Raman silent region - based method for detection of pesticides with cyano group.

Based on the fact that not all chemical substances possess good Raman signals, this article focuses on the Raman silent region signals of pesticides with cyano group. Under the optimized conditions of methanol-water (1:1, v/v) as the solvent, irradiation at 302 nm light source for 20 min, and the use of 0.5 mol/L KI as the aggregating agent, Surface-enhanced Raman spectroscopy (SERS) method for azoxystrobin detection was developed by the Raman silent region signal of 2230 cm-1, and verified by detecting the spiked grapes with different concentrations of azoxystrobin. Other four pesticides with cyano group also could be identified at the peak of 2180 cm-1, 2205 cm-1, 2125 cm-1, and 2130 cm-1 for acetamiprid, phoxim, thiacloprid and cymoxanil, respectively. When azoxystrobin or acetamiprid was mixed respectively with chlorpyrifos without cyano group, their SERS signals in the Raman silent region of chlorpyrifos were not interfered, while mixed with cymoxanil in different ratios (1:4, 1:1 and 4:1), respectively, each two pesticides with cyano group could be distinguished by the changes in the Raman silent region. In further, four pesticides with or without cyano group were mixed together in 1:1:1:1 (acetamiprid, cymoxanil, azoxystrobin chlorpyrifos), and each pesticide still could be identified even at 0.5 mg/L. The results showed that the SERS method combined with UV irradiation may provide a new way to monitor the pesticides with C≡N performance in the Raman silent region without interference from the food matrix.

Residue behavior and risk assessment of pyraclostrobin and tebuconazole in peppers under different growing conditions.

This study evaluates the residue behavior and risks of pyraclostrobin and tebuconazole in peppers. An analytical method for the simultaneous determination of the concentration of these fungicides in peppers was developed using ultra-high performance liquid chromatography-triple quadrupole mass spectrometry. Pepper samples were extracted with acetonitrile and cleaned with primary secondary amine and graphitized carbon black. The average recoveries of pyraclostrobin and tebuconazole under three fortification levels were 86.7-101.4% and 81.7-104.4%, with relative standard deviations of 4.0-7.2% and 3.8-10.9%, respectively. The limit of quantification of both fungicides in peppers was 0.01 mg/kg. The terminal residue trial of 30% pyraclostrobin and tebuconazole suspension concentrate was investigated for samples cultivated in open fields and greenhouses. The results showed that the terminal residues of pyraclostrobin and tebuconazole in peppers were lower than the maximum residue limits established by GB 2763-2021 (0.5 mg/kg for pyraclostrobin and 2 mg/kg for tebuconazole). The results of a statistical t-test indicated that there was no significant difference between samples grown in open fields and greenhouses. According to the international estimate of short-term intake (IESTI) calculation model, provided by the Joint FAO/WHO Meeting on Pesticide Residues, the acute dietary exposure risk of both fungicides in peppers was acceptable for the general population, with an IESTI of 0-3% and 0-5% of the acute reference dose for pyraclostrobin and tebuconazole, respectively.

Dissipation and dietary exposure risk assessment of pyraclostrobin, fluxapyroxad, difenoconazole, and azoxystrobin in the Fritillaria field ecosystem.

Fritillaria (Beimu in Chinese) is a well-known traditional Chinese medicinal herbal and valuable health food, which has attracted more and more attention. In this study, an efficient method was developed to determine pyraclostrobin, fluxapyroxad, difenoconazole, and azoxystrobin in plants, fresh Fritillaria, dry Fritillaria, and soil via liquid chromatography-tandem mass spectrometry. The average recoveries of the method were 78.9-109.7% with relative standard deviations of 0.94-11.1%. The dissipation half-lives of the four fungicides were 4.4-7.7 days in the Fritillaria plant and 11.6-18.2 days in the soil. The terminal residues of four fungicides were 0.033-0.13 mg/kg in fresh Fritillaria, 0.096-0.42 mg/kg in dry Fritillaria, and 0.12-0.74 mg/kg in soil. In the risk assessment of dietary exposure, all the chronic hazard quotient and acute hazard quotient index values were far below 100%, which were both acceptable to consumers. Accordingly, 7 days was recommended as the pre-harvest interval for the four fungicides in Fritillaria. This work could guide the safe use of these fungicides in Fritillaria and also give a reference for the Chinese government to establish the maximum residue limits (MRLs).

