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  • Treatment of selected pharmaceuticals by ferrate(VI): performance, kinetic studies and identification of oxidation products.

Treatment of selected pharmaceuticals by ferrate(VI): performance, kinetic studies and identification of oxidation products.

Journal of pharmaceutical and biomedical analysis (2014-07-27)
Zhengwei Zhou, Jia-Qian Jiang
ABSTRACT

The performance of ferrate(VI) in treating sulfamethoxazole (SMX), diclofenac (DCF), carbamazepine (CBZ) and bezafibrate (BZF) in test solutions containing the four compounds was investigated. A series of jar-test experiments was performed on a bench-scale at pH 6-9 and at a ferrate(VI) dose of 1-5 mg Fe/L. The results suggested that ferrate(VI) can effectively remove SMX, DCF and CBZ from the test solutions, with greater than 80% removal under optimum conditions. However, the removal efficiency of BZF was very low, less than 25% under the studied conditions. Increasing the dose of ferrate(VI) improved the treatment performance, while the influence of solution pH on ferrate(VI) performance varied among the different target compounds. Ferrate(VI) demonstrated the highest reactivity with SMX at pH 8 and pH 9 (20 °C), with apparent second-order rate constants of 360±17 M(-1) s(-1) and 1.26±0.02 M(-1) s(-1), respectively. However, BZF showed the lowest removal by ferrate(VI) with the smallest rate constants (less than 0.5 M(-1) s(-1)) at pH 8 and pH 9. Furthermore, a number of oxidation products (OPs) of SMX, DCF and CBZ during ferrate(VI) oxidation were detected by liquid chromatography and mass spectrometry (LC-MS), and their degradation pathways were tentatively proposed. No OPs of BZF were detected during ferrate(VI) oxidation.

MATERIALS
Product Number
Brand
Product Description

Supelco
Carbamazepine, Pharmaceutical Secondary Standard; Certified Reference Material
Supelco
Diclofenac sodium salt, Pharmaceutical Secondary Standard; Certified Reference Material
Sigma-Aldrich
Ammonium formate, ≥99.995% trace metals basis
Sigma-Aldrich
Ammonium formate, BioUltra, ≥99.0% (calc. based on dry substance, NT)
Supelco
Ammonium formate, eluent additive for LC-MS, LiChropur, ≥99.0%
Sigma-Aldrich
Carbamazepine, powder
Sigma-Aldrich
Carbamazepine, meets USP testing specifications
Sigma-Aldrich
Diclofenac sodium salt
Sigma-Aldrich
Bezafibrate, ≥98%, solid
Sigma-Aldrich
Pentostatin, ≥95% (HPLC)
Carbamazepine, European Pharmacopoeia (EP) Reference Standard
Bezafibrate, European Pharmacopoeia (EP) Reference Standard
USP
Carbamazepine, United States Pharmacopeia (USP) Reference Standard
Supelco
Diclofenac sodium salt, analytical standard
Diclofenac for system suitability, European Pharmacopoeia (EP) Reference Standard
Supelco
Carbamazepine, analytical standard
Sigma-Aldrich
Ammonium formate, reagent grade, 97%
Supelco
Sulfamethoxazole, certified reference material, TraceCERT®, Manufactured by: Sigma-Aldrich Production GmbH, Switzerland
Sigma-Aldrich
Ammonium formate solution, BioUltra, 10 M in H2O
Supelco
Ammonium formate solution, 10 mM in H2O, suitable for HPLC
Supelco
Sulfamethoxazole, Pharmaceutical Secondary Standard; Certified Reference Material
Supelco
Sulfamethoxazole, VETRANAL®, analytical standard
Sigma-Aldrich
Formic acid, ≥95%, FCC, FG
Sigma-Aldrich
Formic acid solution, BioUltra, 1.0 M in H2O
Supelco
Sulfamethoxazole
Sigma-Aldrich
Formic acid, reagent grade, ≥95%
USP
Diclofenac sodium, United States Pharmacopeia (USP) Reference Standard
Sigma-Aldrich
Formic acid, ACS reagent, ≥96%
Diclofenac sodium, European Pharmacopoeia (EP) Reference Standard
Sigma-Aldrich
Formic acid, ACS reagent, ≥88%