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1.
Anal Chim Acta ; 1307: 342624, 2024 Jun 08.
Article En | MEDLINE | ID: mdl-38719414

BACKGROUND: Pesticides are used in agricultural production for prevent and control crop diseases and pests, but it is easy to cause excessive pesticides residues in agricultural products, polluting the environment and endangering human health. Due to their unmatched and sustainable capabilities, nanoextraction procedures are becoming every day more important in Analytical Chemistry. In particular, nanoconfined liquid phase extraction has shown extraction capabilities toward polar, medium polar, and/or nonpolar substances, which can be easily modulated depending on the nanoconfined solvent used. Furthermore, this "green" technique showed excellent characteristics in terms of recoveries, extraction time (≤1 min), reliability, and versatility. (97) RESULTS: In this work, the advantages of this technique have been coupled with those of filtration membrane extraction, making use of carbon nanofibers (CnFs) growth on carbon microspheres (CµS). This substrate has been deposited on a filter, which combined with gas chromatographic mass spectrometry (GC-MS) analysis successfully employed for the nanoextraction of 30 pesticides (18 organochlorine and 12 pyrethroids) in tea samples. Under the optimized extraction conditions, the linear range with standard solutions was from 1 to 1000 ng mL-1 (R2 ≥ 0.99), the limit of detections in tea samples were in the range 0.56-17.98 µg kg-1. The accuracy of the developed method was evaluated by measuring the extraction recovery of the spiked tea samples, and recoveries between 74.41 % and 115.46 %. (119) SIGNIFICANCE: Considering the versatility of nanoconfined liquid phase extraction and the functionality of the filtration membrane extraction procedure, this new extraction method can be considered a powerful candidate for automatized high-throughput analyses of real samples. (34).


Filtration , Hydrocarbons, Chlorinated , Liquid-Liquid Extraction , Pesticides , Pyrethrins , Tea , Tea/chemistry , Pyrethrins/analysis , Pyrethrins/isolation & purification , Hydrocarbons, Chlorinated/analysis , Hydrocarbons, Chlorinated/isolation & purification , Liquid-Liquid Extraction/methods , Filtration/methods , Pesticides/analysis , Pesticides/isolation & purification , Gas Chromatography-Mass Spectrometry/methods , Membranes, Artificial
2.
Mikrochim Acta ; 191(5): 296, 2024 05 03.
Article En | MEDLINE | ID: mdl-38702534

A covalent organic framework-based strategy was designed for label-free colorimetric detection of pesticides. Covalent organic framework-based nanoenzyme with excellent oxidase-like catalytic activity was synthesized. Unlike other artificial enzymes, porphyrin-based covalent organic framework (p-COF) as the oxidase mimic showed highly catalytic chromogenic activity and good affinity toward TMB without the presence of H2O2, which can be used as substitute for peroxidase mimics and H2O2 system in the colorimetric reaction. Based on the fact that the pesticide-aptamer complex can inhibit the oxidase activity of p-COF and reduced the absorbance at 650 nm in UV-Vis spectrum, a label-free and facile colorimetric detection of pesticides was designed and fabricated. Under the optimized conditions, the COF-based colorimetric probe for pesticide detection displayed high sensitivity and selectivity. Taking fipronil for example the limit of detection was 2.7 ng/mL and the linear range was 5 -500,000 ng/mL. The strategy was successfully applied to the detection of pesticides with good recovery , which was in accordance with that of HPLC-MS/MS. The COF-based colorimetric detection was free of complicated modification H2O2, which guaranteed the accuracy and reliability of measurements. The COF-based sensing strategy is a potential candidate for the sensitive detection of pesticides of interests.


