Carbaryl Residues Research Articles

Dual colorimetric/electrochemical sensor of carbaryl in fruits on microfluidic paper-based analytical device connected with smartphone readout

A dual colorimetric/electrochemical sensor integrated with a microfluidic paper-based analytical device (μPAD) is created for rapid and sensitive detection of cabaryl in fruit. For colorimetric sensor, quercetin modified silver nanoparticle (QCT-AgNPs) is synthesized via self-reduction, resulting in the color change from green to dark green in the presence of cabaryl, which can be readily observed via naked eyes. This colorimetric sensor provides a linear response of 5 – 50 μM quantified by Image J software. For electrochemistry, AgNPs/MXene nanocomposite electrode offers high electrocatalytic activity towards the detection of carbarly with a linear range of 0 – 60 µM and a detection limit of 0.01 µM. The limit of detection values obtained from this dual sensor are lower than a cut-off of carbaryl residue in food, which is 7 mg.kg−1 (35 µM) verifying the desired sensitivity of this platform. Ultimately, this dual sensor is successfully applied for on-site detection of carbaryl in the orange samples read out on the smartphone with satisfactory results.

A sensitive electrochemical biosensor for detection of carbaryl based on hollow covalent-organic frameworks-gold nanoparticles nanospheres

Carbaryl as an important insecticide is always used in agricultures to achieve higher yields. So, rapid detection of carbaryl residues in agricultural products is very necessary due to its potential harm to human beings. Herein, a hollow covalent-organic frameworks (HCOFTFPB-DBD) gold nanoparticles (AuNPs) nanospheres was used to construct a sensitive electrochemical carbaryl biosensor. The surface of electrode modified by HCOFTFPB-DBD-AuNPs nanospheres was negatively charged and repelled the [Fe(CN)6]3-/4-. The acetylcholinesterase (AChE) immobilized on HCOFTFPB-DBD-AuNPs nanospheres catalyzed the hydrolysis of acetylcholine chloride to thiocholine (TCh). The obtained positively charged TCh was adsorbed on the electrode surface by Au-S, which made the electrode surface positively charged to adsorb the negatively charged [Fe(CN)6]3-/4-, showing enhanced oxidation current of [Fe(CN)6]3-/4-. After carbaryl was added, the oxidation current of [Fe(CN)6]3-/4- deceased because ChE activity were inhibited by carbaryl. So, the sensitive detection of carbaryl was achieved at a low potential, which resulted in a high selectivity. The biosensor had a detection limit of 0.38 μM, a linear range of 1.10 μM-40.0 μM, a sensitivity of 0.00863 mA μM−1 and better performance in actual sample.

Ultrasensitive and On-Site Detection of Carbaryl Pesticides via Dual-Mode Nanosensors Utilizing Portable Devices

High-efficiency detection technologies of carbaryl residues are significant due to their adverse effects on the environment and human health. To achieve accurate in situ analysis, we designed a portable device integrated with a smartphone sensing platform for rapid, visual quantitative determination of carbaryl via colorimetric and fluorescent signals. Amino-modified gold nanoparticles (AuNPs), blue-emitting silicon quantum dots (Si QDs), and red-emitting cadmium telluride quantum dots (CdTe QDs) were used as opto-sensing centers. The carbaryl triggered the agglomeration of the as-synthesized AuNPs by an electrostatic effect, resulting in a specific change in UV–vis absorption. The blue fluorescence of Si QDs recovered, while the red fluorescence of CdTe QDs quenched, enabling fluorescence color variation from red to blue for visual monitoring. The ratiometric fluorescent signals are available for quantitative analysis in the range of 6 to 200 μM, with a limit of 16.3 nM for fluorescence detection and 49.6 nM for colorimetric sensitivity detection. Coupling widely used three-dimensional print and application software, we constructed the smartphone platform to output the ratio of red and blue channel values of captured fluorescence images to meet the needs of on-site analysis in real samples. This work imposed great improvement in ratiometric sensing for carbamate pesticide residues and broadened the portable quantitative sensing device in chemical sensing applications.

