Implementing EPA OTM-50: TD-GC-MS/MS Analysis of Volatile PFAS in Air

Air Monitoring, Methods, and Technology
Oral Presentation

Presented by P. Vaithee
Prepared by A. Fornadel1, T. Jeffers2, L. Mikaliunaite3, N. Shafer3, D. Cavagnino4, M. Bergna4
1 - Thermo Fisher Scientific, 104 Quinn Road, Severna Park, Maryland, 21146, United States
2 - Thermo Fisher Scientific, , Alachua, Florida, United States
3 - Markes International, , Sacramento, California, United States
4 - Thermo Fisher Scientific, , Milan, , Italy


Contact Information: [email protected]; 443-346-0728


ABSTRACT

The U.S. EPA Other Test Method 50 (OTM-50) provides guidance for monitoring volatile fluorinated compounds (VFCs) in air emissions, particularly those formed during incomplete destruction of per- and polyfluoroalkyl substances (PFAS). Reliable measurement of these volatile by-products is essential for evaluating destruction efficiency, environmental impact, and regulatory compliance. OTM-50 specifies canister-based air sampling followed by thermal desorption and GC–MS analysis; however, successful implementation requires careful optimization of analytical conditions to address the challenges associated with low-molecular-weight fluorinated compounds and complex emission matrices.

In this study, air samples collected in evacuated, passivated stainless-steel canisters according to OTM-50 guidance were analyzed using a Markes thermal desorption system coupled to a Thermo Scientific™ TSQ™ 9610 triple quadrupole GC-MS/MS. Separation was achieved by capillary gas chromatography, and detection was performed using multiple reaction monitoring (MRM) to enhance selectivity and sensitivity. Thermal desorption and MS/MS parameters were optimized to ensure efficient analyte transfer, robust chromatographic performance, and reliable quantitation under variable matrix conditions, including elevated CO₂ levels.

Preliminary results demonstrate effective detection and quantitation of target VFCs relevant to PFAS destruction processes. Compared to single-quadrupole MS, GC-MS/MS provided improved selectivity and reduced matrix interferences, with consistent retention times, reproducible responses, and sufficient sensitivity for low-level measurements anticipated in post-destruction air streams. The approach proved adaptable to varying emission compositions, mitigating quantitative bias associated with fluctuating backgrounds.

Overall, coupling a Markes TD system with the TSQ 9610 GC-MS/MS provides a practical and robust analytical workflow aligned with the objectives of EPA OTM-50, supporting laboratories and facilities engaged in PFAS air monitoring and method implementation.