RESUMO
Agricultural products are vitally important for sustaining life on earth and their production has notably grown over the years worldwide in general and in Brazil particularly. Elevating agricultural practices consequently leads to a proportionate increase in the usage of pesticides that are crucially important for enhanced crop yield and protection. These compounds have been employed excessively in alarming concentrations, causing the contamination of soil, water, and air. Additionally, they pose serious threats to human health. The current study introduces an innovative tool for producing appropriate materials coupled with an electrochemical sensor designed to measure carbendazim levels. The sensor is developed using a molecularly imprinted polymer (MIP) mounted on a glassy carbon electrode. This electrode is equipped with multi-walled carbon nanotubes (MWCNTs) for improved performance. The combined system demonstrates promising potential for accurately quantifying carbendazim. The morphological characteristics of the synthesized materials were investigated using field emission scanning electron microscopy (FESEM) and the Fourier-transform infrared (FTIR) technique. The analytical curve was drawn using the electrochemical method in the range of 2 to 20 ppm while for HPLC 2-12 ppm; the results are presented as the maximum adsorption capacity of the MIP (82.4%) when compared with NIP (41%) using the HPLC method. The analysis conducted using differential pulse voltammetry (DPV) yielded a limit of detection (LOD) of 1.0 ppm and a repeatability of 5.08% (n = 10). The results obtained from the analysis of selectivity demonstrated that the proposed electrochemical sensor is remarkably efficient for the quantitative assessment of carbendazim, even in the presence of another interferent. The sensor was successfully tested for river water samples for carbendazim detection, and recovery rates ranging from 94 to 101% were obtained for HPLC and 94 to 104% for the electrochemical method. The results obtained show that the proposed electrochemical technique is viable for the application and quantitative determination of carbendazim in any medium.
Assuntos
Benzimidazóis , Carbamatos , Técnicas Eletroquímicas , Nanotubos de Carbono , Praguicidas , Carbamatos/análise , Benzimidazóis/análise , Praguicidas/análise , Nanotubos de Carbono/química , Técnicas Biossensoriais , Eletrodos , Materiais Biomiméticos/química , Limite de DetecçãoRESUMO
The ubiquity and impact of pharmaceuticals and pesticides, as well as their residues in environmental compartments, particularly in water, have raised human and environmental health concerns. This emphasizes the need of developing sustainable methods for their removal. Solar-driven photocatalytic degradation has emerged as a promising approach for the chemical decontamination of water, sparking intensive scientific research in this field. Advancements in photocatalytic materials have driven the need for solar reactors that efficiently integrate photocatalysts for real-world water treatment. This study reports preliminary results from the development and evaluation of a solar system for TiO2-based photocatalytic degradation of intermittently flowing water contaminated with doxycycline (DXC), sulfamethoxazole (SMX), dexamethasone (DXM), and carbendazim (CBZ). The system consisted of a Fresnel-type UV solar concentrator that focused on the opening and focal point of a parabolic trough concentrator, within which tubular quartz glass reactors were fixed. Concentric springs coated with TiO2, arranged one inside the other, were fixed inside the quartz reactors. The reactors are connected to a raw water tank at the inlet and a check valve at the outlet. Rotating wheels at the collector base enable solar tracking in two axes. The substances (SMX, DXC, and CBZ) were dissolved in dechlorinated tap water at a concentration of 1.0 mg/L, except DXM (0.8 mg/L). The water underwent sequential batch (~ 3 L each, without recirculation) processing with retention times of 15, 30, 60, 90, and 120 min. After 15 min, the degradation rates were as follows: DXC 87%, SMX 35.5%, DXM 32%, and CBZ 31.8%. The system processed 101 L of water daily, simultaneously removing 870, 355, 256, and 318 µg/L of DXC, SMX, DXM, and CBZ, respectively, showcasing its potential for real-world chemical water decontamination application. Further enhancements that enable continuous-flow operation and integrate highly effective adsorbents and photocatalytic materials can significantly enhance system performance.
