Pesticide Residues In Grapes Research Articles

Dissipation of selected pesticide residues in grapes by using ozone enriched atmosphere

In this research work, by exposing the grapes to an ozone-enriched environment maintained at 4 °C for 14 days, the dissipation of widely used pesticides in grapes that exceeded the maximum residue limit was investigated. The study was completed in two stages. High Performance Liquid Chromatography (HPLC) was used in the first phase to determine whether pesticides were present in the grapes. In the second phase, ozonation was applied to residues that exceeded the maximum residue limit (MRL) for imidacloprid, acetamiprid, and chlorpyrifos. Each pesticide was destroyed by ozonation, but to varying degrees. For imidacloprid (1.236–0.125 ppm), acetamiprid (0.421–0.237 ppm), and chlorpyrifos (3.617–1.146 ppm), the pesticide burden was progressively decreased from 1 day to 14 days of storage. Chlorpyrifos levels were found to have decreased by up to 95 %. Acetamiprid and imidacloprid also shown degradation of roughly 75–85 %. Furthermore, the physicochemical characteristics of grapes, including brix (20.63), total acidity (0.35), weight loss percentage (8.45), and pH (3.72), were not significantly affected by ozone.

Quantitative determination of residue amounts of pesticide active ingredients used in grapes by LC-MS/MS and GC-MS/MS devices and evaluation of these pesticides in terms of public health.

The aim of this study was to quantitatively determine pesticide residues in grapes, one of the most produced and consumed fruits in Turkey and in the world. A total of 226 active ingredients were analyzed in 21 samples collected from Southeastern and Eastern Anatolia regions using QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction method and multiple residue analysis technique and LC-MS/MS and GC-MS/MS devices. In 11 out of 21 samples (52.4%), no active ingredient was detected, while at least one active ingredient was detected in 10 samples (47.6%). Thirteen different active substances (Ametoctradin, Azoxystrobin, Boscalid, Diphenoconazole, Dimethomorph, Fenhexamid, Fluopyram, Flutriafol, Metalaxyl- Metalaxyl-M, Metrafenone, Tebuconazole, Trifloxystrobin) were detected in the samples. The top 3 most detected active substances were Boscalid-Azoxystrobin and Fluopyram, respectively. The active ingredients were found between 0.015 and 0.499 mg kğ-1 values.

Nanosensors in Pesticide Residue Detection in Grapes

Pesticide residues in grapes pose significant risks to human health and necessitate the development of efficient detection methods to ensure food safety. In recent years, nanosensor technology has emerged as a promising approach for sensitive and reliable pesticide residue detection. This review article provides a comprehensive overview of the recent advancements in nanosensor-based detection methods for pesticide residues in grapes. The article discusses various types of nanosensors employed for pesticide residue detection, including nanostructured materials, nanomaterial-based sensors, and nano biosensors. Nanostructured materials, such as nanoparticles, nanowires, and nanocomposites, offer unique properties that enable high sensitivity and selectivity in detecting pesticide residues. Nanomaterial-based sensors, such as carbon-based, metal-based, and semiconductor-based sensors, provide excellent electrical and optical properties for precise and rapid detection. Furthermore, nano biosensors, including enzymatic and DNA-based sensors, offer specificity and sensitivity through bio-recognition elements. Challenges and future perspectives in the field are discussed, including the standardization and validation of nanosensor-based methods, cost-effectiveness, scalability, integration with portable devices and the Internet of Things (IoT), as well as environmental and regulatory considerations. This review summarizes key findings, discusses the potential impact of nanosensors on the grape industry, and identifies future research directions for further advancement and implementation of nanosensor-based detection methods.

Facile synthesis of gold nanostars for the duplex detection of pesticide residues in grapes using SERS.