Colorimetry , Limit of Detection , Metal-Organic Frameworks , Pesticides , Porphyrins , Colorimetry/methods , Pesticides/analysis , Metal-Organic Frameworks/chemistry , Porphyrins/chemistry , Hydrogen Peroxide/chemistry , Oxidoreductases/chemistry , Aptamers, Nucleotide/chemistry
3.
Sci Rep ; 14(1): 10293, 2024 05 04.
Article En | MEDLINE | ID: mdl-38704412

In this study, a sensitive and selective fluorescent chemosensor was developed for the determination of pirimicarb pesticide by adopting the surface molecular imprinting approach. The magnetic molecularly imprinted polymer (MIP) nanocomposite was prepared using pirimicarb as the template molecule, CuFe2O4 nanoparticles, and graphene quantum dots as a fluorophore (MIP-CuFe2O4/GQDs). It was then characterized using X-ray diffraction (XRD) technique, Fourier transforms infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), and transmission electron microscopy (TEM). The response surface methodology (RSM) was also employed to optimize and estimate the effective parameters of pirimicarb adsorption by this polymer. According to the experimental results, the average particle size and imprinting factor (IF) of this polymer are 53.61 nm and 2.48, respectively. Moreover, this polymer has an excellent ability to adsorb pirimicarb with a removal percentage of 99.92 at pH = 7.54, initial pirimicarb concentration = 10.17 mg/L, polymer dosage = 840 mg/L, and contact time = 6.15 min. The detection of pirimicarb was performed by fluorescence spectroscopy at a concentration range of 0-50 mg/L, and a sensitivity of 15.808 a.u/mg and a limit of detection of 1.79 mg/L were obtained. Real samples with RSD less than 2 were measured using this chemosensor. Besides, the proposed chemosensor demonstrated remarkable selectivity by checking some other insecticides with similar and different molecular structures to pirimicarb, such as diazinon, deltamethrin, and chlorpyrifos.


Pesticides , Pyrimidines , Pesticides/analysis , Carbamates/analysis , Carbamates/chemistry , Quantum Dots/chemistry , Molecularly Imprinted Polymers/chemistry , Polymers/chemistry , Spectrometry, Fluorescence/methods , Graphite/chemistry , Molecular Imprinting/methods , Adsorption , Limit of Detection , Spectroscopy, Fourier Transform Infrared , Nanocomposites/chemistry , Nanocomposites/ultrastructure
4.
Environ Monit Assess ; 196(6): 572, 2024 May 23.
Article En | MEDLINE | ID: mdl-38777911

This study analyzes arthropod biomass and abundance to track the changes in arthropod occurrence in relation to pesticide use in three winter wheat cropping systems managed at different intensities (organic, conventional, and hybrid). Arthropod occurrence was surveyed using three collection tools: sweeping nets, eclector traps, and yellow traps. Sampling was conducted over three years from 2020 to 2022 with 588 samples collected. The wet weight of the captured organisms was determined and arthropod abundance calculated. The application of a NOcsPS (no chemical-synthetic pesticides) strategy, a new hybrid cultivation method realized with optimized use of nitrogen fertilizers but without chemical-synthetic pesticides, showed a higher arthropod occurrence and performed more convincingly regarding produced arthropod biomass and abundance than the other cropping variants. The results also demonstrate a dependence of the obtained insect indices on the collection method. Although arthropod biomass and abundance correlated for all collection methods, the combination of various methods as well as multiple procedures of sample analysis gives a more realistic and comprehensive view of the impact of the wheat cultivation systems on the arthropod fauna than one-factor analyses.


Arthropods , Environmental Monitoring , Fertilizers , Nitrogen , Triticum , Triticum/growth & development , Animals , Nitrogen/analysis , Environmental Monitoring/methods , Agriculture/methods , Pesticides/analysis , Pest Control/methods , Biomass
5.
Rev Saude Publica ; 58: 19, 2024.
Article En | MEDLINE | ID: mdl-38747867

OBJECTIVE: To identify the prevalence of contamination by pesticides and their metabolites in the milk of lactating mothers in Latin America. METHODS: In this systematic review, the PubMed, LILACS, Embase, and Scopus databases were searched up to January 2022 to identify observational studies. The Mendeley software was used to manage these references. The risk of bias assessment was evaluated according to the checklist for prevalence studies and writing design, by the Prisma guidelines. RESULTS: This study retrieved 1835 references and analyzed 49 studies. 69.38% of the analyzed studies found a 100% prevalence of breast milk contamination by pesticides among their sample. Main pesticides include dichlorodiphenyltrichloroethane (DDT) and its isomers (75.51%), followed by the metabolite dichlorodiphenyldichloroethylene (DDE) (69.38%) and hexachlorocyclohexane (HCH) (46.93%). This study categorized most (65.30%) studies as having a low risk of bias. CONCLUSIONS: This review shows a high prevalence of pesticide contamination in the breast milk of Latin American women. Further investigations should be carried out to assess contamination levels in breast milk and the possible effects of these substances on maternal and child health.