Assuntos
Fotoquímica , Energia Solar , Poluentes Químicos da Água , Purificação da Água , Água , Catálise/efeitos da radiação , Água/química , Purificação da Água/instrumentação , Purificação da Água/métodos , Humanos , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificação , Doxiciclina/química , Doxiciclina/isolamento & purificação , Sulfametoxazol/química , Sulfametoxazol/isolamento & purificação , Dexametasona/química , Dexametasona/isolamento & purificação , Quartzo , Cromatografia , Temperatura , Fatores de Tempo , Animais , Abastecimento de ÁguaRESUMO
The synergy between eco-friendly biopolymeric films and printed devices leads to the production of plant-wearable sensors for decentralized analysis of pesticides in precision agriculture and food safety. Herein, a simple method for fabrication of flexible, and sustainable sensors printed on cellulose acetate (CA) substrates has been demonstrated to detect carbendazim and paraquat in agricultural, water and food samples. The biodegradable CA substrates were made by casting method while the full electrochemical system of three electrodes was deposited by screen-printing technique (SPE) to produce plant-wearable sensors. Analytical performance was assessed by differential pulse (DPV) and square wave voltammetry (SWV) in a linear concentration range between 0.1 and 1.0 µM with detection limits of 54.9 and 19.8 nM for carbendazim and paraquat, respectively. The flexible and sustainable non-enzymatic plant-wearable sensor can detect carbendazim and paraquat on lettuce and tomato skins, and also water samples with no interference from other pesticides. The plant-wearable sensors had reproducible response being robust and stable against multiple flexions. Due to high sensitivity and selectivity, easy operation and rapid agrochemical detection, the plant-wearable sensors can be used to detect biomarkers in human biofluids and be used in on-site analysis of other hazardous chemical substances.
Assuntos
Praguicidas , Dispositivos Eletrônicos Vestíveis , Humanos , Praguicidas/análise , Paraquat/análise , Inocuidade dos Alimentos , Agricultura , Água/análiseRESUMO
Carbendazim, a fungicide widely used in agriculture, has been classified as a hazardous chemical by the World Health Organization due to its environmental persistence. It is prohibited in several countries; therefore, detecting it in food and environmental samples is highly necessary. A reliable, rapid, and low-cost method uses electrochemical sensors and biosensors, especially those modified with carbon-based materials with good analytical performance. In this review, we summarize the use of carbon-based electrochemical (bio)sensors for detecting carbendazim in environmental and food matrixes, with a particular interest in the role of carbon materials. Focus on publications between 2018 and 2023 that have been describing the use of carbon nanotubes, carbon nitride, graphene, and its derivatives, and carbon-based materials as modifiers, emphasizing the analytical performance obtained, such as linear range, detection limit, selectivity, and the matrix where the detection was applied.
RESUMO
Wearable sensors such as those made with paper are needed for non-destructive routine analysis of pesticides on plants, fruits, and vegetables. Herein we report on electrochemical sensors made with screen-printed carbon electrodes on kraft and parchment papers to detect the fungicide carbendazim. A systematic optimization was performed to find that electrochemical sensors on kraft paper treated in an acidic medium led to the highest performance, with a detection limit of 0.06 µM for carbendazim. The enhanced sensitivity for this sensor was attributed to the porous nature of kraft paper, which allowed for a large electrode surface area, and to the carboxylic groups formed during electrochemical activation. As a proof-of-concept, the electrochemical sensor attached to the skin of apple and cabbage was used to detect carbendazim with the same performance as the gold standard method, thus demonstrating that the sensor can be used in the farm and on supermarket shelves.
Assuntos
Brassica , Malus , Limite de Detecção , Carbamatos/análise , Técnicas Eletroquímicas/métodos , EletrodosRESUMO
In this exploratory study, naturally occurring Salvinia biloba Raddi specimens were assessed for atrazine and carbendazim polluted water remediation. Experiments were carried out over 21 days in glass vessels containing deionized water artificially contaminated with 0, 5, 10, and 20 mg L-1 of atrazine or carbendazim. Atrazine had a pronounced detrimental impact on S. biloba, as no biomass development was observed in all macrophytes exposed to this herbicide in the entire concentration range. However, carbendazim-treated plants were able to grow and survive in the polluted medium even when subjected to the highest concentration of this fungicide (i.e., 20 mg L-1). In addition, increased chlorosis and necrosis were also detected in plants subjected to carbendazim as a result of the high phytotoxicity caused by atrazine. A maximal removal efficiency of ~ 30% was observed for both pesticides at 5 mg L-1 and decreased with increasing concentrations of the pollutants. The spectrum of the FTIR-ATR analysis revealed the existence of various functional groups (e.g., amide, carboxyl, hydroxyl, phosphate, sulfate) on the plants, which could be related to pesticide biosorption. In addition, at the end of the 21-day assay, seven carbendazim-resistant bacteria could be isolated from the roots of fungicide-treated plants. Therefore, the use of autochthonous free-floating S. biloba macrophytes for phytoremediation of aquatic environments contaminated with carbendazim shows great promise. Still, additional research is required to further elucidate the plant-mediated carbendazim elimination process and the role of the herbicide-resistant bacteria, and seek alternative species capable of mitigating atrazine contamination.
