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      Adsorption of Antibiotics on Graphene and Biochar in Aqueous Solutions Induced by π-π Interactions

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          Abstract

          The use of carbon based materials on the removal of antibiotics with high concentrations has been well studied, however the effect of this removal method is not clear on the actual concentration of environments, such as the hospital wastewater, sewage treatment plants and aquaculture wastewater. In this study, experimental studies on the adsorption of 7 antibiotics in environmental concentration of aqueous solutions by carbon based materials have been observed. Three kinds of carbon materials have shown very fast adsorption to antibiotics by liquid chromatography–tandem mass spectrometry (LC-MS-MS) detection, and the highest removal efficiency of antibiotics could reach to 100% within the range of detection limit. Surprisedly, the adsorption rate of graphene with small specific surface area was stronger than other two biochar, and adsorption rate of the two biochar which have approximate specific surface and different carbonization degree, was significantly different. The key point to the present observation were the π-π interactions between aromatic rings on adsorbed substance and carbon based materials by confocal laser scanning microscope observation. Moreover, adsorption energy markedly increased with increasing number of the π rings by using the density functional theory (DFT), showing the particular importance of π-π interactions in the adsorption process.

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          Most cited references 28

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          Urban wastewater treatment plants as hotspots for the release of antibiotics in the environment: a review.

          Urban wastewater treatment plants (UWTPs) are among the main sources of antibiotics' release into various compartments of the environment worldwide. The aim of the present paper is to critically review the fate and removal of various antibiotics in wastewater treatment, focusing on different processes (i.e. biological processes, advanced treatment technologies and disinfection) in view of the current concerns related to the induction of toxic effects in aquatic and terrestrial organisms, and the occurrence of antibiotics that may promote the selection of antibiotic resistance genes and bacteria, as reported in the literature. Where available, estimations of the removal of antibiotics are provided along with the main treatment steps. The removal efficiency during wastewater treatment processes varies and is mainly dependent on a combination of antibiotics' physicochemical properties and the operating conditions of the treatment systems. As a result, the application of alternative techniques including membrane processes, activated carbon adsorption, advanced oxidation processes (AOPs), and combinations of them, which may lead to higher removals, may be necessary before the final disposal of the effluents or their reuse for irrigation or groundwater recharge. Copyright © 2012 Elsevier Ltd. All rights reserved.
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            Occurrence of antibiotics in hospital, residential, and dairy effluent, municipal wastewater, and the Rio Grande in New Mexico.

            This study had three objectives: 1) determine occurrence of antibiotics in effluent from hospitals, residential facilities, and dairies, and in municipal wastewater 2) determine antibiotic removal at a large wastewater treatment plant (WWTP) in Albuquerque, NM, and 3) determine concentrations of antibiotics in the Rio Grande, which receives wastewater from the Albuquerque WWTP. Twenty-three samples of wastewater and 3 samples of Rio Grande water were analyzed for the presence of 11 antibiotics. Fifty-eight percent of samples had at least one antibiotic present while 25% had three or more. Hospital effluent had detections of sulfamethoxazole, trimethoprim, ciprofloxacin, ofloxacin, lincomycin, and penicillin G, with 4 of 5 hospital samples having at least one antibiotic detected and 3 having four or more. At the residential sampling sites, ofloxacin was found in effluent from assisted living and retirement facilities, while the student dormitory had no detects. Only lincomycin was detected in dairy effluent (in 2 of 8 samples, at 700 and 6600 ng/L). Municipal wastewater had detections of sulfamethoxazole, trimethoprim, ciprofloxacin, and ofloxacin, with 4 of 6 samples having at least one antibiotic present and 3 having 3 or more. The relatively high concentrations (up to 35,500 ng/L) of ofloxacin found in hospital and residential effluent may be of concern due to potential genotoxic effects and development of antibiotic resistance. At the Albuquerque WWTP, both raw wastewater and treated effluent had detections of sulfamethoxazole, trimethoprim, and ofloxacin, at concentrations ranging from 110 to 470 ng/L. However, concentrations in treated effluent were reduced by 20% to 77%. No antibiotics were detected in the Rio Grande upstream of the Albuquerque WWTP discharge, and only one antibiotic, sulfamethoxazole, was detected in the Rio Grande (300 ng/L) below the WWTP.
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              Decontamination of bisphenol A from aqueous solution by graphene adsorption.

              The decontamination of bisphenol A (BPA) from aqueous solution by graphene adsorption was investigated. The maximum adsorption capacity (q(m)) of graphene for BPA obtained from a Langmuir isotherm was 182 mg/g at 302.15 K, which was among the highest values of BPA adsorption compared with other carbonaceous adsorbents according to the literature. Both π-π interactions and hydrogen bonds might be responsible for the adsorption of BPA on graphene, and the excellent adsorption capacity of graphene was due to its unique sp(2)-hybridized single-atom-layer structure. Therefore, graphene could be regarded as a promising adsorbent for BPA removal in water treatment. The kinetics and isotherm data can be well described by the pseudo-second-order kinetic model and the Langmuir isotherm, respectively. The thermodynamic studies indicated that the adsorption reaction was a spontaneous and exothermic process. Besides, the presence of NaCl in the solution could facilitate the adsorption process, whereas the alkaline pH range and higher temperature of the solution were unfavorable.
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                Author and article information

                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group
                2045-2322
                18 August 2016
                2016
                : 6
                Affiliations
                [1 ]School of Environmental and Chemical Engineering, Shanghai University , 99 Shangda Road, Shanghai 200444, China
                [2 ]Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences , Shanghai 201800, China
                [3 ]School of Science, Zhejiang Agriculture and Forestry University , Lin’an, Zhejiang 311300, China
                [4 ]Shanghai Applied Radiation Institute, Shanghai University , 99 Shangda Road, Shanghai 200444, China
                Author notes
                [*]

                These authors contributed equally to this work.

                Article
                srep31920
                10.1038/srep31920
                4989150
                27534975
                Copyright © 2016, The Author(s)

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

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