of high-resolution MS or hybrid workflows could aid identification of non-target or novel PFAS in cosmetics and raw materials.
- Further method refinement could address matrix-specific bias for pigmented or lipid-rich cosmetic types, and interlaboratory studies could standardize protocols for regulatory adoption.

Conclusion

A robust analytical procedure combining QuEChERS extraction with Captiva EMR PFAS Food II passthrough cleanup and LC/MS/MS detection was demonstrated for 41 PFAS across diverse cosmetic matrices. The method exhibited excellent calibration linearity, generally acceptable recoveries (70–120% for the majority of analytes), low IMDLs (~0.032 ng/mL; ~0.64 ng/g), and successful detection of trace PFAS in one commercial eyeshadow. The approach offers a practical balance of sensitivity, matrix cleanup efficiency, and operational simplicity suitable for routine monitoring and product safety testing.

References

1. Draft Guideline for Analysis of Prohibited Ingredients in Cosmetics, MFDS Korea, 2024.
2. United States Environmental Protection Agency. Our Current Understanding of the Human Health and Environmental Risks of PFAS. Last Updated November 26, 2024.
3. Zhao L.; Parry E. Determination of 40 PFAS in Tilapia Tissue Following EPA 1633 Method Guidance. Agilent Technologies Application Note, publication 5994-8232EN, 2025.
4. Zhao L. Determination of 43 PFAS in Beer and Wine. Agilent Technologies Application Note, publication 5994-8813EN, 2025.