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  • Electrochemical incineration of omeprazole in neutral aqueous medium using a platinum or boron-doped diamond anode: degradation kinetics and oxidation products.

Electrochemical incineration of omeprazole in neutral aqueous medium using a platinum or boron-doped diamond anode: degradation kinetics and oxidation products.

Water research (2013-01-29)
Eliane Bezerra Cavalcanti, Sergi Garcia-Segura, Francesc Centellas, Enric Brillas
ABSTRACT

The electrochemical incineration of omeprazole, a widely prescribed gastrointestinal drug which is detected in natural waters, has been studied in a phosphate buffer of pH 7.0 by anodic oxidation with electrogenerated H(2)O(2) (AO-H(2)O(2)) operating at constant current density (j). The experiments were carried out in a cell equipped with either a Pt or a boron-doped diamond (BDD) anode and an air-diffusion cathode to continuously produce H(2)O(2). In these systems, organics are mainly oxidized by hydroxyl radicals formed at the Pt or BDD surface from water oxidation. A partial total organic carbon (TOC) abatement close to 78% for omeprazole was achieved by AO-H(2)O(2) with a BDD anode after consumption of 18 Ah L(-1) at 100 mA cm(-2), whereas the alternative use of Pt did not allow mineralizing the drug. However, the drug was totally removed using both anodes, although it decayed more rapidly using BDD. In this latter system, increasing j accelerated the degradation process, but lowering the mineralization current efficiency. Greater drug content also enhanced the degradation rate with higher mineralization degree and current efficiency. The kinetics for omeprazole decay always followed a pseudo-first-order reaction and its rate constant increased with increasing j and with decreasing its concentration. Seven heteroaromatic intermediates and four hydroxylated derivatives were detected by LC-MS, while nine short-linear carboxylic acids were identified and quantified by ion-exclusion HPLC. These acids were largely accumulated using Pt and rapidly removed using BDD, thus explaining the partial mineralization of omeprazole achieved by AO-H(2)O(2) with the latter anode. The release of inorganic ions such as NO(3)(-), NH(4)(+) and SO(4)(2-) was followed by ionic chromatography. A plausible reaction sequence for omeprazole mineralization involving all intermediates detected is proposed.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Boron, ≥95% (boron), amorphous powder
Sigma-Aldrich
Boron, crystalline, −60 mesh, 99% trace metals basis
Sigma-Aldrich
Boron, crystalline, 1 cm, 99.7% trace metals basis
Sigma-Aldrich
Diamond, synthetic monocrystalline powder, ≤1 μm
Sigma-Aldrich
Omeprazole, solid
Sigma-Aldrich
Diamond, nanopowder, <10 nm particle size (TEM), ≥95% trace metals basis
Supelco
Omeprazole, Pharmaceutical Secondary Standard; Certified Reference Material
Sigma-Aldrich
Diamond, nanopowder, <10 nm particle size (TEM), ≥97% trace metals basis
Omeprazole for peak identification, European Pharmacopoeia (EP) Reference Standard