Pesticides In Agricultural Products Research Articles

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.

CdTe@ZnS quantum dots for rapid detection of organophosphorus pesticide in agricultural products

Organophosphorus pesticides (OPPs) constitute the most widely employed class of pesticides. However, the prevalent use of OPPs, while advantageous, raises concerns due to their toxicity, posing serious threats to food safety. Chemical sensors utilizing quantum dots (QDs) demonstrate promising applications in rapidly detecting OPPs residues, thereby facilitating efficient inspection of agricultural products. In this study, we employ an aqueous synthesis approach to prepare low toxic CdTe@ZnS QDs with stable fluorescence properties. To mitigate the risk of imprecise measurements stemming from the inherent susceptibility of fluorescence to quenching, we have adopted the principle of fluorescence resonance energy transfer (FRET) for the construction of the turn-on quantum dot sensor. With a detection limit for chlorpyrifos as low as 10 ppb (10 μg/L), the QDs sensor exhibits notable resistance to interference from various pesticides. Application of this system to detect organophosphorothioate pesticides in apples produced results consistent with those obtained from high-performance liquid chromatography (HPLC) detection, affirming the promising application prospects of this sensing system for the rapid detection of OPPs residues.

Fabrication of a label-free electrochemical immunosensor by functionalized nanofiber membrane for the ultrasensitive detection of quinalphos

The accumulation of quinalphos pesticide in agricultural products have detrimental effects to human body and environment, hence, an efficient and sensitive detection approach is desirable. In this study, a label-free electrochemical immunosensor based on the directly immobilizing nanobody onto functionalized polyvinyl alcohol/gelatin-gold nanoparticles nanofiber membrane (PVA/G-AuNPs NFM) was fabricated. First, a homogeneous PVA/G-AuNPs NFM with multiple-porosity structure and appropriate hydrophilicity was prepared. Then, the electrochemical immunosensor was assembled and under the optimized conditions, the prepared biosensor exhibited good detection performance towards quinalphos with the linear range and limit of detection being 0.06–1000 ng/mL and 50.74 pg/mL (S/N = 3), respectively. Moreover, the sensor presented good specificity, regenerability and stability, maintaining more than 90% activity after 5 times of regeneration and about 90% activity after 6 weeks of storage. Finally, the average recoveries of quinalphos from food samples were 89.68%–110.88% with the coefficient of variation being 1.65%–7.81%, showing good correlation with UPLC-MS/MS (R2 = 0.9859), indicating the accuracy of the proposed electrochemical immunosensor assay. Overall, the label-free electrochemical immunosensor presents a novel approach for the rapid and sensitive detection of quinalphos and other pesticide residues.

MiR-2b-3p Downregulated PxTrypsin-9 Expression in the Larval Midgut to Decrease Cry1Ac Susceptibility of the Diamondback Moth, Plutella xylostella (L.).

Crystal (Cry) toxins, produced by Bacillus thuringiensis, are widely used as effective biological pesticides in agricultural production. However, insects always quickly evolve adaptations against Cry toxins within a few generations. In this study, we focused on the Cry1Ac protoxin activated by protease. Our results identified PxTrypsin-9 as a trypsin gene that plays a key role in Cry1Ac virulence in Plutella xylostella larvae. In addition, P. xylostella miR-2b-3p, a member of the micoRNA-2 (miR-2) family, was significantly upregulated by Cry1Ac protoxin and targeted to PxTrypsin-9 downregulated its expression. The mRNA level of PxTrypsin-9, regulated by miR-2b-3p, revealed an increased tolerance of P. xylostella larvae to Cry1Ac at the post-transcriptional level. Considering that miR-2b and trypsin genes are widely distributed in various pest species, our study provides the basis for further investigation of the roles of miRNAs in the regulation of the resistance to Cry1Ac and other insecticides.

Smart controlled-release nanopesticides based on metal‒organic frameworks

The practical utilization rates of conventional pesticide formulations by target organiams are very low, which results in the pollution of ecological environments and the residue of pesticides in agricultural products....

A Safety Survey for Residual Pesticides in Agricultural Products in Meal-kits

A Safety Survey for Residual Pesticides in Agricultural Products in Meal-kits

Exploring Various Photochemical Processes in Optical Sensing of Pesticides by Luminescent Nanomaterials: A Concise Discussion on Challenges and Recent Advancements.

