Rapid Determination of Per- and Polyfluoroalkyl Substances (PFAS) in Harbour Porpoise Liver Tissue by HybridSPE®–UPLC®–MS/MS

Abstract

A rapid hybrid solid phase extraction (HybridSPE®) protocol tailored to ultra-performance liquid chromatography–electrospray ionization tandem mass spectrometry (UPLC®–ESI–MS/MS) analysis was developed for the determination of 15 per- and polyfluoroalkyl substances (PFAS) in liver tissue from harbour porpoises (Phocoena phocoena). The HybridSPE® technique has been applied in trace concentration bioanalysis, but it was mainly used for liquid biological media until now. In this study, the protocol was applied on tissue matrix, and it demonstrated acceptable absolute recoveries (%) ranging from 44.4 to 89.4%. The chromatographic separation was carried out using a gradient elution program with a total run time of 4 min. The inter-day method precision ranged from 2.15 to 15.4%, and the method limits of detection (LODs) ranged from 0.003 to 0.30 ng/g wet weight (w.w.). A total of 20 liver samples were analyzed to demonstrate the applicability of the developed method in liver tissue from a wildlife species.

Less is more: a methodological assessment of extraction techniques for per- and polyfluoroalkyl substances (PFAS) analysis in mammalian tissues

“…First, the target PFAA cover a wide range of more hydrophilic (e.g., PFBS) to more hydrophobic substances (e.g., PFTeDA), which indicates that the best extraction method may probably not be suitable for all targeted PFAA in the same manner. Second, the protein binding of PFAA [ 3 , 29 , 30 ] and the co-extraction of peptides and (phospho-)lipids from biological samples in high amounts [ 15 , 18 , 31 ] are recognized challenges.…”

“… HybridSPE Phospholipid cartridge ( Hybr ). The method was adapted from Trimmel et al [ 15 ] with slight modifications. Concentrated extracts were diluted with 1.2 mL 100 mM ammonium acetate in methanol and 500 µL water.…”

“…Four different ways of liquid extraction techniques were applied for the primary extraction of PFAA from tissue homogenates (Fig. 1 ), using methanol without additives ( MeOH ) [ 15 – 17 ], or in the presence of formic acid ( MeOH/FA ) [ 18 – 21 ] or sodium hydroxide ( MeOH/NaOH ) [ 21 – 23 ]. Alternatively, the homogenates were slurried with water and PFAA were extracted by methyl- tert -butyl ether (MTBE) after the addition of the ion-pairing tetrabutylammonium (TBA) [ 24 , 25 ].…”

“…Eight SPE methods were compared for further enrichment of PFAA and matrix depletion following the primary solvent extraction (Fig. 1 ): two approaches of dispersive SPE with C18 and ENVI-Carb ( EnvC ) bulk material ( Dsp1 and Dsp2 ) [ 18 , 19 ], three different SPE cartridges, the EnvC column [ 17 ], the Oasis WAX ( OWax ) column [ 11 ], and the HybridSPE phospholipid ( Hybr ) column [ 15 ], and three of the possible permutations ( OWax-EnvC , Hybr-EnvC , and EnvC-Hybr ). The objectives of this study were to evaluate the advantages and disadvantages of the strategies at hand of three parameters.…”

Interplay between pollution and avian influenza virus in shorebirds and waterfowl

“…We also calculated a total PFAS group, consisting of all carboxylates and sulfonates listed above, as well as PFOSA. Analyses were conducted using methodology adapted from Trimmel et al (2021). In brief, ~ 50 mg of red blood cell samples was weighted in a 1.5 mL polypropylene tube and 10 μL of PFOA- 13 C8 and PFOS- 13 C8 (1000 μg/L) was added.…”