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Switchable Hydrophobic MNPs: Pesticide Residue Analysis

Location:India Dindigul, Tamil Nadu 624001, India

The necessary of pesticides: Some of the pests such as mosquitoes, ticks, rats and mice may affect plants, animals and humans; therefore we need to control such type of pests. Hence, pesticides are used to control such type of pests and it also used in agriculture to insect infestation, control weeds, and other diseases. Some of the other chemicals such as herbicides, fungicides, insecticides, etc., along with pesticides are essential for improving the agricultural productivity and harvest to protect the commodity from deterioration during storage and transport. These helped the farmers to grow more food on less land by protecting crops from pests, diseases, weeds and also the raising productivity per hectare.

Image credit to SNB team

Limitations of pesticides: The limitations of the pesticide to widespread of its usage are very significant. Mainly, more dosage of pesticides are contaminated into water, air and high toxicity poses a hazard to the ecosystem. The direct transfer of pesticides from agricultural land to surrounding food products such as berries, vegetables, fruits, etc., the concentrations that range from ng to μg•L−1 [1]. They also include domestic animal contaminations and deaths, loss of natural antagonists to pests, pesticide resistance, honeybee and pollination decline, losses to adjacent crops, bird and fishery losses, and contamination of groundwater. It also reduces bio-diversity, reduce nitrogen fixation, the disappearance of pollinators, threaten fish, destroy bird and animal habitats.

Pimentel (1995) reported that only a small percentage (0.3%) of applied pesticides enter into the target pest while 99.7% went somewhere else into the environment [2]. In 1990, WHO (World Health Organization) was reported that, 80% of all pesticides are used by developing countries [3]. Particularly, developing countries are utilizing high level of pesticides due to lack of proper legislation, improper market regulations and ignorance shown by peoples. ‘Which leads to health issues and environmental contamination associated with pesticide use in the developing countries’.  

Limitations of organochlorine pesticides: Organochlorine pesticides (OCPs) are highly dangerous and toxic to mammals and will accumulate in the tissues of living organisms, among the various organic pesticides. They are the most persistent, toxic, and economical agricultural substances. Therefore, many counties banned their usage in agriculture fields, but still they are used illegally in some places. At the same time it accumulated and renders them persistent in moistened agricultural soil as well as environmental and groundwater [4]. It may cause kidney  and liver damage to humans. It also causes irritation of the skin, eyes, throat, and associated parts with changes in the genetic material. 

The significance of pesticide residue analysis: In 1963, for the first time, P. A. Mills and his co-workers were developed a multi-residue analysis method for organochlorine insecticides [5]. But still the efficient pesticide residue analysis is an important task in the modern analytical chemistry and also for the regulatory European Community authorities that control maximum residue limit (MRL) [6].

Multiclass pesticide analysis has recently gained, considerable attention from researchers because of its more reliable and easy in terms of confirmation and identification. This technique is mainly based on mass spectrometry (MS) [7]. But in this technique has some limitation: Direct determination of trace level concentration of all pesticides including OCPs is complicated due to the low sensitivity of methods and matrix interference (matrix effect). Therefore, prior to quantitative determination of analytes, effective sample preparation and pre-concentration procedures are often required.

Previous reports are employed on pesticide residue analysis, and the QuEChERS sample preparation assay for fruits, vegetables are shown to improve sensitivity of determination [8]. It has become a popular technique in most laboratories around the world for sample preparations of various matrices such as fruits, cereals and vegetables on account of its low cost and availability, combined with its high efficiency.  In 2007, the QuEChERS procedure in combination with the dispersive Solid Phase Extraction (dSPE) method was considered to be one of the advance novel approaches (for sample preparation) was approved by the International Association of Official Analytical Chemists for the determination of multi pesticide residues in fruits and vegetables [9].

Fe3O4@Triton MNPs used as cleanup adsorbents for Pesticide Residue Analysis: Recently, N. G. Kobylinska, and his research team have developed a hydrophobic magnetic nanoparticles (MNPs) used as cleanup adsorbents for pesticide residue analysis in fruit, vegetable, and various soil samples. A cleanup procedure was based on their prepared hydrophobic magnetic nanoparticles for QuEChERS extraction followed by Gas Chromotography - Mass Spectroscopy (GC-MS) method for the simultaneous determination of various 16 organochlorine pesticides was developed [10].