Food safety is a burning global issue in this present era. The prevalence of harmful food additives and contaminants in everyday food is a significant cause for concern as they can adversely affect human health. More particularly, among the different food contaminants, the use of excessive pesticides in agricultural products is severely hazardous. So, the optical detection of residual pesticides is an effective strategy to counter the hazardous effect and ensure food safety. In this perspective, nanomaterials have played a leading role in defending the open threat against food safety instigated by the reckless use of pesticides. Now, nanomaterial-based optical detection of pesticides has reached full pace and needs an inclusive discussion. This Review covers the advancement of photoprocess-based optical detection of pesticides categorically using nanomaterials. Here, we have thoroughly dissected the photoprocesses (aggregation and aggregation-induced emission (AIE), charge transfer and intramolecular charge transfer (ICT), electron transfer and photoinduced electron transfer (PET), fluorescence resonance energy transfer (FRET), hydrogen bonding, and inner filter effect) and categorically demarcated their significant role in the optical detection of pesticides by luminescent nanomaterials over the last few years.

Rapid detection of residual chlorpyrifos and pyrimethanil on fruit surface by surface-enhanced Raman spectroscopy integrated with deep learning approach

Chlorpyrifos and pyrimethanil are widely used insecticides/fungicides in agriculture. The residual pesticides/fungicides remaining in fruits and vegetables may do harm to human health if they are taken without notice by the customers. Therefore, it is important to develop methods and tools for the rapid detection of pesticides/fungicides in fruits and vegetables, which are highly demanded in the current markets. Surface-enhanced Raman spectroscopy (SERS) can achieve trace chemical detection, while it is still a challenge to apply SERS for the detection and identification of mixed pesticides/fungicides. In this work, we tried to combine SERS technique and deep learning spectral analysis for the determination of mixed chlorpyrifos and pyrimethanil on the surface of fruits including apples and strawberries. Especially, the multi-channel convolutional neural networks-gate recurrent unit (MC-CNN-GRU) classification model was used to extract sequence and spatial information in the spectra, so that the accuracy of the optimized classification model could reach 99% even when the mixture ratio of pesticide/fungicide varied considerably. This work therefore demonstrates an effective application of using SERS combined deep learning approach in the rapid detection and identification of different mixed pesticides in agricultural products.

Evolving community structure in the international pesticide trade networks

The statistical properties of the international trade networks of all commodities as a whole have been extensively studied. However, the international trade networks of individual commodities often behave differently. Due to the importance of pesticides in agricultural production and food security, we investigated the evolving community structure in the international pesticide trade networks (iPTNs) of five categories from 2007 to 2018. We reveal that the community structures in the undirected and directed iPTNs exhibit regional patterns. However, the regional patterns are very different for undirected and directed networks and for different categories of pesticides. Moreover, the community structure is more stable in the directed iPTNs than in the undirected iPTNs. We also extract the intrinsic community blocks for the directed international trade networks of each pesticide category. It is found that the largest intrinsic community block is the most stable, appears in every pesticide category, and contains important economies (Belgium, Germany, Spain, France, the United Kingdom, Italy, the Netherlands, and Portugal) in Europe. Other important and stable intrinsic community blocks are Canada and the United States in North America, Argentina and Brazil in South America, and Australia and New Zealand in Oceania. These results suggest that, in the international trade of pesticides, geographic distance and the complementarity of important and adjacent economies are significant factors.

Impacts of Agricultural Pesticide Contamination: An Integrated Risk Assessment of Rural Communities of Eswatini.

Marked reductions in mean annual rainfall associated with climate change in Eswatini in Southern Africa have encouraged the recycling of irrigation water and the increased use of pesticides in agricultural production, raising concerns about potential ecological and health risks due to long-term exposure to pesticide residues in soil and irrigation water. This probabilistic integrated risk assessment used liquid chromatography with tandem mass spectrometry to analyze the concentrations of four commonly used agricultural pesticides (ametryn, atrazine, pendimethalin, and 2,4-dichlorophenoxyacetic acid (2,4-D)) in irrigation water and topsoil samples from farmlands in Eswatini to assess potential ecological and health risks due to exposure. The concentrations of these pesticides ranged from undetectable to 0.104 µg/L in irrigation water and from undetectable to 2.70 µg/g in soil. The probabilistic multi-pathway and multi-route risk assessments conducted revealed hazard indices exceeding 1.0 for all age groups for ametryn and atrazine, suggesting that the daily consumption of recycled irrigation water and produce from the fields in this area may pose considerable health risks. The indices pertaining to ecological risks had values less than 0.1. Adaptation measures are recommended to efficiently manage pesticide use in agriculture, and further research will ensure that agriculture can adapt to climate change and that the general public and ecosystem are protected.