Method validation, residue analysis and dietary risk assessment of trifloxystrobin and trifloxystrobin acid in milk, eggs and pork.

Trifloxystrobin (TFS) is a widely used strobilurin fungicide and its residues accumulating in animal-derived food could result in potential harm to consumers. By optimization of extraction solvents and cleanup sorbents, a residue analysis method for TFS and its metabolite trifloxystrobin acid (TFSA) was established in milk, eggs and pork based on QuEChERS sample preparation and LC-MS/MS. The calibration curves exhibited good linearity with determination coefficients (R2 ) >0.9930 over the range of 0.5-250 ng/ml for both TFS and TFSA. The recoveries of the two analytes were 81-100% with RSD 3-10% and 76-96% with RSD 2-13%, respectively. The limit of quantification (LOQ) was 1 ng/g for both analytes. The milk, egg and pork samples, 30 each, were collected from the 30 main producing regions in China, and residues of TFS and TFSA were analyzed. The concentrations of both analytes were lower than the corresponding LOQs and maximum residue limits. Long-term dietary risk assessment showed that the hazard quotients were 0.001-0.003%, indicating an absence of unacceptable risks in milk, eggs and pork to the health of common consumers in China.

Extraction and determination of strobilurin fungicides residues in apple samples using ultrasound-assisted dispersive liquid-liquid microextraction based on a novel hydrophobic deep eutectic solvent followed by H.P.L.C-U.V.

In this study, several novel and natural hydrophobic deep eutectic solvents (D.E.Ss) were prepared using methyl trioctylammonium chloride (M.T.O.A.C) as H.B.A and different types of straight chain alcohols as H.B.Ds. One of the D.E.Ss composed of M.T.O.A.C and n-butanol was advantageously used to develop an ultrasound-assisted dispersive liquid-liquid microextraction (U.A-D.L.L.M.E) method combined with high-performance liquid chromatography-ultraviolet detection (H.P.L.C-U.V) for the determination of some strobilurin fungicides in apple samples. Several important parameters influencing extraction efficiency were investigated and optimised, including the type and volume of extractant in ultrasound stage, sonication time, the type and volume of D.E.S, sample solution pH and effect of salt addition. Under optimal experimental conditions, the method showed good linearity with correlation coefficients (R2) of 0.9985 - 0.9991 in the linear range of 4-1500 µg kg-1, low limits of detection of 1.5-2 µg kg-1 and acceptable extraction recoveries in the range of 76-92%. Enrichment factor was in the range of 95-115. The proposed method was successfully applied for the extraction and preconcentration of trace fungicides in apple samples, and the results demonstrated the potential of the synthesised D.E.S for the extraction and determination of contaminants in aqueous samples.

Evaluation of acetamiprid and azoxystrobin residues and their hormonal disrupting effects on male rats using liquid chromatography-tandem mass spectrometry.

Endocrine-disrupting compounds as pesticides affect the hormonal balance, and this can result in several diseases. Therefore, the analysis of representative hormones with acetamiprid (AC) and azoxystrobin (AZ) was a good strategy for the investigation of the endocrine-disrupting activity of pesticides. Hence, a sensitive and rapid analytical method using liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed. The method was validated for the analysis of AC, AZ, estriol, estrone, progesterone, and testosterone in the serum, testis, and liver of rats. The correlation between the residues of pesticides and the disturbance of the endocrine system was evaluated. The different mass parameters, mobile phase types, analytical columns, injection volumes, and extraction solvents were compared to get the lowest limit of detection of the studied compounds. The detection limits of AC, AZ, estriol, estrone, progesterone, and testosterone were 0.05, 0.05, 1.0, 10, and 1.0 ng/ml, respectively. The method developed was applied to evaluate the changes in these hormones induced by the duration of exposure to AC and AZ in rat testis and serum. The hormones level in rat serum and testis had a significant decrease as they were oral gavage treated with different high concentrations of studied pesticides. Both pesticides were distributed in the body of rats by the multi-compartment model (liver, testis, and serum).