The main motivation of their study is to use core−shell MNPs modified by hydrophobic Triton X-100 to analyze representative OCPs (16 intestacies) in a fruit (strawberry, avocado (as high oil matrix), watermelon and kiwi), vegetable (radish), and soil (agricultural, pesticide-enriched lab-made and urban) matrixes. They emphasize the point that hydrophobically modified MNPs constitute excellent, novel cleanup materials compared to traditional adsorbents (C18 and GCB, bare MNPs). The modified method was applied to determine OCPs in fruit, vegetable, and soil samples by a budget-conscious laboratory GC-MS system. A further aim is to determine the distribution between the selective pesticides and various matrices via simultaneous analysis of soil samples and the corresponding lab-grown vegetables. Comprehension of the distribution of OCP residues in soil is crucial for determining the transportability of these residues into water, non-target plants, organisms, and humans.

They prepared Fe3O4@Triton MNPs and used as adsorbent for the pesticide analysis and to certify the purification effect of the modified QuEChERS procedure, the developed magnetic adsorbent (Fe3O4@Triton) was compared with the commonly used adsorbents (C18, GCB, and bare MNPs) that supplement the cleanup step for the most complicated and critical extract (avocado). In this study they observed that Fe3O4@Triton could be effectively eliminate organic pigments from studied samples with good OCPs recovery. Thus, Fe3O4@Triton displayed a high affinity toward matrix impurities (including organic pigments) together with satisfactory recovery of multiple OCPs, including planar-ring pesticides in food samples.

Reusability of Fe3O4@Triton: Reusability is an important factor/parameter of good adsorbent for pesticide analysis. Because this multiple time utilization of adsorbent material does not causes any environmental issues. Therefore, the scientists have investigated the reusability of Fe3O4@Triton, the adsorbent was separated and washed with solvents to desorption of the impurities from its surface.

They mainly observed that the magnetic Fe3O4@Triton can be used as a suitable alternative adsorbent to C18/GCB/bare MNPs for the extract cleanup of various complex food or other matrices in QuEChERS procedure. Hence, it was used for further full validation studies.

Our SNB team recommended this research article to enrich our viewer’s knowledge to know about a very simple, fast, and effective procedure based on a modified QuEChERS extraction was elaborated for the determination of multiresidue OCPs in various (fruits, vegetables, and soil) by GC-MS determination. As they developed magnetic Fe3O4@Triton materials as an effective cleanup adsorbent in the extract purification of various matrices for the QuEChERS procedure as a potential alternative cleanup agent to commercial C18, GCB, and bare MNPs. This is a new novel approach regarding the utilization of magnetic core−shell  and  MNPs to remove matrix impurities based on switchable highly hydrophobic functional groups in the QuEChERS procedure. It also indicates the potential for the development of cleanup materials for determination of various pesticides in complex matrixes.

References

  1. A. Environ. Monit. Assess. 185, 497 (2013).
  2. D. Pimentel, J Agric Environ Ethics. 8,17 (1995).
  3. Veil JF. Public health impact of pesticides used in agriculture, Geneva, Switzerland. WHO (World Health Organization); 1990.
  4. E. Halfon, et al., Chemosphere 33, 1543 (1996).
  5. P. A. Mills, J. Assoc. Off. Agric. Chem. 46, 186 (1963).
  6. EU pesticides database, http://ec.europa.eu/sancopesticides/ public/index.cfm#.
  7. D. Tsipi, et al., Mass spectrometry for analysis of pesticide residues and their metabolites; Wiley: 2015.
  8. M. Anastassiades, et al., J. AOAC Int. 86, 412 (2003). M. Anastassiades, et al., J. Chromatogr A 1015, 163 (2003).
  9. S. J. Lehotay, et al., J. AOAC Int. 90, 485 (2007).
  10. T. S. Hubetska, et al., J. Agric. Food Chem. (2020) https://dx.doi.org/10.1021/acs.jafc.0c00601.

--- Dr. A. S. Ganeshraja

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