Lactation , Milk, Human , Pesticides , Humans , Milk, Human/chemistry , Female , Latin America , Pesticides/analysis , Pesticide Residues/analysis , Prevalence , DDT/analysis , Maternal Exposure/adverse effects
6.
Environ Geochem Health ; 46(6): 191, 2024 May 02.
Article En | MEDLINE | ID: mdl-38696024

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 0.62 µg/l (water), 12.37 and 9.20 µg/g/dw (sediment), and 14.27 and 11.29 µg/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.


Environmental Monitoring , Geologic Sediments , Pesticides , Rivers , Water Pollutants, Chemical , Geologic Sediments/chemistry , Water Pollutants, Chemical/analysis , Animals , Rivers/chemistry , Pakistan , Humans , Risk Assessment , Pesticides/analysis , Environmental Monitoring/methods , Seasons , Pesticide Residues/analysis , Cyprinidae , Fishes
7.
Sci Total Environ ; 932: 173025, 2024 Jul 01.
Article En | MEDLINE | ID: mdl-38723955

Contaminants of emerging concern (CECs), including microplastics, have been the focus of many studies due to their environmental impact, affecting biota and human health. The diverse land uses and occupation of watersheds are important parameters driving the occurrence of these contaminants. CECs such as pesticides, drugs, hormones, and industrial-origin substances were analyzed in urban/industrial (Atibaia) and agricultural (Preto/Turvo) watersheds located in São Paulo state, Brazil. A total of 24 CECs were investigated, and, as a result, only 5 (caffeine, carbendazim, atrazine, ametrine and 2-hydroxytrazine) were responsible for 81.73 % of the statistical difference between watersheds contamination profile. The Atibaia watershed presented considerable concentrations of caffeine (ranging from 75 to 2025 ng L-1), while carbendazim (44 to 1144 ng L-1) and atrazine (3 to 266 ng L-1) presented highest levels in Preto/Turvo watershed. In all sampling points, the cumulative potential aquatic life risk assessed by the NORMAN database indicates some level of environmental concern associated to pesticides and caffeine (risk quotient >1). Microplastics had been analyzed in both watersheds, being the white/transparent fragments in size between 100 and 250 µm the most detected in this study. The estimated abundance in the Atibaia watershed ranged from 349 to 2898 items m-3 presenting some influence of pluviosity, while in Rio Preto/Turvo ranged from 169 to 6370 items m-3, being more abundant in the dam area without a clear influence of pluviosity. In both basins, polyethylene and polypropylene were the most detected polymers, probably due to the intense use of single-use plastics in urban areas. Possibly, due to the distinct physic-chemical properties of microplastics and organic CECs, no correlations were observed between their occurrence, which makes us conclude that they have different transport mechanism, behavior, and fate in the environment.


Agriculture , Environmental Monitoring , Microplastics , Water Pollutants, Chemical , Brazil , Water Pollutants, Chemical/analysis , Microplastics/analysis , Pesticides/analysis
8.
Environ Int ; 187: 108722, 2024 May.
Article En | MEDLINE | ID: mdl-38733765

Chinese children are exposed to broad environmental risks ranging from well-known hazards, such as pesticides and heavy metals, to emerging threats including many new man-made chemicals. Although anecdotal evidence suggests that the exposure levels in Chinese children are substantially higher than those of children in developed countries, a systematic assessment is lacking. Further, while these exposures have been linked to a variety of childhood diseases, such as respiratory, endocrine, neurological, behavioral, and malignant disorders, the magnitude of the associations is often unclear. This review provides a current epidemiologic overview of commonly reported environmental contaminants and their potential impact on children's health in China. We found that despite a large volume of studies on various topics, there is a need for more high-quality research and better-coordinated regional and national data collection. Moreover, prevention of such diseases will depend not only on training of environmental health professionals and enhanced research programs, but also on public education, legislation, and networking.


