RESUMO
Chlorpyrifos (CPS) is widely found in food and water sources due to agricultural use, posing health and environmental risks. Therefore, this work introduces a fluorescent sensor design of silver nanoparticle-embedded nano zirconium-based metal-organic frameworks (UiO-66-NH2@AgNPs) for accurate examination of CPS. Briefly, UiO-66-NH2 was synthesized hydrothermally, exhibiting weak luminescence owed to ligand-to-metal charge transfer (LMCT). Here, it limits its direct utility in fluorescence-based detection. To address this limitation, silver nanoparticles (AgNPs) were introduced into UiO-66-NH2, enhancing fluorescence via the metal-enhanced fluorescence (MEF) effect. Briefly, a comprehensive spectral analysis such as XPS, SEM, TEM, PXRD, etc., was performed to validate the synthesis of UiO-66-NH2@AgNPs. Subsequent evaluation revealed that CPS effectively quenched the luminescence intensity of UiO-66-NH2@AgNPs through a static quenching mechanism. The fluorescence intensity exhibited good linearity with CPS concentration in the span of 10 to 1,000 ng/mL, with a recognition limit of 191.5 ng/mL(S/N = 3). The interaction involved Ag-S bond formation and electrostatic interactions, reducing fluorescence intensity. The method was confirmed through successful CPS detection in fruit samples. The UiO-66-NH2@AgNPs nanoprobe offers a simple, sensitive, and accurate platform for CPS sensing, with potential for future use in detecting CPS in fruits and vegetables.
Assuntos
Clorpirifos , Nanopartículas Metálicas , Estruturas Metalorgânicas , Prata , Zircônio , Clorpirifos/análise , Prata/química , Zircônio/química , Estruturas Metalorgânicas/química , Nanopartículas Metálicas/química , Espectrometria de Fluorescência , Limite de Detecção , Inseticidas/análiseRESUMO
Implementation of cost-effective, reliable, and efficient technologies for the sensitive, rapid, and accurate detection of pesticide residues in agriproducts presents a promising solution to the escalating food safety concerns. Herein, a high-performance surface-enhanced Raman scattering (SERS) aptasensor based on nanotag (AuNS@4-MBN@Ag-aptamer) was introduced for ultrasensitive, reliable, and interference-free detection of chlorpyrifos (CPF). This aptasensor featured star-shaped bimetallic nanotag as the principal Raman signal enhancement material and 4-mercaptobenzonitrile (4-MBN) as "biological-silent"-window reporter (at 2228 cm-1). Moreover, cDNA-linked Fe3O4@AuNPs (FA-cDNA) served as magnetic substrates to simplify the separation process of FA-cDNA-combined nanotags. In the aptasensor, the formation of FA-cDNA-aptamer-AuNS@4-MBN@Ag hybrids was hindered by CPF, and its Raman intensity decreased with increasing CPF concentration. Under optimal SERS conditions, the aptasensor exhibited a broad linear detection range from 2.5 × 102 to 5.0 × 104 pgâ mL-1, with an impressively low limit of detection of 220.35 pgâ mL-1 (signal-to-noise ratio = 3). The selectivity and reproducibility assessments highlighted its exceptional sensitivity and interference-free capabilities. Furthermore, practical applications on wheat and apples demonstrated satisfactory spiked recovery rates, ranging from 89.61% to 107.33% (relative standard deviation ≤ 14.55%). Consequently, the high-performance "biological-silent"-window nanotag-based aptasensor is a promising tool for monitoring trace CPF in complex matrices.
Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Clorpirifos , Contaminação de Alimentos , Ouro , Limite de Detecção , Nanopartículas Metálicas , Prata , Análise Espectral Raman , Clorpirifos/análise , Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais/métodos , Ouro/química , Prata/química , Nanopartículas Metálicas/química , Contaminação de Alimentos/análise , Resíduos de Praguicidas/análise , Inseticidas/análise , Inseticidas/isolamento & purificaçãoRESUMO
BACKGROUND: The Centers for Disease Control and Prevention (CDC) bottle bioassay is a commonly used susceptibility test for measuring insect response to insecticide exposure. However, inconsistencies and high variability in insect response when conducting CDC bottle bioassays have been reported in previous publications. We hypothesized that the CDC bottle bioassay results may be compromised when expected and actual insecticide concentrations in the bottles are not equivalent and that inadequate bottle cleaning and/or loss during insecticide introduction and bottle storage steps could be responsible. We explored this hypothesis by quantifying insecticides using gas chromatography tandem mass spectrometry (GC-MS/MS) in bottles that had been cleaned, prepared, and stored according to the CDC guidelines. METHODS: We investigated the bottle cleaning, preparation, and storage methods outlined in the CDC bottle bioassay procedure to identify sources of irreproducibility. We also investigated the effectiveness of cleaning bottles by autoclaving because this method is commonly used in insecticide assessment laboratories. The two insecticides used in this study were chlorpyrifos and lambda-cyhalothrin (λ-cyhalothrin). Insecticides were removed from glass bioassay bottles by rinsing with ethyl-acetate and n-hexane and then quantified using GC-MS/MS. RESULTS: The CDC bottle bioassay cleaning methods did not sufficiently remove both insecticides from the glass bottles. The cleaning methods removed chlorpyrifos, which has higher water solubility, more effectively than λ-cyhalothrin. Chlorpyrifos experienced significant loss during the bottle-coating process whereas λ-cyhalothrin did not. As for bottle storage, no significant decreases in insecticide concentrations were observed for 6 h following the initial drying period for either insecticide. CONCLUSIONS: The CDC bottle bioassay protocol is susceptible to producing inaccurate results since its recommended bottle cleaning method is not sufficient and semi-volatile insecticides can volatilize from the bottle during the coating process. This can lead to the CDC bottle bioassay producing erroneous LC50 values. High levels of random variation were also observed in our experiments, as others have previously reported. We have outlined several steps that CDC bottle bioassay users could consider that would lead to improved accuracy and reproducibility when acquiring toxicity data.
Assuntos
Bioensaio , Centers for Disease Control and Prevention, U.S. , Cromatografia Gasosa-Espectrometria de Massas , Inseticidas , Nitrilas , Piretrinas , Inseticidas/análise , Bioensaio/métodos , Animais , Estados Unidos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Piretrinas/análise , Nitrilas/análise , Reprodutibilidade dos Testes , Clorpirifos/análise , Espectrometria de Massas em TandemRESUMO
This study investigates the behaviour of gold nanoparticles (AuNPs) when exposed to chlorpyrifos, an agricultural pesticide, and its application in detecting the pesticide via surface-enhanced Raman spectroscopy (SERS). Under synergistic addition of NaCl, AuNPs undergo agglomeration at lower chlorpyrifos concentrations but aggregation at higher concentrations, resulting in a distinctive nonlinear SERS response. A linear relationship is obtained between 0.001 and 1 ppm with detection limit (LOD) of 0.009 ppm, while an inverse response is observed at higher concentrations (1-1000 ppm) with a LOD of 1 ppm. Combining the colorimetric response of AuNP solutions, their absorbance spectra, and principal component analysis can improve detection reliability. The assay, coupled with a simple recovery method using acetonitrile swabbing, achieves high reproducibility in detecting chlorpyrifos in cucumber, even at concentrations as low as 0.11 ppm. This approach can be tailored for various chlorpyrifos concentrations not only in cucumbers but also in different food matrices.
