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Highly toxic iodinated products would form in oxidation and disinfection of iodine-containing water. Variation of iodinated aromatic products in ferrate [Fe­(VI)] oxidation of phenolic compounds (phenol, bisphenol A (BPA), and p-hydroxybenzoic acid (p-HBA)) in iodine-containing water was investigated. At pH 5.0, oxidation of phenolic compounds was inhibited by competitive reaction of ferrate with I–, and no formation of iodinated aromatic products was detected. Almost all I– was converted into nontoxic IO3 –. At pH 7.0, 8.0, and 9.0, HOI formed in ferrate oxidation of I– and further reacted with phenols, with the formation of iodinated aromatic products. Mass spectrometry analysis showed that both kinds and contents of iodinated aromatic products were raised with the increase in solution pH and the content of I–, and these iodinated aromatic products were further oxidized by ferrate. Ferrate deprived iodine from iodinated aromatic products and transferred highly toxic organic iodine into nontoxic IO3 –. An electron-donating substituent (alkyl) increased the reactivity of phenol with ferrate and HOI and facilitated ferrate oxidation of iodinated phenols. An electron-drawing substituent (carboxyl) decreased the reactivity of phenol with ferrate and HOI and hindered the further oxidation of iodinated aromatic products. A kinetic model about the variation of phenol, BPA, and p-HBA in reaction with ferrate in iodine-containing water was developed, and the oxidation profile of phenolic compounds could be satisfactorily predicted at various iodide concentrations.

Abstract1‐2‐2‐type Zintl phase compounds have promising thermoelectric properties because of their complex crystal structures and multiple valence‐band structures. In this work, a series of single phase (Yb0.9Mg0.1)MgxZn2−xSb2 (x = 0, 0.2, 0.4, 0.6, 0.8, and 1) compounds are prepared by alloying YbZn2Sb2 with 10 at% MgZn2Sb2 and different amounts of YbMg2Sb2. The incorporation of Mg at the Yb site, as well as at the Zn site, not only leads to an effective orbital alignment confirmed by the dramatically enhanced density of states effective mass and Seebeck coefficients, but also increases the point defect scattering, contributing to a low lattice thermal conductivity ≈0.54 W m−1 K−1 at 773 K. Combined with the optimization of the carrier concentration by Ag doping at the Zn site, a highest ZT value ≈1.5 at 773 K is achieved in (Yb0.9Mg0.1)Mg0.8Zn1.2Ag0.002Sb2, which is higher than that of all the previously reported 1‐2‐2‐type Zintl phase compounds.

In this work, it was found that the most widely used brominated flame retardant tetrabromobisphenol A (TBrBPA) could be transformed by free chlorine over a wide pH range from 5 to 10 with apparent second-order rate constants from 138 to 3210 M(-1)·s(-1). A total of eight products, including one quinone-like compound (i.e., 2,6-dibromoquinone), two dimers, and several simple halogenated phenols (e.g., 4-(2-hydroxyisopropyl)-2,6-dibromophenol, 2,6-dibromohydroquinone, and 2,4,6-tribromophenol), were detected by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) using a novel precursor ion scan (PIS) approach. A tentative reaction pathway was proposed: chlorine initially oxidized TBrBPA leading to the formation of a phenoxy radical, and then this primary radical and its secondary intermediates (e.g., 2,6-dibromo-4-isopropylphenol carbocation) formed via beta-scission subsequently underwent substitution, dimerization, and oxidation reactions. Humic acid (HA) considerably inhibited the degradation rates of TBrBPA by chlorine even accounting for oxidant consumption. A similar inhibitory effect of HA was also observed in permanganate and ferrate oxidation. This inhibitory effect was possibly attributed to the fact that HA competitively reacted with the phenoxy radical of TBrBPA and reversed it back to parent TBrBPA. This study confirms that chlorine can transform phenolic compounds (e.g., TBrBPA) via electron transfer rather than the well-documented electrophilic substitution, which also have implications on the formation pathway of halo-benzoquinones during chlorine disinfection. These findings can improve the understanding of chlorine chemistry in water and wastewater treatment.