thiophanate and carbendazim

Thiophanate-methyl and its metabolite carbendazim are broad-spectrum fungicides used on many crops. The residues of these chemicals could result in potential environmental and human health problems. Therefore, investigations of the dissipation and residue behaviors of thiophanate-methyl and its metabolite carbendazim on cowpeas and associated dietary risk assessments are essential for the safety of agricultural products.. A simple analytical approach using liquid chromatography with tandem mass spectrometry was developed and validated for the determination of thiophanate-methyl and carbendazim concentrations in cowpeas. Good linearity (R. An optimized approach for detecting thiophanate-methyl and carbendazim in cowpeas was applied for the investigation of field-trial samples. The potential acute and chronic dietary risks of thiophanate-methyl, carbendazim and total carbendazim to the health of Chinese consumers were low. These results could guide the safe and proper use of thiophanate-methyl in cowpeas and offer data for the dietary risk assessment of thiophanate-methyl in cowpeas. © 2021 Society of Chemical Industry.

Topics: Benzimidazoles; Carbamates; China; Food Contamination; Fungicides, Industrial; Kinetics; Pesticide Residues; Seeds; Thiophanate; Vigna

Residue analysis to detect thiophanate-methyl and its primary metabolite (carbendazim) during oyster mushroom (Pleurotus ostreatus var. florida) cultivation was done for two consecutive years 2017 and 2018. Wheat straw substrate was chemically treated with different treatments of thiophate-methyl, viz, thiophanate-methyl 30 ppm + formalin 500 ppm (T1), thiophanate-methyl 40 ppm + formalin 500 ppm (T2), thiophanate-methyl 50 ppm + formalin 500 ppm (T3), thiophanate-methyl 60 ppm + formalin 500 ppm (T4), and formalin 500 ppm (T5 as control and recommended concentration), and utilized for cultivation of oyster mushroom. Treatments T3 and T4 exhibited significant difference in pH levels during both the trials. Minimum spawn run, pinhead formation, and fruit body formation time were recorded in treatments T3 and T4. Significantly higher biological efficiency (%) was recorded in treatments T3 and T4 as compared with all other treatments. No incidence of competitor molds was recorded in T3 and T4. Pesticide residue analysis for detection of thiophanate-methyl and its metabolite (carbendazim) was done in the fruit body produced in T3 and T4 treatments using liquid chromatography with tandem mass spectrometry method. No residue of thiophanate-methyl and carbendazim was detected at 50 ppm concentration of thiophanate-methyl during both the trials. However, in trial II, residue of carbendazim (5.39 μg/kg) was detected at 60 ppm. Based on the findings of the trials I and II, T3 (thiophanate-methyl 50 ppm + formalin 500 ppm) may be utilized for substrate sterilization for oyster mushroom cultivation and Pleurotus ostreatus var. florida could be recognized as microorganism which could play a role in degradation of thiophanate-methyl.

Topics: Benzimidazoles; Biodegradation, Environmental; Carbamates; Chromatography, Liquid; Fruit; Pesticide Residues; Pleurotus; Poaceae; Sterilization; Tandem Mass Spectrometry; Thiophanate; Triticum

Winter is the key period for the control of apple diseases, and fungicides are needed to protect the trunk or main branches. Fungicide residue in apple tree bark is an important basis for the action of the pesticide, but there are no reports on analytical methods or dissipation patterns. In this work, thiophanate-methyl, carbendazim, tebuconazole and pyraclostrobin were selected as typical fungicides and a new QuEChERS-HPLC-VWD(QuEChERS extraction followed by high-performance liquid chromatography detection with a variable wavelength detector) analytical method was developed to estimate their residue kinetics in apple tree bark during the winter months. In the pretreatment step, the sorbent for the clean-up of extracts was optimized as 60 mg/ml primary secondary amine and a gradient-elution model followed by a variable wavelength detection was developed for instrumental analysis. Then this method was validated and applied to the analysis of apple tree bark samples with the linearity range of 0.010-50.00 mg/L, quantification limit range of 0.028-0.080 mg/kg and recovery range of 86.1-101.4%. The dissipation kinetics of thiophanate-methyl and pyraclostrobin could be described by the first-order and two-phase kinetics models, respectively. For carbendazim and tebuconazole, two new models were developed to describe their residue kinetics.