Assuntos
Clorpirifos , Cucumis sativus , Contaminação de Alimentos , Ouro , Nanopartículas Metálicas , Análise Espectral Raman , Clorpirifos/análise , Análise Espectral Raman/métodos , Ouro/química , Nanopartículas Metálicas/química , Contaminação de Alimentos/análise , Cucumis sativus/química , Limite de Detecção , Quimiometria , Inseticidas/análise , Inseticidas/químicaRESUMO
Chlorpyrifos (CPF) residues in food pose a serious threat to ecosystems and human health. Herein, we propose a three-dimensional folded paper-based microfluidic analysis device (3D-µPAD) based on multifunctional metal-organic frameworks, which can achieve rapid quantitative detection of CPF by fluorescence-colorimetric dual-mode readout. Upconversion nanomaterials were first coupled with a bimetal organic framework possessing peroxidase activity to create a fluorescence-quenched nanoprobe. After that, the 3D-µPAD was finished by loading the nanoprobe onto the paper-based detection zone and spraying it with a color-developing solution. With CPF present, the fluorescence intensity of the detection zone gradually recovers, the color changes from colorless to blue. This showed a good linear relationship with the concentration of CPF, and the limits of detection were 0.028 (fluorescence) and 0.043 (colorimetric) ng/mL, respectively. Moreover, the 3D-µPAD was well applied in detecting real samples with no significant difference compared with the high-performance liquid chromatography method. We believe it has huge potential for application in the on-site detection of food hazardous substance residues.
Assuntos
Clorpirifos , Contaminação de Alimentos , Estruturas Metalorgânicas , Papel , Clorpirifos/análise , Estruturas Metalorgânicas/química , Contaminação de Alimentos/análise , Colorimetria/métodos , Colorimetria/instrumentação , Limite de Detecção , Resíduos de Praguicidas/análise , Resíduos de Praguicidas/química , Inseticidas/análise , Inseticidas/química , Técnicas Analíticas Microfluídicas/instrumentação , Dispositivos Lab-On-A-ChipRESUMO
This study evaluated the presence of the three pesticides methomyl (MET), carbendazim (CBZ) and chlorpyrifos-ethyl (CPE), as well as the degradation product of CPE (3,5,6-trichloro-2-pyridinol; TCP), in 44 honey samples from all 12 regions of Morocco. With a validated HPLC-UV method occurrence frequencies of 63.6% for MET, 54.5% for CBZ, 95.1% for CPE and 34.1% for TCP were obtained, even at concentrations higher than the maximum residue limits for MET, CPE and TCP. Based on the predominant pesticide, principal component analysis separated sampling regions into three groups. Risk assessment indicated that ingestion of these pesticides, alone or in combination, in honey did not pose a risk to consumers (HQ and HI < 1).
Assuntos
Contaminação de Alimentos , Mel , Resíduos de Praguicidas , Mel/análise , Marrocos , Resíduos de Praguicidas/análise , Contaminação de Alimentos/análise , Humanos , Medição de Risco , Cromatografia Líquida de Alta Pressão , Análise de Componente Principal , Carbamatos/análise , Clorpirifos/análise , BenzimidazóisRESUMO
In the last years, issues related to intensive agriculture have been found in protected areas potentially harming wildlife. This study aimed to analyze a wide range of pesticides in water and sediments of two protected areas namely Doñana Natural Park (DNP) and Tablas de Daimiel National Park (TDNP) performing an environmental risk assessment in order to highlight potential risks to living organisms derived from pesticide burden. Higher pesticide load was found in DNP than TDNP with similar distribution profiles, with pyrethroid insecticides (PYRs) the main detected class. Particularly problematic are two PYRs, cyhalothrin and fenvalerate, which were detected at high concentrations that can pose a high risk to aquatic organisms. In addition, despite being detected at lower concentrations, the presence of chlorpyrifos, cypermethrin, and permethrin in water, and of chlorpyrifos, dicofol, and diflufenican in sediments, must be taken into account due to their potential risks for aquatic organisms. Moreover, some banned pesticides such as dimethoate, terbutryn, diazinon, and tricyclazol were detected in water at levels which deserve further investigation to assess their potential sources, including potential illegal practices.