Child Health , Environmental Exposure , Environmental Pollutants , Humans , China , Child , Environmental Pollutants/analysis , Child, Preschool , Pesticides/analysis
9.
Mikrochim Acta ; 191(6): 319, 2024 05 10.
Article En | MEDLINE | ID: mdl-38727763

The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting the research for smart adsorbents and detection methods. Herein, 2D hemin-bridged MOF nanozyme (2D-ZHM) was fabricated and applied to the efficient removal and ultrasensitive dual-mode aptasensing of OPs. On the one hand, the prepared 2D-ZHM contained Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and high adsorption capacity for OPs (285.7 mg g-1 for glyphosate). On the other hand, the enhanced peroxidase-mimicking biocatalytic property of 2D-ZHM allowed rapid H2O2-directed transformation of 3,3',5,5'-tetramethylbenzidine to oxidic product, producing detectable colorimetric or photothermal signals. Using aptamers of specific recognition capacity, the rapid quantification of two typical OPs, glyphosate and omethoate, was realized with remarkable sensitivity and selectivity. The limit of detections (LODs) of glyphosate were 0.004 nM and 0.02 nM for colorimetric and photothermal methods, respectively, and the LODs of omethoate were 0.005 nM and 0.04 nM for colorimetric and photothermal methods, respectively. The constructed dual-mode aptasensing platform exhibited outstanding performance for monitoring OPs in water and fruit samples. This work provides a novel pathway to develop MOF-based artificial peroxidase and integrated platform for pollutant removal and multi-mode aptasensing.


Glycine , Glyphosate , Hemin , Limit of Detection , Metal-Organic Frameworks , Pesticides , Pesticides/analysis , Pesticides/chemistry , Metal-Organic Frameworks/chemistry , Hemin/chemistry , Glycine/analogs & derivatives , Glycine/chemistry , Glycine/analysis , Colorimetry/methods , Benzidines/chemistry , Adsorption , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Hydrogen Peroxide/chemistry , Dimethoate/analysis , Dimethoate/chemistry , Aptamers, Nucleotide/chemistry , Organophosphorus Compounds/analysis , Organophosphorus Compounds/chemistry
10.
Molecules ; 29(9)2024 May 03.
Article En | MEDLINE | ID: mdl-38731605

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.


Gas Chromatography-Mass Spectrometry , Pesticide Residues , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Pesticide Residues/analysis , Gas Chromatography-Mass Spectrometry/methods , Pesticides/analysis , Crops, Agricultural/chemistry , Republic of Korea , Food Contamination/analysis , Limit of Detection , Solid Phase Extraction/methods
11.
J Pharm Biomed Anal ; 245: 116176, 2024 Aug 01.
Article En | MEDLINE | ID: mdl-38701535

Pesticides play an important role in forensic toxicology and are usually classified as a single class of chemicals. Despite their commonly perceived unity, pesticides encompass a spectrum of compounds, including organophosphates, carbamates, pyrethroids or organochlorines, among others, each with varying degrees of toxicity. Pesticide analysis in post-mortem samples can be difficult due to the complexity of the samples and to the high toxicity of these compounds. The aim of this study was to develop and validate an easy to use, sensitive, and robust method, using ultra-performance liquid chromatography-tandem mass spectrometry to be incorporated in the routine flow for pesticide analysis in post-mortem blood samples. Described herein is a streamlined, expeditious, yet highly efficient method facilitating the screening, qualitative assessment, and quantitative confirmation of 15 pesticides, including acetamiprid, azinphos-ethyl, bendiocarb, carbofuran, chlorfenvinphos, dimethoate, imidaclopride, malathion, methiocarb, methomyl, parathion, pirimicarb, strychnine, tetrachlorvinphos, and thiacloprid in post-mortem blood, recognizing the pivotal role blood plays in forensic investigations. The developed method was linear from 10 to 200 ng/mL; limits of detection were between 1 and 10 ng/mL, depending on the compound; it was successfully evaluated a dilution ratio of 1-2, 5 and 10; and 8 substances showed maximum stability for the time interval studied. This UHPLC-MS/MS method is useful and a powerful tool in a toxicology lab because it is fast, simple, effective, and trustworthy. The results of this validation highlight the robustness of the analytical method, providing a valuable tool for the accurate and sensitive detection of pesticides in post-mortem blood. Poised for routine implementation, this method has already found success in suspected intoxication cases, promising to elevate the standards of forensic pesticide analysis.