Determination of azoxystrobin, topramezone, acetamiprid, fluometuron and folpet in their commercially available pesticide formulations by liquid chromatography.

A rapid, simple, precise and accurate high performance liquid chromatographic (HPLC) analytical method was developed and validated for the determination of the active substances (a.s.) azoxystrobin, topramezone, acetamiprid, fluometuron and folpet in their respective commercially available formulations. The method was used for the analysis of samples under the frame of the national quality control program of plant protection products in the Greek market. Chromatographic separation of the active substances from additives and co-formulants is achieved using isocratic elution with acetonitrile and 0.1% phosphoric acid solution (60:40 v/v) at a flow rate of 0.4 mL min-1 on a C18 monolithic column (Chromolith Performance-RP18e 100 × 4.6 mm) and UV detection at 230 nm. Validation parameters of the method fulfilled acceptability criteria. Recovery of all individual compounds was in the range 97.8-100.9%. Precision expressed as relative standard deviation was lower than the theoretical values of the modified Horwitz equation. Correlation coefficients of linearity of response were better than 0.999. The benefits of the proposed method are significant reduction in analysis time and total cost since all analytes were determined with the same extraction procedures and chromatographic system. Analysis of real samples for all active ingredients confirmed fitness for purpose of the suggested method.

Distribution of organochlorine, organophosphates, carbamate, thiocarbamate, pyrethroids, and strobilurins in surface sediments of the Rio de Ondas watershed by GC-MS.

The determination of some pesticides in surface sediments can provide important information about their distribution in the water column. This work aimed to determine the distribution of the classes of pesticides along the Ondas River's hydrographic basin (ORHB), in eighteen different points, during the dry and rainy periods. The pesticides were extracted from the sediment samples by solid-liquid extraction and then analyzed using a gas chromatograph coupled to mass spectrometry. After the development and validation of the method, nineteen pesticides from the group of organochlorine, organophosphates, carbamate and thiocarbamate, pyrethroids, and strobilurins were quantified in at least one point in the two collection periods, with accuracy varying between 86 and 126%. The average concentrations were 0.020 ng g-1 (carbofuran) to 249.123 ng g-1 (dimethoate) and 0.029 ng g-1 (carbofuran and sulfotep) to 533.522 ng g-1 in the dry and rainy periods, respectively. The results showed a wide distribution of pesticide residues in the ORHB, with higher levels for dimethoate, phenitrothion, and malathion, which may be related to their agricultural use in the region. In Brazil, it does not have specific legislation for maximum permitted values of pesticides in sediment, allowing for inappropriate or prohibited use and, consequently, affecting water quality.

Occurrence and impact of fungicides residues on fermentation during wine production- A review.

Continuous fungicide spraying is required to eliminate fungal pathogens on grapes. However, this practice is associated with several risks, including contamination and environmental imbalance, as well as toxicity to operators and the induction of resistance in pathogens. In addition, a strong correlation has been reported between the presence of fungicides and the occurrence of issues during alcoholic fermentation, resulting in negative impacts on the sensory quality of the final products. Numerous studies have evaluated residue concentrations of phytosanitary products in grapes, juices, and wines, and a significant number of studies have assessed the impact of different agrochemicals on bioprocesses. However, a review compiling the key results of these studies is currently lacking. This review incorporates results obtained in the last decade from research on the presence of fungicide residues, including azoxystrobin, boscalid, captan, copper, fenhexamid, folpet, pyraclostrobin, pyrimethanil and tebuconazole, and their effects on fermentation kinetics. Practical solutions to mitigate these problems, both in vineyards and industry, are also presented and discussed. This review highlights the constant high fungicidal agent concentrations (greater than 1 or 2 mg L-1) used throughout the winemaking process, with the impact of residues being of particular concern, especially with regard to their effect on yeast activity and the fermentation process. Thus, the adoption of methodologies that allow winemakers to control and trace these residues is an important step in avoiding or reducing fermentation problems throughout the winemaking process.[Figure: see text].

