Orthogonal zirconium diol/C18 liquid chromatography–tandem mass spectrometry analysis of poly and perfluoroalkyl substances in landfill leachate

• We developed a fast LC-MS/MS method for measuring PFASs in landfill leachate.
• Method generated little solid and solvent waste, and included 70 analytes.
• Low to sub ng/L detection limits, accurate (81–120%) and precise (5.5–33%).
• Leachate had new phosphorous-containing PFASs and short-chain Me- and EtFASAAs.
• The n:3 fluorotelomer carboxylate is a concentrated new class of PFASs in leachate.

Leachates coming from landfills contain a myriad of compounds of potential environmental and human health concern, including per- and polyfluorinated alkyl substances (PFASs). Micro liquid-liquid extraction was combined with a 900 μl large volume injection (LVI) for the analysis of 70 PFASs in landfill leachate by orthogonal LC-MS/MS. The LVI approach introduced 7 times more extract than conventional injection approaches. Two zirconium-modified diol guard columns effectively retained PFASs from the organic leachate extract and an analytical C18 column was used for separation. Method accuracy and precision for PFASs with analytical grade reference materials ranged from 81–120% and 5.5–33%, respectively. Estimated method detection limits in the low to sub-ng/L. Seven landfill leachates were analyzed by the optimized analytical method for the purposes of method demonstration. Leachates were characterized by a wide variety of PFASs, reporting on 36 previously-unanalyzed PFASs in leachate. Perfluoroalkyl carboxylates were the most abundant class detected while phosphorous-containing PFASs, present in all leachates, were at low concentrations. The 3-perfluoropentyl propanoate (5:3 FTCA) was the most concentrated analyte in most samples and constitutes a previously unreported but significant component of landfill leachate.