A Sensitive Electrochemical Aptasensor Based on Black Phosphorus Nanosheet for Carbaryl Detection

Carbaryl is a broad-spectrum carbamate insecticide widely used to control pests on crops, trees and ornamental plants. Carbaryl residues in fruits and vegetables and other foods can accumulate in the human body and damage human health. Therefore, it is very essential to establish a sensitive and reliable method for determination of carbaryl. Black phosphorene nanosheets (BPNPs) modified glassy carbon electrode was herein prepared using poly(3,4-dioxyethylenethiophene)-poly(styrene sulfonate) (PEDOT: PSS) as both membrane and stabilizer. The nanocomposites (BP-PEDOT: PSS) were synthesized by combining BP at the ratio of PEDOT: PSS, which improved conductivity and stability of BP. In order to enhance the electrochemical signal and build the carbaryl aptamer sensor, the surface of BP-PEDOT: PSS was modified by Au nanoparticles (Au NPs). The carbaryl aptamer modified with sulfhydryl groups was immobilized in the outer layer of Au NPs, and the target carbaryl was specifically recognized and captured by carbaryl aptamer and adsorbed on the electrode surface, thus causing changes in the interfacial electrochemical signal. The conditions were optimized and characterized by cyclic voltammetry (CV), and linear equation was obtained as ΔI(μA) = −11.35logC−29.70, R2 = 0.997. The detection range was 0.01 ng/mL–10 μg/mL, with a limit of detection of 7.0 pg/mL.

Development of a Sensitive and Fast Determination Method for Trace Carbaryl Residues in Food Samples Based on Magnetic COF (TpPa-NH2)@Fe3O4 Nanoparticles and Fluorescence Detection.

Developing a simple and effective method for measuring carbaryl residues in food is urgent due to its widespread use and the associated health risks in agriculture, as well as various defects in existing detection techniques. The COF (TpPa-NH2)@Fe3O4 nanocomposite (amino modification) was synthesized via a two-step method and used as an adsorbent for the extraction of carbaryl from food samples in this study. The results indicated that COF (TpPa-NH2)@Fe3O4 can rapidly and successfully capture carbaryl directly from samples via π–π stacking and hydrophobic interactions, achieving maximum adsorption within 5 min under a small adsorbent quantity using a fluorescence spectrophotometer. Under the optimized conditions, carbaryl exhibited good linearity in the range of 0.2–120 µg·kg−1, and the limit of detection was 0.012 µg·kg−1. The recoveries of the samples were 96.0–107.4%. This method has broad application prospects for the monitoring of carbaryl in food.

A Simple and Reliable Dispersive Liquid-Liquid Microextraction with Smartphone-Based Digital Images for Determination of Carbaryl Residues in Andrographis paniculata Herbal Medicines Using Simple Peroxidase Extract from Senna siamea Lam. Bark.

A simple and reliable dispersive liquid-liquid microextraction (DLLME) coupled with smartphone-based digital images using crude peroxidase extracts from cassia bark (Senna siamea Lam.) was proposed to determine carbaryl residues in Andrographis paniculata herbal medicines. The method was based on the reaction of 1-naphthol (hydrolysis of carbaryl) with 4-aminoantipyrine (4-AP) in the presence of hydrogen peroxide, using peroxidase enzyme simple extracts from cassia bark as biocatalysts under pH 6.0. The red product, after preconcentration by DLLME using dichloromethane as extraction solvent, was measured for blue intensity by daily life smartphone-based digital image analysis. Under optimized conditions, good linearity of the calibration graph was found at 0.10–0.50 mg·L−1 (r2 = 0.9932). Limits of detection (LOD) (3SD/slope) and quantification (LOQ) (10SD/slope) were 0.03 and 0.09 mg·L−1, respectively, with a precision of less than 5%. Accuracy of the proposed method as percentage recovery gave satisfactory results. The proposed method was successfully applied to analyze carbaryl in Andrographis paniculata herbal medicines. Results agreed well with values obtained from the HPLC-UV method at 95% confidence level. This was simple, convenient, reliable, cost-effective and traceable as an alternative method for the determination of carbaryl.

