Decomposition of pharmaceutical micropollutant - diclofenac by photocatalytic nanopowder mixtures in aqueous media: effect of optimization parameters, identification of intermediates and economic considerations

J Environ Sci Health A Tox Hazard Subst Environ Eng. 2020;55(4):483-497. doi: 10.1080/10934529.2019.1701895. Epub 2019 Dec 17.

Abstract

This study evaluates application of three different nanopowder mixtures for decomposition of diclofenac (DCF), one of frequently detected pharmaceutical in wastewater. Analyzed three photocatalytic mixtures ZnO/SnO2, ZnO/TiO2 and ZnO/In2O3 are for the first time used for diclofenac degradation. A set of experiments were performed in order to investigate influence of catalyst concentration (0.10-0.60 mg mL-1), initial concentration of diclofenac (0.002-0.010 mg mL-1) and pH value (5-9). The increase in the catalyst concentration leads to a decrease in the degradation rate constant, which is the most pronounced in the ZnO/TiO2 and ranges from 0.47 (6) min-1 to 0.25 (3) min-1. The influence of pH on efficacy shows completely different effects: ZnO/In2O3 is most effective in alkaline environments, ZnO/TiO2 in neutral environments, while ZnO/SnO2 efficiency is good in both alkaline and acidic environments. Initial concentrations of diclofenac showed a complex effect on the degradation rate. The four dominant intermediates were detected by LC MS/MS technique. In case of all three nanomaterials, intensive degradation was achieved in first 30 minutes. The economical analysis of photocatalytic treatment was provided where the preparation of nanomaterials does not demand high costs and with the highest diclofenac concentration, total operation costs are the lowest (77.14 US$/kWh).

Keywords: Heterogeneous photocatalysis; emerging pollutants; high performance liquid chromatography; nanomaterials; pharmaceuticals; wastewater.

MeSH terms

  • Catalysis
  • Chromatography, Liquid
  • Cost-Benefit Analysis
  • Diclofenac / analysis*
  • Nanoparticles / chemistry*
  • Pharmaceutical Preparations / analysis*
  • Photochemistry
  • Photolysis
  • Powders
  • Semiconductors
  • Surface Properties
  • Tandem Mass Spectrometry
  • Wastewater / chemistry
  • Water Pollutants, Chemical / analysis*
  • Water Purification / economics
  • Water Purification / methods*

Substances

  • Pharmaceutical Preparations
  • Powders
  • Waste Water
  • Water Pollutants, Chemical
  • Diclofenac