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Food Chemistry: X Oct 2023This study developed a method to simultaneously determine 73 multi-class pesticides in okra fruit using LC-MS/MS and GC-MS/MS. The sample was extracted with acetonitrile...
This study developed a method to simultaneously determine 73 multi-class pesticides in okra fruit using LC-MS/MS and GC-MS/MS. The sample was extracted with acetonitrile and subsequent clean-up through dispersive-SPE method. The quantification level of the technique was 0.01 µg g and compliance to the MRLs fixed by the regulatory bodies like EU and FSSAI. The recovery at 10, 50, and 100 µg kg spiked levels; intra and inter-day precision at 50 µg kg were found within 70-120% with RSD less than 15% with LC-MS/MS and GC-MS/MS. Measurement uncertainty was in the range of 1.81 to 12.91 µg kg estimated at 50 µg kg. The matrix effects were slightly higher for LC than GC-compatible pesticides. Risk assessment for pesticides detected in the field and market samples found no hazardous to the consumers except profenofos. The proposed method is highly sensitive, reproducible for the complex matrix like okra, and meets the regulatory standards.
PubMed: 37780267
DOI: 10.1016/j.fochx.2023.100814 -
Foods (Basel, Switzerland) Sep 2023Pesticide residues in kumquat fruits from China, and the quality and chronic/acute intake risks in Chinese consumers, were assessed using the QuEChERS procedure and...
Pesticide residues in kumquat fruits from China, and the quality and chronic/acute intake risks in Chinese consumers, were assessed using the QuEChERS procedure and UHPLC-MS/MS and GC-MS/MS methods. Our 5-year monitoring and survey showed 90% of the 573 samples of kumquat fruits collected from two main production areas contained one or multiple residual pesticides. Overall, 30 pesticides were detected, including 16 insecticides, 7 fungicides, 5 acaricides, and 2 plant growth modulators, of which 2 pesticides were already banned. Two or more residual pesticides were discovered in 81% of the samples, and pesticide residues in 9.4% of the samples surpassed the , such as profenofos, bifenthrin, triazophos, avermectin, spirodiclofen, difenoconazole, and methidathion. The major risk factors on the safety of kumquat fruits before 2019 were profenofos, bifenthrin, and triazophos, but their over-standard frequencies significantly declined after 2019, which was credited to the stricter supervision and management policies by local governments. Despite the high detection rates and multi-residue occurrence of pesticides in kumquat fruits, about 81% of the samples were assessed as qualified. Moreover, the accumulative chronic diet risk determined from is very low. To better protect the health of customers, we shall formulate stricter organic phosphorus pesticide control measures and stricter use guidelines, especially for methidathion, triazophos, chlorpyrifos, and profenofos. This study provides potential data for the design of kumquat fruit quality and safety control guidelines and for the reduction in health risks to humans.
PubMed: 37761133
DOI: 10.3390/foods12183423 -
Journal of Materials Chemistry. B Oct 2023Conventional nanozyme-based pesticide detection often requires the assistance of acetylcholinesterase. In this work, a CuCeTA nanozyme was successfully designed for the...
Conventional nanozyme-based pesticide detection often requires the assistance of acetylcholinesterase. In this work, a CuCeTA nanozyme was successfully designed for the direct colorimetric detection of glyphosate. Direct detection can effectively avoid the problems caused by cascading with natural enzymes such as acetylcholinesterase. By assembling tannic acid, copper sulfate pentahydrate and cerium(III) nitrate hexahydrate, CuCeTA nanoflowers were prepared. The obtained CuCeTA possessed excellent peroxidase-like activity that could catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB in the presence of hydrogen peroxide. Glyphosate could effectively inhibit the peroxidase-like activity of CuCeTA while other pesticides (fenthion, chlorpyrifos, profenofos, phosmet, bromoxynil and dichlorophen) did not show significant inhibitory effects on the catalytic activity of CuCeTA. In this way, CuCeTA could be used for the colorimetric detection of glyphosate with a low detection limit of 0.025 ppm. Combined with a smartphone and imageJ software, a glyphosate test paper was designed with a detection limit of 3.09 ppm. Fourier transform infrared spectroscopy demonstrated that glyphosate and CuCeTA might be bound by coordination, which could affect the catalytic activity of CuCeTA. Our CuCeTA-based nanozyme system exhibited unique selectivity and sensitivity for glyphosate detection and this work may provide a new strategy for rapid and convenient detection of pesticides.
