Behavior of trifloxystrobin and propineb as combination product in tomato (Solanum lycopersicum) and their risk assessment for human health.

Fungicides have their own unique characteristics and modes of action; a combination formulation [combination product (combi product)] of trifloxystrobin and propineb was applied to tomatoes for their dissipation kinetics and to ensure consumer safety. The combi product was applied at a 10-day interval with standard (61.25 + 1072.75 g a.i. ha-1 ) and double (122.5 + 2145.50 g a.i. ha-1 ) doses. The efficient analytical method was established using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach followed by LC-MS. The maximum residue levels of 0.15 and 0.35 mg kg-1 of trifloxystrobin were detected in tomato fruits immediately after application at standard and double doses, respectively. The corresponding levels of propineb as carbon disulfide were 0.47 and 0.90 mg kg-1 , respectively. Considering trifloxystrobin (0.7 mg kg-1 ) codex maximum residue limit and propineb as dithiocarbamate (3.0 mg kg-1 ) European Commission maximum residue limit in tomato, a pre-harvest interval of 1 day can be proposed. The anticipated residue contributions of both fungicides were far less than the acceptable daily intake. The targeted hazard quotient and hazard index were also less than 1 for both fungicides. Furthermore, the theoretical maximum residue contribution was less than its maximum permissible intake, which indicates that the consumption of tomatoes containing the measured value of each fungicide residue could not pose any health risks.

Novel synthesized attapulgite nanoparticles-based hydrophobic monolithic column for in-tube solid-phase microextraction of thiosildenafil, pseudovardenafil, and norneosildenafil in functional foods.

In this study, a novel method which involved in-tube solid-phase microextraction (SPME) using an attapulgite (ATP) nanoparticles-based hydrophobic monolithic column was successfully developed. It was coupled with high-performance liquid chromatography-ultraviolet detection for the determination of three phosphodiesterase-5 (PDE-5) inhibitors, including thiosildenafil, pseudovardenafil, and norneosildenafil, in functional foods. The monolithic column was prepared by one-step polymerization, using 3-trimethoxysilylpropyl methacrylate-modified ATP nanoparticles and 1-butyl-3-vinylimidazolium bromide (VBIMBr) as the functional monomers, and ethylene glycol dimethacrylate (EDMA) as the cross-linker. The obtained poly(ATP-VBIMBr-EDMA) monolith was characterized by scanning electron microscopy equipped with energy-dispersive analysis of X-ray, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. The adsorption capacity, up to 2.00 µg/cm calculated by the Langmuir isotherm model, was about six times that of the poly(VBIMBr-EDMA) monolith. Crucial factors affecting the extraction efficiency, including sample solvent, elution solvent, flow rates of sampling loading and elution, sample loading volume, and elution volume, were investigated in details. Under the optimal in-tube SPME conditions, the proposed method showed good reproducibility with run-to-run, column-to-column, and batch-to-batch relative standard deviations less than 7.2%, and low limits of detection of 0.5-0.9 ng/mL in real samples. Thiosildenafil was detected in four types of functional foods with the contents of 1.30-4.78 µg/g. This newly proposed in-tube SPME method based on poly(ATP-VBIMBr-EDMA) monolith may provide a simple, efficient, and promising alternative to daily monitoring of PDE-5 inhibitors in functional foods.

Degree of conversion of resin cement with varying methacrylate compositions used to cement fiber dowels: A Raman spectroscopy study.