In recent years, concerns have been raised regarding the contamination of grapes with pesticide residues. As consumer demand for safer food products grows, regular monitoring of pesticide residues in food has become essential. This study sought to develop a rapid and sensitive technique for detecting two specific pesticides (phosmet and paraquat) present on the grape surface using the surface-enhanced Raman spectroscopy (SERS) method. Gold nanostars (AuNS) particles were synthesized, featuring spiky tips that act as hot spots for localized surface plasmon resonance, thereby enhancing Raman signals. Additionally, the roughened surface of AuNS increases the surface area, resulting in improved interactions between the substrate and analyte molecules. Prominent Raman peaks of mixed contaminants were acquired and used to characterize and quantify the pesticides. It was observed that the SERS intensity of the Raman peaks changed in proportion to the concentration ratio of phosmet and paraquat. Moreover, AuNS exhibited superior SERS enhancement compared to gold nanoparticles. The results demonstrate that the lowest detectable concentration for both pesticides on grape surfaces is 0.5mg/kg. These findings suggest that SERS coupled with AuNS constitutes a practical and promising approach for detecting and quantifying trace contaminants in food. PRACTICAL APPLICATION: This research established a novel surface-enhanced Raman spectroscopy (SERS) method coupled with a simplified extraction protocol and gold nanostar substrates to detect trace levels of pesticides in fresh produce. The detection limits meet the maximum residue limits set by the EPA. This substrate has great potential for rapid measurements of chemical contaminants in foods.

Determination, temporal variation and potential health risk assessment of pesticide residues in grapes from South and Southwest China

Pesticide residues in grapes from South and Southwest China were determined using the QuEChERS procedure and UHPLC-MS/MS and GC-MS/MS methods. The 4-year monitoring and survey showed 94.6% of the 1341 samples of grapes collected from eight main production areas contained one or multiple pesticide residues (above the respective LOQs). Overall, 40 pesticides were detected, including 24 fungicides, 12 insecticides, 2 acaricides and 2 plant growth modulators, of which one pesticide was unauthorised for use in treating grapes. Two or more pesticide residues were discovered in 87.4% of the samples (above the respective LOQs), and pesticide residues in 5.7% of the samples exceeded the MRLs, such as difenoconazole, cyhalothrin, propiconazole, etc. The main risk factors affecting the safety of grape before 2019 were difenoconazole, cyhalothrin and cyazofamid. After 2019, however, the frequency of occurrence of the above pesticides significantly declined, and the banned or restricted pesticides including omethoate were not found, 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 grapes, about 84% of the samples were compliant with regulatory standards. Moreover, the accumulative chronic diet risk determined from ADI is very low. This study and timely monitoring can ensure that grape growers comply with GAP and minimise the occurrence of residues.

Interaction between Six Waxy Components in Summer Black Grapes (Vitis vinifera) and Mancozeb and Its Effect on the Residue of Mancozeb.

Mancozeb, an antifungal typically used for the growth of fruits, has the characteristic of non-internal absorption, and has a risk of binding to the waxy components of fruits. This work investigated the interaction of pesticide molecules with the waxy layer on the grape surface and their effects on pesticide residues in grapes. The study observed significant changes in the compositions of the waxy layer on the grape surface after soaking in a mancozeb standard solution. The six substances-oleanolic acid, ursolic acid, lupeol, octacosanol, hexacosanal, and γ-sitosterol-with discernible content differences were chosen for molecular docking. Docking results were further visualized by an independent gradient model based on Hirshfeld partition (IGMH). Hydrogen bonds and van der Waals forces were found between mancozeb and the six waxy components. Moreover, the negative matrix effects caused by the presence or absence of wax for the determination of mancozeb were different through the QuEChERS-HPLC-MS method. Compared with the residue of mancozeb in grapes (5.97 mg/kg), the deposition of mancozeb in grapes after dewaxing was significantly lower (1.12 mg/kg), which further supports that mancozeb may interact with the wax layer compositions. This work not only provides insights into the study of the interaction between pesticides and small molecules but also provides theoretical guidelines for the investigation of the removal of pesticide residues on the surface of fruits.