Topics: Peroxidase; Acetylcholinesterase; Colorimetry; Peroxidases; Coloring Agents; Pesticides; Glyphosate
PubMed: 37750214
DOI: 10.1039/d3tb01455j -
Analytica Chimica Acta Oct 2023Chlorpyrifos (CPF) is a commonly used insecticide found in many water sources and is related to several health and environmental effects. Biosensors based on aptamers...
Chlorpyrifos (CPF) is a commonly used insecticide found in many water sources and is related to several health and environmental effects. Biosensors based on aptamers (single-stranded nucleic acid oligonucleotides) are promising alternatives to achieve the detection of CPF and other pesticides in natural waters. However, several challenges need to be addressed to promote the real application of functional aptasensing devices. In this work, an ssDNA aptamer (S1) is combined with carbon quantum dots (CD) and graphene oxide (GO) to produce a stable fluorescent aptasensor characterized through spectrophotometric and electrophoretic techniques. For a deeper understanding of the system, the mechanism of molecular interaction was studied through docking modeling using free bioinformatic tools like HDOCK, showing that the stem-loops and the higher guanine (G) content are crucial for better interaction. The model also suggests the possibility of generating a truncated aptamer to improve the binding affinity. The biosensor was evaluated for CPF detection, showing a low LOD of 0.01 μg L and good specificity in tap water, even compared to other organophosphates pesticides (OPs) like profenofos. Finally, the recovery of the proposed aptasensor was evaluated in some natural water using spiked samples and compared with UPLC MS-MS chromatography as the gold standard, showing a good recovery above 2.85 nM and evidencing the need of protecting ssDNA aptamers from an erratic interaction with the aromatic groups of dissolved organic matter (humic substances). This work paves the way for a better aptasensors design and the on-site implementation of novel devices for environmental monitoring.
Topics: Chlorpyrifos; Carbon; Insecticides; Pesticides; Coloring Agents; DNA, Single-Stranded; Environmental Pollutants
PubMed: 37709453
DOI: 10.1016/j.aca.2023.341711 -
Proteins Jan 2024Methyl parathion hydrolase (MPH) is an enzyme of the metallo-β-lactamase superfamily, which hydrolyses a wide range of organophosphates (OPs). Recently, MPH has...
Methyl parathion hydrolase (MPH) is an enzyme of the metallo-β-lactamase superfamily, which hydrolyses a wide range of organophosphates (OPs). Recently, MPH has attracted attention as a promising enzymatic bioremediator. The crystal structure of MPH enzyme shows a dimeric form, with each subunit containing a binuclear metal ion center. MPH also demonstrates metal ion-dependent selectivity patterns. The origins of these patterns remain unclear but are linked to open questions about the more general role of metal ions in functional evolution and divergence within enzyme superfamilies. We aimed to investigate and compare the binding of different OP pesticides to MPH with cobalt(II) metal ions. In this study, MPH was modeled from Ochrobactrum sp. with different OP pesticides bound, including methyl paraoxon and dichlorvos and profenofos. The docked structures for each substrate optimized by DFT calculation were selected and subjected to atomistic molecular dynamics simulations for 500 ns. It was found that alpha metal ions did not coordinate with all the pesticides. Rather, the pesticides coordinated with less buried beta metal ions. It was also observed that the coordination of beta metal ions was perturbed to accommodate the pesticides. The binding free energy calculations and structure-based pharmacophore model revealed that all the three substrates could bind well at the active site. However, profenofos exhibit a stronger binding affinity to MPH in comparison to the other two substrates. Therefore, our findings provide molecular insight on the binding of different OP pesticides which could help us design the enzyme for OP pesticides degradation.
Topics: Methyl Parathion; Organophosphates; Hydrolases; Ochrobactrum; Phosphoric Monoester Hydrolases; Pesticides; Metals; Ions
PubMed: 37646471
DOI: 10.1002/prot.26579 -
Mikrochimica Acta Aug 2023A split-type photoelectrochemical (PEC) sensor was designed for the detection of profenofos (PFF) depending on the magnetic-assisted exciton-plasmon interactions (EPI)...
