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      Simultaneous Degradation of Estrone, 17β-Estradiol and 17α-Ethinyl Estradiol in an Aqueous UV/H 2O 2 System

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          Abstract

          UV/H 2O 2, which is an advanced treatment technology used to reduce multiple contaminants, is effective in potable water treatment. Simultaneous degradation effects and kinetics of three types of coexisting micropollutant estrogens (steroid estrogens, SEs), including estrone (E1), 17β-estradiol (E2) and 17α-ethinyl estradiol (EE2), in deionized water were studied. Experiments were carried out with ultraviolet-C (UVC) radiation, together with hydrogen peroxide (H 2O 2), in a cylinder photoreactor. The results demonstrated that the degradation processes of all of the estrogens strongly fit first-order kinetics. Single solutions of E1, E2 and EE2 showed higher degradation rates and removal efficiencies under the same reaction conditions compared with those under mixed conditions. Coexisting combinations of estrogens were put into the UV/H 2O 2 system to estimate their possible competitive influences on each other by examining their removal efficiencies and reaction rate constant, k, values. E1 is predominantly reduced rapidly during the competition, while the presence of other estrogens has negligible impacts on E1; however, the degradation of E2 and EE2 is affected by the competitive background, not in relation to the types but to the existing amounts. In the UV/H 2O 2 system, photocatalysis of the estrogens can stably produce an intermediate X, with the highest quantity coming from E1, while considerably lower quantities are obtained from E2 and EE2.

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          Determination of endocrine-disrupting phenolic compounds and estrogens in surface and drinking water by HRGC-(NCI)-MS in the picogram per liter range.

          A method for the analysis of phenolic estrogenic active compounds in surface and drinking water in the picogram per liter range is described. Besides the widely used monomer bisphenol A, 4-tert-octylphenol [4-(1,1,3,3-tetramethylbutyl)phenol] and the technical isomer mixture of 4-nonylphenol; phenolic steroid hormones such as the endogenous estrogens estrone, 17alpha-estradiol, and 17beta-estradiol; and the exogenous estrogen 17alpha-ethinylestradiol were determined in water at the 20-200 pg/L level. Water samples from 1 to 5 L were extracted by solid-phase extraction (SPE) on a cartridge system containing LiChrolut EN as sorbent. The phenols and steroids were converted into their pentafluorobenzoylate esters in an extractive derivatization reaction. The derivatives were then determined by high-resolution gas chromatography with negative chemical ionization mass spectrometric detection (HRGC-(NCI)-MS) in the selected ion mode (SIM). All results were also confirmed by HRGC with electron capture detection (ECD). This highly sensitive and specific method gives a limit of detection (LOD) of 20 pg/L for bisphenol A and 4-tert-octylphenol in drinking water samples and 50 pg/L in STW effluent, respectively. The LODs for technical 4-nonylphenol, 17alpha-ethinylestradiol, and other estrogens are in the range of 50 pg/L in drinking water to 200 pg/L in STW effluent, respectively. In all river water samples in southern Germany, bisphenol A was found in concentrations ranging from 500 pg/L up to 16 ng/L, 4-nonylphenol was from 6 up to 135 ng/L, and the steroids were from 200 pg/L up to 5 ng/L. In drinking water, bisphenol A was found in concentrations ranging from 300 pg/L to 2 ng/L, 4-nonylphenol was from 2 to 15 ng/L, 4-tert-octylphenol was from 150 pg/L to 5 ng/L, and the steroids were from 100 pg/L to 2 ng/L. Mean recoveries over the whole analytical protocol, measured in bidistilled water, generally exceeded 70%. These results indicate that environmental endocrine-disrupting estrogens are not completely removed in the process of sewage treatment but are carried over into the general aquatic environment. After ground passage, they can eventually be found in drinking water.
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            Effects of endocrine disrupting chemicals on in vitro global DNA methylation and adipocyte differentiation.

            Recent studies suggest that endocrine disrupting chemicals (EDCs) may form a risk factor for obesity by altering energy metabolism through epigenetic gene regulation. The goal of this study is to investigate the effects of a range of EDCs with putative obesogenic properties on global DNA methylation and adipocyte differentiation in vitro. Murine N2A and human SK-N-AS neuroblastoma cells and murine preadipocyte fibroblasts (3T3-L1) were exposed to tributyltin (TBT), diethylstilbestrol (DES), bisphenol A (BPA), 2,3,7,8-tetrachlorodibenzo-[p]-dioxin (TCDD), 2,2',4,4',5,5'-hexachlorobiphenyl (PCB-153), hexachlorobenzene (HCB), hexabromocyclododecane (HBCD), 2,2',4,4'-tetrabrominated diphenyl ether (BDE-47) , perfluorinated octyl acid (PFOA) and perfluorinated octyl sulfonate (PFOS). A modest decrease in global DNA methylation was observed in N2A cells exposed to 10 μM DES, BPA, TCDD, BDE-47, PCB-153 and 1 μM HCB, but no changes were found in the human SK-N-AS cells. We reveal for the first time that BDE-47 increases adipocyte differentiation in a dose-dependent manner (2.5-25 μM). Adipocyte differentiation was also enhanced by TBT (≥ 10 nM) and BPA (>10 μM) and inhibited by TCDD (≥ 0.1 nM). The other chemicals showed either modest or no effects on adipocyte differentiation at the concentrations tested (PFOA, PFOS and HBCD at 10 μM; PCB-153, 3.4 μM and HCB, 1 μM). This study demonstrates that selected EDCs can induce functional changes in murine adipocyte differentiation in vitro which are accompanied by decreased global DNA methylation. Copyright © 2013 Elsevier Ltd. All rights reserved.
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              Determining estrogenic steroids in Taipei waters and removal in drinking water treatment using high-flow solid-phase extraction and liquid chromatography/tandem mass spectrometry.