STATEMENT OF PROBLEM: Studies on the degree of conversion of dental cement in relation to the number of methacrylate components are lacking. PURPOSE: The purpose of this in vitro study was to evaluate the degree of conversion of single- and multicomponent methacrylate-containing dental cements around opaque and translucent fiber dowels at varying depths. MATERIAL AND METHODS: Teeth were prepared for standard endodontic therapy, and a dowel space was created. Opaque and translucent fiber dowels consisting of Aestheti-Plus (AP) and FiberKleer were cemented with 4 methacrylate (MA)-containing cements, including RelyX U100 (R), which contains TEGDMA; Duolink (D), which contains TEGDMA and BisGMA; and Variolink N LC (V) and Breeze (B), which contain TEGDMA, BisGMA, and UDMA. Light-emitting diode polymerization was performed for 60 seconds. The specimens were immediately cut into halves and measured within the first hour at depths of 1, 3, and 5 mm using Raman spectroscopy, and the degree of conversion (DC) of resin cement was calculated. Data were analyzed using 3-way ANOVA and the Tukey multiple comparison test (α=.05). RESULTS: The measured dowel regions were not significantly different at various depths (P=.10). The dowel and cement types significantly influenced the degree of conversion of the cement (P<.05). The V and B cements exhibited a higher DC than D and R cements. With AP dowels, the DC of cement D was lower than that of the V, B, and R cements. CONCLUSIONS: Within the limitations of this in vitro study, the degrees of conversion of the tested resin cements were not affected by the tested dowel depths. Higher DC was found in cement with more than 2 types of flexible MA. Opaque dowels produced a lower DC than translucent dowels.

In vitro and field efficacy of fungicides against sheath blight of rice and post-harvest fungicide residue in soil, husk, and brown rice using gas chromatography-tandem mass spectrometry.

Rice is a staple food for about 65% of the India's population. India ranks first in area under rice and second in production of rice in the world. In India, it is cultivated over 43.39 m ha with a production and productivity of 104.32 million tons and 2404 kg/ha, respectively. Besides ensuring food security of the nation, it is an export commodity and earns a huge foreign exchange. In this study, we investigated the efficacy of five fungicides against Rhizoctonia solani Kuhn AG-1 IA, inciting sheath blight of rice in vitro and under field conditions along with post-harvest residue of the fungicides found effective in disease management. In vitro growth inhibition tests revealed that the EC50 values of azoxystrobin 18.2% + difenoconazole 11.4% SC, pencycuron 22.9% SC, thifluzamide 23.9% SC, hexaconazole 4% + zineb 68% WP, and validamycin 3% L against Rhizoctonia solani ranged from 0.006 to 354.81 ppm a.i., whereas the corresponding EC90 values were 0.758 to 1202.26 ppm a.i. Thifluzamide 23.9% SC was found to be the most inhibitory with EC50 and EC90 values of 0.006 and 0.758 ppm a.i. followed by hexaconazole 4% + zineb 68% WP. The complete inhibition of sclerotia formation was observed at 1 ppm, 20 ppm, and 25 ppm a.i. of thifluzamide 23.9% SC, hexaconazole 4% + zineb 68% WP, and azoxystrobin 18.2% + difenoconazole 11.4% SC, respectively. In field trials, azoxystrobin 18.2% + difenoconazole 11.4% SC was the best treatment in reducing sheath blight and in enhancing grain yield of rice followed by thifluzamide 23.9% SC, pencycuron 22.9% SC, and validamycin 3% L, whereas hexaconazole 4% + zineb 68% WP was the least effective fungicide. Benefit-cost ratio (B:C) of different fungicides reflected that pencycuron 22.9% SC (B:C 5.06) and azoxystrobin 18.2% + difenoconazole 11.4% SC(B:C 4.65) sprayed at single/recommended doses of 1 ml/l were highly economical in managing sheath blight disease of rice. Double dose of pencycuron 22.9% SC further enhanced the B:C to 7.24 while the double dose of azoxystrobin 18.2% + difenoconazole 11.4% SC was less economical (B:C 2.84) compared to their recommended doses. Samples of rice matrices were processed using QuEChERS method and analyzed for the presence of fungicide residues by gas chromatography-tandem mass spectrometry (GC-MS/MS). The post-harvest residues of azoxystrobin, difenoconazole, and pencycuron, sprayed at single/recommended and double doses with a pre-harvest interval (PHI) of 44 days, were found below the limit of quantification (LOQ), i.e., 0.01 and 0.005 mg kg-1 for azoxystrobin and difenoconazole and 0.05 mg kg-1 for pencycuron in brown rice, cropped soil, paddy straw, and husk. These results clearly demonstrated that treatment of azoxystrobin 18.2% + difenoconazole 11.4% SC and pencycuron 22.9% SC could be taken as safe for crop protection and environmental contamination point of view. The findings of this research work will have a positive impact on rice export and use.

