Analysis Of Pesticides Research Articles

Molecularly imprinted polymers using high-performance liquid chromatography to detect and determine ethion pesticide in apricot, grapes, strawberry and soil samples

ABSTRACT This paper demonstrates the synthesis of molecularly imprinted polymers-solid phase extraction-liquid chromatography method at room temperature using bulk polymerisation of ethion pesticide, by high sensitivity, low costs and high stability. By making MIP for ethion as ethion-MIP, which could be detected with a UV-Vis spectrophotometer at 276 nm, a functional monomer of acrylic acid with cross-linking ethylene glycol dimethyl acrylate. The high-performance liquid chromatography methods developed in this study are accurate, sensitive, and precise to apricot, grapes, strawberry and soil samples. The elution process to the template ethion from the ethion-MIP, caused by minimum volume using solution of 1.0 mL of methanol-acetic acid (9:1) was obtained. Different factors affecting the reaction were studied and optimised. The calibration plot is linear in the concentration range of (0.02 to 1.0 µg mL−1). The relative standard deviations of (±2.0%) and detection limit of the method are 0.02 µg mL−1, and the maximum imprinting factor of ethion-MIP was 6.8 mgg−1. The results obtained the evidence of efficiency and reliability of the method for the ethion pesticide analysis and estimation for the capacitance of molecular imprinted polymer, analytical technical method by molecularly imprinted polymer and high-performance liquid chromatography.

Comparative Analysis of Organic and Chemical Pesticides: Impacts on Crop Health and Environmental Sustainability

Pesticides are indispensable tools in modern agriculture, aiding in the protection of crops against pests and diseases. Nevertheless, the adverse effects of chemical pesticides on human health and the environment have catalyzed a shift towards organic alternatives. This review critically assesses the use of both organic and chemical pesticides, evaluating their respective impacts on crop health and environmental sustainability. We delve into aspects such as efficiency, safety, environmental footprint, and regulatory frameworks surrounding these two types of pesticides, drawing insights from recent research. By synthesizing current knowledge, our aim is to provide a comprehensive understanding of the advantages and limitations of organic and chemical pesticides, empowering stakeholders to make informed decisions towards sustainable agricultural practices.

Simultaneous Analysis of 272 Pesticides in Agricultural Products by the QuEChERS Method and Gas Chromatography with Tandem Mass Spectrometry.

The aim of this study is to develop a rapid and accurate method for simultaneous analysis of multi-residue pesticides and conduct pesticide monitoring in agricultural products produced by the production and distribution stage in Korea. The representative agricultural products were selected as brown rice, soybean, potato, mandarin, and green pepper and developed using gas chromatography with tandem mass (GC-MS/MS) for the analysis of 272 pesticide residues. The experimental samples were extracted by the QuEChERS-EN method and then cleaned up by using d-SPE, including MgSO4 and primary secondary amine (PSA) sorbents. The established method was validated in accordance with Codex CAC-GL/40, and the limit of quantitation (LOQ) was determined to be 0.01 mg/kg. A total of 243 pesticides satisfied the guidelines in five samples at three levels with values of 60 to 120% (recovery) and ≤45% (coefficient of variation, CV). The remaining 29 pesticides did not satisfy the guidelines, and these pesticides are expected to be used as a screening method for the routine inspection of agricultural products. As a result of analyzing 223 agricultural products in South Korea by applying the simultaneous analysis method, none of the detected levels in the samples exceeded the standard values based on maximum residue limits (MRLs). The developed method in this study will be used to inspect residual pesticides in agricultural products, and it is anticipated to contribute to the distribution of safe agricultural products to consumers.

Analyzing the impact of pesticides on the indus river: contamination levels in water, sediment, fish, and associated human health risks.