The interaction effects of pesticides with Saccharomyces cerevisiae and their fate during wine-making process

Pesticide residues in grapes could be transferred to fermentation system during the wine-making process, which may interfere the normal proliferation of Saccharomyces cerevisiae and subsequently affect the safety and quality of wine products. However, the interaction between pesticides and Saccharomyces cerevisiae is still poorly understood. Herein, the fate, distribution and interaction effect with Saccharomyces cerevisiae of five commonly-used pesticides during the wine-making process were evaluated. The five pesticides exerted varied inhibition on the proliferation of Saccharomyces cerevisiae, and the order of inhibition intensity was difenoconazole > tebuconazole > pyraclostrobin > azoxystrobin > thiamethoxam. Compared with the other three pesticides, triazole fungicides difenoconazole and tebuconazole showed stronger inhibition and played a major role in binary exposure. The mode of action, lipophilicity and exposure concentration were important factors in the inhibition of pesticides. Saccharomyces cerevisiae had no obvious impacts on the degradation of target pesticides in the simulated fermentation experiment. However, the levels of target pesticides and their metabolite were significantly reduced during the wine-making process, with the processing factors ranged from 0.030 to 0.236 (or 0.032 to 0.257) during spontaneous (or inoculated) wine-making process. As a result, these pesticides were significantly enriched in the pomace and lees, and showed a positive correlation (R2 ≥ 0.536, n = 12, P < 0.05) between the hydrophobicity of pesticides and distribution coefficients in the solid-liquid distribution system. The findings provide important information for rational selection of pesticides on wine grapes and facilitate more accurate risk assessments of pesticides for grape processing products.

Determination of Pesticide Residues in Grapes Consumed in Natura and for Juice and Wine Production by High-Performance Liquid Chromatography with High Resolution Mass Spectrometry (HPLC-HRMS)

The grape is the fifth most consumed fruit around the world with a production of approximately 85 million tons that requires pesticide use; however, some of these compounds may damage to the environment, as well as have implications for human and animal health. Therefore, the present work aims to evaluate the pesticide residues present in grapes of different varieties for in natura consumption as well as for production of wine and juice. As a result, the methodology was validated having limits of quantification ranging from 14.86 (for chlorantraniliprole) to 308.01 µg L−1 (for etofenprox), recovery values between 82 and 119%, and relative standard deviations less than 20%. Thus, the method was applied to 10 real samples produced in south Brazil, targeting 92 pesticides of different classes by high-performance liquid chromatography coupled to high resolution mass spectrometry (HPLC-HRMS). Approximately 80% of the samples have residues of at least one compound, including 6 pesticides not approved for grape cultivation: atrazine, carbaryl, carbendazim, etoxazole, malathion, and simazine. Fenarimol is allowed to be used in this culture in Brazil; however, it was present in a concentration higher than its maximum residue level (MRL) in 57% of the samples. Thus, in this work, we present the application of a valid method by HLC-HRMS for grapes. These results show that, regardless of the variety and purpose of the grapes, many pesticides are present in this fruit, requiring greater control by farmers as well as supervisory bodies because the toxicological effects of these compounds in high concentrations have already been demonstrated in both consumers and farmers who have been directly exposed.

Modern Analytical Methods for the Analysis of Pesticides in Grapes: A Review.

Currently, research on the determination of pesticides in food products is very popular. Information obtained from research conducted so far mainly concerns the development of a methodology to determine the content of pesticides in food products. However, they do not describe the content of the pesticide used in viticulture in the resulting product. Over the past decade, this study has examined analytical methodologies for assessing pesticide residues in grapes. Scopus, Web of Science, Science Direct, PubMed, and Springer databases were searched for relevant publications. The phrases “pesticides” and “grapes” and their combinations were used to search for articles. The titles and annotations of the extracted articles have been read and studied to ensure that they meet the review criteria. The selected articles were used to compile a systematic review based on scientific research and reliable sources. The need to study the detection of pesticide residues in grapes using advanced analytical methods is confirmed by our systematic review. This review also highlights modern methods of sample preparation, such as QuEChERS, SPME, PLE, dLLME, and ADLL-ME, as well as the most used methods of separation and identification of pesticides in grapes. An overview of the countries where residual grape pesticide amounts are most studied is presented, along with the data on commonly used pesticides to control pests and diseases in grape cultivation. Finally, future possibilities and trends in the analysis of pesticide residues in grapes are discussed by various analytical methods.

