Analytical Solutions for PFAS Testing

Significance of the topic

Per- and polyfluoroalkyl substances (PFAS) are a chemically diverse class of fluorinated organics with extreme environmental persistence, bioaccumulative potential and widespread use in industrial and consumer products. Their resistance to degradation and mobility in water, air and soils have driven global regulatory attention and created urgent needs for sensitive, reliable analytical workflows that support monitoring, compliance and remediation efforts.

Objectives and overview of the document

This technical overview presents a suite of analytical strategies and instrument workflows for both routine regulated PFAS testing and discovery-driven screening across environmental and food matrices. Key goals are to demonstrate instrument performance relative to EPA, AOAC, ISO and ASTM methods, to show approaches that reduce sample-preparation burden (including direct injection and on-line SPE), and to illustrate high-throughput and non-targeted screening capabilities for complex matrices such as drinking water, wastewater, soil, tissue, foodstuffs, ambient air and consumer products.

Methodology and analytical approach

The document surveys multiple complementary analytical techniques optimized for different PFAS classes and sample types:

• LC-MS/MS (triple quadrupole) for regulated targeted quantitation (EPA 533, 537.1, 544/545, ASTM D8421, ISO 21675, EPA 1633/1633A).
• High-sensitivity triple-quad systems (LCMS-8065XE, LCMS-8060RX, LCMS-8060/8065 series) enabling direct injection and low-ng/L quantitation.
• High-resolution accurate-mass (HRAM) QTOF (LCMS-9030/9050/9050 series) using DIA for suspect and untargeted PFAS discovery.
• Gas chromatography–MS with thermal desorption (GCMS-QP2020 NX + TD-30R) for volatile/neutral PFAS (e.g., FTOHs).
• Combustion ion chromatography (CIC; HIC-ESP + AQF-5000H) for Adsorbable Organic Fluorine (AOF) screening per EPA 1621 to estimate total organic fluorine load including non-target PFAS.
• Single-quadrupole LCMS-2050 for cost-effective quantitation where ultra-trace detection is not required.
• Energy-dispersive X-ray fluorescence (EDXRF; EDX-8100) as a rapid screening tool for elemental fluorine in coatings and textiles.

Sample preparation strategies described include solid-phase extraction (SPE) for aqueous samples, QuEChERS and automated extraction workflows for food and tissue, online SPE with stacked injections for increased sensitivity, and simplified solvent extraction/tumbling for consumer products to avoid labor-intensive cleanups.

Instrumentation used

Instruments and modules demonstrated in the applications include:

• Triple-quadrupole LC-MS systems: LCMS-8060RX, LCMS-8065XE, LCMS-8060/8065 series, LCMS-8060NX
• High-resolution QTOF: LCMS-9030 / LCMS-9050
• Compact single-quadrupole: LCMS-2050
• Gas chromatograph–mass spectrometer: GCMS-QP2020 NX with TD-30R thermal desorption
• Combustion ion chromatograph: HIC-ESP IC combined with AQF-5000H combustion unit
• EDXRF spectrometer: EDX-8100
• UHPLC and autosampler systems including Nexera series, online SPE traps, and PFAS-delay chromatographic columns (Nexcol PFAS Delay)

Main results and discussion

Key performance highlights and findings across matrices are summarized below:

