Pesticides In Vegetables Research Articles

Simultaneous enantioselective determination of 22 chiral pesticides in fruits and vegetables using chiral liquid chromatography coupled with tandem mass spectrometry.

This paper presents a novel multi-residue method for the enantioselective analysis of 22 chiral pesticides in cucumber, tomato, cabbage, grape, mulberry, apple and pear at enantiomeric levels. Pesticides were efficiently extracted by magnetic solid-phase extraction based on graphene as sorbent. Response surface methodology was used to assist the multivariable optimization. The perfect chiral separation of the enantiomers was achieved on a Chiralpak IG column within 47 min by reversed-phase liquid chromatography coupled with tandem mass spectrometry, which is a significant improvement to resolve a large group of chiral compounds under one set of conditions. The method was validated in terms of selectivity, linearity, sensitivity, trueness and precision, which all satisfy the requirement for pesticides residue analysis. The proposed method was successfully applied for monitoring the occurrence and enantiomeric composition of pesticides in different fruits and vegetables, demonstrating its applicability for the routine analysis of chiral pesticide residues in food samples.

Comprehensive toxicological study over 160 processing factors of pesticides in selected fruit and vegetables after water, mechanical and thermal processing treatments and their application to human health risk assessment

The challenge of the present comprehensive toxicological study was to evaluate water, mechanical and thermal processing factors (PFs) of twenty four pesticides (acetamiprid, alpha‑cypermethrin, azoxystrobin, boscalid, bupyrimate, chlorpyrifos, chlorothalonil, cyprodinil, deltamethrin, difenoconazole, fenazaquin, fenhexamid, fludioxonil, folpet, iprodione, lambda‑cyhlothrin, metalaxyl, pirymicarb, propargite, pyraclostrobin, tetraconazole, tiophanate methyl, thiram, trifloxystrobin) in different fruit and vegetables and estimate health risk for adults and children. The water (PF = 0,09–0,94), mechanical (PF = 0,13–0,32) and thermal (PF = 0,02–0,57) technology significantly or completely reduced concentrations of twenty one active substances in broccoli, tomatoes, strawberries and black currants. Pyrethroid insecticides (alpha‑cypermethrin, deltamethrin and lambda‑cyhalothrin) exhibited PF above one in berries influenced by high temperatures. Comprehensive processing factor database technology/pesticide/matrix (over 160 PFs) for 24 pesticides in selected fruit and vegetable species after different processing treatments was created. This paper for the first time compares health risk assessments of acute and chronic of two subpopulations of adults and the most critical group of small children using two mathematical models, without (I) and with including (II) calculated PF values. More realistic estimation of the dietary intakes of the pesticides was achieved using PFs. The hazard quotients (HQs) estimated from chronic and acute dietary exposure (Model l) were above 20% and after intake correction (Model II) were reduced to HQs = 11.5% after water, 3% mechanical and 9.5% thermal treatment.

Magnetite-sporopollenin/graphene oxide as new preconcentration adsorbent for removal of polar organophosphorus pesticides in vegetables.

In this study, a new magnetic adsorbent based on magnetite-sporopollenin/graphene oxide (Fe3O4-SP/GO) was successfully developed. The adsorbent was applied for magnetic solid phase extraction (MSPE) of three selected polar organophosphorus pesticides (OPPs), namely, dimethoate, phenthoate, and phosphamidon, prior to gas chromatography analysis with electron capture detection (GC-μECD). The Fe3O4-SP/GO adsorbent combines the advantages of superior adsorption capability of the modified sporopollenin (SP) with graphene oxide (GO) and magnetite (Fe3O4) for easy isolation from sample solution. Several MSPE parameters were optimized. Under optimized conditions, excellent linearity (R2 ≥ 0.9994) was achieved using matrix match calibration in the range of 0.1 to 500ngmL-1. The limit of detection (LOD) method (S/N = 3) was from 0.02 to 0.05ngmL-1. The developed Fe3O4-SP/GO MSPE method was successfully applied for the determination of these three polar OPPs in cucumber, long beans, bell pepper, and tomato samples. Good recoveries (81.0-120.0%) and good relative standard deviation (RSD) (1.4-7.8%, n = 3) were obtained for the spiked OPPs (1ngmL-1) from real samples. This study is beneficial for adsorptive removal of toxic pesticide compounds from vegetable samples.

