Emerging pollutants and plants – Metabolic activation of diclofenac by peroxidases

• Published in: Chemosphere (Oxford) Vol. 146; pp. 435 - 441
• Main Authors: Huber, Christian, Preis, Martina, Harvey, Patricia J., Grosse, Sylvia, Letzel, Thomas, Schröder, Peter
• Format: Journal Article
• Language: English
• Published: England Elsevier Ltd 01.03.2016
• Subjects: Activation; Activation, Metabolic; Armoracia - enzymology; Biodegradation, Environmental; Chromatography, High Pressure Liquid; Contaminants; Diclofenac; Diclofenac - analysis; Diclofenac - chemistry; Diclofenac - metabolism; Horseradish Peroxidase - chemistry; Horseradish Peroxidase - metabolism; Human; Humans; Iminoquinone; LC-MS; Oxidation-Reduction; Peroxidase; Phase transformations; Plants (organisms); Stopped flow spectroscopy; Tandem Mass Spectrometry; Waste Water - chemistry; Wastewater treatment; Water Pollutants, Chemical - analysis; Water Pollutants, Chemical - chemistry; Water Pollutants, Chemical - metabolism; Water Purification - methods; LC-MS; Peroxidase; Iminoquinone; Stopped flow spectroscopy; Diclofenac
• ISSN: 0045-6535; 1879-1298
• DOI: 10.1016/j.chemosphere.2015.12.059

Human pharmaceuticals and their residues are constantly detected in our waterbodies, due to poor elimination rates, even in the most advanced waste water treatment plants. Their impact on the environment and human health still remains unclear. When phytoremediation is applied to aid water treatment, plants may transform and degrade xenobiotic contaminants through phase I and phase II metabolism to more water soluble and less toxic intermediates. In this context, peroxidases play a major role in activating compounds during phase I via oxidation. In the present work, the ability of a plant peroxidase to oxidize the human painkiller diclofenac was confirmed using stopped flow spectroscopy in combination with LC-MS analysis. Analysis of an orange colored product revealed the structure of the highly reactive Diclofenac-2,5-Iminoquinone, which may be the precursor of several biological conjugates and breakdown products in planta. •First report of a plant peroxidase oxidizing the human painkiller diclofenac.•Enzymatic reaction followed by stopped flow spectroscopy.•Identification of Diclofenac-2,5-Iminoquinone by LS-MS/MS and TOF high resolution MS with accurate mass determination.