Metal Organic Framework-Based Dispersive Solid-Phase Microextraction of Carbaryl from Food and Water Prior to Detection by Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry

In this work, metal organic frameworks (A100 Al-based MOFs) were used in dispersive solid-phase microextraction (DSPME) for the isolation and preconcentration of the carbaryl from vegetable, fruit and water samples. The A100 Al-based MOFs showed excellent behavior for the adsorption of carbaryl from a water–ethanol solution; additionally, carbaryl was easily desorbed with ethyl acetate for detection by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-TMS). The analytical process of DSPME together with UPLC-TMS provides the accurate monitoring of trace carbaryl residues. The results show that the optimal recovery% of carbaryl was obtained at a sample apparent pH of 5, with the application of 1 mL of ethyl acetate to elute the carbaryl from the A100 Al-based MOFs. The limit of detection (LOD) and the limit of quantification (LOQ) were 0.01 mg.L−1 and 0.03 mg.L−1, respectively. The RSD% was 0.8–1.9, and the preconcentration factor was 45. DSPME and UPLC-TMS were successfully used for the isolation and detection of carbaryl in food and water samples.

Validation of Pesticides Multi-Residual Testing Method on Nutmeg by Using UPLC-MS/MS

The use of pesticides in nutmeg still leaves an accumulation of pesticide residues that can endanger human health and damage the ecological balance. In addition, nutmeg with high pesticide residue content will be rejected by nutmeg export destination countries. This research was conducted to validate the method of testing pesticide residues of carbaryl, carbofuran, acetate, and dimethoate on nutmeg. This pesticide residue test uses the QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) optimization method and is analyzed using UPLC-MS/MS (Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry). This method meets the validation requirements according to SANTE/12682/2019. The limit of quantification (LOQ) of the analyte is below the Maximum Residue Limit (MRL) set by the European Union through Regulation (EC) No. 396/2005.

Detection of the Carbaryl in Wastewater by HPLC-DAD

A method for determination of the carbaryl pesticide residue in wastewater by high performance liquid chromatography (HPLC). HPLC using Agilent ZORBAX SB-C18 column as a separate column; the use of volume ratio(55:45) of methanol: water as the mobile phase; the use of a diode array detector(DAD) detection at 268 nm at carbaryl residues; pretreatment of water samples using the extraction method is simple and feasible method of operation; laboratory water samples from wastewater, test results show: accuracy relative standard deviation(RSD) was 0.67%, and the recovery rates were in the range of 102 to 112%.

EFFECT OF HOUSEHOLD PROCESSING ON REMOVAL OF MULTI-CLASSES OF PESTICIDES FROM TOMATOES

In this paper, twenty-two pesticide residues were monitored in tomatoes.72 marketed samples were extracted and purified with QuEChERS method, and analyzed with liquid and gas Chromatography. The mean recoveries ranged from 90.75%to105.31%. The relative standard deviation was 1% to 7.5%. The limits of detection and quantification ranged from 0.0004 to 0.0231 mg.kg−1 and 0.0012 to 0.0693 mg.kg−1, and good linearity was obtained. Out of total analyzed samples, 34 samples (47.22%) were contaminated with tested pesticide residues; out of which 10 samples (13.89%) exceeded the maximum residue limits. The effects of four processing techniques (washing with tap water, washing with solution of acetic acid, peeling and boiling) on the residual pattern of five insecticides (dimethoate, carbaryl, chlorpyrifos, cypermethrin and fenvalerate) and one herbicide (2,4 dichlorophenoxy acetic acid (2,4D)) were evaluated. The reaction of the pesticides depends obviously on the physico-chemical features and also on the systemic character of the pesticides. Both of the washings lowered clearly the residues for all detected pesticides with removing up to 63.08%. Peeling was found to totally remove the residues of fenvalerate, carbaryl, cypermethrin and chlorpyrifos. Results obtained from the boiling indicated that a complete removal of 2,4D and dimethoate residues was finally achieved. In addition to that, the concentrations of cypermethrin and fenvalerate increased and processing factors above 1 were observed, the results can be seen as valuable base for monitoring of pesticides in tomatoes and supply more comprehension of residue demeanor after household processing. These implementations are important to protect consumer health from the damage of pesticide residues in food.