BUDIDAYA TANAMAN MAHONI (Sweitenia macrophylla) DAN PEMANFAATANNYA SEBAGAI TANAMAN OBAT

Batukau Mount with its dense forest as the lungs of Tabanan Regency. As a buffer zone, water sources can irrigate existing subak, one of them is Jatiluwih Subak which is a World Cultural Heritage. At the south foothill of Mount Batukau Mount there is Sad Kahyangan Temple, Batukau Temple. Nature preservation around the temple is still maintained, but over time there are areas that need to be greened. Based on this situation, community service around Batukau Temple is carried out with the theme "Mahogany Cultivation (Sweitenia macrophylla) and Its Use as Medicinal Plants". The community service method was carried out with a lecture system to several community members in Batukau Temple. Conclusions obtained in the cultivation of mahogany plants that need to be considered are hatcheries and nurseries, planting and maintenance. As a medicinal plant, mahogany seed extract can be used as an environmentally friendly vegetable pesticide to control Plutella xylostella and Crosidolomia binolalis in cabbage when pests were in the larval stage and seeds of mahogany fruit contain various substances including flavonoids and saponins that function as bacteriocytes.
 Key Word : cultivation, Mahogany plant, medicinal plants

Surface-enhanced Raman scattering of core-shell Au@Ag nanoparticles aggregates for rapid detection of difenoconazole in grapes

The residual of pesticides in fruit and vegetables is one of the major food safety concerns for consumers. There is a demand for easy and rapid analytical methods to sense pesticide residues in foods. In this study, a core-shell Au@Ag nanoparticles aggregates (Au@AgNAs) based surface-enhanced Raman scattering (SERS) method was developed to detect trace amount of difenoconazole. Results suggested that by targeting the characteristic peaks at 700 and 808 cm−1, the logarithmic SERS signal intensities and logarithmic difenoconazole concentrations in the range from 5 × 10−7 to 2.5 × 10−5 M showed linear relationship with the coefficient of determination (R2) of 0.990 and 0.985, and limit of detection (LOD) values of 5.01 × 10−8 and 2.8 × 10−8 M, respectively. The Quick Easy Cheap Effective Rugged and Safe (QuEChERS) sample preparation method was used to extract difenoconazole in grapes for SERS measurements. The LOD of difenoconazole in grapes using this developed method was as low as 48 μg/kg, which was significantly lower than the maximum residue limit (MRL) values prescribed by European Union and China. This study demonstrated that the Au@AgNAs-based SERS method can be used as a simple, rapid and sensitive approach for sensing trace contaminants in food.

Simultaneous determination of carbamate and benzoylurea pesticides in vegetables and fruits with QuEChERS method

Simultaneous determination of carbamate and benzoylurea pesticides in vegetables and fruits with QuEChERS method

An analytical method for quantifying diazinon, chlorfenapyr, and lufenuron in Napa cabbage using QuEChERS and HPLC-UV

A QuEChERS method was developed for the analysis of diazinon, chlorfenapyr, and lufenuron in Napa cabbage. These pesticides represent three different chemical classes and are commonly used in cabbage production in Korea. The objective of the proposed method is a fast, inexpensive, and easy extraction of pesticides, followed by rapid analysis. The proposed method involves a microscale extraction using acetonitrile and dispersive solid phase extraction (SPE), allowing for time and materials savings. The pesticides were separated and quantified using reversed-phase HPLC-UV at 220 nm. The calibration curves showed good linearity (R2>0.97), and the limits of detection and quantification were ≤0.05 and 1 mg/kg, respectively. Intraday and interday recoveries were in the range 97-116% and 101-112% with RSD% ≤9% for concentrations between 0.5-5 mg/kg. Abnormal recoveries and a substantial matrix effect were initially observed for lufenuron, signaling that optimization of lufenuron recovery requires a slight modification of the method. The proposed method was tested on cabbage samples sold at local markets, which showed no detectable residues of the target pesticides. The proposed method could thus be used for monitoring these pesticides in cabbage and similar vegetables.