Assuntos
Monitoramento Ambiental , Sedimentos Geológicos , Praguicidas , Piretrinas , Poluentes Químicos da Água , Sedimentos Geológicos/química , Poluentes Químicos da Água/análise , Praguicidas/análise , Espanha , Medição de Risco , Piretrinas/análise , Clorpirifos/análise , Nitrilas/análiseRESUMO
Elasmobranchs are good indicators of marine pollution as they accumulate pollutants from water and food, and occupy different trophic levels. Concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and chlorpyrifos were quantified in muscle, liver, gonads, gills, and brain in both sexes and maturity stages of the Southern Eagle Ray, Myliobatis goodei, captured in Argentine coastal waters. Moreover, possible histological alterations in the liver and gonads were analyzed. Pollutant concentrations were pervasive across all tissues, with PCBs > OCPs > chlorpyrifos. Elevated pollutant levels were notably found in the liver and gills. We identified thirty-six PCB congeners in tissues, with low-chlorine congeners prevailing. Among OCPs, ∑DDT and ∑endosulfan were predominant. Females exhibited higher pollutant levels in most tissues compared to males, except in the gonads, and adults generally displayed elevated pollutant levels. Histological analysis revealed the presence of atretic follicles and melanomacrophages (MM). Continuous monitoring of pollutant levels, alongside their effects on physiological and ecological traits, is imperative for effective management and conservation efforts.
Assuntos
Clorpirifos , Monitoramento Ambiental , Gônadas , Hidrocarbonetos Clorados , Bifenilos Policlorados , Rajidae , Poluentes Químicos da Água , Animais , Clorpirifos/análise , Poluentes Químicos da Água/análise , Bifenilos Policlorados/metabolismo , Bifenilos Policlorados/análise , Feminino , Masculino , Hidrocarbonetos Clorados/metabolismo , Praguicidas/metabolismo , Fígado , Brânquias , ArgentinaRESUMO
Free enzymes cause difficulties in many applications due to their insufficient stability, loss of activity in a short time, and most importantly, although they are costly, they are used only once in reactions, lose their effect and cannot be recovered from the environment. Magnetic nanoparticles coated with biocompatible polymeric material are potential candidates for promising enzyme carriers due to their multifunctional pore surfaces, easy removal from the environment provided by the magnetization, ability to main stability under various harsh conditions. This study prepared a biosensor candidate based on the inhibiting acetylcholinesterase enzyme by organophosphate pesticides from chitosan-coated magnetic nanoparticles doped with gold. Transmission electron microscopy, scanning electron microscopy, X-ray diffraction diffractometry, and Fourier transform infrared spectroscopy analysis confirmed the structure of synthesized nanocomposites. Magnetic characteristics of the nanocomposites were assessed using VSM. Bio-nanocomposite (Fe3O4@Cht/Au/AChE) was used to determine environmental pollutants qualitatively. Remediation of organophosphate-containing wastewater is an essential issue for environmental sustainability. In this work, Dichlorvos and Chlorpyrifos were selected as organic pollutants to assess the enzymatic activity of immobilized Fe3O4@Cht/Au/AChE. Optimum conditions for AChE enzyme were immobilized nanostructures (Fe3O4@Cht/Au/AChE) were determined. The optimum pH for the immobilized enzyme was found to be 8, and the optimum temperature was found to be 60 °C. Retained immobilized enzyme activity is found to be around 50% for the 20th reuse. In the presence of 150 µL pesticide, retained immobilized enzyme activity is found to be around 25%. Method validation was performed for pesticides. When using immobilized AChE, the LOD (limit of detection)-LOQ (limit of quantitation) values for Dichlorovos and Chlorpyrifos was obtained in the range of 0.0087-0.029 nM and 0.0014-0.0046 nM, respectively. The relative standard deviation (RSD%) values, which are indicators of precision, were found to be below 2%.
Assuntos
Acetilcolinesterase , Clorpirifos , Enzimas Imobilizadas , Nanocompostos , Praguicidas , Acetilcolinesterase/química , Acetilcolinesterase/metabolismo , Enzimas Imobilizadas/química , Nanocompostos/química , Praguicidas/química , Clorpirifos/análise , Quitosana/química , Técnicas Biossensoriais , Nanopartículas de Magnetita/química , Diclorvós , Ouro/químicaRESUMO
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.
