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European Journal of Applied Sciences – Vol. 12, No. 6

Publication Date: December 25, 2024

DOI:10.14738/aivp.126.17957.

Thangaraju, U., & Mathi, M. (2024). Detoxification of Triazophos Pesticide Residues in Foxtail Millets (Setaria Italica) Using Mid- Infrared Rays. European Journal of Applied Sciences, Vol - 12(6). 427-447.

Services for Science and Education – United Kingdom

Detoxification of Triazophos Pesticide Residues in Foxtail Millets

(Setaria Italica) Using Mid-Infrared Rays

Umakanthan Thangaraju

Veterinary Surgeon, Gokulam Annadhan Temple Complex,

Plot no.: 1684, Meenavilakku-Meenakshipuram Road,

Anaikaraipatty Post, Bodinayakanur Taluk, Theni Dt,

Tamil Nadu, India - 625582

Madhu Mathi

Veterinary claims expert, Allianz Services Private Limited,

Technopark, Trivandrum, Kerala – 695581, India

ABSTRACT

Pesticide residues in agricultural products are currently inevitable and pose

severe risks to human health and the environment. Present detoxification

technologies for residues are less effective, not eco-friendly, reduce sensory

attributes and nutrients of the agro products, and are uneconomical. To overcome

this challenge to a certain extent, we developed a 2-6 μm mid-infrared generating

atomizer, the mid-infrared was tried in the detoxification of pesticide viz.

Triazophos. MIRGA accommodates water-based imbalance ionic solution. MIRGA

spraying was performed externally over packaged (polythene >50 microns) foxtail

millet (Setaria italica) mixed with different concentrations (5 to 10,000 ppm - 13

batches) of the commonly used pesticide Triazophos. The foraging behavior of fire

ants was used as an indicator to evaluate triazophos toxicity. The foraging

property was more significant in MIRGA-irradiated millet samples containing 5,

10, 50, and 100 ppm needed with 1-3 sprayings, 500-1000 ppm needed 2-5

sprayings, 2000 ppm needed 3 sprayings, 3000 ppm needed 2-4 sprayings, and

6000 ppm needed 4 or 5 sprayings than in non-irradiated (control) samples. As a

result, we demonstrated the efficacy of 2–6 μm mid-IR detoxification. The 2-6 μm

mid-infrared radiation generated by MIRGA was able to pass through the

packaging material and interacted with the interior of foxtail millet. It was noted

that foxtail millets sprayed with MIRGA containing 5 to 3000 ppm and 6000 ppm

triazophos were eagerly consumed by ants. However, samples with 4000-5000

ppm and 7000-10,000 ppm were refused by the ants, while the blank control

samples were consumed. The process of detoxification was studied by a variety of

instrumentations and analytical investigations. The appearance of small peaks in

the chromatogram data indicated a change in the components of the sample,

resulting in the creation of new molecules that attracted ants more effectively.

Two specific compounds identified post-spraying were 9,12-octadecadienoic acid

(Z, Z) and 1-nonadecene, which explains the increased attractiveness of ants. The

mid-IR radiation emitted during spraying led to the breakdown of some

carbohydrates, releasing simpler sugars that are sweeter and naturally appealing

to ants. The sprayed sample showed a fivefold increase in oleic acid content

compared to the control sample, which may account for the reduced preference by

ants. Furthermore, spraying induced alterations in various components such as

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European Journal of Applied Sciences (EJAS) Vol. 12, Issue 6, December-2024

aliphatic protons, methyl groups, olefinic protons, and aromatic protons within

the samples. The application of MIRGA on foxtail millet containing triazophos

induced structural changes at the micron level, as evidenced by particle

agglomeration and the disappearance of elongated structures. The MIRGA

technology proves to be a safe, cost-efficient, and environmentally friendly

method. This outcome also hints at the potential of MIRGA in detoxifying residues

of other agricultural chemicals.

Keywords: MIRGA, 2-6 μm mid-IR, Foxtail millet, Pesticide residues, Triazophos,

Degradation, Economy, Ecofriendly, Safe.

INTRODUCTION

Global crop losses due to pests, including insects, pathogens, and weeds, are estimated to be

significant, with arthropods alone destroying 18-26% of annual crop production worldwide,

valued at over $470 billion [1, 2, 3]. In developing countries, where future population growth

is expected to be concentrated, losses are even higher, emphasizing the urgent need for

precise estimation of food loss and waste to develop sustainable pest management strategies

[2]. Crop pest infestations can have significant implications for food safety and security. Insect

pests in stored grains can lead to reductions in protein and lipid content, affecting the quality

of raw materials [4]. Thus, pesticides use plays a crucial role in combating pests to prevent

significant crop losses, despite the widespread concern over pesticide residues in food and

their potential adverse effects on human health.