Topics: Benzimidazoles; Carbamates; Chromatography, High Pressure Liquid; Fungicides, Industrial; Linear Models; Malus; Pesticide Residues; Plant Bark; Reproducibility of Results; Sensitivity and Specificity; Spectrophotometry, Ultraviolet; Strobilurins; Thiophanate; Triazoles

A multi-residue method for the determination of 107 pesticide residues in wolfberry has been developed and validated. Similar pretreatment approaches were compared, and the linearity, matrix effect, analysis limits, precision, stability and accuracy were validated, which verifies the satisfactory performance of this new method. The LODs and LOQs were in the range of 0.14-1.91 µg/kg and 0.46-6.37 µg/kg, respectively. The recovery of analytes at three fortification levels (10 µg/kg, 50 µg/kg, 100 µg/kg) ranged from 63.3-123.0%, 72.0-118.6% and 67.0-118.3%, respectively, with relative standard deviations (RSDs) below 15.0%. The proposed method was applied to the analysis of fifty wolfberry samples collected from supermarkets, pharmacies and farmers' markets in different cities of Shandong Province. One hundred percent of the samples analyzed included at least one pesticide, and a total of 26 pesticide residues was detected in fifty samples, which mainly were insecticides and bactericide. Several pesticides with higher detection rates were 96% for acetamiprid, 82% for imidacloprid, 54% for thiophanate-methyl, 50% for blasticidin-S, 42% for carbendazim, 42% for tebuconazole and 36% for difenoconazole in wolfberry samples. This study proved the adaptability of the developed method to the detection of multiple pesticide residues in wolfberry and provided basis for the research on the risks to wolfberry health.

Topics: Benzimidazoles; Carbamates; Chromatography, High Pressure Liquid; Humans; Liquid-Liquid Extraction; Lycium; Neonicotinoids; Nitro Compounds; Nucleosides; Pesticide Residues; Tandem Mass Spectrometry; Thiophanate; Triazoles

As one of the main fungicides for the apple leaf disease control, thiophanate-methyl (TM) mainly exerts its fungicidal activity in the form of its metabolite carbendazim (MBC), whose dissipation kinetics is very distinct from that of its parent but has been paid little attention. The aim of this work was to investigate the dissipation kinetics of TM and its active metabolite MBC in apple leaves using a modified QuEChERS-UPLC-MS/MS method. The results showed that TM and MBC could be quickly extracted by this modified QuEChERS procedure with recoveries of 81.7-96.5%. The method linearity was in the range of 0.01-50.0 mg kg

Topics: Adsorption; Benzimidazoles; Carbamates; Chromatography, High Pressure Liquid; Linear Models; Malus; Pesticide Residues; Plant Leaves; Reproducibility of Results; Sensitivity and Specificity; Tandem Mass Spectrometry; Thiophanate

An efficient method was developed and validated for simultaneous determination of tebuconazole, thiophanate-methyl and its metabolite carbendazim in grape and soil using QuEChERS procedure and liquid chromatography-tandem mass spectrometry. The average recoveries of the method were 83.2%-105.4%, the limit of detection (LOD) ranged from 2.1 × 10

Topics: Benzimidazoles; Carbamates; China; Chromatography, Liquid; Dietary Exposure; Food Contamination; Half-Life; Humans; Limit of Detection; Pesticide Residues; Risk Assessment; Soil Pollutants; Tandem Mass Spectrometry; Thiophanate; Triazoles; Vitis

Topics: Benzimidazoles; Carbamates; Chromatography, High Pressure Liquid; Chromatography, Liquid; Citrus; Pesticide Residues; Pyrazoles; Soil; Strobilurins; Tandem Mass Spectrometry; Thiophanate

Surface-enhanced Raman scattering (SERS) imaging coupling with multivariate analysis in spectral region of 200 to 1800cm

Topics: Benzimidazoles; Capsicum; Carbamates; Least-Squares Analysis; Spectrum Analysis, Raman; Support Vector Machine; Teratogens; Thiophanate