A copper nanoparticle-based electrochemical immunosensor for carbaryl detection

A hapten-protein conjugate with copper nanoparticles (Hap-Car-BSA@CuNPs) was first synthesized in the present work for the determination of carbaryl. The copper nanoparticles (CuNPs) of the conjugate were used as electrochemical labels in the direct solid-phase competitive determination of carbaryl residues in flour from different crops. The signal was read by linear sweep anodic stripping voltammetry (LSASV) of copper (through the electrochemical stripping of accumulated elemental copper) on a gold-graphite electrode (GGE). To form a recognition receptor layer of monoclonal antibodies against the carbaryl on the surface of the GGE, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) and 1-hydroxy-2,5-pyrrolidinedione (NHS) were used as the best covalent cross-linkers. The concentrations of the antibodies and the Hap-Car-BSA@CuNPs conjugate were optimized for carbaryl detection by the electrochemical immunosensor. The electrochemical immunosensor can be used for highly sensitive determination of carbaryl residues in flour samples in the concentration range 0.8–32.3 μg·kg−1, with a limit of detection 0.08 μg·kg−1. The present work paves the path for a novel method for monitoring carbaryl in other food products, drinks, and soil samples.

COPPER-LABELED VOLTAMMETRIC IMMUNOSENSOR FOR CARBARYL DETECTION

A hapten-protein conjugate for determining carbaryl using copper nanoparticles was first synthesized in the present work. The copper nanoparticles were used as electrochemical labels in the direct solid-phase competitive analysis of carbaryl residues in flour from some crops. Copper nanoparticles stabilized by chitosan and a hapten-protein conjugate with copper nanoparticles stabilized by chitosan by UV/VIS - spectroscopy, transmission electron microscopy, and dynamic light scattering are characterized. To form a recognition receptor layer of monoclonal antibodies against the carbaryl on the surface of a gold-graphite electrode, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, dicyclohexylcarbodiimide and 1-hydroxy-2,5-pyrrolidinedione were found to be the best covalent cross-linkers. When selection the electrochemical immunosensor conditions, working dilutions of the antibodies and the hapten-protein conjugate with copper nanoparticles copper nanoparticles stabilized by chitosan were selected to detect the carbaryl. The effect of ethyl alcohol on the performance of the electrochemical immunosensor for the determination of carbaryl was evaluated. The specificity of the developed electrochemical immunosensor was investigated by testing structurally related carbaryl compounds; the results did not exceed 7%. The electrochemical immunosensor can be used for highly sensitive determination of carbaryl residues in flour samples with a detection limit of 0.08 μg /kg within a range of detectable contents of 0.8-32.3 μg/kg.

Persistence of carbaryl pesticide in environment using system dynamics model

Carbaryl, one of the carbamate insecticides are used extensively for pest control in agriculture. The chemical is highly valued for its rapid action and relatively short environmental persistence. Because of its widespread and intensive use, residues of carbaryl have the potential to contaminate the environment. This study aims to formulate a system dynamics model to simulate a degradation process of carbaryl. Since carbaryl was not readily volatilizing, this study only estimates the concentration and degradation of carbaryl in soil and water. The result revealed that carbaryl degraded rapidly, with a half-life of 7 days in soil and two days in water. The model was validated with a laboratory experiment using solid phase extraction reversed-phase high-performance liquid chromatography to determine carbaryl concentration. 12.82 % percentage error compared to the experimental value indicated that the developed model’s prediction was acceptable. The model can be used to estimate the presence of carbaryl pesticide in soil and water. Findings from this study can be used to assess the fate and the impact of carbaryl pesticide in the environment.