Assuntos
Compostos de Cádmio , Transferência Ressonante de Energia de Fluorescência , Compostos Organofosforados , Praguicidas , Pontos Quânticos , Sulfetos , Telúrio , Compostos de Zinco , Pontos Quânticos/química , Compostos de Cádmio/química , Compostos de Zinco/química , Praguicidas/análise , Sulfetos/química , Transferência Ressonante de Energia de Fluorescência/métodos , Telúrio/química , Compostos Organofosforados/análise , Limite de Detecção , Malus/química , Clorpirifos/análise , Contaminação de Alimentos/análiseRESUMO
The development of advanced biosensors for tracking chemical residues and detecting environmental pollution is of great significance. Insect chemical sensory proteins, including chemosensory proteins (CSPs), are easy to synthesize and purify and have been used to design proteins for specific biosensor applications. Chlorpyrifos is one of the most commonly used chemicals for controlling insect pests in agriculture. This organophosphate is harmful to aquatic species and has long-term negative consequences for the ecosystem. CSPs can bind and carry a variety of environmental chemicals, including insecticides. However, the mechanism by which CSPs bind to insecticides in aphids has not been clarified. In this study, we discovered that RpCSP1 from Rhopalosiphum padi has a higher affinity for chlorpyrifos, with a Ki value of 4.763 ± 0.491 µM. Multispectral analysis revealed the physicochemical binding mechanism between RpCSP1 and chlorpyrifos. Computational simulation analysis demonstrated that the main factor promoting the development of the RpCSP1-chlorpyrifos complex is polar solvation energy. Four residues (Arg33, Glu94, Gln145, Lys153) were essential in facilitating the interaction between RpCSP1 and chlorpyrifos. Our research has improved knowledge of the relationship between CSPs and organophosphorus pesticides. This knowledge contributes to the advancement of biosensor chips for tracking chemical residues and detecting environmental pollution through the use of CSPs.
Assuntos
Clorpirifos , Proteínas de Insetos , Inseticidas , Clorpirifos/metabolismo , Clorpirifos/análise , Animais , Inseticidas/metabolismo , Proteínas de Insetos/metabolismo , Afídeos , Monitoramento Ambiental/métodos , Receptores Odorantes/metabolismo , Técnicas Biossensoriais , Resíduos de Praguicidas/análiseRESUMO
Exploring efficient photoactive material presents an intriguing opportunity to enhance the analytical performance of photoelectrochemical (PEC) sensor in the environmental analysis. In this work, a sandwich-structured multi-interface Co9S8@ZnIn2S4/CdSe QDs dual Z-Scheme heterojunction, derived from metal-organic framework (MOF), was synthesized as a sensing platform for chlorpyrifos detection, by integrating with enzyme-induced in situ insoluble precipitates strategy. The meticulously designed Co9S8@ZnIn2S4/CdSe QDs exhibited enhanced charge separation efficiency and was proved to be a highly effective sensing platform for the immobilization of biomolecules, attributing to the intrinsic dual Z-Scheme heterojunction and the distinctive hollow structure. The proposed PEC sensing platform combined with enzyme-induced in situ precipitate signal amplification strategy achieved superior performance for sensing of chlorpyrifos (CPF), showing in wide linear range (1.0 pg mL-1-100 ng mL-1), with a limit of detection (0.6 pg mL-1), excellent selectivity, and stability. This work offers valuable insights for the design of novel advanced photoactive materials aimed at detecting environmental pollutants with low level concentration.