Pesticides are frequently used to protect crop yields and manage malaria vectors; however, their inadvertent transport into aquatic habitats poses a significant concern. Various anthropogenic activities influence the Indus River in Pakistan. This study aimed to assess the presence of eight pesticide residues at three different sites (Kalabagh, Kundian, and Chashma) in water, sediment, and the fish species (Labeo rohita) during both dry and wet seasons to measure the intensity of this pressure. Pesticide analysis was carried out using gas chromatography equipped with an electron capture detector. The results revealed the highest concentrations of pesticides during both dry and wet seasons at all sites, measuring 0.83 and 0.62μg/l (water), 12.37 and 9.20μg/g/dw (sediment), and 14.27 and 11.29μg/g/ww (L. rohita), respectively. Overall, pesticide concentrations were higher in the dry season than in the wet season across all study sites. Based on detection frequency and concentration in both seasons at all sites, dominant pesticides included cypermethrin and carbofuran (in water), as well as endosulfan and cypermethrin (in sediment and fish tissue). Levels of endosulfan and cypermethrin exceeded standard limits. Moreover, principal component analysis (PCA) indicated no correlation among pesticides in fish tissue, sediment, and water. However, pesticides exhibited different behavior in different seasons. Furthermore, endosulfan and triazophos impose great human health risk, as indicated by the THQ value (> 1). The overall HI value was greater for site 1 in the dry season (8.378). The study concluded that the presence of agricultural pesticides in the Indus River poses a risk to aquatic life and has the potential to disrupt the entire food chain. This highlights the importance of sustainable practices for the study area and Pakistan overall agricultural and environmental sustainability. It is further recommended to strengthen regulations for reduced pesticide use and promote eco-friendly pest management.

Ultrasonic-induced grafted lanthanum sulfide decorated multi-walled carbon nanotube onto bacterial cellulose applied for adsorption of pesticides in environmental waters

A new biosorbent was fabricated by modification of bacterial cellulose biopolymer grafted with lanthanum sulfide decorated carboxylated multiwall carbon nanotube (La2S3@MWCNT@BC). The sorbent was employed in a green alternative dispersive-solid phase extraction of a variety of 14 pesticides in environmental water samples. The analyses were performed using GC-µECD. The properties and structure of La2S3@MWCNT@BC nanocomposite were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and adsorption-desorption isotherms. The composition of the sorbent was also investigated to evaluate the adsorptive properties of its constituents. The impact of various parameters influencing extraction efficacies such as sorbent dose, adsorption time, sample pH, ionic strength, and desorption conditions was investigated. The method was validated by specificity, matrix effect% (-0.4 to -7.4), enrichment factor (4-10), limits of quantification (0.007–0.31 μg L−1), matrix-matched calibration linearity (0.01-200 µg L−1), determination coefficients (r2=0.9921-0.9998), and precision. The optimized method was applied for the analysis of multiclass pesticides in seven environmental and drinking waters and the recoveries were obtained in the 81-108 % range with RSDs of 2.5-4.7%. This paper is the first report on the synthesis and use of La2S3@MWCNT@BC nanocomposite to extract pesticides from different water samples. The greenness of the procedure was evaluated by the AGREE protocols.

Integrating transformer-based machine learning with SERS technology for the analysis of hazardous pesticides in spinach

This study introduces an innovative strategy for the rapid and accurate identification of pesticide residues in agricultural products by combining surface-enhanced Raman spectroscopy (SERS) with a state-of-the-art transformer model, termed SERSFormer. Gold-silver core-shell nanoparticles were synthesized and served as high-performance SERS substrates, which possess well-defined structures, uniform dispersion, and a core-shell composition with an average diameter of 21.44 ± 4.02nm, as characterized by TEM-EDS. SERSFormer employs sophisticated, task-specific data processing techniques and CNN embedders, powered by an architecture features weight-shared multi-head self-attention transformer encoder layers. The SERSFormer model demonstrated exceptional proficiency in qualitative analysis, successfully classifying six categories, including five pesticides (coumaphos, oxamyl, carbophenothion, thiabendazole, and phosmet) and a control group of spinach data, with 98.4% accuracy. For quantitative analysis, the model accurately predicted pesticide concentrations with a mean absolute error of 0.966, a mean squared error of 1.826, and an R2 score of 0.849. This novel approach, which combines SERS with machine learning and is supported by robust transformer models, showcases the potential for real-time pesticide detection to improve food safety in the agricultural and food industries.