Determination of strobilurin fungicide residues in fruits and vegetables by nonaqueous micellar electrokinetic capillary chromatography with indirect laser-induced fluorescence.

A nonaqueous micellar electrokinetic capillary chromatography method with indirect LIF was developed for the determination of strobilurin fungicide residues in fruits and vegetables. Hydrophobic CdTe quantum dots (QDs) synthesized in aqueous phase were used as background fluorescent substance. The BGE solution, QD concentration, and separation voltage were optimized to obtain the best separation efficiency and the highest signal intensity. The optimal BGE solution consists of 40 mM phosphate, 120 mM sodium dodecyl sulfate, 15% v/v water and 15% v/v hydrophobic CdTe QDs in formamide, of which apparent pH is 9.5. The optimized separation voltage is controlled as 25 kV. The resultant detection limits of azoxystrobin, kresoxim-methyl, and pyraclostrobin are all 0.001 mg/kg, their linear dynamic ranges are 0.005-2.5 mg/kg, and the recoveries of the spiked samples are 81.7-96.1%, 86.5-95.7%, and 87.3-97.4%, respectively. This method has been proved to be sensitive enough to detect the aforementioned fungicides in fruits and vegetables at the maximum residue limits.

Analysis of organic components in resin-modified pulp capping materials: critical considerations.

The purpose of this study was to elucidate the organic composition and eluates of three resin-based pulp-capping materials in relation to their indications and safety data sheets. Uncured samples of Theracal LC, Ultra-Blend Plus, and Calcimol LC were investigated using gas chromatography-mass spectrometry (GC-MS) and ultra-performance liquid chromatography-mass spectrometry (UPLC-MS). Identification/quantification of 7-d leachables of cured samples was performed using GC-MS for 2-hydroxyethyl methacrylate (HEMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), camphorquinone (CQ), ethylene glycol dimethacrylate (EGDMA), ethyl-4-(dimethylamino)benzoate (DMABEE), and triethylene glycol dimethacrylate (TEGDMA). A similar organic composition was found for Ultra-Blend and Calcimol; however, only Ultra-Blend is indicated for direct pulp-capping. In contrast to the other materials analysed, Theracal contained substances of high molecular weight. The safety data sheets of all materials were incomplete. We detected HEMA, CQ, and TEGDMA in eluates from Ultra-Blend and Calcimol, and it was considered that HEMA might have originated from decomposition of diurethane dimethacrylate (UDMA) in the GC-injector. For Theracal, additives associated with light curing (DMABEE and CQ) were detected in higher amounts (4.11 and 19.95 µg mm-2 ) than in the other materials. Pores were quantified in all samples by micro-computed tomography (micro-CT) analysis, which could influence leaching. The organic substances in the investigated materials might affect their clinical suitability as capping agents, especially for direct capping procedures.

Simultaneous determination of difenoconazole, trifloxystrobin and its metabolite trifloxystrobin acid residues in watermelon under field conditions by GC-MS/MS.