Autopsy , Forensic Toxicology , Pesticides , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Chromatography, High Pressure Liquid/methods , Humans , Pesticides/analysis , Pesticides/blood , Forensic Toxicology/methods , Reproducibility of Results , Autopsy/methods , Limit of Detection
12.
J Chromatogr A ; 1726: 464941, 2024 Jul 05.
Article En | MEDLINE | ID: mdl-38749274

Method development in comprehensive two-dimensional liquid chromatography (LC×LC) is a challenging process. The interdependencies between the two dimensions and the possibility of incorporating complex gradient profiles, such as multi-segmented gradients or shifting gradients, make trial-and-error method development time-consuming and highly dependent on user experience. Retention modeling and Bayesian optimization (BO) have been proposed as solutions to mitigate these issues. However, both approaches have their strengths and weaknesses. On the one hand, retention modeling, which approximates true retention behavior, depends on effective peak tracking and accurate retention time and width predictions, which are increasingly challenging for complex samples and advanced gradient assemblies. On the other hand, Bayesian optimization may require many experiments when dealing with many adjustable parameters, as in LC×LC. Therefore, in this work, we investigate the use of multi-task Bayesian optimization (MTBO), a method that can combine information from both retention modeling and experimental measurements. The algorithm was first tested and compared with BO using a synthetic retention modeling test case, where it was shown that MTBO finds better optima with fewer method-development iterations than conventional BO. Next, the algorithm was tested on the optimization of a method for a pesticide sample and we found that the algorithm was able to improve upon the initial scanning experiments. Multi-task Bayesian optimization is a promising technique in situations where modeling retention is challenging, and the high number of adjustable parameters and/or limited optimization budget makes traditional Bayesian optimization impractical.


Algorithms , Bayes Theorem , Chromatography, Liquid/methods , Pesticides/isolation & purification , Pesticides/analysis
13.
J Chromatogr A ; 1726: 464967, 2024 Jul 05.
Article En | MEDLINE | ID: mdl-38749275

Infant formulas (IF) can contain harmful chemical substances, such as pesticides and mycotoxins, resulting from the contamination of raw materials and inputs used in the production chain, which can cause adverse effects to infants. Therefore, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) methodology prior ultra-high performance liquid chromatography coupled to triple quadrupole mass spectrometry (UHPL-QqQ-MS/MS) analysis was applied for the determination of 23 contaminants, in 30 samples of Brazilian IF. The method was validated in terms of limit of detection (0.2 to 0.4 µg/kg), limits of quantification (1 and 10 µg/kg), and recovery (64 % to 122 %); precision values, in terms of relative standard deviation (RSD), were ≤ 20 %. Fenitrothion, chlorpyrifos, and bifenthrin were the pesticides detected in the samples, but the values did not exceed the limit set by the European Union (EU), and ANVISA, and they were detected under their limits of quantification. Additionally, suspect screening and unknown analysis were conducted to tentatively identify 32 substances, including some compounds not covered in this study, such as pesticides, hormones, and veterinary drugs. Carbofuran was identified, confirmed and quantified in 10 % of the samples.