Different sized gold nanoparticles for array-based sensing of pesticides and its application for strawberry pollution monitoring

The use of pesticides plays an essential role in improving crop quality and yield, however, it causes air, water, and soil pollution and the residue of these pesticides in agricultural products threatens the ecosystem and human life. Therefore, it is highly desirable to develop rapid, simple, and cost-effective methods for regular monitoring of pesticide residues in agricultural products especially strawberry that is consumed fresh and unpeeled. In this study, gold nanoparticles (AuNPs) of varying sizes have been exploited as sensing units to design a non-enzymatic colorimetric sensor array for the detection and discrimination of various pesticides including; bifenazate (BF), paraquat (PQ), diazinon (DZ), thiometon (TM), and carbendazim (CD) and chlorpyrifos (CP). Because of their strong size- and environmentally-dependent properties, AuNPs with different sizes produced distinguished plasmonic patterns in the presence of pesticides at a vast range of concentrations (25–800 ng mL−1). Plasmonic patterns of sensor units have been analyzed by various data visualization (bar plots and heat maps) and pattern recognition methods (linear discriminant analysis (LDA)). The multivariate calibrations showed linear responses ranging from 50 to 800 ng mL−1 for carbendazim, chlorpyrifos, paraquat, and bifenazate and 25–800 ng mL−1 for diazinon and thiometon. The limit of detection (LOD) was calculated to be 17.7, 22.8, 22.4, 9.7, 7.4, and 23.8 ng mL−1 for carbendazim, chlorpyrifos, paraquat, diazinon, thiometon, and bifenazate respectively. Finally, the applicability of the designed sensor was evaluated in real samples comprising tap water, well water, soil, and fruit, leave, drainage water, and culture substrate of strawberry.

Chitosan-thymol nanoparticle with pH responsiveness as a potential intelligent botanical fungicide against Botrytis cinerea

The practical application of essential oils (EOs) as an alternative for synthetic pesticides in agricultural production is severely limited because of their instability, high volatility, and water insolubility. Nanoencapsulation of EOs is an important strategy to overcome these limitations. In view of this, this study aimed to develop chitosan-thymol nanoparticle (NCS-Thy) with pH-responsive which can be used as an intelligent botanical fungicide to control Botrytis cinerea. The NCS-Thy nanoparticle was prepared by ionic crosslinking method with the loading capacity and encapsulation efficiency of 29.87% and 41.92%, respectively. The synthesized NCS-Thy nanoparticle was further characterized by Fourier transform infrared spectroscopy analysis, transmission electron microscopy observation, and dynamic lights scattering. The results of release kinetics and antifungal activity of NCS-Thy under different pH conditions were determined. The results showed that the NCS-Thy nanoparticle had excellent pH-responsiveness and can release more thymol under acidic conditions formed by B. cinerea, thereby achieving higher antifungal effects. Therefore, compared with unencapsulated thymol, the NCS-Thy nanoparticle had higher antifungal activity against B. cinerea in vitro. In addition, both the protective and curative efficacies of detached leaf test and pot experiment were significantly higher than those of unencapsulated thymol. Among them, the protective efficacy of NCS-Thy in the pot experiment was 78.73%, which was significantly higher than that of unencapsulated thymol with 61.13%. Therefore, the pH-responsive chitosan-thymol nano-preparation had a promising prospect of application in practical management of gray mold as an intelligent botanical fungicide.

Effect of chlorpyrifos on freshwater microbial community and metabolic capacity of zebrafish

Chlorpyrifos is a widely used organophosphorus insecticide because of its high efficiency and overall effectiveness, and it is commonly detected in aquatic ecosystems. However, at present, the impact of chlorpyrifos on the aquatic micro-ecological environment is still poorly understood. Here, we established aquatic microcosm systems treated with 0.2 and 2.0 µg/L chlorpyrifos, and employed omics biotechnology, including metagenomics and 16S rRNA gene sequencing, to investigate the effect of chlorpyrifos on the composition and functional potential of the aquatic and zebrafish intestinal microbiomes after 7 d and 14 d chlorpyrifos treatment. After 14 d chlorpyrifos treatment, the aquatic microbial community was adversely affected in terms of its composition, structure, and stability, while its diversity showed only a slight impact. Most functions, especially capacities for environmental information processing and metabolism, were destroyed by chlorpyrifos treatment for 14 d. We observed that chlorpyrifos increased the number of risky antibiotic resistance genes and aggravated the growth of human pathogens. Although no clear effects on the structure of the zebrafish intestinal microbial community were observed, chlorpyrifos treatment did alter the metabolic capacity of the zebrafish. Our study highlights the ecological risk of chlorpyrifos to the aquatic environment and provides a theoretical basis for the rational use of pesticides in agricultural production.