A novel method for the simultaneous separation and determination of four benzimidazole fungicides (i.e., carbendazim, fuberidazole, thiophanate-methyl and thiophanate) in high salinity samples was developed by using salting-out assisted liquid-liquid extraction (SALLE) via water-miscible acetonitrile as the extractant coupled with high-performance liquid chromatography. Box-Behnken design and response surface were employed to assist the optimization of SALLE conditions, including volume of salting-out solvent, the pH of sample solution and salting-out solvent as variable factors. The optimal salting-out parameters were obtained as follows: 2 mL of acetonitrile was added to 2 mL of sample solution with pH=4 and then 2 mL salting-out solvent containing 5 mol L(-1) sodium chloride at a pH of 7 was added to the solution for extraction. This procedure afforded a convenient and cost-saving operation with good cleanup ability for the benzimidazole fungicides, such as good linear relationships (R>0.996) between peak area and concentration from 2.5 ng mL(-1) to 500 ng mL(-1), low limits of detection between 0.14 ng mL(-1) and 0.38 ng mL(-1) and the intra-day precisions of retention time below 1.0%. The method recoveries obtained at fortified three concentrations for three seawater samples ranged from 60.4% to 99.1%. The simple, rapid and eco-benign SALLE based method proved potentially applicable for trace benzimidazole fungicides analysis in high salinity samples.

Topics: Acetonitriles; Benzimidazoles; Carbamates; Chromatography, High Pressure Liquid; Fungicides, Industrial; Humans; Hydrogen-Ion Concentration; Limit of Detection; Liquid-Liquid Extraction; Reproducibility of Results; Salinity; Seawater; Solvents; Thiophanate; Water; Water Pollutants, Chemical

To select representative crop among leaf vegetables which may contain the highest residue after fungicide uses, open field applications with thiophanate-methyl on six crops including pakchoi, rape, crown daisy, amaranth, spinach and lettuce were designed and conducted. In this study, a high-performance liquid chromatography and electrospray ionization-tandem mass spectrometry with selected reaction monitoring was used to simultaneously determine thiophanate methyl and its metabolite carbendazim residue in various samples. The limit of quantification for thiophanate methyl and carbendazim were established in the range of 0.005-0.01 mg kg(-1) for all samples. It was shown that recoveries ranged from 67.8 % to 102.3 % for thiophanate methyl, and 72.0 %-112.6 % for carbendazim at spiked levels of 0.01-0.1 mg kg(-1). It's found that thiophanate methyl converts to carbendazim very quickly. In supervised field trials, the half-lives of thiophanate methyl in six leaf vegetables were in the range of 1.26-2.65 days, and the half-lives of carbendazim were in the range of 2.53-4.28 days. It was also found that thiophanate methyl residue in spinach and amaranth was higher than others after application. It's recommended that spinach or amaranth can be selected as representative crop in leaf vegetables in study of systemic fungicides with similarity as thiophanate methyl.

Topics: Amaranthus; Benzimidazoles; Brassica napus; Brassica rapa; Carbamates; Chrysanthemum; Fungicides, Industrial; Lactuca; Pesticide Residues; Species Specificity; Spinacia oleracea; Thiophanate; Vegetables

A method was developed for the determination of thiophanate-methyl and carbendazim residues in cucumber and soil by using QuEChERS-high performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The residues in the samples were extracted by acetonitrile, cleaned up by developed QuEChERS method, and then analyzed by using LC-MS/MS in multiple reaction monitoring (MRM) mode via positive electrospray ionization with an Agilent ZORBAX SB-C, column (30 mm x 2.1 mm, 5 microm) as the analytical column. The recoveries of thiophanate-methyl spiked at four levels of 0.01, 0.05, 0.1 and 1.0 mg/kg were from 87.3% to 96.0% with the relative standard deviations (RSDs) of 8.0%-9.3% in cucumber, from 88.8% to 93.4% with the RSDs of 5.3%-9.9% in soil; the recoveries of carbendazim spiked at the same levels as those of thiophanate-methyl were from 87.1% to 92.3% with the RSDs of 5.2%-7.5% in cucumber, from 85.8% to 90.9% with the RSDs of 5.3%-13.2% in soil. The method is simple, rapid and characterized with acceptable sensitivity and accuracy to meet the requirements of the pesticide residue analysis. This method is applicable to confirm the residues of thiophanate-methyl and carbendazim

Topics: Benzimidazoles; Carbamates; Chromatography, High Pressure Liquid; Cucumis sativus; Food Contamination; Fungicides, Industrial; Soil; Soil Pollutants; Tandem Mass Spectrometry; Thiophanate

