Removal of quinolone antibiotics from wastewaters by sorption and biological degradation in laboratory-scale membrane bioreactors

Laboratory-scale batch experiments were developed to investigate the main removal routes for 6 commonly found quinolones (ciprofloxacin, moxifloxacin, norfloxacin, ofloxacin, pipemidic acid, and piromidic acid), in wastewaters from a wastewater treatment plant, at mu g L-1 levels in an aerobic sludge system from a membrane bioreactor (MBR) pilot plant. It was demonstrated that sorption and biotransformation were the main removal routes for the target antibiotics over other possible pathways, as volatilization or hydrolysis, under the experimental conditions. Mass balances indicated that sorption on sludge played a dominant role in the elimination of antibiotics from waters. The sorption coefficient K-d depended strongly on temperature and on the quinolone type and were higher at lower temperatures and for piperazinylic quinolones. K-d values were between 516 and 3746 L kg(-1) in the temperature range of 9-38 degrees C. Higher mixed liquor suspended solids (MISS) increased quinolone removal efficiency mainly by sorption. Quinolone biodegradation constituted a secondary pathway, and could be described by first-order kinetics with degradation-rate constants ranging from 8.0x10(-4) h(-1) to 1.4x10(-2) h(-1) within the same temperature range and MISS from 7000 to 15,000 mg L-1. Biodegradation depended on the MISS and temperature, but also on the initial chemical oxygen demand (COD). Higher biodegradation rates were observed at higher MISS and temperature, as well as at low initial COD. Ciprofloxacin and moxifloxacin registered the highest biodegradation percentages (52.8% and 47.2%, respectively, at 38 degrees C and 15,000 mg L-1 MLSS), which is evidence that, despite the known persistence of this group of antibiotics and removal from waters mainly by sorption, it was possible to improve their removal by biodegradation, with an appropriate selection of conditions and control of process variables, as a preliminary step towards the elimination of these antibiotics from the environment. Further research is needed on the possibilities of removing sorbed antibiotics from sludge. (C) 2012 Elsevier B.V. All rights reserved.