An optimized quick, easy, cheap, effective, rugged and safe method for the simultaneous determination of difenoconazole, trifloxystrobin and its metabolite trifloxystrobin acid residues in watermelon and soil was developed and validated by gas chromatography with tandem mass spectrometry. The samples were extracted with acetonitrile (1% formic acid) and cleaned up by dispersive solid-phase extraction with octadecylsilane sorbent. The limit of quantification of the method was 0.01 mg/kg, and the limit of detection was 0.003 mg/kg for all three analytes. The recoveries of the fungicides in watermelon, pulp and soil were 72.32-99.20% for difenoconazole, 74.68-87.72% for trifloxystrobin and 78.59-92.66% for trifloxystrobin acid with relative standard deviations of 1.34-14.04%. The dissipation dynamics of difenoconazole and trifloxystrobin in watermelon and soil followed the first-order kinetics with half-lives of 3.2-8.8 days in both locations. The final residue levels of difenoconazole and trifloxystrobin were below 0.1 mg/kg (maximum residue level [MRL] set by China) and 0.2 mg/kg (MRL set by European Union), respectively, in pulp samples collected 14 days after the last application. These results could help Chinese authorities to establish MRL of trifloxystrobin in watermelon and provide guidance for the safe and proper application of both fungicides on watermelon.

Quantitative Evaluation of MDP-Ca Salt and DCPD after Application of an MDP-based One-step Self-etching Adhesive on Enamel and Dentin.

PURPOSE: To investigate the effects of an experimental 10-methacryloyloxydecyl dihydrogen phosphate (MDP)-based one-step self-etching adhesive (EX adhesive) applied to enamel and dentin on the production of calcium salt of MDP (MDP-Ca salt) and dicalcium phosphate dehydrate (DCPD) at various periods. MATERIALS AND METHODS: The EX adhesive was prepared. Bovine enamel and dentin reactants were prepared by varying the application period of the EX adhesive: 0.5, 1, 5, 30, 60 and 1440 min. Enamel and dentin reactants were analyzed using x-ray diffraction and solid-state phosphorus-31 nuclear magnetic resonance (31P NMR). Curvefitting analyses of corresponding 31P NMR spectra were performed. RESULTS: Enamel and dentin developed several types of MDP-Ca salts and DCPDs with amorphous and crystalline phases throughout the application period. The predominant molecular species of MDP-Ca salt was determined as the monocalcium salt of the MDP monomer. Dentin showed a faster production rate and greater produced amounts of MDP-Ca salt than did enamel, since enamel showed a knee-point in the production rate of the MDP-Ca salt at the application period of 5 min. In contrast, enamel developed greater amounts of DCPD than did dentin and two types of DCPDs with different crystalline phases at application periods > 30 min. The amounts of MDP-Ca salt developed during the 30-s application of the EX adhesive on enamel and dentin were 7.3 times and 21.2 times greater than DCPD, respectively. CONCLUSION: The MDP-based one-step adhesive yielded several types of MDP-Ca salts and DCPD with an amorphous phase during the 30-s application period on enamel and dentin.

Residual behavior and risk assessment of the mixed formulation of benzene kresoxim-methyl and fluazinam in cucumber field application.

Benzene kresoxim-methyl (BKM) is a new strobilurin fungicide mixed with fluazinam (Flu) into 40 % suspension concentrate (SC) formulation to improve fungicidal efficacy and to reduce the risk of resistance on cucumber. However, the fate of the fungicide residues in a cucumber plantation remains unclear. Thus, an efficient method of ultra-performance liquid chromatography combined with a modified quick, easy, cheap, effective, rugged, and safe sample preparation was developed to simultaneously determine the BKM and Flu residues in cucumber and soil samples to investigate their residual behavior and risk assessment in the cucumber plantation. This analytical method revealed that the detection limits of BKM and Flu were 1.64 × 10(-3) and 1.82 × 10(-3) mg L(-1), respectively, and their average recoveries in the cucumber and soil samples were 77.5-106.9 %. The respective half-lives of BKM and Flu were 2.2-3.4 and 1.0-2.5 days in cucumber; in soil, the half-lives of BKM and Flu were 2.6-5.0 and 2.4-5.3 days, respectively. Seven days after application, the terminal residues of BKM and Flu in cucumber were less than 0.02 mg kg(-1). The residual profiles of BKM and Flu suggested that these fungicides could rapidly degrade in cucumber plantations. Their hazard quotient values were all less than 1 on the preharvest intervals of 3, 5, and 7 days, indicating that the dietary risk of BKM and Flu 40 % SC with the recommended usage on cucumber is negligible.

