Vesicles exhibit high-performance removal of per-and polyfluoroalkyl substances (PFAS) depending on their hydrophobic groups.

The removal of per- and polyfluoroalkyl substances (PFAS) from drinking water is urgently needed. Here, we demonstrated high performance of vesicles on PFAS adsorption. Vesicles used in this study were enclosed amphiphile bilayers keeping their hydrophobic groups inside and their hydrophilic groups outside in water. The distribution coefficient Kd of perfluorooctane sulfonic acid (PFOS) for vesicles was 5.3 × 105 L/kg, which is higher than that for granulated activated carbon (GAC), and Kd of perfluorooctanoic acid (PFOA) for vesicles was 103-104 L/kg. The removal efficiencies of PFOA and PFOS adsorption on DMPC vesicles were 97.1 ± 0.1% and 99.4 ± 0.2%, respectively. The adsorption behaviors of PFOA and PFOS on vesicles were investigated by changing the number of cis-double bonds in the hydrophobic chains of the vesicle constituents. Moreover, vesicles formed by membranes in the different phases were also tested. The results revealed that, when vesicles are formed of a membrane in the liquid-crystalline (liquid-like) phase, the adsorption amounts of both PFOA and PFOS increased as the cis-double bond in the hydrocarbon chains decreased, which is considered due to molecular shape similarity. When vesicles are formed of a membrane in the gel (solid-like) phase, they do not adsorb PFAS as much as in the liquid-crystalline phase, even though the hydrocarbon chains do not have any cis-double bond. Our findings demonstrate that vesicles can be utilized as PFAS adsorbents by optimizing the structure of vesicle constituents and their thermodynamical phase. Indeed, the vesicles (DMPC) were demonstrated that they can adsorb PFOA and PFOS, and be coagulated by a coagulant even in environmental water. The coagulation will enable the removal of PFOA and PFOS from the water after adsorption.

Desorption of Ammonia Adsorbed on Prussian Blue Analogs by Washing with Saturated Ammonium Hydrogen Carbonate Solution.

Prussian blue analogs (PBAs) have been reported as promising ammonia (NH3) adsorbents with a high capacity compared to activated carbon, zeolite, and ion exchange resins. The adsorbed NH3 was desorbed by heating and washing with water or acid. Recently, we demonstrated that desorption was also possible by washing with a saturated ammonium hydrogen carbonate solution (sat. NH4HCO3aq) and recovered NH3 as an NH4HCO3 solid by introducing CO2 into the washing liquid after desorption. However, this has only been proven for copper ferrocyanide and the relationship between the adsorption/desorption behavior and metal ions in PBAs has not been identified. In this study, we investigated the adsorption/desorption behavior of PBAs that are complexes of first row transition metals with hexacyanometalate anions. Six types of PBAs were tested in this study and copper ferricyanide exhibited the highest desorption/adsorption ratio. X-ray diffraction results revealed high structural stability for cobalt hexacyanocobaltate (CoHCC) and nickel ferricyanide (NiHCF). The Fourier transform infrared spectroscopy results showed that the NH3 adsorbed on the vacancy sites tended to desorb compared to the NH3 adsorbed on the interstitial sites as ammonium ions. Interestingly, the desorption/adsorption ratio exhibited the Irving-Williams order.