Electrochemical degradation of the antibiotic ciprofloxacin in a flow reactor using distinct BDD anodes: Reaction kinetics, identification and toxicity of the degradation products

Chemosphere. 2019 Nov:234:461-470. doi: 10.1016/j.chemosphere.2019.06.053. Epub 2019 Jun 11.

Abstract

The performances of distinct BDD anodes (boron doping of 100, 500 and 2500 ppm, with sp3/sp2 carbon ratios of 215, 325, and 284, respectively) in the electrochemical degradation of ciprofloxacin - CIP (0.5 L of 50 mg L-1 in 0.10 M Na2SO4, at 25 °C) were comparatively assessed using a recirculating flow system with a filter-press reactor. Performance was assessed by monitoring the CIP and total organic carbon (TOC) concentrations, oxidation intermediates, and antimicrobial activity against Escherichia coli as a function of electrolysis time. CIP removal was strongly affected by the solution pH (kept fixed), flow conditions, and current density; similar trends were obtained independently of the BDD anode used, but the BDD100 anode yielded the best results. Enhanced mass transport was achieved at a low flow rate by promoting the solution turbulence within the reactor. The fastest complete CIP removal (within 20 min) was attained at j = 30 mA cm-2, pH = 10.0, and qV = 2.5 L min-1 + bypass turbulence promotion. TOC removal was practically accomplished only after 10 h of electrolysis, with quite similar performances by the distinct BDD anodes. Five initial oxidation intermediates were identified (263 ≤ m/z ≤ 348), whereas only two terminal oxidation intermediates were detected (oxamic and formic acids). The antimicrobial activity of the electrolyzed CIP solution was almost completely removed within 10 h of electrolysis. The characteristics of the BDD anodes only had a marked effect on the CIP removal rate (best performance by the least-doped anode), contrasting with other data in the literature.

Keywords: Activity against E. coli; Boron-doped diamond anode; Electrooxidation; Filter-press reactor; Mass transport enhancement.

MeSH terms

  • Anti-Bacterial Agents / analysis
  • Anti-Bacterial Agents / chemistry
  • Boron
  • Carbon / analysis
  • Carbon / chemistry
  • Ciprofloxacin / analysis
  • Ciprofloxacin / chemistry*
  • Diamond
  • Electrodes
  • Electrolysis / methods*
  • Escherichia coli / drug effects
  • Kinetics
  • Oxidation-Reduction
  • Water Pollutants, Chemical / analysis
  • Water Pollutants, Chemical / chemistry*

Substances

  • Anti-Bacterial Agents
  • Water Pollutants, Chemical
  • Ciprofloxacin
  • Carbon
  • Diamond
  • Boron