Dissipation rates and residues of fungicide azoxystrobin in ginseng and soil at two different cultivated regions in China.

The maximum residue limit (MRL) for fungicide azoxystrobin in ginseng has not yet been established in China. This is partially due to the lack of its dissipation and residue data at China's main ginseng production areas. In this work, the dissipation rates and residue levels of azoxystrobin in ginseng roots, plant parts (stems and leaves), and soil in Beijing and Jilin Province, China were determined using gas chromatograph-mass spectrometry (GC-MS). The mean half-life of azoxystrobin in ginseng plant parts was 1.6 days with a dissipation rate of 90 % over 21 days. The mean half-life in soil was 2.8 days with a dissipation rate of 90 % over 30 days. Dissipation rates from two geographically separated experimental fields differed, suggesting that these were affected by local soil characteristics and climate. Maximum final residues of azoxystrobin in ginseng roots, plant parts, and soil were determined to be 0.343, 9.40, and 0.726 mg kg(-1), respectively. Our results, particularly the high residues of azoxystrobin observed in ginseng plant parts, provide a quantitative basis for revising the application of this pesticide to ginseng.

The influence of effective microorganisms (EM) and yeast on the degradation of strobilurins and carboxamides in leafy vegetables monitored by LC-MS/MS and health risk assessment.

The aim of this study was to determine the behaviour of strobilurin and carbocyamides commonly used in chemical protection of lettuce depending on carefully selected effective microorganisms (EM) and yeast (Y). Additionally, the assessment of the chronic health risk during a 2-week experiment was performed. The statistical method for correlation of physico-chemical parameters and time of degradation for pesticides was applied. In this study, the concentration of azoxystrobin, boscalid, pyraclostrobin and iprodione using liquid chromatography-mass spectrometry (LC-MS/MS) in the matrix of lettuce plants was performed, and there was no case of concentration above maximum residues levels. Before harvest, four fungicides and their mixture with EM (1 % and 10 %) and/or yeast 5 % were applied. In our work, the mixtures of 1%EM + Y and 10%EM + Y both stimulated and inhibited the degradation of the tested active substances. Adding 10%EM to the test substances strongly inhibited the degradation of iprodione, and its concentration decreased by 30 %, and in the case of other test substances, the degradation was approximately 60 %. Moreover, the addition of yeast stimulated the distribution of pyraclostrobin and boscalid in lettuce leaves. The risk assessment for the pesticides ranged from 0.4 to 64.8 % on day 1, but after 14 days, it ranged from 0.0 to 20.9 % for children and adults, respectively. It indicated no risk of adverse effects following exposure to individual pesticides and their mixtures with EM and yeast.

MALDI-MS Imaging Analysis of Fungicide Residue Distributions on Wheat Leaf Surfaces.

Improved retention and distribution of agrochemicals on plant surfaces is an important attribute in the biological activity of pesticide. Although retention of agrochemicals on plants after spray application can be quantified using traditional analytical techniques including LC or GC, the spatial distribution of agrochemicals on the plants surfaces has received little attention. Matrix assisted laser desorption/ionization (MALDI) imaging technology has been widely used to determine the distribution of proteins, peptides and metabolites in different tissue sections, but its application to environmental research has been limited. Herein, we probed the potential utility of MALDI imaging in characterizing the distribution of three commercial fungicides on wheat leaf surfaces. Using this MALDI imaging method, we were able to detect 500 ng of epoxiconazole, azoxystrobin, and pyraclostrobin applied in 1 µL drop on the leaf surfaces using MALDI-MS. Subsequent dilutions of pyraclostrobin revealed that the compound can be chemically imaged on the leaf surfaces at levels as low as 60 ng of total applied in the area of 1 µL droplet. After application of epoxiconazole, azoxystrobin, and pyraclostrobin at a field rate of 100 gai/ha in 200 L water using a track sprayer system, residues of these fungicides on the leaf surfaces were sufficiently visualized. These results suggest that MALDI imaging can be used to monitor spatial distribution of agrochemicals on leaf samples after pesticide application.