A simple and reliable liquid chromatographic-tandem mass spectrometric (LC-MS/MS) method was developed for carbendazim (MBC), thiophanate (TE), thiophanate-methyl (TM) and benomyl (BM) in agricultural products. These compounds were extracted from agricultural products with methanol after addition of sodium L-ascorbate. BM was hydrolyzed to MBC during the extraction with methanol. TE and TM were cyclized to ethyl 2-benzimidazole carbamate (EBC) and MBC by refluxing at 120 °C for 30 min with copper acetate in 50% acetic acid. MBC and EBC were cleaned up by an n-hexane wash and extraction with ethyl acetate and determined by LC-MS/MS. The mean recoveries from 10 agricultural products were in the range of 75.8-100.0%, and the relative standard deviations of 5 experiments were in the range of 1.5-9.2% at concentrations equal to the maximum residue limits (MRLs). The calibration curves were made by using commercial MBC and EBC as reference analytical standards without refluxing. The quantification limits were 0.01 mg/kg (as MBC), which is the uniform limit in the positive list system for agricultural chemical residues in foods in Japan.

Topics: Benomyl; Benzimidazoles; Carbamates; Chromatography, Liquid; Crops, Agricultural; Fungicides, Industrial; Pesticide Residues; Tandem Mass Spectrometry; Thiophanate

An ultra performance liquid chromatography-tandem mass spectrometric method (UPLC-MS/MS) was established for the simultaneous determination of imidacloprid, carbendazim, thiophanate-methyl, propamocarb, methomyl and dimethomorph residues in tomato paste. The samples were extracted by methanol-water (1: 1, v/v) containing 0.1% (v/v) acetic acid. The separation was performed on a Waters Acquity UPLC system with a BEH C18 column with the gradient elution of methanol and water (containing 10 mmol/L ammonium acetate). The six pesticides were determined in the modes of electrospray positive ionization (ESI+) and multiple reaction monitoring (MRM). The analytes were quantified by matrix-matched standard solution, and the calibration curves showed good linearity within the concentrations of 0.005 to 0.2 mg/L and the correlation coefficients (r) were more than 0.995. The average recoveries of the six pesticides ranged from 66.8% to 102.9% in the three spiked levels of 0.02, 0.05 and 0.2 mg/kg. The relative standard deviations (RSDs) were all less than 15%. The limits of quantification (LOQ, S/N > 10) were 0.02 mg/kg for the all analytes. The results indicate that the method is easier, faster, more sensitive, and suitable for the qualitative and quantitative confirmation of the six pesticide residues from tomato paste.

Topics: Benzimidazoles; Carbamates; Chromatography, High Pressure Liquid; Food Contamination; Imidazoles; Neonicotinoids; Nitro Compounds; Pesticide Residues; Solanum lycopersicum; Tandem Mass Spectrometry; Thiophanate

This work reports a new sensitive multi-residue liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for detection, confirmation and quantification of forty-six pesticides and transformation products belonging to different chemical classes in wines. The proposed method makes use of a solid-phase extraction (SPE) procedure with Oasis HLB cartridges that combines isolation of the pesticides and sample clean-up in a single step. Analysis is performed by liquid chromatography-electrospray ionisation-tandem mass spectrometry (LC-MS/MS) operated in the selected reaction monitoring (SRM) mode, acquiring two specific precursor-product ion transitions per target compound. An investigation of matrix effects has been performed during method validation showing medium to low effects for the majority of the compounds. Limits of detection (LODs) were in the range 0.0003-0.003 mg L(-1) and limits of quantification (LOQs) were in the range 0.001-0.01 mg L(-1). The average recoveries, measured at two concentration levels (0.010 and 0.050 mg L(-1)), were in the range 70-110% for most of the compounds tested with % relative standard deviations below 20%, while a value of 0.010 mg L(-1) has been established as the method limit of quantification (MLOQ) for all target species. Expanded uncertainty values were in the range 10-40% while the Horrat ratios were below 1. The method has been successfully applied to the analysis of 60 wine samples in the course of an annual monitoring study with carbendazim-benomyl, thiophanate-methyl and carbaryl being the most frequently determined pesticides.

