Efficient cephalexin degradation using active chlorine produced on ruthenium and iridium oxide anodes: Role of bath composition, analysis of degradation pathways and degradation extent

The elimination of cephalexin (CPX) using electro-generated Cl2-active on Ti/RuO2-IrO2 anode was assessed in different effluents: deionized water (DW), municipal wastewater (MWW) and urine. Single Ti/RuO2 and Ti/IrO2 catalysts were prepared to compare their morphologies and electrochemical behavior...

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Published inThe Science of the total environment Vol. 648; pp. 377 - 387
Main Authors Perea, Lic A., Palma-Goyes, Ricardo E., Vazquez-Arenas, Jorge, Romero-Ibarra, Issis, Ostos, Carlos, Torres-Palma, Ricardo A.
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LanguageEnglish
Published Netherlands Elsevier B.V 15.01.2019
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Abstract The elimination of cephalexin (CPX) using electro-generated Cl2-active on Ti/RuO2-IrO2 anode was assessed in different effluents: deionized water (DW), municipal wastewater (MWW) and urine. Single Ti/RuO2 and Ti/IrO2 catalysts were prepared to compare their morphologies and electrochemical behavior against the binary DSA. XRD and profile refinement suggest that Ti/RuO2-IrO2 forms a solid solution, where RuO2 and IrO2 growths are oriented by the TiO2 substrate through substitution of Ir by Ru atoms within its rutile-type structure. SEM reveals mud-cracked structures with flat areas for all catalysts, while EDS analysis indicates atomic ratios in the range of the oxide stoichiometries in the nominal concentrations used during synthesis. A considerably higher CPX degradation is achieved in the presence of NaCl than in Na2SO4 or Na3PO4 media due to the active chlorine generation. A faster CPX degradation is reached when the current density is increased or the pH value is lowered. This last behavior may be ascribed to an acid-catalyzed reaction between HClO and CPX. Degradation rates of 22.5, 3.96, and 0.576 μmol L−1 min−1 were observed for DW, MWW and urine, respectively. The lower efficiency measured in these last two effluents was related to the presence of organic matter and urea in the matrix. A degradation pathway is proposed based on HPLC-DAD and HPLC-MS analysis, indicating the fast formation (5 min) of CPX-(S)-sulfoxide and CPX-(R)-sulfoxide, generated due the Cl2-active attack at the CPX thioether. Furthermore, antimicrobial activity elimination of the treated solution is reached once CPX, and the initial by-products are considerably eliminated. Finally, even if only 16% of initial TOC is removed, BOD5 tests prove the ability of electro-generated Cl2-active to transform the antibiotic into biodegradable compounds. A similar strategy can be used for the abatement of other recalcitrant compounds contained in real water matrices such as urine and municipal wastewaters. [Display omitted] •XRD and profile refinement indicate that Ti/RuO2-IrO2 forms a solid solution.•Ti/RuO2-IrO2 anode experienced a higher active chlorine production.•Cephalexin degradation on Ti/RuO2-IrO2 was carried out in urine and MWW.•Initial organic byproducts were identified, and pH and j evaluated.•Antimicrobial activity was removed and biodegradable byproducts were obtained.
AbstractList The elimination of cephalexin (CPX) using electro-generated Cl -active on Ti/RuO -IrO anode was assessed in different effluents: deionized water (DW), municipal wastewater (MWW) and urine. Single Ti/RuO and Ti/IrO catalysts were prepared to compare their morphologies and electrochemical behavior against the binary DSA. XRD and profile refinement suggest that Ti/RuO -IrO forms a solid solution, where RuO and IrO growths are oriented by the TiO substrate through substitution of Ir by Ru atoms within its rutile-type structure. SEM reveals mud-cracked structures with flat areas for all catalysts, while EDS analysis indicates atomic ratios in the range of the oxide stoichiometries in the nominal concentrations used during synthesis. A considerably higher CPX degradation is achieved in the presence of NaCl than in Na SO or Na PO media due to the active chlorine generation. A faster CPX degradation is reached when the current density is increased or the pH value is lowered. This last behavior may be ascribed to an acid-catalyzed reaction between HClO and CPX. Degradation rates of 22.5, 3.96, and 0.576 μmol L  min were observed for DW, MWW and urine, respectively. The lower efficiency measured in these last two effluents was related to the presence of organic matter and urea in the matrix. A degradation pathway is proposed based on HPLC-DAD and HPLC-MS analysis, indicating the fast formation (5 min) of CPX-(S)-sulfoxide and CPX-(R)-sulfoxide, generated due the Cl -active attack at the CPX thioether. Furthermore, antimicrobial activity elimination of the treated solution is reached once CPX, and the initial by-products are considerably eliminated. Finally, even if only 16% of initial TOC is removed, BOD tests prove the ability of electro-generated Cl -active to transform the antibiotic into biodegradable compounds. A similar strategy can be used for the abatement of other recalcitrant compounds contained in real water matrices such as urine and municipal wastewaters.
