First electrochemistry of herbicide pethoxamid and its quantification using electroanalytical approach from mixed commercial product
Introduction
Nowadays, the chemical plant protection agents, pesticides, are indispensable in the agriculture. They assure mass production of quality food, while, on the other hand, they are one of the most serious environmental pollutants [1]. Although the development of these compounds are moving in the direction of stricter legal regulations about their monitoring and use and also designing of pesticides that fit in the concept of “ecological plant protection” (EPP) [2], still their application have a wide range of negative impacts on the environment. Agricultural soil is the first recipient of pesticides after their application, but depending of their mechanism of sorption and desorption from soil particles, pesticides can easily be transferred into the grown and surface waters and sometimes into the atmosphere, affecting the living beings, including humans [3,4]. Herbicide pethoxamid (Scheme 1), chemically named [2-chloro-N-(2-ethoxyethyl)-N-(2-phenylprop-1-enyl-2-methyl) acetamide], belongs to group of chloroacetamides. It inhibits the germination of target weeds in corn, soybeans, peas and beans, tobacco and other crops [5]. It is found that it can affects on herbicide-resistant weeds and pethoxamid received full approval for use in EU in 2006 (risk assessment in 2017) [6], while the approval for US and Canada is expected soon. Some important properties of this herbicide are high solubility in water (up to 0.4 g/L (20 °C) [5]) and almost no sorption in soils [3], so the leaching and runoff of this compound in ground and surface water is a real threat. Pethoxamid residues (and the most of other pesticides) in soil, water food and feed of plant origin usually were monitored using liquid chromatography with tandem mass spectrometry (LC–MS/MS) [6], but other analytical methods were also employed for this purpose [7]. Among reported methods, the electroanalytical methods are noted as fast and cost-effective methods for determination of these chemical agents [7,8]. Unfortunately, many of pesticides are not electroactive and that fact limits greater application of these methods.
This paper aims to application of electrochemical approach for the determination of herbicide pethoxamid at unmodified boron-doped diamond electrode (BDDE). Some of prestigious electrochemical properties of this type of carbon electrodes are wide “potential window” with low and stable background current, corrosion resistance, high thermal conductivity and high current densities [9,10]. The BDDE overcoming the limitations of conventional carbon materials, especially in determination of, as previously thought, oxidisable organic substances such as amines, polyaromatic hydrocarbons, aminothiols, etc. [[11], [12], [13], [14], [15]]. H or O surface termination at BDDE greatly contributes to application of these electrodes to large number of organic analytes which were rarely detectable or cannot be separated from similar structure compounds at other bare carbon electrodes [9]. Nowadays, several research groups, including our, are dedicated to development of new electrochemical methods for various bioactive [[16], [17], [18], [19], [20], [21], [22], [23]], polluting [[24], [25], [26], [27], [28]] and other analytes of interest [9,10] using BDDE. According to our knowledge, this is a first report of electrochemical activity of pethoxiamid and its electroanalytical sensing. This resulted in development of the simple, fast and reproductive electroanalytical procedure for determination of POA which was successfully tested on spiked surface water samples and commercial formulation.
Section snippets
Chemicals, reagents and standard solutions
Pethoxamid, terbuthylazine, clomazone, sulcotrione and mesotrione were used as received from Sigma Aldrich. The standard solutions (10−3 M) of pethoxamid and clomazone were prepared in water while for other pesticides were prepared in methanol. Britton-Robinson buffer solutions (BR) (pH 2 to10) were used in electrochemical studies. Working solutions (1–100 μM, in volume of 5 mL) were freshly prepared by diluting of standard solution with BR buffer solution, pH 4. Water was purified with
Electrochemical behavior of POA at BDDE and influence of pH
Stabile micro structure of BDD results in electrode stability at extreme cathodic and anodic potentials, high resistance to surface “poisoning” by reaction products and other present chemical species and easy regeneration of active electrode surface [9]. Bearing in mind those advantages of BDDE among other carbon or metal electrodes, cyclic voltammogram of 100 μM of POA was recorded in potential range from −1.5–2 V (Fig. 1). Electroactivity of POA was noticed, observing well-defined
Conclusion
This work reports a first electrochemical procedure for herbicide pethoxamid analysis, based on its fast and accurate SWV determination at BDDE at high anodic potential. The selectivity of the proposed method in presence of few common herbicides was investigated and it was successfully applied for selective quantification of this plant chemical agent from mixed pesticide formulation Successor T SE in river water. The results were in good agreement with those obtained by comparative HPLC
Acknowledgement
Financial support for this study was granted by the Ministry of Science and Technological Development of the Republic of Serbia, Project Number III45022, OI172030 and Magbiovin project (FP7- ERAChairs-Pilot Call-2013, Grant agreement: 621375).
References (33)
- et al.
Currently and recently used pesticides in Central European arable soils
Sci. Total Environ.
(2018) - et al.
Pesticides in surface and ground waters
Water Res.
(2003) - et al.
Analysis of the 16 Environmental Protection Agency priority polycyclic aromatic hydrocarbons by high performance liquid chromatography-oxidized diamond film electrodes
J. Chromatogr. A
(2006) - et al.
Novel strategy for electroanalytical detection of antipsychotic drugs chlorpromazine and thioridazine; possibilities for simultaneous determination
Int. J. Electrochem. Sci.
(2017) - et al.
Simultaneous determination of antihypertensive drugs by flow injection analysis using multiple pulse amperometric detection with a cathodically pretreated boron-doped diamond electrode
J. Electroanal. Chem.
(2015) - et al.
Sensitive determination of anticancer drug imatinib in spiked human urine samples by differential pulse voltammetry on anodically pretreated boron-doped diamond electrode
Diam. Relat. Mater.
(2016) - et al.
Amperometric quantification of the pesticide ziram at boron doped diamond electrodes using flow injection analysis
Sensor. Actuator. B Chem.
(2016) - et al.
Boron-doped diamond electrode — a prestigious unmodified carbon electrode for simple and fast determination of bentazone in river water samples
Diam. Relat. Mater.
(2018) - et al.
Green electrochemical sensor for environmental monitoring of pesticides: determination of atrazine in river waters using a boron-doped diamond electrode
Sens. Actuators, B
(2013) - et al.
Electrochemical oxidation of propanil and related N-substituted amides
Anal. Chim. Acta
(2001)
Impact of pesticides use in agriculture: their benefits and hazards
Interdiscipl. Toxicol.
Chemical plant protection. Past. Present. Future?
Ecocycles
Pethoxamid, Monograph, (Draft Assessment Report)
Peer review of the pesticide risk assessment of the active substance pethoxamid
EFSA J.
Analytical methods for pesticide residues
Water Environ. Res.
Electrochemical methods in pesticides control
Anal. Lett.
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