Assuntos
Técnicas Biossensoriais , Clorpirifos , Técnicas Eletroquímicas , Limite de Detecção , Estruturas Metalorgânicas , Pontos Quânticos , Clorpirifos/análise , Estruturas Metalorgânicas/química , Técnicas Eletroquímicas/métodos , Pontos Quânticos/química , Compostos de Cádmio/química , Compostos de Selênio/química , Cobalto/química , Inseticidas/análiseRESUMO
Evaluating biomarkers of stress in amphibians is critical to conservation, yet current techniques are often destructive and/or time-consuming, which limits ease of use. In the present study, we validate the use of dermal swabs in spotted salamanders (Ambystoma maculatum) for biochemical profiling, as well as glutathione (GSH) stress response following pesticide exposure. Thirty-three purchased spotted salamanders were acclimated to laboratory conditions at Washington College (Chestertown, MD, USA) for 4 weeks. Following acclimation, salamanders were randomly sorted into three groups for an 8-h pesticide exposure on soil: control with no pesticide, 2,4-dichlorophenoxyacetic acid (2,4-D), or chlorpyrifos. Before and after exposure, mucus samples were obtained by gently rubbing a polyester-tipped swab 50 times across the ventral and dorsal surfaces. Salamanders were humanely euthanized and dissected to remove the brain for acetylcholinesterase and liver for GSH and hepatic metabolome analyses, and a whole-body tissue homogenate was used for pesticide quantification. Levels of GSH were present in lower quantities on dermal swabs relative to liver tissues for chlorpyrifos, 2,4-D, and control treatments. However, 2,4-D exposures demonstrated a large effect size increase for GSH levels in livers (Cohen's d = 0.925, p = 0.036). Other GSH increases were statistically insignificant, and effect sizes were characterized as small for 2,4-D mucosal swabs (d = 0.36), medium for chlorpyrifos mucosal swabs (d = 0.713), and negligible for chlorpyrifos liver levels (d = 0.012). The metabolomics analyses indicated that the urea cycle, alanine, and glutamate metabolism biological pathways were perturbed by both sets of pesticide exposures. Obtaining mucus samples through dermal swabbing in amphibians is a viable technique for evaluating health in these imperiled taxa. Environ Toxicol Chem 2024;43:1126-1137. © 2024 SETAC.
Assuntos
Glutationa , Metabolômica , Animais , Glutationa/metabolismo , Muco/metabolismo , Clorpirifos/análise , Praguicidas/metabolismo , Ácido 2,4-Diclorofenoxiacético , Pele/metabolismo , Pele/química , Pele/efeitos dos fármacos , Ambystoma/metabolismo , Biomarcadores/metabolismo , Biomarcadores/análiseRESUMO
Argentina is a leading honey producer and honey bees are also critical for pollination services and wild plants. At the same time, it is a major crop producer with significant use of insecticides, posing risks to bees. Therefore, the presence of the highly toxic insecticide chlorpyrifos, and forbidden contaminants (organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)) was investigated in honey bee, beebread, wax and honey samples in apiaries from three contrasting regions of Argentina. Chlorpyrifos was detected in all samples with higher levels during period 1 (spring) in contrast to period 2 (fall), agreeing with its season-wise use in different crops, reaching 3.05 ng/g in honey bees. A subsequent first-tier pesticide hazard analysis revealed that it was relevant to honey bee health, mainly due to the high concentrations found in wax samples from two sites, reaching 132.4 ng/g. In addition, wax was found to be the most contaminated matrix with a prevalence of OCPs (∑OCPs 58.23-172.99 ng/g). Beebread samples showed the highest concentrations and diversity of pesticide residues during period 1 (higher temperatures). A predominance of the endosulfan group was registered in most samples, consistent with its intensive past use, especially in Central Patagonia before its prohibition. Among the industrial compounds, lighter PCB congeners dominated, suggesting the importance of atmospheric transport. The spatio-temporal distribution of pesticides shows a congruence with the environmental characteristics of the areas where the fields are located (i.e., land use, type of productive activities and climatic conditions). Sustained monitoring of different pollutants in beekeeping matrices is recommended to characterize chemical risks, assess the health status of honey bee hives and the pollution levels of different agroecosystems. This knowledge will set a precedent for South America and be helpful for actions focused on the conservation of pollination services, apiculture and ecosystems in Argentina.