PEMANFAATAN DAUN MIMBA SEBAGAI PESTISIDA ORGANIK DI KECAMATAN KADEMANGAN KOTA PROBOLINGGO

Science Program for Wiayah (IbW) is intended to empower the community to form Kademangan Sub-district in Probolinggo City which is more advanced, more prosperous and more faithful. This objective will be achieved by empowering communities through the development of science and technology based areas with a planned approach, in which communities are involved in the planning, implementation, evaluation and utilization of results. In particular the IbW Program is: (1) To identify potential, realistic, realistic, real, and realistic human resources, condition, and resources in Kademangan sub-district, Probolinggo Municipality; (2) To formulate the potential of human resources and natural resources so that it can be used as a commodity of superior territory; (3) Conducting training activities in the framework of technology transfer produced by Higher Education to the community. The methods used in this Program are survey, and observation. Preparation of action programs conducted through workshop activities. The results of the IbW program are: (1) The socialization of IbW Program with the Local Government of Probolinggo Municipality and the Pohsangit Kidul and Pilang Village Farmer Groups; (2) Counseling on the Benefits and Use of Pesticide Neighbors; (3) Training and practice of Mimba Leaf Processing Becoming Plant Pesticide. The conclusion of the IbW program is that it is very potential to develop bio-pesticide biological agents from neem. To cultivate vegetable pesticides especially from neem by farmers still needed the process and time because farmers are still familiar with chemical pesticides.

Pesticide residues in fruits and vegetables of the argentine domestic market: Occurrence and quality

The presence of pesticides in fruits and vegetables has been a growing concern in Argentina. Only three of the major marketplaces there have the necessary infrastructure to determine pesticide residues in produce. The aim of this study was to investigate the presence of such residues in nationally produced fruits and vegetables for domestic consumption in order to evaluate the present state of the market. A total of 135 of the most widely consumed fruits and vegetables were analyzed for 35 pesticides. The analyses utilized a QuEChERS™ multiresidue-extraction kit along with tandem gas chromatography–mass spectrometry. The results were evaluated according to maximum residue limits (MRLs) for each commodity and pesticide according to national regulation. Pesticides were detected in 65% of the total samples, in 44% of the positive samples at or below the MRLs, and in 56% above the MRLs. Oranges had the highest pesticide concentration detected, but carrots had the highest frequency of noncompliance among the produce items sampled. Five pesticides were detected at frequencies above 10%, the highest being chlorpyrifos in 25.9% of the total samples. In other countries, the percentage of samples above the MLR is 4 times lower than our findings, and 7 times lower for exported products. An implementation of programs designed to facilitate awareness, capacitation, and monitoring is urgently recommended.

Kombinasi Biopestisida Formulasi Bacillus subtilis BNt8 dan Pestisida Nabati untuk Pengendalian Penyakit Hawar Daun Bipolaris maydis pada Jagung

Maydis leaf blight disease caused by Bipolaris maydis can attack corn plants in the vegetative and generative phase and can reduce yield up to 70%. Biological control of plant diseases with the use of biopesticides alone or in combination with other botanical materials can be efficient because it is easy to obtain, cheaper price, also environmentally friendly. The objective of the study was to obtain a combination of B. subtilis formulation with a botanical pesticide which has the potential to control the growth and development of maydis leaf blight. In addition to this, we also observed the effect of the application of the combination of botanical pesticides and B. subtilis formulation on plant growth. The study was conducted on February till June 2016 at the Plant Pathology Laboratory of ICERI with a complete randomized design and the Bajeng Experimental Farm using a randomized block design. In vitro testing, the treatment with vegetable pesticide of clove leaf extract gave better results in suppressing B. maydis. Similarly, in field testing, the application of B. subtilis formulation combined with clove leaf extract also gave a better effect in suppressing the development of maydis leaf blight disease and increasing yield. Applications of B. subtilis formulation can suppress maydis leaf blight disease by up to 13% and potentially increase yield by 26%.

Screening of 485 Pesticide Residues in Fruits and Vegetables by Liquid Chromatography-Quadrupole-Time-of-Flight Mass Spectrometry Based on TOF Accurate Mass Database and QTOF Spectrum Library.