Topics: Benzimidazoles; Carbamates; Carbaryl; Chromatography, Liquid; Linear Models; Pesticides; Reproducibility of Results; Sensitivity and Specificity; Solid Phase Extraction; Tandem Mass Spectrometry; Thiophanate; Wine

Microwave-assisted extraction (MAE) was carried out for the determination of the fungicides thiophanate methyl [1.2-alpha-(3-methoxycarbonyl-2-thioureido)benzene] and carbendazim (methyl benzimidazol-2-ylcarbamate) in vegetable samples. Two vegetable samples, cabbage and tomatoes, were fortified with the two pesticides and subjected to MAE followed by cleanup to remove co-extractives prior to analysis by high-performance liquid chromatography (HPLC). Using the selected microwave exposure time and power setting, the recoveries of carbendazim ranged from 69 to 75%. But thiophanate methyl could not be recovered as the parent compound. It was converted and recovered as carbendazim. The conversion was quantitative as confirmed by high-performance liquid chromatography-mass spectrometry (HPLC-MS).

Topics: Benzimidazoles; Carbamates; Chemical Fractionation; Chromatography, High Pressure Liquid; Microwaves; Molecular Structure; Reproducibility of Results; Thiophanate; Vegetables

Topics: Agar; Animals; Antifungal Agents; Benomyl; Benzimidazoles; Carbamates; Cell Culture Techniques; Chlamydomonas reinhardtii; Culture Media; Thiophanate

A new bioassay has been developed combining the simplicity of direct bioautography with the improved chromatographic resolution of 2D-TLC. Mixtures of structurally diverse antifungal agents were tested to establish the validity and utility of this method in the discovery of new natural products with activity against agriculturally important fungal pathogens.

Topics: Acrylates; Aniline Compounds; Antifungal Agents; Ascomycota; Benzimidazoles; Biological Assay; Captan; Carbamates; Chromatography, Thin Layer; Colletotrichum; Dimethyldithiocarbamate; Fungicides, Industrial; Guanidines; Maneb; Methacrylates; Nitriles; Nitrobenzenes; Oxazoles; Piperazines; Plant Diseases; Plants; Pyrimidines; Strobilurins; Thiabendazole; Thiophanate; Triazoles

Simple methods for the analysis of carbendazim, benomyl and thiophanate methyl in fruits and vegetables and of 2,4-D in citrus fruits are presented. Sample preparation involves supercritical fluid extraction with carbon dioxide and further analysis is performed without any additional clean-up by GC-MS after derivatisation or directly by HPLC-diode array detection. The SFE methods presented are clearly faster and more cost effective than traditional solvent based approaches. The recoveries, detection limits and repeatabilities achieved, meet the needs of tolerance level monitoring of these compounds in fruits and vegetables.

Topics: 2,4-Dichlorophenoxyacetic Acid; Benomyl; Benzimidazoles; Carbamates; Chromatography; Fruit; Hydrogen-Ion Concentration; Pesticide Residues; Thiophanate; Vegetables

The cytogenetic effects of three benzimidazoles, i.e., benomyl, methyl thiophanate and methyl 2-benzimidazolecarbamate (MBC), were studied in mouse bone marrow cells by analyzing three genetic endpoints: micronuclei, structural chromosome aberrations plus or minus gaps, and aneugenic effects (hyperdiploidy or polyploidy). In general, the effects were small, but it was observed that benomyl and MBC significantly induced micronuclei as well as aneugenic effects, hyperdiploidy (no metaphases with more than one or two extra chromosomes, 2n + 1 or 2n + 2, were observed) and polyploidy (4n). The induction of chromosome gaps and breaks was less evident. Methyl thiophanate significantly induced micronuclei, but it was less effective than benomyl and MBC. Our results showed that micronuclei are a good indicator of aneugenic effects in mouse bone marrow cells. A curvilinear trend test has been devised to fit the curves originating from the time-dependent responses.

Topics: Analysis of Variance; Aneuploidy; Animals; Benomyl; Benzimidazoles; Bone Marrow; Bone Marrow Cells; Carbamates; Chi-Square Distribution; Chromosome Aberrations; Male; Mice; Micronucleus Tests; Mutagens; Regression Analysis; Thiophanate

Topics: Aniline Compounds; Basidiomycota; Benomyl; Benzimidazoles; Captan; Carbamates; Chromatography, Thin Layer; Fruit; Fungicides, Industrial; Penicillium; Pesticide Residues; Phthalimides; Sulfonamides; Thiophanate; Thiram; Vegetables