title: Oxidative decarboxylation of diclofenac by manganese oxide bed filter.
abstract: Diclofenac (DCF) was eliminated by fast chemical oxidation on natural manganese oxide in a column reactor. Identification of transformation by-products of DCF by HPLC-UV-MS(n) gave evidence of decarboxylation, iminoquinone formation and dimerization. The fast oxidation of DCF is also accompanied by a strong adsorption of organic carbon that was explained by the sorption of dimer products on the surface of manganese oxide. Decarboxylation and dimerization increased the hydrophobic interactions with manganese oxide and reduced the presence of potentially toxic by-products in the effluent. The rate of oxidation was first order with respect to DCF and was slowed down by the presence of organic buffer MOPS (3-morpholinopropane-1-sulfonic acid). The first order rate constant in absence of MOPS was extrapolated by considering a surface site-binding model and MOPS as a co-adsorbate. The rate constant was 0.818 min(-1) at pH 7 and 10 mM NaCl corresponding to empty bed residence time of 50 s only for 50% removal of DCF. Rate constants increased when pH decreased from pH 8.0 to 6.5 and when ionic strength increased. Manganese oxide bed filter can be considered as an alternative treatment for polishing waste water effluent or for remediation of contaminated groundwater.
authors.affiliation: Université de Poitiers, CNRS UMR 7285 IC2MP, ENSIP, 1 rue Marcel Doré, 86022 Poitiers Cedex, France. melissa.huguet@univ-poitiers.fr
authors.forename: Mélissa
authors.initials: M
authors.lastname: Huguet
authors.forename: Marie
authors.initials: M
authors.lastname: Deborde
authors.forename: Sébastien
authors.initials: S
authors.lastname: Papot
authors.forename: Hervé
authors.initials: H
authors.lastname: Gallard
mesh_terms: D002851:Chromatography, High Pressure Liquid; D003653:Decarboxylation; D004008:Diclofenac / Q000737:chemistry*; D019281:Dimerization; D005374:Filtration / Q000295:instrumentation / Q000379:methods*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D017895:Manganese Compounds / Q000737:chemistry; D009994:Osmolar Concentration; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry; D014874:Water Pollutants, Chemical / Q000737:chemistry*; D018508:Water Purification / Q000379:methods
chemical_list: D017895:Manganese Compounds; D010087:Oxides; D014874:Water Pollutants, Chemical; D004008:Diclofenac; C027424:manganese oxide
keywords: Adsorption; Catalytic oxidation; Column reactor; Dimerization; Iminoquinone