A split-type photoelectrochemical (PEC) sensor was designed for the detection of profenofos (PFF) depending on the magnetic-assisted exciton-plasmon interactions (EPI) between the semiconductor substrate and Au NPs. The core-shell BiS nanorods@MoS nanosheets (BiS NRs@MoS NSs) heterostructure nanomaterial with fascinating performance was synthesized and used as the photovoltaic conversion substrate and signal molecules absorption platform. The PEC sensor is operated by co-incubating with the released Au NPs-cDNA from the surface of magnetic beads, originating from the target-triggered DNA double-stranded structure opening event. Due to the strong EPI effects, the photocurrent of BiS NRs@MoS NSs decreased and varied with the PFF concentrations. The proposed PEC sensor exhibited outstanding analytical performances, including a wide linear range (1.0 pg mL~1.0 μg mL), low detection limitation (0.23 pg mL, at 3 σ/m), excellent specificity, high stability, and applicability. Overall, this work provides a new signal strategy for PEC biosensors and extends its application in environmental analysis.
Topics: Molybdenum; Electrochemical Techniques; Nanotubes; Magnetic Phenomena
PubMed: 37574467
DOI: 10.1007/s00604-023-05927-4 -
Chemosphere Oct 2023The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land...
The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land use have been associated to water pollution problems, including the emission of untreated urban wastewater and pesticides. Here we provide the first report on the influence of urbanization and intensive agriculture expansion on water quality parameters, pesticide contamination and the ecological status of Amazonian freshwater ecosystems of Ecuador. We monitored 19 water quality parameters, 27 pesticides, and the macroinvertebrate community in 40 sampling locations of the Napo River basin (northern Ecuador), including a nature conservation reserve and sites in areas influenced by African palm oil production, corn production and urbanization. The ecological risks of pesticides were assessed using a probabilistic approach based on species sensitivity distributions. The results of our study show that urban areas and areas dominated by African palm oil production have a significant influence on water quality parameters, affecting macroinvertebrate communities and biomonitoring indices. Pesticide residues were detected in all sampling sites, with carbendazim, azoxystrobin, diazinon, propiconazole and imidacloprid showing the largest prevalence (>80% of the samples). We found a significant effect of land use on water pesticide contamination, with residues of organophosphate insecticides correlating with African palm oil production and some fungicides with urban areas. The pesticide risk assessment indicated organophosphate insecticides (ethion, chlorpyrifos, azinphos-methyl, profenofos and prothiophos) and imidacloprid as the compounds posing the largest ecotoxicological hazard, with pesticide mixtures potentially affecting up to 26-29% of aquatic species. Ecological risks of organophosphate insecticides were more likely to occur in rivers surrounded by African palm oil plantations, while imidacloprid risks were identified in corn crop areas as well as in natural areas. Future investigations are needed to clarify the sources of imidacloprid contamination and to assess its effects for Amazonian freshwater ecosystems.
Topics: Pesticides; Ecuador; Insecticides; Water Quality; Ecosystem; Palm Oil; Urbanization; Environmental Monitoring; Water Pollutants, Chemical; Agriculture; Fresh Water; Rivers; Chlorpyrifos
PubMed: 37379974
DOI: 10.1016/j.chemosphere.2023.139286 -
Analytica Chimica Acta Jul 2023The long-term and excessive use of organophosphorus pesticides (OPs) leads to hazardous residues in the environment, which threatens human health to a considerable...
Facile colorimetric smartphone-based biosensor for rapid detection of organophosphorus pesticides residues in environment using the aptamer-enhanced oxidase activity of octahedral AgO particles.
