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      High surface area DPA-hematite for efficient detoxification of bisphenol A via peroxymonosulfate activation

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          Abstract

          DPA-hematite was synthesized for bisphenol A detoxification via peroxymonosulfate (PMS) activation. Correlation between the initial oxone dosage, apparent rate constant and surface area was obtained. Acute toxicity study was conducted. The function of DPA in mediating the PMS activation is schematically illustrated.

          Abstract

          A novel dipicolinic acid-functionalized hematite (DPA-hematite) with high surface area was prepared by co-precipitation of a Fe( iii)–DPA complex. It was used as a catalyst to activate peroxymonosulfate (PMS) for bisphenol A (BPA) detoxification. The XRD, FESEM, TEM and FTIR characterization indicated that nano-sized DPA-hematite with aggregated quasi-nanosphere morphology was obtained with a 1 : 1 ratio of Fe( iii) to DPA. Higher catalytic activity of DPA-hematite over other Fe( iii)-based catalysts was observed for BPA oxidation in the presence of oxone. The kinetics of BPA removal was investigated using a kinetic model with BPA concentration, initial oxone dosage and surface area of DPA-hematite. For the first time, the acute toxicity of BPA solution over time with elimination of oxone toxicity interference was studied using Vibrio fischeri bacteria and the results indicated that the evolution of acute toxicity was highly dependent on the initial oxone dosage. Under deficit oxone conditions, BPA was completely transformed to by-products along with decreased intrinsic toxicity but ring-opening reactions were barely observed which can be explained based on the dimerization–mineralization degradation pathways. Under excess oxone conditions, the intrinsic toxicity of BPA solution decreased along with ring-opening reactions leading to a greater extent of mineralization. The DPA-hematite can be reused for BPA detoxification for at least three cycles in the presence of 2.0 g L −1 oxone.

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          Radical generation by the interaction of transition metals with common oxidants.

          Nine transition metals were tested for the activation of three oxidants and the generation of inorganic radical species such as sulfate, peroxymonosulfate, and hydroxyl radicals. From the 27 combinations, 14 M/Ox couples demonstrated significant reactivity toward transforming a model organic substrate such as 2,4-dichlorophenol and are further discussed here. It was found that Co(II) and Ru(III) are the best metal catalysts for the activation of peroxymonosulfate. As expected on the basis of the Fenton reagent, Fe(III) and Fe(II) were the most efficient transition metals for the activation of hydrogen peroxide. Finally, Ag(I) showed the best results toward activating persulfate. Quenching studies with specific alcohols (tert-butyl alcohol and ethanol) were also performed to identify the primary radical species formed from the reactive M/Ox interactions. The determination of these transient species allowed us to postulate the rate-determining step of the redox reactions taking place when a metal is coupled with an oxidant in aqueous solution. It was found that when Co(II), Ru(III), and Fe(II) interact with peroxymonosulfate, freely diffusible sulfate radicals are the primary species formed. The same was proven for the interaction of Ag(I) with persulfate, but in this case caged or bound to the metal sulfate radicals might be formed as well. The conjunction of Ce(III), Mn(II), and Ni(II) with peroxymonosulfate showed also to generate caged or bound to the metal sulfate radicals. A combination of sulfate and hydroxyl radicals was formed from the conjunction of V(III) with peroxymonosulfate and from Fe(II) with persulfate. Finally, the conjunction of Fe(III), Fe(II), and Ru(III) with hydrogen peroxide led primarily to the generation of hydroxyl radicals. It is also suggested here that the redox behavior of a particular metal in solution cannot be predicted based exclusively on its size and charge. Additional phenomena such as metal hydrolysis as well as complexation with other counterions present in solution might affect the thermodynamics of the overall process and are further discussed here.
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            Bisphenol A and human health: a review of the literature.

            There is growing evidence that bisphenol A (BPA) may adversely affect humans. BPA is an endocrine disruptor that has been shown to be harmful in laboratory animal studies. Until recently, there were relatively few epidemiological studies examining the relationship between BPA and health effects in humans. However, in the last year, the number of these studies has more than doubled. A comprehensive literature search found 91 studies linking BPA to human health; 53 published within the last year. This review outlines this body of literature, showing associations between BPA exposure and adverse perinatal, childhood, and adult health outcomes, including reproductive and developmental effects, metabolic disease, and other health effects. These studies encompass both prenatal and postnatal exposures, and include several study designs and population types. While it is difficult to make causal links with epidemiological studies, the growing human literature correlating environmental BPA exposure to adverse effects in humans, along with laboratory studies in many species including primates, provides increasing support that environmental BPA exposure can be harmful to humans, especially in regards to behavioral and other effects in children. Copyright © 2013 Elsevier Inc. All rights reserved.
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              Production of sulfate radical from peroxymonosulfate induced by a magnetically separable CuFe2O4 spinel in water: efficiency, stability, and mechanism.

              A simple, nonhazardous, efficient and low energy-consuming process is desirable to generate powerful radicals from peroxymonosulfate (PMS) for recalcitrant pollutant removal. In this work, the production of radical species from PMS induced by a magnetic CuFe(2)O(4) spinel was studied. Iopromide, a recalcitrant model pollutant, was used to investigate the efficiency of this process. CuFe(2)O(4) showed higher activity and 30 times lower Cu(2+) leaching (1.5 μg L(-1) per 100 mg L(-1)) than a well-crystallized CuO at the same dosage. CuFe(2)O(4) maintained its activity and crystallinity during repeated batch experiments. In comparison, the activity of CuO declined significantly, which was ascribed to the deterioration in its degree of crystallinity. The efficiency of the PMS/CuFe(2)O(4) was highest at neutral pH and decreased at acidic and alkaline pHs. Sulfate radical was the primary radical species responsible for the iopromide degradation. On the basis of the stoichiometry of oxalate degradation in the PMS/CuFe(2)O(4), the radical production yield from PMS was determined to be near 1 mol/mol. The PMS decomposition involved an inner-sphere complexation with the oxide's surface Cu(II) sites. In situ characterization of the oxide surface with ATR-FTIR and Raman during the PMS decomposition suggested that surface Cu(II)-Cu(III)-Cu(II) redox cycle was responsible for the efficient sulfate radical generation from PMS.
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                Author and article information

                Journal
                JMCAET
                J. Mater. Chem. A
                J. Mater. Chem. A
                Royal Society of Chemistry (RSC)
                2050-7488
                2050-7496
                2014
                2014
                : 2
                : 38
                : 15836-15845
                Affiliations
                [1 ]Nanyang Environment and Water Research Institute (NEWRI)
                [2 ]Nanyang Technological University
                [3 ]Singapore 637141, Singapore
                [4 ]Division of Environmental and Water Resources Engineering
                [5 ]School of Civil and Environmental Engineering, Nanyang Technological University
                [6 ]School of Materials Science and Engineering
                [7 ]Singapore 639798, Singapore
                Article
                10.1039/C4TA02758B
                9afeeb3f-08bb-4b3d-8646-855354dc16d3
                © 2014
                History

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