Detection of Pesticide Residue Level in Grape Using Hyperspectral Imaging with Machine Learning.

Rapid and accurate detection of pesticide residue levels can help to prevent the harm of pesticide residue. This study used visible/near-infrared (Vis-NIR) (376–1044 nm) and near-infrared (NIR) (915–1699 nm) hyperspectral imaging systems (HISs) to detect the level of pesticide residues. Three different varieties of grapes were sprayed with four levels of pesticides. Logistic regression (LR), support vector machine (SVM), random forest (RF), convolutional neural network (CNN), and residual neural network (ResNet) models were used to build classification models for pesticide residue levels. The saliency maps of CNN and ResNet were conducted to visualize the contribution of wavelengths. Overall, the results of NIR spectra performed better than those of Vis-NIR spectra. For Vis-NIR spectra, the best model was ResNet, with the accuracy of over 93%. For NIR spectra, LR was the best, with the accuracy of over 97%, but SVM, CNN, and ResNet also showed closed and fine results. The saliency map of CNN and ResNet presented similar and closed ranges of crucial wavelengths. Overall results indicated deep learning performed better than conventional machine learning. The study showed that the use of hyperspectral imaging technology combined with machine learning can effectively detect the level of pesticide residues in grapes.

Effect of ozone application on the removal of pesticides from grapes and green bell peppers and changes in their nutraceutical quality

The present study evaluates the efficacy of ozonated water for the removal of pesticide residues in grapes and green bell peppers. Fruit fortified with pesticides (azoxystrobin, chlorothalonil, chlorpyrifos, cypermethrin, hexaconazole and methyl parathion) were subjected to 15 and 30 min aqueous ozone treatment. GC analysis of ozonated fruits showed a 48.67% to 96.95% decrease in pesticide residues of different pesticides. Methyl paraoxon, a toxic degradation product of methyl parathion, was detected in the ozonated water sample. To assess the effect of ozonation on the nutraceutical quality of fruits, the concentrations of eleven polyphenols and ascorbic acid were analyzed. The individual polyphenols showed different trend in 15 and 30 min treatment. Overall, there was an increase in the levels of all the polyphenols in grapes after 30 min ozonation treatment. In peppers, there was a net increase in quercetin, quercetin-3-O-glucoside, rutin and kaempferol in 30 min while other polyphenols were decreased. The ascorbic acid content of both the fruits was decreased by more than 70% upon ozonation. Thus, ozonation treatment was effective in pesticide removal. However, it changed the nutraceutical quality of grapes and green bell peppers.

Determination of Pesticide Residues in Grapes From Vineyards Implemented Good Agricultural Practice in Uşak

This study was conducted to determine pesticides residue levels in grapes samples which taken from vineyards implemented good agricultural practice in Uşak province in 2017 growing seasons. A total of 51 grape samples from three districts were collected. Liquid chromatography with mass spectrometry (LC-MS/MS) and gas chromatography with mass spectrometry (GC-MS/MS) devices were used for all analyses. In 45.1% of the samples taken weren’t detected any pesticide residue. In 54.9% of grape samples found residue, none of this pesticides exceeded the maximum residue limits given in Turkish Food Codex. The most common pesticides detected in grape samples with residue were spinosad, pyrimethanil and boscalid respectively. Thirteen different pesticide active substances were detected below the MRL in the samples. All pesticides detected in the samples were fungicides (85%) and insecticides (15%).

Evaluation of QuEChERS Sample Preparation and Gas Chromatography Coupled to Mass Spectrometry for the Determination of Pesticide Residues in Grapes

An effective analytical method for pesticides multiresidue determination in grape samples was developed and validated. A modified quick, easy, cheap, effective, robust and safe (QuEChERS) method was used to extract the target compounds. Several sorbent materials were tested for the clean-up step using dispersive solid phase extraction (d-SPE) and Florisil® was selected. Samples extracts were evaporated before injection in the gas chromatography with mass spectrometry (GC-MS) system in order to improve detectability. Recoveries from blank samples spiked at 0.04, 0.3 and 1.0 mg kg−1 ranged from 95 to 102% with relative standard deviation (RSD) from 1.3 to 19.7%. Method limits of detection (LODm) and quantification (LOQm) ranged from 0.006 to 0.012 and 0.02 to 0.04 mg kg−1, respectively. The positive matrix effect caused an increase in the peak areas of all compounds and matrix matched calibration curve linearity (coefficient of determination, r2) was higher than 0.98 for all target analytes. The validated method was successfully applied for the determination of 19 pesticides in grape samples.

