Reaction of Lincosamide Antibiotics with Manganese Oxide in Aqueous Solution

Abstract

Lincosamides are among the most frequently detected antibacterial agents in effluents from wastewater treatment plants and surface runoff at agricultural production systems. Little is known about their transformations in the environment. This study revealed that manganese oxide caused rapid and extensive decomposition of clindamycin and lincomycin in aqueous solution. The reactions occurred mainly at the pyranose ring of lincosamides, initially by formation of complexes with Mn and cleavage of the ether linkage, leading to the formation of a variety of degradation products via subsequent hydrolytic and oxidative reactions. The results of LC-MS/MS and FTIR analysis confirm cleavage of the C-O-C bond in the pyranose ring, formation of multiple carbonyl groups, and transformation of the methylthio moiety to sulfur oxide. The overall transformation was controlled by interactions of cationic species of lincosamides with MnO(2) surfaces. The presence of electrolytes (i.e., NaCl, CaCl(2), and MnCl(2)) and dissolved organic matter in aqueous solution, and increase of solution pH, diminished lincosamide binding to MnO(2) hence reducing the rate and magnitude of the transformations. Results from this study indicate that manganese dioxides in soils and sediments could contribute to the decomposition of lincosamide antibiotics released into the environment.

Sorption and desorption of tetracycline on layered manganese dioxide birnessite

“…Recently, studies have been conducted to investigate the birnessite-facilitated destruction of TC or ciprofloxacin (CIP) in aqueous solutions (Zhang and Huang 2005;Rubert and Pedersen 2006;Chen and Huang 2011;). An extensive decomposition of clindamycin and lincomycin in aqueous solution could be achieved using synthetic manganese dioxide (d-MnO 2 ) (Chen et al 2010). The transformation of sulfadiazine and sulfonamide antimicrobial sulfamethazine (SMZ) by birnessite-type d-MnO 2 was also reported (Liu et al 2009;Gao et al 2012).…”

Identification of the unknown transformation products derived from lincomycin using LC‐HRMS technique

“…Conversely, for the isomer 373-B, the formation of either the ion at m/z 337.1752, resulting from the loss of two water molecules, and of the one at m/z 251.1749, due to the cleavage of the pyranonic ring, allows to locate both oxo functions on the pyranose ring and to claim for the cleavage of pyranose ring itself. In a close analogy with what occurs to clindamycin on MnO 2 , (6) pyranose ring opening occurs via hydrolytic attack at C1 and sequential oxidation.…”

Pharmaceutical removal from water with iron- or manganese-based technologies: A review

“…Both Fe(V) and Fe(VI) have a higher standard redox potential of C2.2 V under acidic pH 4-5 than under neutral pH 7 (Fig. 1A) (Jiang, 2007;Chen et al, 2010;Jiang, 2014). These ferrate compounds can react with pharmaceuticals which contain electron-rich moieties (Lee et al, 2009;Yang et al, 2012;, which leads to the formation of nontoxic by-products and Fe(III) (Sharma et al, 2005;.…”