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Per- and polyfluoroalkyl substances (PFASs) are emerging contaminants detected ubiquitously and have negative impacts on human health and ecosystem; thus, developing in-situ sensing technique is important to ensure safety. Herein, we report a novel colorimetric-based sensor with perfluoroalkyl receptor attached to citrate coated gold nanoparticles (Citrate-Au NPs) that can detect several PFASs including perfluorocarboxylates with different chain lengths (PFHxA, PFOA, PFNA, PFDA), perfluorooctanoic sulfonate (PFOS), and perfluorooctanoic phosphonate (PFOPA). The sensor detects PFASs utilizing fluorous interaction between PFASs and the perfluoroalkyl receptor of Citrate-Au NPs in a solution at a fixed salt concentration, inducing changes in nanoparticle dispersity and the solution color. The rate of spectrum shift was linearly dependent on PFASs concentrations. Citrate-Au NPs with size between 29 – 109 nm were synthesized by adjusting citrate/Au molar ratios, and 78 nm showed the best sensitivity to PFOA concentration (with level of detection of 4.96 µM). Citrate-Au NPs only interacted with PFASs with perfluoroalkyl length > 4 and not with non-fluorinated alkyl compound (nonanoic acid). The performance of Citrate-Au NP based sensor was strongly dependent on the chain length of the perfluoroalkyl group and the head functional group; higher sensitivity was observed with longer chain over shorter chain, and with sulfonate functional group over carboxylate and phosphonate. The sensor was tested using real water samples (i.e., tap water, filtered river water), and it was found that the sensor is capable of detecting PFASs in these conditions if calibrated with the corresponding water matrix. While further optimization is needed, this study demonstrated new capability of Citrate-Au NPs based sensor for detection of PFASs in water.

Perfluoroalkyl substances (PFAS) are emerging contaminants present in various water sources. Their bioaccumulation and potential toxicity necessitate proper treatment to ensure safe water quality. Although iron-based monometallic photocatalysts have been reported to exhibit rapid and efficient PFAS degradation, the impact of bimetallic photocatalysts is unknown. In addition, the mechanistic effects of utilizing a support are poorly understood and solely based on physicochemical properties. This study investigates the efficacy of bimetallic photocatalysts (Fe2O3/Mn2O3) in inducing the photo-Fenton reaction for the degradation of perfluorooctane sulfonate (PFOS) and perfluorononanoic acid (PFNA) under various conditions. The rapid removal of both PFAS was observed within 10 min, with a maximum efficiency exceeding 97 % for PFOS under UV exposure, aided by the photocatalytic activation (photo-Fenton) of the oxidant (H2O2). Contrary to expectations, the use of the SiO2 support material did not significantly improve the removal efficiency. The efficacy of PFNA decreased despite SiO2 providing larger surface areas for Fe2O3/Mn2O3 loading. Further analysis revealed that the adsorption of PFAS onto the catalyst surfaces owing to electrostatic interactions contributed to the removal efficiency, where the degradation efficacy was worse than that of the catalyst with SiO2. This is because adsorption hindered the effective contact of H2O2 with catalytic reaction sites, thereby impeding the generation of hydroxyl (·OH) radicals. This study indicates the importance of considering chemical properties, including surface charge, in catalyst design to ensure effective degradation, focusing on physicochemical properties, such as surface area might overlook crucial factors.

Per- and polyfluoroalkyl substances (PFAS) are widely detected environmental contaminants, and there is a great need for development of sensor technologies for rapid and continuous monitoring of PFAS. In this study, we have developed fluorescence based aptasensor that can possibly monitor perfluorooctanoic acid (PFOA) in water with limit of detection (LOD) of 0.17 μM. This is first to report the successful isolation of PFAS binding ssDNA aptamers. The obtained aptamer selectively binds PFOA with dissociation constant (KD) of 5.5 μM. Specific aptamer binding sites to PFOA were identified and the length of the fluorinated carbons was a key binding factor rather than the functional group. The aptamer binding to structurally similar PFAS compounds (i.e., perfluorocarboxylic acids and perfluorosulfonic acids with 4–8 carbon chains) was also investigated; the aptamer KD values were 6.5 and 3.3 μM for perfluoroheptanoic acid and perfluorohexanesulfonic acid, respectively, while other analogs did not bind to the aptamer. The presence of major inorganic ions and dissolved organic matter had negligible influences on the aptamer performance (