Food Contamination , Infant Formula , Limit of Detection , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Chromatography, High Pressure Liquid/methods , Brazil , Infant Formula/chemistry , Food Contamination/analysis , Pesticides/analysis , Humans , Pesticide Residues/analysis , Reproducibility of Results , Mycotoxins/analysis , Infant , Pyrethrins/analysis
14.
Sci Total Environ ; 931: 172911, 2024 Jun 25.
Article En | MEDLINE | ID: mdl-38705305

Breastfeeding provides numerous health benefits for both infants and mothers, promoting optimal growth and development while offering protection against various illnesses and diseases. This study investigated the levels of polychlorinated biphenyls (PCB), organochlorine pesticides (OCP) and polycyclic aromatic hydrocarbons (PAH) in human milk sampled in Zadar (Croatia). The primary objectives were twofold: firstly, to evaluate the individual impact of each compound on the total antioxidant capacity (TAC) value, and secondly, to assess associated health risks. Notably, this study presents pioneering and preliminary insights into PAH levels in Croatian human milk, contributing to the limited research on PAH in breast milk worldwide. PCB and OCP levels in Croatian human milk were found to be relatively lower compared to worldwide data. Conversely, PAH levels were comparatively higher, albeit with lower detection frequencies. A negative correlation was established between organic contaminant levels and antioxidative capacity, suggesting a potential link between higher antioxidative potential and lower organic contaminant levels. Diagnostic ratio pointed towards traffic emissions as the primary source of the detected PAH. The presence of PAH suggests potential health risk, underscoring the need for further in-depth investigation.


Antioxidants , Hydrocarbons, Chlorinated , Milk, Human , Polycyclic Aromatic Hydrocarbons , Milk, Human/chemistry , Humans , Polycyclic Aromatic Hydrocarbons/analysis , Hydrocarbons, Chlorinated/analysis , Risk Assessment , Croatia , Female , Persistent Organic Pollutants , Pesticides/analysis , Environmental Monitoring , Polychlorinated Biphenyls/analysis , Adult , Environmental Pollutants/analysis
15.
J Environ Manage ; 359: 121046, 2024 May.
Article En | MEDLINE | ID: mdl-38728981

The increasing concern over pesticide pollution in water bodies underscores the need for effective mitigation strategies to support the transition towards sustainable agriculture. This study assesses the effectiveness of landscape mitigation strategies, specifically vegetative buffer strips, in reducing glyphosate loads at the catchment scale under realistic conditions. Conducted over six years (2014-2019) in a small agricultural region in Belgium, our research involved the analysis of 732 water samples from two monitoring stations, differentiated by baseflow and event-driven sampling, and before (baseline) and after the implementation of mitigation measures. The results indicated a decline in both the number and intensity of point source losses over the years. Additionally, there was a general decrease in load intensity; however, the confluence of varying weather conditions (notably dry years during the mitigation period) and management practices (the introduction of buffer strips) posed challenges for a statistically robust evaluation of each contributing factor. A reduction of loads was measured when comparing mitigation with baseline, although this reduction is not statistically significant. Glyphosate loads during rainfall events correlated with a rainfall index and runoff ratio. Overall, focusing the mitigation strategy on runoff and erosion was a valid approach. Nevertheless, challenges remain, as evidenced by the continuous presence of glyphosate in baseflow conditions, highlighting the complex dynamics of pesticide transport. The study concludes that while progress has been made towards reducing pesticide pollution, the complexity of interacting factors necessitates further research. Future directions should focus on enhancing farmer engagement in mitigation programs and developing experiments with more intense data collection that help to assess underlying dynamics of pesticide pollution and the impact of mitigation strategies in more detail, contributing towards the goal of reducing pesticide pollution in water bodies.


