Feasibility of IR-MALDESI Mass Spectrometry Imaging of PFAS

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are a class of emerging contaminants that have been in use industrially since the 1940s. Their long-term and extensive commercial use has led to their ubiquitous presence in the environment. The ability to measure the bioconcentration and distribution of PFAS in the tissue of aquatic organisms helps elucidate the persistence of PFAS as well as environmental impacts. Traditional analysis by LC-MS/MS can measure total PFAS concentrations within an organism but cannot provide comprehensive spatial information regarding PFAS concentrations within the organism. In the current study, we used infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) to determine the limit of detection (LOD) of several PFAS utilizing a commercial standard mix spotted on mouse liver tissue. The traditional ice matrix and an alternative matrix, 1,8-bis (tetramethylguanidino)naphthalene (TMGN), were explored when determining the limits of detection for various PFAS by IR-MALDESI. The ice matrix alone resulted in a higher response than the combination of TMGN and ice. The resulting LOD for perfluorooctane sulfonic acid (PFOS) on a per voxel basis was 0.16 fmol/voxel. For comparison, zebrafish that were exposed to perfluorooctanoic acid (PFOA), PFOS, and perfluorohexanesulfonic acid (PFHxS) at different concentrations were homogenized, and PFAS were extracted by solid-liquid extraction, purified by solid phase extraction, and analyzed by LC-MS/MS to determine the level of bioaccumulation in the zebrafish. PFOS resulted in the highest level of bioaccumulation (731.9 μg/kg, or 234.2 fg/voxel). A zebrafish that had been exposed to a PFAS mixture of PFOA (250 ng/L), PFOS (250 ng/L), and PFHxS (125 ng/L) was cryosectioned and analyzed by IR-MALDESI. Images could not be generated as the accumulation of PFAS in the sectioned tissue was below detection limit of the technique.