Degradation Products, Mineralization, and Toxicity Assessment of Pesticides Malathion and Fenitrothion

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Degradation Products, Mineralization, and Toxicity Assessment of Pesticides Malathion and Fenitrothion Marija V. Pergal & Igor D. Kodranov & Miodrag M. Pergal & Uroš Gašić & Dalibor M. Stanković & Branka B. Petković & Dragan D. Manojlović

Received: 16 April 2020 / Accepted: 29 July 2020 # Springer Nature Switzerland AG 2020

Abstract The aim of this study was to investigate, analyze, and compare applied techniques suitable for achieving efficient removal of organophosphorus pesticides (OPPs) (malathion and fenitrothion) from aqueous solutions and analyze the degradation products and processes. Pesticide degradation efficiency (%) was monitored by highperformance liquid chromatography (HPLC) equipped with a photodiode array detector (DAD), while mineralization degree was determined by total organic carbon analysis (TOC). Daphnia magna was used for screening the environmental safety aspects of the degradation methods, i.e., for assessing the toxicity of solutions obtained after degradation. Additionally, a surface river water was utilized to examine the likely influence of organic matter on the pesticides’ degradation. Pesticide degradation products were identified using gas chromatography with a triple quadrupole mass detector (GC-MS/MS) as well as ultrahigh-performance liquid chromatography coupled with a linear ion trap, Orbitrap mass spectrometer (UHPLC-

LTQ Orbitrap MS), and a simple pesticide degradation mechanism is proposed. Removal of pesticides from water using chlorine dioxide was successful, resulting in high degradation efficiency (98% for malathion and 81% for fenitrothion). Partial mineralization was achieved, and Daphnia magna mortality decreased in the waters containing degradation products (compared with the parent pesticides), indicating that the solutions formed were less toxic than the parent pesticides. Lower degradation rates (80% for malathion and 72% for fenitrothion) in Sava River water were measured, indicating the influence of the organic matter contained in this naturally occurring surface water. The results prove that chlorine dioxide could be used as an agent for successful removal of these OPPs from water.

M. V. Pergal (*) Institute of Chemistry, Technology and Metallurgy, National Institute of the Republic of Serbia, University of Belgrade, Njegoševa 12, Belgrade 11000, Serbia e-mail: [email protected]

Belgrade 11060, Serbia

I. D. Kodranov : M. M. Pergal : D. D. Manojlović Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade 11000, Serbia U. Gašić Department of Plant Physiology, Institute for Biological Research Siniša Stanković, National Institute of the Republic of Serbia, University of Belgrade, Bulevar despota Stefana 142,

Keywords Organophosphorus pesticides degradation . River water . Degradation product and pathway . LCOrbitrap MS . GC-MS/MS

D. M. Stanković The Vinca Institute of Nuclear Sciences, University of Belgrade, POB 522, Belgrade 11001, Serbia B. B. Petković Faculty of Sciences, University of Priština, Lole Ribara 29, 38220, Kosovsk