Simultaneous determination of tebuconazole, trifloxystrobin, and its metabolite trifloxystrobin acid residues in gherkin under field conditions.

A rapid, simple, and selective analytical method for the simultaneous determination of tebuconazole, trifloxystrobin, and its metabolite trifloxystrobin acid residues in gherkin and soil was developed and validated by gas chromatography coupled with mass spectrometry. The samples were extracted with acetonitrile and cleaned up by dispersive solid-phase extraction with primary secondary amine sorbent. The limit of quantification of the method was 0.05 mg/kg for all three compounds. The method was validated using blank samples spiked at three levels and recoveries ranged from 83.5 to 103.8% with a relative standard deviation of 1.2 to 4.8%. The developed method was validated and applied for the analysis of a degradation study sample. The residues of trifloxystrobin and tebuconazole were found to dissipate following first-order kinetics with half-life ranging between 3.31-3.38 and 3.0-3.04 days, respectively, for two different dosages. Pesticide residues were below the European Union maximum residue level after seven days for trifloxystrobin (0.2 mg/kg) and ten days for tebuconazole (0.05 mg/kg), which suggested the use of this fungicide mixture to be safe to humans. These results can be utilized in formulating the spray schedule and safety evaluation on trifloxystrobin and tebuconazole in gherkin crop.

Aquatic risk assessment of a novel strobilurin fungicide: A microcosm study compared with the species sensitivity distribution approach.

The ecotoxicological effects of pyraoxystrobin, a novel strobilurin fungicide, were studied using outdoor freshwater microcosms and the species sensitivity distribution approach. The microcosms were treated with pyraoxystrobin at concentrations of 0, 1.0, 3.0, 10, 30 and 100µg/L. Species sensitivity distribution (SSD) curves were constructed by means of acute toxicity data using the BurrliOZ model for fourteen representatives of sensitive invertebrates, algae and fish and eleven taxa of invertebrates and algae, respectively. The responses of zooplankton, phytoplankton and physical and chemical endpoints in microcosms were studied. Zooplankton, especially Sinodiaptomus sarsi was the most sensitive to pyraoxystrobin exposure in the microcosms. Short-term toxic effects (<8 weeks) on zooplankton occurred in 1µg/L treatment group. The duration of toxic effects on S. sarsi could not be evaluated within the initial 56 days. Significant long-term toxic effects were observed at 10, 30 and 100µg/L (>281 days) for S. sarsi and the zooplankton community. Based on the results obtained from the organisms in the microcosm system, 1µg/L was recommended as the NOEAEC (no observed ecologically adverse effect concentration). Also, 0.33µg/L was derived as the Regulatory Acceptable Concentration based on the ecological recovery option (ERO-RAC) of pyraoxystrobin. For all fourteen tested species, the median HC5 (hazardous concentration affecting 5% of species) was 0.86µg/L, and the lower limit HC5 (LL-HC5) was 0.39µg/L. For the eleven taxa of invertebrates and algae tested, the median HC5 was 1.1µg/L, and the LL-HC5 was 0.26µg/L. The present study positively contributes to the suggestion of adequately using acute L(E)C50-based HC5/ LL-HC5 for deriving protective concentrations for strobilurin fungicides, and it should be valuable for full comprehension of the potential toxicity of pyraoxystrobin in aquatic ecosystems.

Adsorption-desorption and leaching behavior of kresoxim-methyl in different soils of India: kinetics and thermodynamic studies.