This paper uses the LC-quadrupole-time-of-flight MS technique to evaluate the behavioral characteristics of MS of 485 pesticides under different conditions and has developed an accurate mass database and spectra library. A high-throughput screening and confirmation method has been developed for the 485 pesticides in fruits and vegetables. Through the optimization of parameters such as accurate mass number, time of retention window, ionization forms, etc., the method has improved the accuracy of pesticide screening, thus avoiding the occurrence of false-positive and false-negative results. The method features a full scan of fragments, with 80% of pesticide qualitative points over 10, which helps increase pesticide qualitative accuracy. The abundant differences of fragment categories help realize the effective separation and qualitative identification of isomer pesticides. Four different fruits and vegetables-apples, grapes, celery, and tomatoes-were chosen to evaluate the efficiency of the method at three fortification levels of 5, 10, and 20μg/kg, and satisfactory results were obtained. With this method, a national survey of pesticide residues was conducted between 2012 and 2015 for 12 551 samples of 146 different fruits and vegetables collected from 638 sampling points in 284 counties across 31 provincial capitals/cities directly under the central government, which provided scientific data backup for ensuring pesticide residue safety of the fruits and vegetables consumed daily by the public. Meanwhile, the big data statistical analysis of the new technique also further proves it to be of high speed, high throughput, high accuracy, high reliability, and high informatization.

Comparative LC-MS based non-targeted metabolite profiling of the Chinese mitten crab Eriocheir sinensis suffering from hepatopancreatic necrosis disease (HPND)

Hepatopancreatic necrosis disease (HPND) is a newly emerged disease in the Chinese mitten crab, and has caused significant economic damage to crab farmers. However, the exact pathogenesis of crab HPND has not been elucidated. To understand the metabolic shifts in the pathogenesis of the disease, we used LC-MS for metabolite profiling of the hepatopancreas of crabs with HPND. Diseased (DC) and healthy crabs (HC) from the ponds with disease occurrence, and healthy crabs (HHC) from adjacent ponds free from HPND, were analyzed. Histopathologic characteristics and potential pathogens in the hepatopancreas of the healthy and diseased crabs were preliminary investigated. Cellular damage or necrosis, including cell swelling, rupturing, vacuole formation and nuclear fragmentation were observed in diseased crabs. Pathogen screening revealed that, Hepatospora eriocheir, a parasite which was ever deemed to be the agent of the disease before, was unlikely the cause of HPND. Partial least squares discriminant analysis (PLS-DA) score plots revealed a significant metabolic difference between DC and HC in positive ionization modes (R2 = 0.96807, Q2 = 0.74558), while HC and HHC were grouped closely together. Fourty-five differential metabolites were identified and used for further functional pathway analyses. Two potential pathogenic factors, including fatty acid metabolic abnormalities and high concentrations of propamocarb (a widely used pesticide in vegetables), were found to be likely associated with HPND in the Chinese mitten crab. The identified metabolites and regulation pathways, and screening of potential pathogens in diseased crabs, should provide useful information for the prevention of the disease in the future.

Analysis of pyrethroid pesticides in Chinese vegetables and fruits by GC–MS/MS

A rapid and economical method using modified QuEChERS sample pretreatment coupled with high-sensitivity gas chromatography/triple quadrupole mass spectrometry was established to simultaneously determine ten pyrethroid pesticides in fruits and vegetables. All pesticides were detected within 20 min of one injection. Concurrent backflushing provided column protection, greatly facilitating instrument maintenance. For quantitation, matrix-matched calibration was used to compensate for signal-enhancement effects and to ensure the precision of the method. The limit of detection (LOD) was in the range of 0.3–4.9 μg/kg. The recovery rate was from 78.8 to 118.6%, with relative standard deviation (RSD) below 14.8%. The developed method is suitable for rapid and sensitive multi-residue analysis of pyrethroid pesticides in fruits and vegetables. It is good for users in professional institutions that implement safety controls for testing hundreds of agricultural product samples everyday.

Coupling Ion Chromatography to Q-Orbitrap for the Fast and Robust Analysis of Anionic Pesticides in Fruits and Vegetables.

