Toward Comprehensive Per- and Polyfluoroalkyl Substances Annotation Using FluoroMatch Software and Intelligent High-Resolution Tandem Mass Spectrometry Acquisition

Thousands of per-
and polyfluoroalkyl substances (PFAS) exist in
the environment and pose a potential health hazard. Suspect and nontarget
screening with liquid chromatography (LC)–high-resolution tandem
mass spectrometry (HRMS/MS) can be used for comprehensive characterization
of PFAS. To date, no automated open source PFAS data analysis software
exists to mine these extensive data sets. We introduce FluoroMatch,
which automates file conversion, chromatographic peak picking, blank
feature filtering, PFAS annotation based on precursor and fragment
masses, and annotation ranking. The software library currently contains
∼7 000 PFAS fragmentation patterns based on rules derived
from standards and literature, and the software automates a process
for users to add additional compounds. The use of intelligent data-acquisition
methods (iterative exclusion) nearly doubled the number of annotations.
The software application is demonstrated by characterizing PFAS in
landfill leachate as well as in leachate foam generated to concentrate
the compounds for remediation purposes. FluoroMatch had wide coverage,
returning 27 PFAS annotations for landfill leachate samples, explaining
71% of the all-ion fragmentation (CF2)n related fragments. By improving the throughput and coverage
of PFAS annotation, FluoroMatch will accelerate the discovery of PFAS
posing significant human risk.