Agriculture , Glyphosate , Belgium , Water Pollutants, Chemical/analysis , Environmental Monitoring , Glycine/analogs & derivatives , Glycine/analysis , Pesticides/analysis
16.
Molecules ; 29(10)2024 May 14.
Article En | MEDLINE | ID: mdl-38792172

Pyrethroid pesticides (PYRs) have found widespread application in agriculture for the protection of fruit and vegetable crops. Nonetheless, excessive usage or improper application may allow the residues to exceed the safe limits and pose a threat to consumer safety. Thus, there is an urgent need to develop efficient technologies for the elimination or trace detection of PYRs from vegetables. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous purification and enrichment of five PYRs in vegetables, employing the magnetic covalent organic framework nanomaterial COF-SiO2@Fe3O4 as an adsorbent. COF-SiO2@Fe3O4 was prepared by a straightforward solvothermal method, using Fe3O4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO2@Fe3O4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on the extraction efficiency was investigated to optimize the MSPE conditions, including the adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00-100 µg·kg-1 (1.00-100 µg·kg-1 for bifenthrin and 2.5-100 µg·kg-1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3-1.5 µg·kg-1, and the limits of quantification (LOQs) were 0.9-4.5 µg·kg-1. The recoveries were 80.2-116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.


Pesticides , Pyrethrins , Silicon Dioxide , Solid Phase Extraction , Vegetables , Solid Phase Extraction/methods , Silicon Dioxide/chemistry , Vegetables/chemistry , Pyrethrins/isolation & purification , Pyrethrins/analysis , Pyrethrins/chemistry , Pesticides/isolation & purification , Pesticides/chemistry , Pesticides/analysis , Gas Chromatography-Mass Spectrometry , Adsorption , Food Contamination/analysis , Limit of Detection , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Ferric Compounds/chemistry , Cobalt
17.
Xi Bao Yu Fen Zi Mian Yi Xue Za Zhi ; 40(5): 428-434, 2024 May.
Article Zh | MEDLINE | ID: mdl-38790099

Objective To establish a colloidal gold immunochromatography and develop the corresponding test strip for detecting organophosphorus compounds including omethoate, phoxim, dipterex, and parathion in fruits, vegetables and drinking water. Methods Artificial antigen molecules of organophosphorus compounds were synthesized using N-hydroxysuccinimide esters. Acetylcholinesterase antigen was prepared and purified, and the serum containing the corresponding antibody was prepared, purified, and labeled. The working parameters of the test strip were optimized, and the performance evaluation of it was conducted. Results The titer of the antisera ranged from 1:32 to 1:64, with a protein content of approximately 2 mg/mL. The purified polyclonal antibodies displayed target bands at relative molecular masses (Mr) of 25 000 and 55 000, indicating satisfactory purity. The reaction time of the test strips was between 5 to 10 minutes, with a detection limit for samples at 200 ng/mL. Both specificity and accuracy were satisfactory, and the test strip remained valid for 6 months. Conclusion A simple and rapid colloidal gold immunochromatography is established successfully for detecting several organophosphorus compounds and may be useful for on-site preliminary screening of samples in large quantities.


Chromatography, Affinity , Gold Colloid , Organophosphorus Compounds , Pesticides , Gold Colloid/chemistry , Organophosphorus Compounds/analysis , Chromatography, Affinity/methods , Pesticides/analysis , Animals , Vegetables/chemistry , Fruit/chemistry , Acetylcholinesterase
18.
Molecules ; 29(10)2024 May 10.
Article En | MEDLINE | ID: mdl-38792109

This review article is a comprehensive and current overview on chalcones, covering their sources, identification methods, and properties with a particular focus on their applications in the agricultural sector. The widespread use of synthetic pesticides has not only led to increased resistance among weeds and pests, resulting in economic losses, but it has also raised significant health concerns due to the overuse of these chemicals. In line with the European Green Deal 2030 and its Farm to Fork strategy, there is a targeted 50% reduction in the use of chemical pesticides by 2030, emphasizing a shift towards natural alternatives that are more environmentally sustainable and help in the restoration of natural resources. Chalcones and their derivatives, with their herbicidal, fungicidal, bactericidal, and antiviral properties, appear to be ideal candidates. These naturally occurring compounds have been recognized for their beneficial health effects for many years and have applications across multiple areas. This review not only complements the previous literature on the agricultural use of chalcones but also provides updates and introduces methods of detection such as chromatography and MALDI technique.