              River water and wastewater treatment plant (WWTP) effluents from metropolitan Taipei, Taiwan were tested for the presence of the pollutants estrone (E1), estriol (E3), 17beta-estradiol (E2), and 17alpha-ethinylestradiol (EE2) using a new methodology that involves high-flow solid-phase extraction and liquid chromatography/tandem mass spectrometry. The method was also used to investigate the removal of the analytes by conventional drinking water treatment processes. Without adjusting the pH, we extracted 1-L samples with PolarPlus C18 Speedisks under a flow rate exceeding 100 mL/min, in which six samples could be done simultaneously using an extraction station. The adsorbent was washed with 40% methanol/60% water and then eluted by 50% methanol/50% dichloromethane. The eluate was concentrated until almost dry and was reconstituted by 20 microL of methanol. Quantitation was done by LC-MS/MS-negative electrospray ionization in the selected reaction monitoring mode with isotope-dilution techniques. The mobile phase was 10 mM N-methylmorpholine aqueous solution/acetonitrile with gradient elution. Mean recoveries of spiked Milli-Q water were 65-79% and precisions were within 2-20% of the tested concentrations (5.0-200 ng/L). The method was validated with spiked upstream river water; precisions were most within 10% of the tested concentrations (10-100 ng/L) with most RSDs<10%. LODs of the environmental matrixes were 0.78-7.65 ng/L. A pre-filtration step before solid-phase extraction may significantly influence the measurement of E1 and EE2 concentrations; disk overloading by water matrix may also impact analyte recoveries along with ion suppression. In the Taipei water study, the four steroid estrogens were detected in river samples (ca. 15 ng/L for E2 and EE2 and 35-45 ng/L for E1 and E3). Average levels of 19-26 ng/L for E1, E2, and EE2 were detected in most wastewater effluents, while only a single effluent sample contained E3. The higher level in the river was likely caused by the discharge of untreated human and farming waste into the water. In the drinking water treatment simulations, coagulation removed 20-50% of the estrogens. An increased dose of aluminum sulfate did not improve the performance. Despite the reactive phenolic moiety in the analytes, the steroids were decreased only 20-44% of the initial concentrations in pre- or post-chlorination. Rapid filtration, with crushed anthracite playing a major role, took out more than 84% of the estrogens. Except for E3, the whole procedure successfully removed most of the estrogens even if the initial concentration reached levels as high as 500 ng/L.
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                Author and article information

                Contributors
                Role: Academic Editor
                Journal
                Int J Environ Res Public Health
                Int J Environ Res Public Health
                ijerph
                International Journal of Environmental Research and Public Health
                MDPI
                1661-7827
                1660-4601
                25 September 2015
                October 2015
                : 12
                : 10
                : 12016-12029
                Affiliations
                [1 ]College of Civil Engineering and Architecture, Zhejiang University of Technology, Hangzhou 310014, China; E-Mails: mayaner620@ 123456163.com (X.M.); 15268157494@ 123456sina.cn (C.Z.); seudjing@ 123456163.com (J.D.)
                [2 ]School of Civil Engineering and Architecture, Zhejiang University of Science and Technology, Hangzhou 310023, China; E-Mail: yali_song@ 123456sina.com
                [3 ]Water Resources and Environmental Institute, Xiamen University of Technology, Xiamen 361005, China; E-Mail: Leeqingsong@ 123456163.com
                [4 ]College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310014, China
                [5 ]College of Civil Engineering and Architecture, Zhejiang University, Hangzhou 310058, China
                Author notes
                [* ]Authors to whom correspondence should be addressed: E-Mails: mayaner@ 123456zjut.edu.cn (Y.G.); congil@ 123456zju.edu.cn (C.L.); Tel.: +86-101-385-804-3191 (Y.G. & C.L.); Fax: +86-0571-88320460 (Y.G. & C.L.).
                Article
                ijerph-12-12016
                10.3390/ijerph121012016
                4626952
                26404330
                d3ab8000-9c3c-4e87-94d1-00a54b863a0b
                © 2015 by the authors; licensee MDPI, Basel, Switzerland.

                This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 25 June 2015
                : 21 September 2015
                Categories
                Article

                Public health
                uv/h2o2,steroid estrogens,competitive degradation,photocatalysis,water treatment
                Public health
                uv/h2o2, steroid estrogens, competitive degradation, photocatalysis, water treatment

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