A Novel Multi-purpose MIP for SPE-HPLC and QCM Detection of Carbaryl Residues in Foods

In this work, two detection methods of solid-phase extraction–high-performance liquid chromatography (SPE-HPLC) and quartz crystal microbalance (QCM) were established, based on a surface molecularly imprinted polymer material (MIP). The material can be used as a selective solid-phase extraction filler and as a coating for sensitive quartz crystal microbalances by virtue of the polyhydroxy structure of grafted silicon spheres together with the network structure from cross-linked polymerization. The adsorption properties of the prepared MIP were analysed by dynamic and static adsorption tests, and the experimental conditions for SPE-HPLC and QCM analysis were optimized. Under the optimal conditions, the linear range of MIP-SPE-HPLC for the detection of carbaryl was 0.5–60 μg L−1 (R2 = 0.99913), and the detection limit was 0.0573 μg L−1. The proposed QCM sensor displayed a linear relationship between the frequency shift and the concentration of carbaryl ranging from 5 to 80 μg L−1 with a low detection limit of 0.6845 μg L−1 (signal-to-noise ratio, S/N = 3). Through a series of experiments, it was shown that the prepared MIP has good adsorption and selectivity for carbaryl, and the MIP-based HPLC and QCM sensor can be applied to the detection of actual food samples.

A ratiometric fluorescence nanoprobe using CdTe QDs for fast detection of carbaryl insecticide in apple

In this study, a novel, simple and sensitive ratiometric fluorescence method is presented for the detection of very low quantities of the carbaryl in Iranian apple using cadmium telluride quantum dots (CdTe QDs) nanoprobe. The principle of the proposed strategy relies on the rapid hydrolysis of the carbaryl under an alkaline condition and production of the 1-naphthol with a blue emission at 470 nm. Besides, using the CdTe QDs with a yellow emission at 580 nm, as a reference, improves the visual tracking of carbaryl through changes in color tonality. The herein described methodology is applied for enzyme-free visual detection of carbaryl with satisfactory results in the presence of other common pesticides in Iranian apple sample. Additionally, the calculated limit of detection (LOD) of 0.12 ng mL−1 for carbaryl is much lower than the maximum residue limits of carbaryl warned value reported by the European Union and United States pesticides database, which is so promising for carbaryl sensing in the monitoring of fruits. Furthermore, the ability of the proposed method for the detection of carbaryl residues in Iranian apple was confirmed by the high-performance liquid chromatography (HPLC) method as a standard method through statistical analysis. This fast and highly sensitive naked-eye ratiometric sensor may hold great promise to provide the technical support for the rapid and valid detection of other targets in food safety fields.

Occurrence of Carbaryl, DDT and Deltamethrin Residues in Bovine Milk in Chhattisgarh, India and Risk Assessment to Human Health

The aim of this study was to determine the occurrence of pesticide residues in bovine milk and associated health risks in human. To assess the pesticide residues, a total of 200 milk samples were analyzed using High Performance Liquid Chromatography (HPLC) with Photo Diode Array Detector (PDA).The residues of carbaryl, 4’4’ DDT and deltamethrin pesticides were found in the 27.5%, 11% and 5% milk samples, respectively. The spatial distribution of pesticide residues in milk samples indicated that carbaryl was wide spread over the entire study area. The non-significance differences in mean residual concentrations of all three pesticides in cow and buffalo milk samples were recorded. The human health risk assessment in terms of non-carcinogenic and carcinogenic health hazard was calculated based on both lower bound [LB (mean residue levels)] and upper bound [UB (95th percentile level)] limits at current levels of pesticides in bovine milk samples. The estimated average daily dietary intake (EADDI) of studied pesticides was found below the acceptable dietary intake (ADI) for both adult and children, at mean as well as 95th percentile upper bound (UB) levels. The values suggesting lower carcinogenic and non-carcinogenic health risk to adult however children are at greater health risk.

Development of a sensitive liquid-liquid extraction and ultra-performance liquid chromatography-tandem mass spectrometry method for the analysis of carbaryl residues in fresh vegetables sold in Riyadh

An UPLC- mass spectrometry method has been proposed for the screening of carbaryl residues in fresh vegetables. Carbaryl treated samples of lettuce, cucumber and spinach were procured and analyzed for a time period of fifteen days to find out the amount of carbaryl residue. A simple and effective liquid–liquid sample extraction technique has been implemented for extraction of carbaryl. Multiple reactions monitoring analysis mode considering two daughter transitions was used for quantitation and confirmation analysis of carbaryl. The developed method has been authenticated by establishing various validation parameters including, linear ranges (0.001–5.0 µg/mL), percent recovery, reproducibility (precision), limits of detection (0.0003 µg/mL) and limits of quantification (0.0009 µg/mL). The recoveries were obtained in the range of 96.0 and 99.5% (RSD < 3.8%, n = 3). All fresh vegetable samples have shown unlike carbaryl contamination for a certain time interval. The results were clearly designated that the residue quantities of the inspected pesticide does not cross the established maximum residue limits (MRLs).