Agriculture , Chalcones , Chalcones/chemistry , Chalcones/pharmacology , Pesticides/chemistry , Pesticides/analysis , Pesticides/pharmacology , Herbicides/chemistry , Herbicides/pharmacology
19.
J Hazard Mater ; 472: 134486, 2024 Jul 05.
Article En | MEDLINE | ID: mdl-38714052

Peanuts, known for their nutritional value, health benefits, and delicious taste, are susceptible to agricultural chemical contamination, posing a challenge to the peanut industry in China. While tristyrylphenol ethoxylates (TSPEOs) have garnered attention for their widespread use in pesticide formulations, their dissipation and potential risks in peanuts remain a gap in knowledge. This study, unique in its focus on TSPEOs, investigates their dissipation and potential risks under two common application modes: spraying and root irrigation. The concentration of total TSPEOs in peanut plants was significantly higher when sprayed (435-37,693 µg/kg) than in root irrigation (24-1602 µg/kg). The dissipation of TSPEOs was faster in peanuts and soil when sprayed, with half-lives of 3.67-5.59 d (mean: 4.37 d) and 5.41-7.07 d (mean: 5.95 d), respectively. The residue of TSPEOs in peanut shells and soil were higher with root irrigation (8.9-65.2 and 25.4-305.1 µg/kg, respectively) than with spraying (5.4-30.6 and 8.8-146.5 µg/kg, respectively). These results indicated that the dissipation behavior of TSPEOs in peanuts was influenced by application modes. While the healthy and ecological risk assessments of TSPEOs in soil and peanut shells showed no risks, root irrigation might pose a higher potential risk than spraying. This research provides valuable data for the judicious application of pesticides during peanut cultivation to enhance pesticide utilization and reduce potential risks.


Agricultural Irrigation , Arachis , Plant Roots , Soil Pollutants , Soil Pollutants/analysis , Soil Pollutants/chemistry , Risk Assessment , Pesticide Residues/analysis , Pesticides/toxicity , Pesticides/chemistry , Pesticides/analysis , Agriculture , China
20.
Sci Total Environ ; 933: 173020, 2024 Jul 10.
Article En | MEDLINE | ID: mdl-38719047

This study investigated 32 persistent organic pollutants, including 9 organochlorine pesticides, 15 polychlorinated biphenyls, 6 polycyclic aromatic hydrocarbons, and 2 organophosphate pesticides in the hair samples of domestic cats and dogs living in an urban area in Samsun, Turkiye. Hair samples were collected from 35 cats and 38 dogs, grouped by sex and age (<3 or >3 years old). Samples were extracted using a liquid-liquid extraction method and analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). The results revealed the presence of organochlorine pesticides (n = 58, 468.65 ± 92.30 ng/g), polycyclic aromatic hydrocarbons (n = 57, 15.65 ± 3.91 ng/g), polychlorinated biphenyls (n = 55, 54.11 ± 9.47 ng/g), and organophosphate pesticides (n = 25, 568.43 ± 113.17 ng/g) in the samples. PCBs 81, 118, 128, 208, and 2,4-DDE were not detected in any samples. Only one sample did not contain any of the searched compounds. Fluorene was the most frequently detected pollutant (n = 53, 72.6 %), followed by ß-hexachlorocyclohexane (n = 34, 46.6 %). The highest maximum concentration was observed for hexachlorobenzene (2748.03 ng/g), followed by aldrin (2313.45 ng/g) and fenitrothion (2081.13 ng/g). Pollutant concentrations did not differ between cats and dogs, sexes, and ages (p > 0.05). This study highlights the significant threat that urban areas pose to pets, and therefore, POPs should be monitored periodically in hair and other samples. To the best of our knowledge, this is the first report to investigate POP levels in hair samples from cats and dogs in Turkiye.


Environmental Monitoring , Hair , Persistent Organic Pollutants , Polychlorinated Biphenyls , Animals , Dogs , Cats , Hair/chemistry , Environmental Monitoring/methods , Polychlorinated Biphenyls/analysis , Male , Female , Pesticides/analysis , Turkey , Polycyclic Aromatic Hydrocarbons/analysis , Gas Chromatography-Mass Spectrometry , Hydrocarbons, Chlorinated/analysis , Environmental Pollutants/analysis
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