Post-synthetic modification of covalent organic framework for efficient adsorption of organochlorine pesticides from cattle's milk

Analysis of organochlorine pesticides (OCPs) residues in milk faces a significant challenge. Herein, a sea urchin structured covalent organic framework bearing boric acid groups named COF-B(OH)2 was synthesized and applied as a coating material for solid-phase microextraction (SPME) of the OCPs in cattle’s milk. Its performance was superior to that of three commonly used commercial SPME fibers, which could be due to the coexistence of hydrogen bonding, halogen bonding, π-stacking and electrostatic interactions. Besides, the fiber coating displayed good stability and reusability. After optimization, a COF-B(OH)2 based SPME coupled with gas chromatography-electron capture detection was established for the sensitive detection of the OCPs from milk samples. The limits of detection (S/N = 3) were between 0.04 and 1.0 μg kg−1. Satisfactory accuracy was achieved with the method recoveries in the range of 87.5 % to 112.5 %. These results manifest the feasibility of the COF-B(OH)2 coated fiber for the enrichment of the trace OCPs from milk samples.

Isotopic, mycotoxin, and pesticide analysis for organic authentication along the production chain of wheat-derived products

Wheat-based products are staples in diets worldwide. Organic food frauds continuously threaten consumer trust in the agri-food system. A multi-method approach was applied for organic authentication and safety assessment along the production chain of pasta and bakery products. Bulk and compound-specific (CS) stable isotope ratio mass spectrometry (IRMS) suggested the δ15Nbulk, δ15Nleucine and δ15Nproline as promising organic markers, with CS able to distinguish between pairs which bulk analysis could not. Processing significantly affected the δ15Nleucine, δ13Cproline and δ13Cleucine. Multi-mycotoxin analysis (HT-2, T-2, DON, ZEN, OTA, AFB1) showed higher contamination in conventional than organic samples, while both milling and baking/drying significantly reduced mycotoxin content. Lastly, from the analysis of 400 residues, isopyrazam was present at the highest concentration (0.12 mg/kg) in conventional wheat, exhibiting a 0.12 processing factor (PF), while tebuconazole levels remained unchanged in pasta production (90 °C) but reduced below LOQ in biscuits and crackers (180–250 °C).

Facile synthesis of magnetic layered double hydroxide/metal–organic framework MIL-100(Fe) for simultaneous extraction and enantiomeric determination of three chiral triazole fungicides in water and juice samples

For the first time, magnetic layered double hydroxide/metal–organic framework (Fe3O4@CuZnAl-LDH@MIL-100(Fe)) was successfully fabricated and applied for enrichment of triazole fungicides from water and juice samples prior to chiral HPLC-UV analysis. Several key parameters influencing the extraction efficiency including extraction time, desorption time, sample solution pH, the ionic strength of sample solution, adsorbent amount, desorption volume, desorption solvent and sample volume were investigated by Plackett-Burman design and Box-Behnken design. Under the optimum conditions, the limit of detections (LODs) and limit of quantifications (LOQs) were in the ranges of 0.35 to 1.20 μg L−1 and from 1.00 to 3.80 μg L−1, respectively. The average spiked recoveries and enrichment factors ranged from 86.28-98.22 % and 21.6–23.8, respectively. The linearity was in the range of (5–1000 μg L−1) with satisfactory correlation coefficients (R2) values (0.9987–0.9999) and a good precision (RSDs ≤ 5.74 %). Moreover, the computational simulation was first employed to analyze adsorption properties of MIL-100(Fe) against triazole fungicides. This work provides a promising method for trace chiral pesticide analysis in aqueous samples.

Perennial Baki™ Bean Safety for Human Consumption: Evidence from an Analysis of Heavy Metals, Folate, Canavanine, Mycotoxins, Microorganisms and Pesticides.

Global food production relies on annual grain crops. The reliability and productivity of these crops are threatened by adaptations to climate change and unsustainable rates of soil loss associated with their cultivation. Perennial grain crops, which do not require planting every year, have been proposed as a transformative solution to these challenges. Perennial grain crops typically rely on wild species as direct domesticates or as sources of perenniality in hybridization with annual grains. Onobrychis spp. (sainfoins) are a genus of perennial legumes domesticated as ancient forages. Baki™ bean is the tradename for pulses derived from sainfoins, with ongoing domestication underway to extend demonstrated benefits to sustainable agriculture. This study contributes to a growing body of evidence characterizing the nutritional quality of Baki™ bean. Through two studies, we investigated the safety of Baki™ bean for human consumption. We quantified heavy metals, folate, and canavanine for samples from commercial seed producers, and we quantified levels of mycotoxins, microorganisms, and pesticides in samples from a single year and seed producer, representing different varieties and production locations. The investigated analytes were not detectable or occurred at levels that do not pose a significant safety risk. Overall, this study supports the safety of Baki™ bean for human consumption as a novel pulse crop.