Environmental threats to beekeeping in the Western Balkan countries - beekeepers’ perceptions

The subject of the paper refers to the research on beekeepers’ perceptions of environmental threats to beekeeping in the Western Balkan region. The following environmental threats were supposed to be the most pronounced: cutting of melliferous perennial plants and clearing of forests, urbanisation and environmental pollution, use of pesticides in agricultural production, pests and agents of bees’ diseases, climate changes. The aim of the research was to find out how beekeepers perceived these threats, to determine the presence of the threats and to define their intensity as well as their mutual relationship. For the purpose of this research, the authors created a structured questionnaire which was filled in by randomly selected beekeepers living in the Western Balkans. The research results show that most beekeepers in the studied area evaluated the assumed threats as strong to very strong, while the greatest percentage of beekeepers believes that climate change represents the greatest threat to beekeeping in the region. All assumed environmental threats show the same tendency, while they have the most serious effect on large apiaries with more than 150 bee colonies, located in lowland areas up to 200 meters above sea level with intensive farming. Findings of this research are important in order to adapt the current beekeeping practice in the region to more sustainable solutions, through improvement of the existing beekeeping legislation and advisory services.

Competitive fluorescent immunosensor based on catalytic hairpin self-assembly for multiresidue detection of organophosphate pesticides in agricultural products

Simple and rapid multiresidue trace detection of organophosphate pesticides (OPs) is extremely important for various reasons, including food safety, environmental monitoring, and national health. Here, a catalytic hairpin self-assembly (CHA)-based competitive fluorescent immunosensor was developed to detect OPs in agricultural products, involving enabled dual signal amplification followed by a CHA reaction. The developed method could detect 0.01–50 ng/mL triazophos, parathion, and chlorpyrifos, with limits of detection (LODs) of 0.012, 0.0057, and 0.0074 ng/mL, respectively. The spiked recoveries of samples measured using this assay ranged from 82.8 % to 110.6 %, with CV values ranging between 5.5 % and 18.5 %. This finding suggests that the CHA-based competitive fluorescent immunosensor is a reliable and accurate method for detecting OPs in agricultural products. The results correlated well with those obtained from the liquid chromatography-tandem mass spectrometry (LC–MS/MS) method, indicating that the CHA-based biosensor is able to accurately detect OPs and can be used as a reliable alternative to the LC–MS/MS method. Additionally, the CHA-based biosensor is simpler and faster than LC–MS/MS, which makes it a more practical and cost-effective option for the detection of OPs. In summary, the CHA-based competitive fluorescent immunosensor can be considered a promising approach for trace analysis and multiresidue determination of pesticides, which can open up new horizons in the fields of food safety, environmental monitoring, and national health.

Simultaneous detection of four pesticides in agricultural products by a modified QuEChERS method and LC-MS/MS

A modified QuEChERS pretreatment method and LC-MS/MS technique were performed to simultaneously determine four pesticide (Hexachlorophene, Dinex, Dinosam, Dinoterb) residues in agricultural products. Through the optimization of LC-MS/MS detection parameters in SIM mode, the optimal instrument conditions are obtained. The modified QuEChERS method was used to pretreat the samples. Solid phase extractants PSA, C18 and GCB were used for sample purification. The research results showed that the correlation coefficients of the four pesticides were all greater than 0.991, which had a good linear relationship. The limits of quantitation (LOQ) of the four pesticides were 0.05–0.56 μg/kg. The recoveries were 70.51–113.20% with relative standard deviations (RSDS) of 1.6–11.2%. The developed method can provide reliable data support for the subsequent simultaneous detection of these four pesticides.

Improved Method for the Detection of Highly Polar Pesticides and Their Main Metabolites in Foods of Animal Origin: Method Validation and Application to Monitoring Programme

The application of polar pesticides in agricultural production has been of great interest due to their low costs and their high effectiveness. For this reason, the possibility of their transfer to foods of animal origin is of great concern for human health. The manuscript describes the implementation and validation of an analytical method to detect polar pesticides, at regulatory levels, in three foods of animal origin, including bovine fat, chicken eggs, and cow milk. The method was fully validated to detect glyphosate, glufosinate, and their respective metabolites in the above-mentioned foods obtaining fit-for-purpose sensitivity, recoveries (76–119%), repeatability (≤20%), within-laboratory reproducibility (≤20%), and experimental measurement uncertainty less than 50% as required by the SANTE/11312/2021 criteria. Given the satisfactory results, the applicability of the method to additional molecules belonging to the same category (AMPA, cyanuric acid, ethephon, fosetyl aluminum, HEPA, maleic hydrazide, and N-acetyl-glyphosate) was also evaluated in order to meet possible future requests. Finally, the implemented method was applied to analyse samples over the period of March 2021 to August 2022 from two Italian regions (Umbria and Marche) within the national monitoring programme. In agreement with previously available data, none of the samples analysed showed the presence of glyphosate and glufosinate at levels above the legal limit.