The sorption and leaching behavior of kresoxim-methyl was explored in four different soils, viz., clay, sandy loam, loamy sand, and sandy loam (saline), representing vegetables and fruits growing regions of India. Adsorption of kresoxim-methyl in all the soils reached equilibrium within 48 h. The rate constants for adsorption and desorption at two different temperatures were obtained from the Lindstrom model, which simultaneously evaluated adsorption and desorption kinetics. The data for rate constants, activation energies, enthalpy of activation, entropy of activation, and free energy indicated physical adsorption of kresoxim-methyl on soil. The relative adsorptivity of the test soils could be attributed to different organic matter and clay contents of the soils. A good fit to the linear and Freundlich isotherms was observed for both adsorption as well as desorption. The groundwater ubiquity score (GUS) for different soils varied between 0 and 2.26. The GUS and leaching study indicated moderately low leaching potential of kresoxim-methyl. The adsorption on four soil types largely depended on the soil physicochemical properties such as organic carbon content, cation-exchange capacity, and texture of the soil.

Field dissipation of trifloxystrobin and its metabolite trifloxystrobin acid in soil and apples.

The dissipation of trifloxystrobin and its metabolite trifloxystrobin acid in apples and soil was studied, and the half-life (DT50) was estimated in a field study carried out at three different locations for apples and four different locations for soil. Trifloxystrobin was sprayed on apples at 127 g a.i./ha for the dissipation study. Samples of apple and soil for the dissipation experiment were collected at time intervals of 0, 1, 3, 7, 14, 21, 30, and 45 days after treatment. The quantification of residues was done by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The DT50 of trifloxystrobin ranged from 0.54 to 8.8 and 4.8 to 9.5 days in soil and apples at different latitude sites. Photolysis may be the main dissipation pathway for trifloxystrobin, and the number of sunshine hours may be the main factor affecting the trifloxystrobin dissipation rate in the field. For trifloxystrobin acid residues in soil and apples, it first increased and then began decreasing. It was indicated that the risk of trifloxystrobin application in shorter sunshine hour area should be considered.

Dissipation, residues, and safety evaluation of trifloxystrobin and tebuconazole on ginseng and soil.

Supervised field trials at two locations in 2012 and 2013 were conducted to evaluate the dissipation, terminal residues, and safety evaluation of Nativo 75 water dispersible granule (WG) (25 % trifloxystrobin + 50 % tebuconazole) on ginseng and soil following foliar application at a recommended dose 150 (50 + 100) and 1.5 times of the recommended dosage 225 (75 + 150) g a.i. ha(-1). The average recoveries of trifloxystrobin and tebuconazole at three spiking levels in ginseng root, stem, and leaf and in soil were in the ranges of 81.0-96.8 % and 80.2-97.5 % with relative standard deviations (RSDs) of 4.92-13.13 % and 4.67-8.35 %, respectively. The half-lives of trifloxystrobin and tebuconazole were 5.92-9.76 days and 4.59-7.53 days, respectively. The terminal residues were all below the maximum residue limits (MRLs) of EU, USA, Canada, Japan, and South Korea. The food safety was evaluated by comparing the estimated daily intake (IEDI) with its acceptable daily intake (ADI). IEDI values calculated from residue data were found to be far less than the ADI on ginseng. Therefore, it would be unlikely to cause health problems induced by Nativo 75 WG use on ginseng at a dosage of 150-225 g a.i. ha(-1).

Residue levels and dissipation behaviors for trifloxystrobin and tebuconazole in mango fruit and soil.