Spherical fluorinated covalent organic polymer for highly efficient and selective extraction of fipronil and its metabolites in soil

Covalent organic polymers (COPs) have garnered considerable attention as promising adsorbents of online solid phase extraction (online SPE). Morphology modulation provides an appealing solution to enhance adsorption efficiency and reduce back-pressure in the absorbent. However, the synthesis of COPs with regular geometric shapes and specific adsorption selectivity remains challenging. In this study, a uniform spherical fluorinated COP (F-sCOP, average diameter: 2.14 μm) was successfully synthesized by Schiff base reaction of 1,3,5-triformylphoroglucinol (TP) and 2,2’-bis(trifluoromethyl)benzidine (TFMB). The F-sCOP had a large surface area (BET: 346.2 m2 g−1), remarkable enrichment capacity (enrichment factors: 186–782), high selectivity toward fipronil and its metabolites (adsorption efficiency >93.1%), and admirable service life (>60 times). Based on the adsorbent, a novel μ-matrix cartridge extraction-online-μ-solid phase extraction-high performance liquid chromatography-mass spectrometry (μ-MCE-online-μ-SPE-HPLC-MS) method was constructed and used to track trace fipronil and its metabolites in soil. The proposed method exhibited a wide linear range (0.05–1000 ng g−1), low quantitation limits (LOQs: 0.0027–0.011 ng g−1), high recoveries (90.1–119.6%) and good repeatability (RSD ≤10.5%, n = 3) for fipronil analysis. This study paves the way for pesticide analysis in soil risk assessment.

Application of silanized melamine sponges in matrix purification for rapid analysis of multiple pesticides and veterinary drugs in honey by UPLC-MS/MS

Application of silanized melamine sponges in matrix purification for rapid analysis of multiple pesticides and veterinary drugs in honey by UPLC-MS/MS

Analysis of carbamate and organophosphorus pesticide in agricultural irrigation water by Liquid Chromatography - Mass Spectrometry

So far, the ultra-trace concentration of pesticide residues in environmental samples has challenged many analytical techniques, which are used to detect simultaneously organophosphorus and carbamate with various polarities. In this study, the OASIS-HLB column was modified by the reagent 1,8-Dihydroxy-2-(4-sulfophenylazo)naphthalene-3,6-disulfonic to enhance the retention of polar pesticides. Both real irrigation water and distilled water samples were applied to validate the determination method of ten carbamates and thirty-eight organophosphorus pesticides all together using LC-MS. According to the results, the linear interval of the method ranged from 1.0 to 100 µg/L, the detection limit was as low as 5.0 µg/L, the relative standard deviations presented less than 8.0%, and the recoveries were ranging between 60% and 112%. Moreover, in the irrigation water samples which were collected in both dry and rainy seasons in ten stations around the agricultural area, five compounds were found, including fenamiphos, terbufos, aldicarb, propoxur, and methiocarb. In the midst of those sampling areas, the Environmental Impact Quotient Field Use Rating of detected pesticide residues presented a high value - 272 at one station, which indicates a high risk for the surrounding environment as well as the local people’s health.

Application of solid-phase extraction materials from ion liquids for the analysis of carbamate pesticide

In this study, ionic liquid immobilised onto silica gel material SiO2-(CH2)3-N(Oct)3Br was successfully synthesised and characterised by Fourier-transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). This material was applied as the stationary phase of solid-phase extraction for the enrichment of trace amounts of carbamate pesticides in water. The cartridge was eluted with 5 ml of acetonitrile (ACN), blow-dried with nitrogen gas, and re-dissolved in ACN:H2O (40:60, v/v) and analysed by high-performance liquid chromatography - ultraviolet (HPLC-UV) at 210 and 245 nm. Within this process, elution of the cartridge with 5 ml of acetonitrile (ACN) was followed by nitrogen gas blow-drying and subsequent re-dissolution in ACN:H2O (40:60, v/v), culminating in analysis by HPLC-UV at 210 and 245 nm. Optimisation of conditions facilitated the analysis of carbamate pesticides, with the limit of quantitation (LOQ)ranging from 0.36-2.00 μg/l for tap water and 0.4-3.5 μg/l for river water. Furthermore, the method exhibited favourable repeatability, with a relative standard deviation (RSD) of less than 10%, thereby meeting the Association of Official Analytical Collaboration (AOAC) standards.