Effect of pesticide residues in grapes on alcoholic fermentation and elimination of chlorothalonil inhibition by chlorothalonil hydrolytic dehalogenase

The effect of different kinds of pesticide residues in grapes on alcoholic fermentation by Saccharomyces cerevisiae was evaluated. Among four types of pesticides added into the grape slurry, omethoate, triadimefon and cyhalothrin did not inhibit the alcoholic fermentation at their proposed spraying concentration of 0.21, 0.10 and 0.10 g L−1, respectively, whereas chlorothalonil concentration above 0.03 g L−1 behaved significantly negative influence on both S. cerevisiae growth and alcoholic fermentation efficiency. When the chlorothalonil concentration was lower than 0.01 g L−1, the fermentation proceeded smoothly without any degradation of chlorothalonil. Considering the cumulative toxicity and adverse effect of chlorothalonil on fermentation, chlorothalonil hydrolytic dehalogenase (Chd) extracellularly expressed from the recombinant Bacillus subtilis WB800 was used to pretreat the chlorothalonil-contaminated grape slurry. After treatment by the Chd enzyme in an activity of 7.25 mU L−1 slurry for 60 min, the inhibition effect could be substantially eliminated even at an initial concentration of 0.10 g L−1 chlorothalonil. This study provides a potential approach for solving the conflict in fermentation industry with pesticides inhibition.

Multiresidue Analysis of Pesticides and Metabolites from Fruits and Vegetables by Gas Chromatography—Time-of-Flight Mass Spectrometry

This work describes the comparison of five sample extraction methods for the determination of pesticide residues in grapes and vegetables by using gas chromatography—time-of-flight mass spectrometry (GC—TOF-MS). These methods were based on original methods QuEChERS, mini-Luke, ethyl acetate, and DIN EN 15637, and some of these were slightly modified to increase the number of identified and quantified pesticides, to improve their quantification limits, and to be fast and less expensive in terms of material cost. The acceptable performance parameters combined with the properties of easy and quick handling and cost-effectiveness have made mini-Luke modified extraction method as the most favorable in the pesticide residues analysis from grapes and tomatoes by GC—TOF-MS. The efficiency of the chosen extraction method was also verified for lettuce; for this matrix, a cleanup step with graphitized black carbon (GBC) was added. Analysis of extracts was carried out by GC—TOF-MS within 29.2 min run time. The GC met...

Proficiency test on the determination of pesticide residues in grapes with multi-residue methods

This manuscript presents the results of the International Measurement Evaluation Programme 37 (IMEP-37) study, a proficiency test (PT) which was organised to assess the world-wide performance of food control laboratories on the determination of pesticide residues in grapes. This PT supports the implementation of Regulation (EC) No 396/2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin. Eighty-one participants reported results, forty from EU Member States and forty-one from outside the EU. The test item was a grape sample spiked with 20 selected pesticides. The results of the participants were rated with z- and zeta (ζ-) scores in accordance with ISO 13528 and ISO 17043. The standard deviation for the proficiency assessment, σˆ, of this PT was set at 25% for the 20 measured pesticides based on previous experience with similar measurands. The results reported to IMEP-37 showed that the participants performed satisfactorily, ranging from 81% (carbendazim) to 97% (azoxystrobin, penconazole, pyrimethanil) of the participating laboratories. However, only 30% of the participants managed to analyze all pesticides satisfactorily. Overall, the performance of the participants in this PT was good but there is room for improvement in the development of multi-residue methods for the simultaneous analysis of a large number of pesticides with an increased accuracy.