Assuntos
Atrazina , Fungicidas Industriais , Herbicidas , Praguicidas , Traqueófitas , Poluentes Químicos da Água , Atrazina/análise , Fungicidas Industriais/análise , Herbicidas/análise , Praguicidas/análise , Biodegradação Ambiental , Água/análise , Poluentes Químicos da Água/análiseRESUMO
Carbendazim is a systemic fungicide used in several countries, particularly in Brazil. However, studies suggest that it is related to the promotion of tumors, endocrine disruption, and toxicity to organisms, among other effects. As a result, carbendazim is not allowed in the United States, Australia, and some European Union countries. Therefore, further studies are necessary to evaluate its effects, and zebrafish is a model routinely used to provide relevant information regarding the acute and long-term effects of xenobiotics. In this way, zebrafish water tank samples (water samples from aquari containing zebrafish) and liver samples from animals exposed to carbendazim at a concentration of 120 µg/L were analyzed by liquid chromatography coupled to high-resolution mass spectrometry, followed by multivariate and univariate statistical analyses, using the metabolomics approach. Our results suggest impairment of lipid metabolism with a consequent increase in intrahepatic lipids and endocrine disruption. Furthermore, the results suggest two endogenous metabolites as potential biomarkers to determine carbendazim exposure. Finally, the present study showed that it is possible to use zebrafish water tank samples to assess the dysregulation of endogenous metabolites to understand biological effects. Environ Toxicol Chem 2023;42:437-448. © 2022 SETAC.
Assuntos
Poluentes Químicos da Água , Peixe-Zebra , Animais , Peixe-Zebra/metabolismo , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/metabolismo , Metabolômica/métodos , Fígado , Lipídeos , Água/metabolismoRESUMO
The present study analyzed the performance of photochemical and electrochemical techniques in the degradation and mineralization of the pesticide carbendazim (CBZ). Direct photolysis (DP), heterogeneous photocatalysis (HP), photoelectrocatalysis (PEC), and electrochemical oxidation (EO) were tested, and the influence of UV radiation, current density (j), and supporting electrolyte concentration were evaluated. The results suggest that CBZ is only degraded by DP when UV-C254nm is used. For HP, the CBZ degradation was observed both when UV-A365nm or UV-C254nm were used, which is related to the reactive oxygen species (ROS) formed by the photocatalytic activity (photon-ROS). Neither DP nor HP were able to mineralize CBZ, demonstrating its resistance to photomediated processes. For EO, regardless of the j, there were higher CBZ degradation and mineralization than those observed when using DP and HP. The increase in the supporting electrolyte concentration (Na2SO4) did not affect the levels of degradation and mineralization of CBZ. Concerning the PEC, a CBZ mineralization of 52.2% was accomplished. These findings demonstrate that the EO is the main pathway for CBZ mineralization, suggesting an additional effect of the electro-ROS on the photon-ROS and UV-C254nm. The values of mineralization, kinetics, and half-life show that PEC UV-C254nm with a j of 15 mA cm-2 was the best setting for the degradation and mineralization of CBZ. However, when the values of specific energy consumption were considered for industrial applications, the use of EO with a j of 3 mA cm-2 and 4 g L-1 of Na2SO2 becomes more attractive. The assessment of by-products formed after this best cost-efficient treatment setting revealed the presence of aromatic and aliphatic compounds from CBZ degradation. Acute phytotoxicity results showed that the presence of sodium sulfate can be a representative factor regarding the toxicity of samples treated in electrochemical systems.
Assuntos
Poluentes Químicos da Água , Benzimidazóis , Carbamatos , Oxirredução , Fotólise , Raios Ultravioleta , Poluentes Químicos da Água/químicaRESUMO
On-site monitoring the presence of pesticides on crops and food samples is essential for precision and post-harvest agriculture, which demands nondestructive analytical methods for rapid, low-cost detection that is not achievable with gold standard methods. The synergy between eco-friendly substrates and printed devices may lead to wearable sensors for decentralized analysis of pesticides in precision agriculture. In this paper we report on a wearable non-enzymatic electrochemical sensor capable of detecting carbamate and bipyridinium pesticides on the surface of agricultural and food samples. The low-cost devices (Assuntos
Técnicas Biossensoriais
, Praguicidas
, Dispositivos Eletrônicos Vestíveis
, Agricultura
, Inocuidade dos Alimentos
, Praguicidas/análise
, Poliésteres
RESUMO
Carbendazim (CBZ) is a fungicide employed in grape crop disease controls, and its maximum residue limit in food is regulated by specialized agencies. This study aimed to determine the CBZ content in the grape juices in a semi-quantitative classification model based on portable Ultraviolet-Visible spectroscopy and partial least squares with discriminant analysis. The sensitivity and specificity of the obtained model ranged from 83 to 100%, with the external validation set. These results are therefore promising for industrial application, and the model presents robustness for the evaluation of grape juices produced from a different grape variety. The VIP scores allowed identifying important variables involved in class modeling. This study suggests a methodology that is fast and demands minimal sample preparation (only dilution), besides being less expensive compared to the traditional methods, free of reagent/solvent, contributing to quality control in the juice industry.