Assuntos
Monitoramento Ambiental , Poluentes Ambientais , Mel , Abelhas , Argentina , Animais , Mel/análise , Poluentes Ambientais/análise , Bifenilos Policlorados/análise , Ceras/análise , Ceras/química , Éteres Difenil Halogenados/análise , Praguicidas/análise , Estações do Ano , Clorpirifos/análiseRESUMO
Pesticides are used in vegetable farming to control pests and diseases, reduce crop losses and improve yield. The study examined pesticide residues in irrigation waters and leafy green vegetables grown in some farming areas in Accra, Ghana. Three types of irrigation water sources (n = 23) and two exotic and four indigenous Ghanaian leafy vegetables (n = 34) from 10 farming areas in Accra, Ghana were collected and examined for 15 organochlorines, 13 organophosphorus and 9 synthetic pyrethroids pesticide residues using the modified QuEChERS procedure. Pesticide residues were detected on 50% (17/34) of the leafy vegetable and 52% (12/23) of the irrigation water samples analysed. Chlorpyrifos and deltamethrin were the most detected pesticide residues in the vegetables and irrigation water. About 26.5% of the vegetables contained pesticide residues exceeding the EU maximum residue limits, so vegetable farmers should be encouraged to comply with appropriate measures on pesticide use to enhance food safety.
Assuntos
Irrigação Agrícola , Contaminação de Alimentos , Resíduos de Praguicidas , Verduras , Gana , Resíduos de Praguicidas/análise , Verduras/química , Irrigação Agrícola/métodos , Contaminação de Alimentos/análise , Humanos , Piretrinas/análise , Nitrilas/análise , Clorpirifos/análise , Poluentes Químicos da Água/análise , Folhas de Planta/química , Compostos Organofosforados/análiseRESUMO
Bioaccumulation of Chlorpyrifos (CP) as pesticides due to their aggrandized use in agriculture has raised serious concern on the health of ecosystem and human beings. Moreover, their degraded products like 3,5,6-trichloro-2-pyridinol (TCP) has enhanced the distress due to their unpredictable biotoxicity. This study evaluates and deduce the comparative in vivo mechanistic biotoxicity of CP and TCP with zebrafish embryos through experimental and computational approach. Experimental cellular and molecular analysis showed higher induction of morphological abnormalities, oxidative stress and apoptosis in TCP exposed embryos compared to CP exposure due to upregulation of metabolic enzymes like Zhe1a, Sod1 and p53. Computational analysis excavated the differential discrepancies in intrinsic atomic interaction as a reason of disparity in biotoxicity of CP and TCP. The mechanistic differences were deduced due to the differential accumulation and internalisation leading to variable interaction with metabolic enzymes for oxidative stress and apoptosis causing physiological and morphological abnormalities. The study unravelled the information of in vivo toxicity at cellular and molecular level to advocate the attention of taking measures for management of CP as well as TCP for environmental and human health.
Assuntos
Clorpirifos , Animais , Humanos , Clorpirifos/toxicidade , Clorpirifos/análise , Peixe-Zebra , Ecossistema , Piridonas/toxicidadeRESUMO
Throughout this research, a new magnetic molecularly imprinted polymer on fibrous silica nanosphere was prepared through self-polycondensation. The selective extraction of chlorpyrifos was performed by the synthesized sorbent and as a determination system, a gas chromatography-electron capture was applied. The formation of sorbent was confirmed through the use of Fourier transform infrared spectroscopy and field emission scanning electron microscopy techniques. The parameters affecting the extraction efficacy of the proposed method were scrutinized in an optimized way. The linear range and the detection limit of the studied method were 0.003-0.3 and 0.001 ng mL-1, respectively. The relative standard deviations were 4.1-5.2 and 5.6-7.6 % for intra- and inter-day (n = 3), respectively. To assess the performance of the proposed method, some water and fruit samples were analyzed and the extraction recoveries of 83-109 % were obtained. These results revealed the method's performance in the analysis of chlorpyrifos in real samples.
