Metal-Organic Frameworks for the Trace Multiplexed Adsorption and Quantitation of 50 Per- and Polyfluoroalkyl Substances

27 September 2024, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants that pose significant health risks. With recent regulatory guidelines lowering safe drinking water advisory limits to parts-per-quadrillion (ppq) levels, the need for methods capable of detecting and quantifying many PFAS simultaneously in trace amounts has become increasingly critical. In this study, six metal-organic frameworks were evaluated as solid-phase extraction sorbents for multiplexed adsorption of PFAS, followed by quantitative liquid chromatography-tandem mass spectrometry. UiO-66 demonstrated the highest performance with 87% adsorption efficiency and 85% recovery for 33 PFAS spiked at 2 parts per billion. In multiplexed adsorption for 50 PFAS at concentrations of 200 ppq, UiO-66 achieved an average recovery of 75%, with detection limits as low as 4 ppq and an average detection limit of 108 ppq. Validation using six environmental water samples revealed quantifiable PFAS in all samples with 25 PFAS detected. Compared to polymeric resins, which typically detect PFAS in the 1–80 parts per trillion range, UiO-66 demonstrated enhanced sensitivity for multiplexed adsorption, capable of detecting concentrations in the low ppq range. These findings highlight the potential of UiO-66 for large-scale PFAS monitoring under increasingly stringent environmental regulations.

Keywords

Per- and polyfluoroalkyl substances
metal-organic frameworks
ZIF-8
UiO-66
liquid chromatography mass spectrometry
quantitative mass spectrometry
adsorption

Supplementary materials

Title
Description
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Title
Additional methodological details, materials characterisation data, and performance results.
Description
This document provides detailed experimental data and methodologies on the adsorption and elution of per- and polyfluoroalkyl substances (PFAS) using metal-organic frameworks (MOFs), specifically ZIF-8, UiO-66 and their related materials. It includes tables of PFAS standards, isotopically labeled standards, and internal standards, along with mass spectrometry (MS) and liquid chromatography mass spectrometry (LC-MS) conditions. Characterization data, such as surface areas, powder diffraction patterns, and thermogravimetric analysis of the MOFs and their analogues, are also included. Additionally, the document presents adsorption and elution performance data, PFAS recovery results from water samples, and calibration curves. Synthetic procedures for the MOFs and quantification of PFAS adsorption efficiency are also provided.
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