A faster and more accessible method for the analysis of acephate and methamidophos in water samples by LC-MS/MS

ABSTRACT Pesticide pollution on environmental matrices has attracted increasing attention worldwide. Pesticide runoff from agricultural crops into surface waters may impact ecosystems and human health through drinking water consumption in pesticide-polluted areas. This study aims to develop and validate a simpler, faster, and more accessible methodology for the analysis of organophosphate pesticides, such as acephate and methamidophos, using HPLC-ESI-MS (QqQ). Acephate and methamidophos are two of the most common and efficient systemic pesticides in the organophosphate family, known for their high effectiveness against insects and pests. Firstly, different extractions were tested: liquid-liquid extraction (LLE), low-temperature partitioning extraction (LTPE) and solid-phase extraction (SPE) with a usual and accessible cartridge, C18. LLE and LTPE showed low sensitivities, probably because acephate and methamidophos are extremely hydrophilic compounds, like many organophosphorus pesticides. Thus, they have low interaction with the extractor solvent, resulting in low extraction rates. SPE with C18 cartridge led to the best extraction of acephate and methamidophos in water matrices and was chosen for the validated process. The selected method ensured acceptable recoveries, within the same range found in the scientific literature (9–49%) and within relative standard deviations below 20%. However, future efforts regarding other types of cartridges are encouraged. The limit of detection (LOD) and limit of quantification (LOQ) of the analytical method were 0.02 and 0.05 μg/L for acephate and methamidophos, values lower than those reported in the scientific literature. The developed method was used to quantify the levels of such organophosphate pesticides in samples from Brazilian surface water and none of the target pesticides were detected in these aquatic matrices.

Qualitative and quantitative analysis of pesticide isomers based on collision-induced dissociation of high-resolution mass spectrometry

Pesticide isomers are widely present in agricultural production, while their biological activity, efficacy, and toxicity may vary significantly. Due to structural similarity, chromatographic and mass spectrometric analysis of isomeric pesticides are challenging. In this experiment, representative isomeric pesticides with great differences in toxicity and maximum residue limits among countries were studied. Based on collision-induced dissociation (CID) of high-resolution mass spectrometry, the fragmentation pathways of substituent position isomer, functional group position isomer, carbon frame isomer, functional group isomer, and cis–trans isomer were analyzed to attribute fragment ions. In addition, for the isomers with the same product ions and different abundance ratios, the abundance differences at different energy-resolved mass spectrometry were analyzed, which was combined with the computational chemical density functional theory to simulate the specific process of fragmentation and to explain the reasons for the differences in fragment ions and abundance ratios. Based on the above study, a high-resolution mass spectrometry method was established for the separation and analysis of pesticide isomers. Twelve pesticide isomers were distinguished by retention time, fragment ions, and relative abundance ratio. This method was applied to the detection of real fruit and vegetable samples.

Design of a Novel Green Algae‐Based Biological Photovoltaic Cell with High Photocurrent and a Photoelectrochemical Biosensing Approach Utilizing the BPV for Pesticide Analysis in Water