Ratiometric Strategy for Electrochemical Sensing of Carbaryl Residue in Water and Vegetable Samples.

Accurate analysis of pesticide residue in real samples is essential for food safety and environmental protection. However, a traditional electrochemical sensor based on single-signal output is easily affected by background noise, environmental conditions, electrode diversity, and a complex matrix of samples, leading to extremely low accuracy. Hence, in this paper, a ratiometric strategy based on dual-signal output was adopted to build inner correction for sensing of widely-used carbaryl (CBL) for the first time. By comparison, Nile blue A (NB) was selected as reference probe, due to its well-defined peak, few effects on the target peak of CBL, and excellent stability. The effects of a derivatization method, technique mode, and pH were also investigated. Then the performance of the proposed ratiometric sensor was assessed in terms of three aspects including the elimination of system noise, electrode deviation and matrix effect. Compared with traditional single-signal sensor, the ratiometric sensor showed a much better linear correlation coefficient (r > 0.99), reproducibility (RSD < 10%), and limit of detection (LOD = 1.0 μM). The results indicated the introduction of proper reference probe could ensure the interdependence of target and reference signal on the same sensing environment, thus inner correction was fulfilled, which provided a promising tool for accurate analysis.

Spatial distribution of environmental pollutants in natural honeys collected from some regions of Saudi Arabia

Natural honeys produced in some regions located in Saudi Arabia (KSA) were characterized on the basis of their physicochemical properties and the contents of heavy metals and pesticide residues. Some of the investigated samples fit most of the national and international specifications with geographical and seasonal variations. The levels of Pb2+, Cd2+, and Cu2+ in most of the tested samples were below the guideline values of 0.1, 0.05, and 5 mg/kg, respectively; however, Zn2+ and Fe3+ levels in most of the tested samples exceeded the guideline values of 5 and 15 mg/kg, respectively. The high levels of Mn2+ and Ni2+ have been found in all the tested samples which can be attributed either to the production stages of honey or the region from where the honey has been taken. Also, the present results revealed that some pesticides such as chlorothalonil, carbaryl, dicofol, and monocrotophos residues were detected in some samples. It can be concluded that some metals and pesticide residues are not in safety baseline levels for human consumption and may pose a health risk to consumers.

Carbaryl residue concentrations, degradation, and major sinks in the Seto Inland Sea, Japan.

The fate of carbaryl in the Seto Inland Sea (west Japan) was predicted using a mass distribution model using carbaryl concentrations in river and sea water samples, degradation data, and published data. The predicted carbaryl concentrations in water in Kurose River and the Seto Inland Sea were 4.320 and 0.2134μg/L, respectively, and the predicted concentrations in plankton, fish, and sediment were 0.4140, 2.436, and 1.851μg/g dry weight, respectively. The carbaryl photodegradation and biodegradation rates were higher for river water (0.330 and 0.029day-1, respectively) than sea water (0.23 and 0.001day-1, respectively). The carbaryl photodegradation rates for river and sea water (0.33 and 0.23day-1, respectively) were higher than the biodegradation rates (0.029 and 0.001day-1, respectively). The hydrolysis degradation rate for carbaryl in sea water was 0.003day-1, and the half-life was 231days. Land (via rivers) was the main source of carbaryl to the Seto Inland Sea. The model confirmed carbaryl is distributed between sediment, plankton, and fish in the Seto Inland Sea. Degradation, loss to the Open Ocean, and sedimentation are the main carbaryl sinks in the Seto Inland Sea, accounting for 43.81, 27.90, and 17.68%, respectively, of total carbaryl inputs. Carbaryl source and sink data produced by the model could help in the management of the negative impacts of carbaryl on aquatic systems and human health.