Assuntos
Clorpirifos , Impressão Molecular , Nanosferas , Clorpirifos/análise , Polímeros Molecularmente Impressos , Dióxido de Silício/química , Polímeros/química , Extração em Fase Sólida/métodos , Adsorção , Fenômenos Magnéticos , Impressão Molecular/métodosRESUMO
Mancozeb residue estimation was done using second derivative ultraviolet spectroscopy by Shimadzu ultraviolet-visible spectrophotometer, and chlorpyrifos was estimated by QuEChERS technique using GC-FPD. The persistence for chlorpyrifos was carried out at two locations, and for mancozeb, persistence studies were carried out at four locations. Initial deposits of mancozeb on apple fruits ranged from 1.33 to 1.63 mg/kg at the recommended dose and from 2.55 to 3.26 mg/kg at double the recommended dose at all four locations. Chlorpyrifos residues in apple fruits had an initial deposit of 0.94-0.99 mg/kg at recommended dose and 1.75-1.92 mg/kg at double the recommended dose. Mancozeb residues in apple fruit were below the detection limit (BDL) after 20 days at recommended dose and after 25 days at double the recommended dose at two locations, while mancozeb residue at the other two locations and the residues of chlorpyrifos at all locations reached BDL after 15 and 20 days at recommended and double the recommended doses, respectively. Half-life of mancozeb varied from 3.07 to 4.02 days at recommended dose and from 3.30 to 4.32 days at double the recommended dose, whereas chlorpyrifos residues dissipated to half their initial concentration on 2.33-2.35 days at recommended dose and 2.89-2.90 days at double the recommended dose. The soil samples showed no presence of residues of chlorpyrifos and mancozeb at harvest. The risk assessment revealed that hazard quotient for the intake of mancozeb was in the range of 0.06-0.13% and 0.20-0.44% for rural and urban population, while for the intake of chlorpyrifos, hazard quotient was in the range of 0.10-0.12% for rural population and 0.33-0.38% for urban population, and theoretical maximum dietary intake (9.67 × 10-5 mg/person and 3.18 × 10-4 mg/person for rural population and urban population in case of mancozeb and 3.22 × 10-5 mg/person and 1.06 × 10-4 mg/person for rural population and urban population in case of chlorpyrifos) was also found to be less than maximum permissible intake (1.38 mg/kg for mancozeb and 0.60 mg/kg for chlorpyrifos). The results of risk assessment thereby indicated that apple consumption does not pose a risk to human health.
Assuntos
Clorpirifos , Malus , Resíduos de Praguicidas , Poluentes do Solo , Humanos , Clorpirifos/análise , Frutas/química , Solo/química , Resíduos de Praguicidas/análise , Poluentes do Solo/análise , Monitoramento Ambiental/métodos , Medição de Risco , Meia-VidaRESUMO
Se realizó un estudio descriptivo de las condiciones de exposición a clorporifos de los embolsadores de dos fincas bananeras en el viejo, Chinandega a 43 trabajadores de las fincas bananeras los que se dedican a diferentes actividades entre ellas, la de embolsar los racimos con la "bolsa Dursban". En el estudio se pudo comprobar que las concentraciones de clorporifós existentes en las bolsas Dursban está entre 1.09-1.18 porciento lo que indica que estan entre los párametros establecidos internacionalmente que son (0.5- 2 porciento) para que la bolsa cumpla su función de protección del racimo desde su nacimiento hasta el momento de la cosecha. Pero al mismo tiempo representa una directa manipulación de productos organofosforado por los trabajadores. En vista que el principal efecto de la exposición a productos organofosforado es la depresión de las colines se considero necesario realizar un monitoreo biológico conel objetivo de establecer medidas cuantitativas de pesticida absorvida. A través del presente estudio se lograrón realizar algunas medidas de intervención ya que se había encontrado intoxicaciones sub-clínicas en el grupo ded trabajadores expuestos, logrando modificar parcialmente la fuente como es la condición insegura de la elliminación de la bolsa de Dusban,así mismo se logro el retiro de la exposición directa aproductos organofosforado de estos trabajadores. Lográndose una recuperación parcial en los niveles de colinesterasa plasmática en un tiempo después