AbstractIn this research, a green alga (Paulschulziapseudovolvox sp.) based biological photovoltaic cell (BPV) was designed. This clean energy‐friendly BPV produced photocurrent as a result of illuminating the photoanode and cathode electrodes immersed in the aqueous medium with solar energy. For this purpose, both electrodes were first coated with conductive polymers with aniline functional groups on gold electrodes. In the cell, the photoanode was first coated with a gold‐modified poly 4‐(2,5‐di(thiophen‐2‐yl)‐1H‐pyrrol‐1‐yl)benzamine polymer, (P(SNS‐NH2)). Cytochrome C (Cyt. C) material was used to provide crosslink formation with bis‐aniline covalent bonds with the conductive polymer using electrochemical techniques. Paulschulziapseudovolvox sp., one of the green algae that can convert light energy into chemical energy, is attached to this layered electrode surface. The cathode of the cell is attached to the gold electrode surface with poly 4‐(4HDithieno[3,2‐b : 2′,3′‐d]pyrrole‐4‐yl)aniline (P(DTP‐Aryl‐Amine)). Then, the bilirubin oxidase enzyme was immobilized on this film surface with glutaraldehyde activation. This cell, which can use light thanks to green algae, oxidizes and splits water, and oxygen is obtained at the photoanode electrode. At the cathode electrode, the oxygen gas is reduced to water by the bio‐electro‐catalytic method. To obtain high photocurrent from the BPV, necessary electrochemical and chemical optimizations were made during the design of the system to increase the amount of electrons that were transferred and fasten its transfer rate. While the photocurrent value generated by the designed BPV in optimum conditions and in the pseudo‐steady state is 10 mA/m2, the maximum power value obtained is 46.5 mW/m2. In addition to the production of the green algae‐based BPV generating highly efficient electricity which is the main of target of this study, some studies have also been carried out to show whether this system can be used as a pesticide biosensor. Atrazine and diuron biosensing via the BPV system was analytically characterized and recovery and interference studies related to pesticide biosensor property of the BPV were also investigated.

Risk mitigation strategy and mechanism analysis of neonicotinoid pesticides on earthworms

Neonicotinoid insecticides (NNIs) are a new class of widely used insecticides with certain risks to non-target organisms, like earthworms. The gray correlation method was used to calculate the comprehensive risk effect value of acute toxicity (LC50) and bioaccumulation (logKow) of NNIs on earthworms. A comprehensive effects three-dimensional quantitative structure–activity relationship (3D-QSAR) model was constructed, using NNIs molecular structures and the comprehensive effect value as the independent and dependent variables, respectively. One of the representatives guadipyr (GUA) was selected as the template molecule for the molecular design and modification. A total of 63 NNIs alternatives were designed with a reduced comprehensive value higher than 10%, and as high as 42%. After screening, 15 NNIs alternatives were screened with decreased acute toxicity to earthworms, bioaccumulation effects and improved functional property. The calculated primary acute risk quotient of earthworms shows that the designed NNIs alternatives have lower earthworm risks (reduction of 70.48–99.99%). Results also found that the electronic, geometric and topological parameters of NNIs are the key descriptors that affect NNIs alternatives' toxicity. The number of hydrophobic interaction amino acid residues in NNIs molecules also contributes to the acute toxicity and the bioaccumulation of NNIs alternatives on earthworms. This study aims to design and screen functionally improved and environmentally friendly NNIs alternatives that have low risk to earthworms and provide theoretical methods and new ideas for the risk control and development of pesticides represented by NNIs.

METHOD OF SUBSTANDARD PESTICIDES UTILIZATION

The article is devoted to topical issues of utilization of unusable pesticides buried and stored in toxic waste landfills on the territory of the Russian Federation.Aim and objectives are analysis of sub-standard pesticides handling in the Russian Federation and development of a method of their utilization to obtain components for chemical production.The materials for the study were unusable pesticides.The sources of information were official documents containing analytical information on the quality of the natural environment (Annual State Reports on the State of the Natural Envi-ronment in the Subjects of the Russian Federation) and generalized results of thesurvey of Russian soils for the content of pesticide residues in them (Yearbooks «State of Pesticide Contamination of Natural Environmental Objects of the Russian Federation»).The paper analyzes the amount of unusable pesticides currently stored in the Russian Federation on the basis of official data.The qualitative composition of pesticides requiring utilization and stored in warehouses and landfills of the Russian Federation is considered.The principal scheme of utilization of unusable pesticides with obtaining components for chemical production, which can be used as secondary raw materials, is proposed.

Multiresidue Pesticide Analysis in Onion Using GC-MS/MS Using Modified QuEChERS Method with Zirconium Oxide Nanoparticle

Multiresidue Pesticide Analysis in Onion Using GC-MS/MS Using Modified QuEChERS Method with Zirconium Oxide Nanoparticle