title: Transformation of sulfamethazine by manganese oxide in aqueous solution.
abstract: The transformation of the sulfonamide antimicrobial sulfamethazine (SMZ) by a synthetic analogue of the birnessite-family mineral vernadite (δ-MnO(2)) was studied. The observed pseudo-first-order reaction constants (k(obs)) decreased as the pH increased from 4.0 to 5.6, consistent with the decline in δ-MnO(2) reduction potential with increasing pH. Molecular oxygen accelerated SMZ transformation by δ-MnO(2) and influenced the transformation product distribution. Increases in the Na(+) concentration produced declines in k(obs). Transformation products identified by tandem mass spectrometry and the use of (13)C-labeled SMZ included an azo dimer self-coupling product and SO(2) extrusion products. Product analysis and density functional theory calculations are consistent with surface precursor complex formation followed by single-electron transfer from SMZ to δ-MnO(2) to produce SMZ radical species. Sulfamethazine radicals undergo further transformation by at least two pathways: radical-radical self-coupling or a Smiles-type rearrangement with O addition and then extrusion of SO(3). Experiments conducted in H(2)(18)O or in the presence of (18)O(2)(aq) demonstrated that oxygen both from the lattice of as-synthesized δ-MnO(2) and initially present as dissolved oxygen reacted with SMZ. The study results suggest that the oxic state and pH of soil and sediment environments can be expected to influence manganese oxide-mediated transformation of sulfonamide antimicrobials.
authors.affiliation: State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093, People's Republic of China.
authors.forename: Juan
authors.initials: J
authors.lastname: Gao
authors.forename: Curtis
authors.initials: C
authors.lastname: Hedman
authors.forename: Cun
authors.initials: C
authors.lastname: Liu
authors.forename: Tan
authors.initials: T
authors.lastname: Guo
authors.forename: Joel A
authors.initials: JA
authors.lastname: Pedersen
mesh_terms: D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D017895:Manganese Compounds / Q000737:chemistry*; D013058:Mass Spectrometry; D010087:Oxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D012964:Sodium / Q000737:chemistry; D012996:Solutions; D013418:Sulfamethazine / Q000737:chemistry*; D013816:Thermodynamics; D014874:Water Pollutants, Chemical / Q000737:chemistry*
chemical_list: D017895:Manganese Compounds; D010087:Oxides; D012996:Solutions; D014874:Water Pollutants, Chemical; D013418:Sulfamethazine; C027424:manganese oxide; D012964:Sodium; D010100:Oxygen