An evaluation of residue levels of trifloxystrobin and tebuconazole was carried out on mango fruits after treatments with the combined formulation, trifloxystrobin (25 % w/w) and tebuconazole (50 % w/w), at standard and double doses of 250 + 500 and 500 + 1000 g a.i. ha(-1), respectively. Extraction and purification of the mango fruit samples were carried out by the QuEChERS method after validating the analytical parameters. Determination of the fungicides was carried out by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The limits of detection (LOD) and limits of quantification (LOQ) for both fungicides were 0.015 µg mL(-1) and 0.05 mg kg(-1), respectively. The residue levels of trifloxystrobin for standard and double-dose treatments were 0.492 and 0.901 mg kg(-1) and for tebuconazole were 0.535 and 1.124 mg kg(-1), respectively. A faster dissipation of tebuconazole in mango fruit was observed compared with that for tebuconazole. Dissipation of trifloxystrobin and tebuconazole in mango followed first-order kinetics, and the half-lives were 9 and 6 days, respectively. The preharvest intervals (PHI), the time taken for the combined residues of trifloxystrobin and tebuconazole to dissipate to their permissible levels (maximum residue limits), were 14 and 20 days for standard and double doses, respectively. At harvest, mature mango fruit and soil were free from fungicide residues.

Comparison of the residue persistence of trifloxystrobin (25%) + tebuconazole (50%) on gherkin and soil at two locations.

Residue study of trifloxystrobin and tebuconazole on gherkin was carried out at two locations (Bangalore and Gouribiddunur, India) after applications at the standard and double doses of 75 + 150 and of 150 + 300 g ha(-1) of the formulated product, trifloxystrobin (25%) + tebuconazole (50%) (Nativo 75 WG). The fungicides were determined by gas chromatography (GC) and confirmed by gas chromatography-mass spectrometry (GC-MS). Extraction and purification of the samples were carried out by Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method after validating the analytical parameters. Initial residues of trifloxystrobin on gherkin fruits were 0.335 and 0.65 mg kg(-1) at Bangalore, and 0.34 and 0.615 mg kg(-1) at Gouribiddunur. Tebuconazole residues were 0.842 and 1.682 mg kg(-1) at Bangalore, and 0.71 and 1.34 mg kg(-1) at Gouribiddunur. Residue dissipation of the fungicides followed first-order rate kinetics. Trifloxystrobin residues dissipated at the half-life of 2.9-3.7 days, and tebuconazole at 3.2 days. At the standard dose treatment, trifloxystrobin residues dissipated to below the maximum residue limit (MRL) of 0.2 mg kg(-1) (European Union) within 3 days at both the locations. Residues of the metabolite CGA 321113 was less than the limit of quantification (LOQ; 0.05 mg kg(-1)) on all sampling days. Tebuconazole residues dissipated to below its MRL (0.05 mg kg(-1)) within 14 and 11 days, at Bangalore and Gouribiddunur, respectively. From the two trials, it was concluded that the required pre-harvest interval (PHI) for the combination formulation was 14 days. Application of Nativo 75 WG should be given before flowering to allow the residues to dissipate below the MRLs at harvest.

Dissipation behavior of hexaconazole and kresoxim-methyl residues in ginseng and soil under field conditions.

The dissipation and terminal residues of a fungicide suspension (5% hexaconazole, 25% kresoxim-methyl) in ginseng and soil were investigated by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). At fortified levels of 0.01, 0.02, and 0.20 mg kg(-1), the recoveries of hexaconazole and kresoxim-methyl were in the range of 80.6∼94.8% and 82.4∼98.8% with relative standard deviation of 3.42-9.12% and 3.19-8.58%, respectively. The half-lives were 7.09-10.73 days in root, 6.80-7.95 days in stem, 5.31-8.49 days in leaf, and 6.30-7.97 days in soil. The terminal residues were all below the maximum residue limits (MRLs) of EU and South Korea. Risk assessment results indicated that the risk of hexaconazole and kresoxim-methyl use in ginseng at dosage of 60-90 g a.i. ha(-1) was negligible to humans. This work would help the government to establish the MRL and provide guidance on the proper and safe use of hexaconazole and kresoxim-methyl in ginseng.