The long-term and excessive use of organophosphorus pesticides (OPs) leads to hazardous residues in the environment, which threatens human health to a considerable extent. Colorimetric methods can quickly and readily identify pesticide residue, but they still have various challenges in accuracy and stability. Herein, a smartphone-assisted and non-enzymatic colorimetric biosensor was constructed for rapid monitoring of multiple OPs based on the enhanced effect of aptamer on the catalytic ability of octahedral AgO. It was demonstrated that the aptamer sequence could enhance the affinity of colloidal AgO to chromogenic substrates, and accelerate the generation of oxygen radicals such as superoxide radical (·O) and singlet oxygen (O) from dissolved oxygen, thereby significantly increasing the oxidase activity of octahedral AgO. The color change of the solution can be easily converted to the corresponding RGB values by a smartphone for quantitative and rapid detection of multiple OPs. Hence, the smartphone-based and visual biosensor of multiple OPs was acquired with limit of detection of 10 μg L, 28 μg L and 40 μg L for isocarbophos, profenofos and omethoate, respectively. The colorimetric biosensor also exhibited good recoveries in several environmental and biological samples, showing that it may have broad application prospects for detecting OPs residues.
Topics: Humans; Pesticide Residues; Pesticides; Organophosphorus Compounds; Colorimetry; Oxidoreductases; Smartphone; Oligonucleotides; Biosensing Techniques
PubMed: 37230725
DOI: 10.1016/j.aca.2023.341325 -
Environmental Science and Pollution... Jun 2023Profenofos (PFF) is an organophosphorus pesticide frequently detected in surface waters, soil habitats, and even biota. Some studies have demonstrated the potential...
Profenofos (PFF) is an organophosphorus pesticide frequently detected in surface waters, soil habitats, and even biota. Some studies have demonstrated the potential risks of PFF to aquatic organisms. However, most of these studies were focused on its acute rather than chronic impacts, and the subjects are usually large vertebrates. Here, we treated D. magna (< 24 h) with PFF at doses of 0, 0.07, 0.28, and 1.12 mg/L for 21 days to study its long-term toxic impacts. Exposure to PFF largely decreased the survival rate and inhibited the growth and reproduction of D. magna. Then, PCR arrays were used to evaluate the changes in the expression of 13 genes related to growth, reproduction, and swimming behavior. The results revealed that the expression of several genes was dramatically changed by exposure to each dose of PFF, which might be responsible for the observed toxic effects of PFF. In summary, our findings imply that long-term PFF exposure can be highly hazardous to the growth, development, and reproduction of D. magna.
Topics: Animals; Daphnia; Organophosphorus Compounds; Pesticides; Reproduction; Transcription, Genetic; Water Pollutants, Chemical
PubMed: 37209339
DOI: 10.1007/s11356-023-27669-9 -
Ecotoxicology and Environmental Safety Jul 2023As an environmental pollutant, profenofos (PFF) can seriously endanger human health through the food chain. Albicanol is a sesquiterpene compound with antioxidant,...
As an environmental pollutant, profenofos (PFF) can seriously endanger human health through the food chain. Albicanol is a sesquiterpene compound with antioxidant, anti-inflammatory, and anti-aging properties. Previous studies have shown that Albicanol can antagonize apoptosis and genotoxicity caused by PFF exposure. However, the toxicity mechanism of PFF regulating hepatocyte immune function, apoptosis, and programmed necrosis and the role of Albicanol in this process have not been reported yet. In this study, grass carp hepatocytes (L8824) were treated with PFF (200 μM) or combined with Albicanol (5 ×10 μg mL) for 24 h to establish an experimental model. The results of JC-1 probe staining and Fluo-3 AM probe staining showed increased free calcium ions and decreased mitochondrial membrane potential in L8824 cells after PFF exposure, suggesting that PFF exposure may lead to mitochondrial damage. Real-time quantitative PCR and Western blot results showed that PFF exposure could increase the transcription of innate immunity-related factors (C3, Pardaxin 1, Hepcidin, INF-γ, IL-8, and IL-1β) in L8824 cells. PFF up-regulated the TNF/NF-κB signaling pathway and the expression of caspase-3, caspase-9, Bax, MLKL, RIPK1, and RIPK3 and down-regulated the expression of Caspase-8 and Bcl-2. Albicanol can antagonize the above-mentioned effects caused by PFF exposure. In conclusion, Albicanol antagonized the mitochondrial damage, apoptosis, and necroptosis of grass carp hepatocytes caused by PFF exposure by inhibiting the TNF/NF-κB pathway in innate immunity.
Topics: Humans; Animals; NF-kappa B; Immunity, Innate; Apoptosis; Sesquiterpenes; Carps
PubMed: 37196524
DOI: 10.1016/j.ecoenv.2023.115014