THYROID CANCER INCIDENCE IN THE POPULATION OF UKRAINE AND ITS EPIDEMIOLOGICAL DETERMINANTS: IONIZING RADIATION AND ENDOCRINE DISRUPTORS.

to estimate the risk of thyroid cancer incidence in the population of Ukraine in connection with its exposure to radioactive iodine fallout of Chornobyl origin and the use of pesticides in agricultural production in the country. Incidence rates of thyroid cancer in the population of Ukraine in 2001-2019, average regional radiation doses absorbed by the thyroid because of the Chornobyl accident, the volume of use of various groups of pesticides in the regions of Ukraine. statistical, mathematical and cartographic. The study covering the period of 2001-2019, revealed significant temporal and regional differences in the thyroid cancer incidence in the population of the Ukraine regions in 2001-2019. The existence of a significant correlation between the thyroid cancer incidence and the amount of radiation exposure to the thyroid associated with the Chornobyl accident was established. The existence of a significant correlation between the thyroid cancer incidence and the degree of pesticide use intensity in agriculture in the Ukraine regions was established. A significant value of multiple correlation r = 0.5866 (p < 0.05) was found between the thyroid cancer incidence in Ukraine andthe average regional radiation doses and the pesticide use intensity in agricultural production in the country. A reliable value of the multiple correlation between the value of the average regional radiation exposure doses to the thyroid associated with the Chornobyl accident and the degree of pesticide use intensity in the national economy of Ukraine and the thyroid cancer incidence in the population was determined.

Preparation, biocontrol activity and growth promotion of biofertilizer containing Streptomyces aureoverticillatus HN6.

Nowadays, due to the excessive dependence on chemical fertilizers and pesticides in agricultural production, many problems, such as soil hardening and soil-borne diseases, have become increasingly prominent, which seriously restrict the sustainable development of agriculture. The application of microbial fertilizer prepared by biocontrol microorganisms can not only improve soil structure and increase fertility but also have the function of controlling diseases. Streptomyces aureoverticillatus HN6 has obvious disease prevention and growth promotive effect, which can improve the rhizosphere fertility of plants and even regulate the rhizosphere microbial community of plants. Based on the comparison of frame composting and natural composting, we used the response surface method to optimize the preparation conditions of Streptomyces HN6 bacterial fertilizer. The results showed that natural composting not only produced higher composting temperatures and maintained long high temperature periods in accordance with local conditions, but was also more suitable for composting in the field according to local conditions. Therefore, the substrate's conductivity changed more, the ash accumulation increased, and the substrate decomposed more thoroughly. Thus, this composting method is highly recommended. Additionally, Streptomyces HN6 microbial fertilizer EC20 can reduce cowpea fusarium wilt and promote cowpea growth. The number of plant leaves, plant height and fresh weight, increased significantly in the microbial fertilizer EC20. Moreover, Streptomyces HN6 fertilizer EC20 could significantly induce soil invertase, urease and catalase activities. Our study highlights the potential use of Streptomyces HN6 as a biofertilizer to improve plant productivity and biological control of plant pathogenic fungi.

An Alternative Source of Biopesticides and Improvement in Their Formulation-Recent Advances.

Plant protection in contemporary agriculture requires intensive pesticide application. Their use has enabled the increase in yields, simplifying cultivation systems and crop protection strategies, through successful control of harmful organisms. However, it has led to the accumulation of pesticides in agricultural products and the environment, contaminating the ecosystem and causing adverse health effects. Therefore, finding new possibilities for plant protection and effective control of pests without consequences for humans and the environment is imperative for agricultural production. The most important alternatives to the use of chemical plant protection products are biopesticides. However, in order to increase their application and availability, it is necessary to improve efficacy and stability through new active substances and improved formulations. This paper represents an overview of the recent knowledge in the field of biopesticides and discusses the possibilities of the use of some new active substances and the improvement of formulations.