Periodically reversing electrocoagulation technique for efficient removal of short-chain perfluoroalkyl substances from contaminated groundwater around a fluorochemical facility.

Widespread distributions of short-chain perfluoroalkyl substances (PFASs) has been recognized as a crucial environmental issue. However, multiple treatment techniques were ineffective due to their high polarity and mobility, contributing to a never-ending existence in the aquatic environment ubiquitously. The present study revealed potential technique of periodically reversing electrocoagulation (PREC) to perform efficient removal of short-chain PFASs including experimental factors (in the conditions of 9 V for voltage, 600 r/min of stirring speed, 10 s of reversing period, and 2 g/L of NaCl electrolyte), orthogonal experiments, actual application, and removal mechanism. Accordingly, based upon the orthogonal experiments, the removal efficiencies of perfluorobutane sulfonate (PFBS) in simulated solution could achieve 81.0% with the optimal parameters of Fe-Fe electrode materials, addition of 665 µL H2O2 per 10 min, and pH at 3.0. The PREC was further applied for treating the actual groundwater around a fluorochemical facility, consequently the removal efficiencies for typical short-chain perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), PFBS, and perfluoropentane sulfonate (PFPeS) were 62.5%, 89.0%, 96.4%, 90.0%, and 97.5%, respectively. The other long-chain PFASs contaminants had superior removal with the removal efficiencies up to 97%-100%. In addition, a comprehensive removal mechanism related to electric attraction adsorption for short-chain PFASs could be verified through the morphological analysis of ultimate flocs composition. The oxidation degradation was further revealed as the other removal mechanism by suspect and nontarget screening of intermediates formed in simulated solution, as well as density functional theory (DFT) calculation theory. Moreover, the degradation pathways about one CF2O molecule or CO2 eliminated with one C atom removed in PFBS by ·OH generated from the PREC oxidation process were further proposed. As a result, the PREC would be a promising technique for the efficient removal of short-chain PFASs from severely contaminated water bodies.

Anion chelation-induced porphyrin protonation and its application for chloride anion sensing.

The protonation of a simple meso-tetraphenylporphyrin in an organic-aqueous system was found to be induced by the counteranions. During the process of protonation, the counteranion of the proton sources binds with the porphyrin core and thus promotes the complexation of the porphyrin and protons. The interaction of porphyrin and anion was characterized by fluorescence, UV-visible, cyclic voltammetry, (1)H NMR, and IR. Moreover, it could be exploited in selective fluorescent sensing of Cl(-). The sensing mechanism was based on extraction of protons from the aqueous phase into the organic phase by free base porphyrin and simultaneous coextraction of Cl(-), which promoted porphyrin protonation, and hence resulted in significant changes of the porphyrin fluorescence spectra. Selectivity trends turned out to be dependent upon the lipophilicity of anion and the binding affinity and structure complementarity between the protonated porphyrin and anions. The fluorescence enhancement of the porphyrin band at 684 nm showed modest selectivity for Cl(-) and NO(3)(-).