Excessive use of pesticides, which remain as residues in agricultural products carries a

health risk. The residues cause nausea, headaches, chronic neuro and respiratory symptoms,

as well as cancer [5]. Children are more susceptible to such diseases [6, 7, 8]. Globally

estimated maximum residue levels (MRLs) in agro harvest are now high, especially in

developing countries where pesticides are used indiscriminately [9]. Pesticide contamination

of surface and groundwater can be substantial even in organic agriculture areas. Prime

importance should be given to the degradation/detoxification of residues. Traditionally

washing, peeling, drying, cooking, salting, and addition of chemicals were practiced. However,

it is well known that pesticide residues have a higher likelihood of persisting down the food

chain, affecting the environment and consumer health. Also, even during food processing,

residual pesticides are converted to more hazardous metabolic products than residues [10].

The impact of pesticides on human health is particularly concerning for vulnerable

populations like children, pregnant women, and the elderly, who are more sensitive to the

effects of these toxic substance. Therefore, while pesticides are essential for protecting crops

from pests, it is crucial to prioritize human health by promoting safer alternatives and proper

handling practices to minimize exposure and associated health risks. Currently, the scientific

methods used for pesticide detoxification are chlorine dioxide solution, chlorine dioxide gas

[11], electrical current and ultrasonication [12], electrolyzed water, chlorine dioxide,

photocatalyst [13], and photochemical methods [14]. Recently ozone treatment has been

relatively more advantageous than the other methods [10]. All these methods are not without

associated limitations which include loss of sensory attributes and nutrition [15, 16] and risk

[17]. As a result, there is an urgent need for more effective sustainable methods to

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Thangaraju, U., & Mathi, M. (2024). Detoxification of Triazophos Pesticide Residues in Foxtail Millets (Setaria Italica) Using Mid-Infrared Rays.

European Journal of Applied Sciences, Vol - 12(6). 427-447.

URL: http://dx.doi.org/10.14738/aivp.126.17957

degrade/detoxify pesticide residues to protect human health. As far as photodegradation is

concerned, irradiation with gamma rays, ultraviolet, pulsed electric field, and ultrasound are

used to degrade pesticide residues, but the ionizing nature poses a risk [10].

Although these methodologies offer a broad array of choices for the management of pesticide

residues, they possess inherent constraints in terms of sophistication, application at the field

level, operational intricacy, and cost implications. This necessitates a quest for more efficient

and secure alternatives to maintain the intricate balance between pest control methodologies

and the well-being of ecosystems. Hence, a balance approach that considers both the food

safety and ecosystem services is crucial for ensuring sustainable pest management in the

realm of agriculture. Consequently, we have opted for the utilization of the non-ionizing

infrared spectrum, a technique commonly employed in both traditional and contemporary

food processing practices. This type of radiation, constituting 66% of the solar radiation [18],

presents a safer avenue for exploration.

Mid-infrared is a specific wavelength in the infrared spectrum. The frequency of all living

entities, including humans, animals, and plants is in the mid-infrared range. The magnetic

frequency of all living entities, including agro products, humans, animals, and plants, is in the

mid-infrared spectrum. Mid-infrared radiation is biologically safe and can penetrate most

intervening media. To be short, the majority of earthly molecules' vibrational frequencies are

in the mid-infrared region [19]. And also, pesticides observe mid-infrared and cause changes

in the chemical bond.

The Foxtail millets were contaminated with varying concentrations of Triazophos ranging

from 5 to 10000 ppm. The MIRGA generated mid-infrared ray was applied over the pesticide

(Triazophos) contaminated foxtail millet for detoxification. The most common foraging

preference of trained ants was used as an indicator of pesticide residue detoxification. MIRGA

technology in found to be more advantageous than the existing methods (detailed in Result

and Discussion section).

Therefore, this study aimed to detoxify the pesticide residues present in agricultural products

by using mid-infrared radiation. The irradiation caused the chemical compound

transformation, was analyzed by liquid chromatography-mass spectrometry (LC-MS) and Gas

chromatography-mass spectrometry (GC‒MS). The chemical bond changes were determined

by Fourier transform infrared spectroscopy (FTIR), and Proton nuclear magnetic resonance

(NMR). The structural changes were analyzed by Powder X-ray diffraction (PXRD). The

particle configuration changes were detected by Transmission electron microscopy (TEM).

Overall, MIRGA technology, due to its effective, noninvasive nature and easy application,

showcases its broad applicability in industrial settings to detoxify pesticides residues in tons

and tons of agroproducts ensuring the consumers health and acceptance.

MATERIALS AND METHODS

Preparation of Samples

Triazophos (40% EC; Crop Chemical India Ltd.) was purchased from a local market.

Triazophos (O, O-diethyl-O-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate) is a broad- spectrum systemic insecticide and acaricide organophosphate compound that is extensively