Ion chromatography coupled to a quadrupole Orbitrap mass analyzer was used to develop a multiresidue method for the determination of highly polar pesticides and their metabolites (chlorate, perchlorate, fosetyl-aluminum, glyphosate, aminomethylphosphonic acid (AMPA), phosphonic acid, N-acetyl AMPA, and N-acetyl glyphosate) in fruits and vegetables. After extraction with methanol, samples were diluted 5× with water. No derivatization was applied. Pesticides were separated in an anion-exchange column. Water was used as the ion chromatography mobile phase. A gradient was created by increasing the concentration of KOH in the mobile phase. Ion chromatography provided good and stable retention and separation for all studied compounds. All investigated pesticides had an LOQ of 0.01 mg/kg and a linear range of 0.01-0.50 mg/kg. The ion ratio of the m/z ions produced was stable and adequate (deviation <30%) in all cases. The obtained mass errors (always in full-scan MS and MS2 mode) were <0.2 mDa. The high resolution (>100 000) provided by the Orbitrap analyzer with the low m/z ions obtained (e.g., m/z 80) was effective in obtaining low background matrix signals. The influence of postcolumn infusion of organic solvent on sensitivity was investigated. Acetonitrile was found to be more effective than methanol, increasing the sensitivity 3× with respect to water. The method was validated for five vegetable-based matrixes. Both the sample processing and the analytical measurement were very fast. Hence, the methodology is ideal for high-throughput work.

Comparison of uptake, translocation and accumulation of several neonicotinoids in komatsuna (Brassica rapa var. perviridis) from contaminated soils

The accumulation of pesticides in vegetables may have serious effects on human health and ecosystems via food chains; therefore, it is of great importance to investigate the uptake and accumulation behaviours of pesticides in vegetable tissues. In the present study, the uptake, translocation and accumulation of five neonicotinoids, thiamethoxam (THIM), clothianidin (CLO), thiacloprid (THID), acetamiprid (ACE) and dinotefuran (DIN), in komatsuna (Brassica rapa var. perviridis, a vegetable) were investigated. The concentrations of neonicotinoids in vegetable tissues ranged from 0.068 ± 0.002 to 29.6 ± 2.5 mg/kg. During the cultivation (except for the first day), the concentration of each neonicotinoid in shoots was the highest, followed by roots and the soil. The concentrating of neonicotinoids from the soil to roots followed the order of THIM > CLO > THID > DIN > ACE, while the order of the ability of translocation neonicotinoids from roots to shoots was the just opposite. The difference in uptake and translocation behaviours of the test neonicotinoids seems to be not correlated with the octanol/water partition coefficient (logKow), water solubility or dissociation constant (pKa), but significantly correlated with molecular weight. In addition, a greater concentration of the THIM-metabolite clothianidin (M-CLO) was detected in vegetable shoots than in roots and the soil.

Rapid Detection of Flusilazole in Pears with Au@Ag Nanoparticles for Surface-Enhanced Raman Scattering.

Residual pesticides in vegetables or fruits have been become one of the world’s most concerned food safety issues. Au-Ag core-shell nanoparticles (Au@Ag NPs) coupled with surface-enhanced Raman spectroscopy (SERS) was used for analysis of flusilazole which was widely applied in pears. Three different diameters of Au@Ag NPs were prepared to select the best SERS substrate for analyzing flusilazole. The Au@Ag NPs sizes of 90 ± 7 nm showed the highest enhancement effect and could be detected flusilazole standard solution and the minimum detectable concentration was 0.1 mg/L. Flusilazole in pear could also identified at as low as 0.1 μg/g. The amount of adsorbent is critical in the sample preparation process and the best amount of each absorber dosage was 0.6 g MgSO4, 0.2 g C18 and 0.2 g primary secondary amine (PSA). The experimental results indicated a good linear relationship between the Raman intensities of chief peaks and the concentrations of flusilazole solutions (R2 = 0.924–0.962). This study shows that Au@Ag as SERS substrate has great potential to analyze of flusilazole in food matrices.