• Drinking water: Methods following EPA 537.1 and 533 were achieved with good linearity (R2 > 0.997), repeatability (%RSD < 11% at low calibration levels), and spike recoveries meeting method criteria. The LCMS-8065XE enabled direct-injection analysis of 29 PFAS in a single 18-minute run with quantitation below 1 ng/L and recoveries of 80–120%.
• Multi-method switching: A single triple-quadrupole system (LCMS-8060RX) successfully alternated automated methods for PFAS and cyanotoxins (EPA 533/544/545) with a short rinse protocol and maintained accuracy and low %RSD across extended runs.
• Wastewater and non-potable waters: ASTM D8421 workflows quantified 44 PFAS plus 24 isotopically labeled surrogates with optimized chromatography (co-injection and column selection) to improve early-eluting peak shapes; calibration and recovery metrics met ASTM performance criteria. ISO 21675 extraction plus mixed-mode SPE provided acceptable recoveries across 30 PFAS, noting potential blank interferences at very low spike levels in wastewater.
• Soil robustness: The LCMS-8060RX demonstrated very stable performance in a challenging soil matrix with 500 consecutive injections of spiked soil, showing normalized peak-area RSDs typically 4.8–6.8% and QC recoveries between 80–120%.
• Tissue (EPA 1633A): LCMS-8065XE achieved LLOQs up to 80-fold lower than EPA 1633A requirements in neat standards and retained chromatographic separation (e.g., >1 min separation between PFOS and cholic acids) needed to avoid ionization interferences during tissue analysis. The system sustained >900 continuous injections with stable calibration.
• AOF (CIC): Combustion-IC AOF screening per EPA 1621 provided MDL ~1.27 µg/L and good recovery/precision for spiked PFHxS as fluoride equivalent, supporting use as a total organic fluorine screen complementary to targeted methods.
• Ambient air (GC–TD–MS): Thermal desorption GC–MS detected volatile PFAS (FTOHs, FTACs, FOSAs) down to 0.05 ng with good linearity (R > 0.998) and spike recoveries 77–106% in air-sampling tubes.
• Environmental screening and discovery (HRAM-DIA): QTOF HRAM-DIA workflows detected PFAS at sub-ng/mL levels (mass accuracy < ±3.3 ppm) and enabled untargeted detection and structural assignment; 16 PFAS-like features were discovered in an environmental sample and confirmed by library matching.
• Food matrices: Validated triple-quad methods quantified 30 AOAC-target PFAS in fish fillet (LOQ 0.1 µg/kg) and milk (LOQ down to 0.01 µg/kg) with recoveries and repeatabilities meeting AOAC SMPR criteria. Automated QuEChERS plus online SPE (Nexera UHPLC) quantified 27 PFAS in egg matrices at ng/mL levels using stacked injections to boost sensitivity.
• Food-contact materials and consumer products: A direct LC-MS/MS workflow quantified 15 PFAS in food contact materials with measured levels in selected fast-food packaging well below historical guideline limits (ng/dm2 range). A simplified extraction protocol for consumer products (tumble + filtration + pH adjustments) achieved surrogate recoveries of 70–130% across plastics and nonstick foil and met proposed ASTM reporting limits for 46 PFAS.
• EDXRF screening for fluorine in textiles: EDXRF rapidly detected elemental fluorine on treated fabrics with qualitative detection at approximately the 1% (10,000 ppm) level and a quantitative LOD reported near 486 ppm under the test conditions, providing a fast prescreen for fluorinated coatings.

Benefits and practical applications of the methods

Collectively these workflows provide laboratories with:

• Regulatory-compliant targeted quantitation for drinking water, wastewater, soil and food matrices supporting EPA, ISO, ASTM and AOAC methods.
• High-throughput options (direct injection, online SPE, stacked injections) that reduce sample-prep time and increase laboratory throughput.
• Multi-method flexibility on single platforms (automatic method switching) to handle diverse analyte classes (PFAS + cyanotoxins) without cross-contamination when configured correctly.
• Complementary screening strategies: CIC/AOF for total fluorine screening, HRMS for suspect/unknown discovery, GC–TD–MS for volatile PFAS, and EDXRF for rapid product prescreens.
• Robustness in complex matrices as demonstrated by hundreds of consecutive injections with stable performance and QC recoveries, supporting routine monitoring programs.

Future trends and potential uses

Emerging directions and opportunities include:

• Greater adoption of HRMS workflows for suspect and non-target PFAS discovery, combined with expanding spectral libraries and automated assignment tools to keep pace with the rapidly growing PFAS universe.
• Wider use of total fluorine/AOF screening as a fast prioritization step before targeted analysis to capture unknown or polymeric fluorinated species.
• Continued method standardization and turnkey method packages to improve inter-laboratory comparability and accelerate regulatory compliance.
• Improvements in chromatographic delay columns and low-background hardware to reduce PFAS artifacts and permit ultra-trace direct-injection methods.
• Automation of sample handling and online SPE to enable large-scale monitoring, surveillance during contamination events, and faster turnaround for public-health decision-making.
• Integration of analytical results with remediation and exposure models to evaluate treatment efficacy and human/ ecological risk.

Conclusion

The surveyed analytical solutions illustrate a pragmatic, multi-technology approach to PFAS monitoring: sensitive, validated LC-MS/MS workflows for regulatory compliance; HRMS for discovery and unanticipated compounds; GC–TD–MS for volatile PFAS; CIC for total organic fluorine screening; and rapid product prescreens via EDXRF. Combining high-sensitivity instruments, optimized chromatographic methods, automated sample preparation and robust QC enables laboratories to meet tightening regulatory limits and expand PFAS surveillance across environmental, food and consumer-product matrices.

Reference

Shimadzu Corporation. Analytical Solutions for PFAS Testing: Routine to Discovery Analysis in Environmental Samples and Consumer Products. First Edition March 2026; C10G-E109. For research use only. Not for use in diagnostic procedures.