Определение остаточных количеств пестицидов в винограде и томатах методом масс-спектрометрии высокого разрешения

Определение остаточных количеств пестицидов в винограде и томатах методом масс-спектрометрии высокого разрешения

Coupled Turbulent Flow Chromatography: LC–MS/MS Method for the Analysis of Pesticide Residues in Grapes, Baby Food and Wheat Flour Matrices

This paper describes an on-line sample preparation method for the simultaneous determination of 48 pesticides in grapes, baby food and wheat flour matrices. Target pesticides were selected to represent a wide variety of chemical structures and three typical matrices were selected. Turbulent flow chromatography was applied for on-line sample cleanup directly coupled to LC–MS/MS. The aim of the method was to reduce total analysis time, eliminate manual laboratory work, provide clean extracts and achieve reproducible results. Single laboratory method validation was conducted establishing limits of detection between 0.8 and 6.0 ng g−1 for baby food, and 0.8–10.3 ng g−1 for other matrices. Within-day precision values varied between 4 and 18 %, while between-day precisions were in the range 5–22 %. Method recovery ranged from 67 to 124 %, and method accuracy was demonstrated by analysis of external quality control samples. The method was also tested on 24 different survey samples from both bio and organic origin. The method was shown to be convenient, fast and fit for purpose in meeting regulatory requirements for pesticide residue monitoring.

Simultaneous Determination of 346 Multiresidue Pesticides in Grapes by PSA-MSPD and GC-MS-SIM

The article demonstrates a method of simultaneous determination for 352 pesticide residues in grapes using primary-secondary amine (PSA) matrix solid phase dispersion (MSPD) cleanup and gas chromatography-mass spectrometry-selected ion monitoring (GC-MS-SIM). Grape samples (15 g) were mixed with 6 g of anhydrous magnesium sulfate and 1.5 g of sodium chloride, and then extracted with acetonitrile (15 mL) and cleaned up with 0.3 g of dispersive PSA. The analytes were determined by GC-MS-SIM. Four injections for one sample were acquired to cover a total of 352 pesticides. The limit of detection (LOD) for the method was 0.0017-0.2667 mg kg(-1), depending on the nature of compounds. The linear correlation coefficient (r) was equal to or greater than 0.95; at low, medium, and high fortification levels, recoveries ranged from 45% to 136% for 352 pesticides, among which the recoveries between 60%-120% accounted for 97%. The pesticides for which the relative standard deviations (RSD) were equal to or below 20% accounted for 95%. A positive of nine varieties of grape samples was detected out, one of which was abtained Changli city, Hebei province, China. Pesticides were identified by the retention time, molecule ions, fragment ions, and the abundance ratio of the selected ions. The analytical method was rugged, quick, cheap and effective, and suitable for the determination of a wide scope of 346 pesticides in grapes.

Response surface optimization for determination of pesticide residues in grapes using MSPD and GC-MS: assessment of global uncertainty

In this work, a simple and low-cost method based on matrix solid-phase dispersion (MSPD) and gas chromatography to determine eight multi-class pesticides such as vinclozolin, dichlofluanid, penconazol, captan, quinoxyfen, fluquinconazol, boscalid, and pyraclostrobin in grapes is described. Fungicide residues were identified and quantified using gas chromatography-mass spectrometry in selected ion monitoring mode (GC-MS, SIM). The experimental variables that affect the MSPD method, such as the amount of solid phase, solvent nature and elution volume were optimized using an experimental design. The best results were obtained using 0.5 g of grapes, 1.0 g of silica as clean-up sorbent, 1.50 g of C(18) as bonded phase and 10 mL of dichloromethane/ethyl acetate (1:1, v/v) as eluting solvent. Significant matrix effects observed for most of the pesticides tested were eliminated using matrix-matched standards. The pesticide recoveries in grapes samples were better than 80% except for captan. Intra-laboratory precision in terms of Horwitz ratio of the pesticides evaluated was below 0.5, suggesting ruggedness of the method. The quantification limits of the pesticides were in the range of 3.4-8.7 microg kg(-1), which were lower than the maximum residue limits (MRLs) of the pesticides in grapes samples established by the European legislation. Decision limits (CCalpha) and detection capability (CCbeta) have been calculated. The expanded uncertainties at two levels of concentration were <20% for all analytes.