Investigating the causes of low detectability of pesticides in fruits and vegetables analysed by high-performance liquid chromatography – Time-of-flight

Because of the high number of possible pesticide residues and their chemical complexity, it is necessary to develop methods which cover a broad range of pesticides. In this work, a qualitative multi-screening method for pesticides was developed by use of HPLC-ESI-Q-TOF. 110 pesticides were chosen for the creation of a personal compound database and library (PCDL). The MassHunter Qualitative Analysis software from Agilent Technologies was used to identify the analytes. The software parameter settings were optimised to produce a low number of false positive as well as false negative results. The method was validated for 78 selected pesticides. However, the validation criteria were not fulfilled for 45 analytes. Due to this result, investigations were started to elucidate reasons for the low detectability. It could be demonstrated that the three main causes of the signal suppression were the co-eluting matrix (matrix effect), the low sensitivity of the analyte in standard solution and the fragmentation of the analyte in the ion source (in-source collision-induced dissociation). In this paper different examples are discussed showing that the impact of these three causes is different for each analyte. For example, it is possible that an analyte with low signal intensity and an intense fragmentation in the ion source is detectable in a difficult matrix, whereas an analyte with a high sensitivity and a low fragmentation is not detectable in a simple matrix. Additionally, it could be shown that in-source fragments are a helpful tool for an unambiguous identification.

Multi-Residue Determination of Pesticides in Vegetables on Dalian Market by Gas Chromatograph, 2009-10

This paper presents results from surveillance of pesticide multi-residues in vegetables carried out in 2009-10. 420 samples of 10 different types of fresh vegetables were analyzed for their pesticide multi-residue contents using gas chromatograph and NY/T 761-2008 pesticide multi-residue screen methods. The residues exceeded MRLs of forbidden pesticides found were: carbofuran 0.110 mg/kg (kidney bean) and methamidophos 0.037 mg/kg (celery) in January 2009, methamidophos 0.037 mg/kg (tomato) in May 2009, aldicarb 0.013 mg/kg (kidney bean) in September 2009, omethoate 2.200 mg/kg (celery) in November 2009, carbofuran 0.052 mg/kg (green pepper) in April 2010, parathion 0.056 mg/kg (celery) and carbofuran 0.030 mg/kg (celery) in July 2010. Also, chlorpyrifos used as unforbidden pesticide was most frequently found above MRL, rape (0.820 mg/ kg) and celery (0.365 mg/kg) in January 2009, celery (0.330 mg/kg) in May 2009, lettuce (0.298 mg/kg) in September 2009, rape (0.910 mg/kg) in April 2010 and lettuce (0.230 mg/kg) in July 2010. In addition, cypermethrin used as unforbidden pesticide was found above MRL only once in rape (1.270 mg/kg) in May 2009 and none of unforbidden pesticides above MRL was found in November 2009 and January 2010. Most of the samples (96%) were up to the national standard.

Determination of 105 pesticide residues in vegetables by QuEChERS-liquid chromatography-tandem mass spectrometry

After optimization of the QuEChERS pretreatment method, combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) technology, a multi-residue determination method was established for 105 typical insecticides, bactericides, herbicides, and plant growth regulators in vegetables. The target compounds were extracted by acetonitrile, purified with 150 mg primary secondary amine (PSA), 150 mg EC-C18, and 30 mg graphitized carbon black (GCB) adsorbents. The standard curves of 105 target compounds were linear in the concentration range of 0.010-0.200 mg/L, with correlation coefficients (r)>0.99. The limit of quantification was 0.010 mg/kg, the recoveries were between 68.2% and 108% at three spiked levels, and the RSDs of the method were between 1.02% and 11.8%. The method is suitable for the rapid determination of the common pesticides in vegetables owing to its advantages of rapidity, simplicity, and better purification.

Classification and Identification of Pesticide Residues in Cucumber Based on Near Infrared Spectroscopy

To explore the feasibility of Near Infrared spectroscopy (NIR) for rapid and nondestructive qualitative identification of pesticide residues in vegetables, this paper presents a qualitative classification and discrimination method based on Support Vector Machine (SVM) with Gaussian Radial Basis Function (RBF). The cucumber with three kinds of pesticide residue levels (no pesticide, standard pesticide residue, severe excess) was used as the research object. The total reflectance NIR spectra of two groups of cucumber were collected after spraying 24 hours and 48 hours of pesticide respectively. First, Principal Component Analysis (PCA) was applied to dimensionality reduction of spectral data. Then normalize the spectrum. Next, the SVM training model based on RBF was established, and then SVM prediction was carried out. The correct recognition rate of the training set was 100%, and the correct prediction rate of the test set was 94.4444% and 95.5556%, respectively. Experiments show that this method is accurate and fast for qualitative classification and identification of pesticide residues in cucumbers with different concentrations, and provides a new idea for rapid non-destructive detection of vegetable pesticide residues.