The elimination of cephalexin (CPX) using electro-generated Cl2-active on Ti/RuO2-IrO2 anode was assessed in different effluents: deionized water (DW), municipal wastewater (MWW) and urine. Single Ti/RuO2 and Ti/IrO2 catalysts were prepared to compare their morphologies and electrochemical behavior against the binary DSA. XRD and profile refinement suggest that Ti/RuO2-IrO2 forms a solid solution, where RuO2 and IrO2 growths are oriented by the TiO2 substrate through substitution of Ir by Ru atoms within its rutile-type structure. SEM reveals mud-cracked structures with flat areas for all catalysts, while EDS analysis indicates atomic ratios in the range of the oxide stoichiometries in the nominal concentrations used during synthesis. A considerably higher CPX degradation is achieved in the presence of NaCl than in Na2SO4 or Na3PO4 media due to the active chlorine generation. A faster CPX degradation is reached when the current density is increased or the pH value is lowered. This last behavior may be ascribed to an acid-catalyzed reaction between HClO and CPX. Degradation rates of 22.5, 3.96, and 0.576 μmol L−1 min−1 were observed for DW, MWW and urine, respectively. The lower efficiency measured in these last two effluents was related to the presence of organic matter and urea in the matrix. A degradation pathway is proposed based on HPLC-DAD and HPLC-MS analysis, indicating the fast formation (5 min) of CPX-(S)-sulfoxide and CPX-(R)-sulfoxide, generated due the Cl2-active attack at the CPX thioether. Furthermore, antimicrobial activity elimination of the treated solution is reached once CPX, and the initial by-products are considerably eliminated. Finally, even if only 16% of initial TOC is removed, BOD5 tests prove the ability of electro-generated Cl2-active to transform the antibiotic into biodegradable compounds. A similar strategy can be used for the abatement of other recalcitrant compounds contained in real water matrices such as urine and municipal wastewaters. [Display omitted] •XRD and profile refinement indicate that Ti/RuO2-IrO2 forms a solid solution.•Ti/RuO2-IrO2 anode experienced a higher active chlorine production.•Cephalexin degradation on Ti/RuO2-IrO2 was carried out in urine and MWW.•Initial organic byproducts were identified, and pH and j evaluated.•Antimicrobial activity was removed and biodegradable byproducts were obtained.
Author Romero-Ibarra, Issis
Ostos, Carlos
Perea, Lic A.
Vazquez-Arenas, Jorge
Palma-Goyes, Ricardo E.
Torres-Palma, Ricardo A.
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  givenname: Carlos
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  surname: Torres-Palma
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  organization: Grupo de Investigación en Remediación Ambiental y Biocatálisis (GIRAB), Instituto de Química, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21, Medellín, Colombia
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Keywords Active chlorine
RuO2-IrO2
β-Lactam
Urine effluent
Wastewater treatment
Electrochemical oxidation
RuO-IrO
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Snippet The elimination of cephalexin (CPX) using electro-generated Cl2-active on Ti/RuO2-IrO2 anode was assessed in different effluents: deionized water (DW),...
The elimination of cephalexin (CPX) using electro-generated Cl -active on Ti/RuO -IrO anode was assessed in different effluents: deionized water (DW),...
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StartPage 377
SubjectTerms Active chlorine
Electrochemical oxidation
RuO2-IrO2
Urine effluent
Wastewater treatment
β-Lactam
Title Efficient cephalexin degradation using active chlorine produced on ruthenium and iridium oxide anodes: Role of bath composition, analysis of degradation pathways and degradation extent
URI https://dx.doi.org/10.1016/j.scitotenv.2018.08.148
https://www.ncbi.nlm.nih.gov/pubmed/30121037
Volume 648
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