Terminal residue and dietary intake risk assessment of prothioconazole-desthio and fluoxastrobin in wheat field ecosystem.

BACKGROUND: Wheat is one of the most important cereal crops worldwide, and use of fungicides is an essential part of wheat production. Both prothioconazole and fluoxastrobin give excellent control of important seed and soilborne pathogens. The combination of these two fungicides shows a complementary mode of action and has a wide usage around the world. But the residue levels of these fungicides in the wheat matrix are still unknown. RESULTS: In the current study, a simple, low-cost and highly sensitive method using modified QuECHERS procedure combined with high-performance liquid chromatography-tandem mass spectrometry was developed to simultaneously quantify E- and Z-fluoxastrobin and the main metabolite prothioconazole-desthio of prothioconazole in the wheat matrix. The recoveries of prothioconazole-desthio, E-fluoxastrobin and Z-fluoxastrobin ranged from 84% to 101%, with relative standard deviation of less than 13.2%. The terminal residues of prothioconazole-desthio and E- and Z-fluoxastrobin were studied in wheat grain and straw under field conditions. The results showed that the terminal residue of the target compounds ranged from <0.01 to 0.029 mg kg-1 and <0.05 to 7.6 mg kg-1 in wheat grain and straw (expressed as dry weight), respectively. The risk quotients of prothioconazole-desthio and fluoxastrobin were 0.2% and 3.2%. CONCLUSIONS: The residue levels of the target analytes in wheat grain were lower than the maximum residue limits recommended by the Chinese Ministry of Agriculture. And the calculated risk quotient values were far below 100%, indicating a low dietary intake health risk to consumers. © 2021 Society of Chemical Industry.

Relative comparison of strobilurin fungicides at environmental levels: Focus on mitochondrial function and larval activity in early staged zebrafish (Danio rerio).

Strobilurin fungicides are used globally and have been detected in microgram per liter concentrations in aquatic environments. Here, we determined the potential toxicity of four commonly used strobilurins (azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin) on mitochondrial function and locomotor activity of larval zebrafish at an environmentally relevant level. As the mode of action of strobilurins in fungi is binding to cytochrome bc1 in mitochondrial complex III, we evaluated exposure effects on mitochondrial oxidative phosphorylation of zebrafish, by measuring oxygen consumption rates, mitochondria-related enzyme activities, and transcripts levels for genes associated with the electron transfer chain and citric acid cycle. We found that 50 nM pyraclostrobin and trifloxystrobin lowered basal respiration, oligomycin-induced ATP respiration, and maximal respiration of embryos. Dysfunction in mitochondrial bioenergetics was associated with changes in mitochondrial complex III activity and transcripts of oxidative respiration and stress-related genes. Lower activity of complex III, and reduced cytb mRNA levels were hypothesized to contribute to reduced electron supply to complex IV and V. Both coxI and atp6 were up-regulated, suggesting a compensatory response to impaired oxidative respiration. Cluster analysis indicated that strobilurin-induced oxidative stress and cytb transcript were related to impaired oxidative phosphorylation. We also assessed larval behavior responses, as reduced ATP can affect activity. We observed that pyraclostrobin and trifloxystrobin induced hypoactive responses in zebrafish. At 50 nM, azoxystrobin and kresoxim-methyl exerted no effects on mitochondrial function nor locomotion of zebrafish. Studies such as this are important for determining sublethal toxicity to these fungicides, as widespread detection of strobilurins in aquatic environments suggests there is a potential for adverse effects in aquatic organisms.

Dissipation kinetics and safety evaluation of pyraclostrobin and its desmethoxy metabolite BF 500-3 in a cucumber greenhouse agroecosystem.

Pyraclostrobin (PYR), a fungicide of the strobilurin class, is used to control many different kinds of fungal diseases in greenhouses and on agricultural fields. In the present study, an efficient method was established for simultaneously determining PYR and its metabolite BF 500-3 in cucumber fruits, leaves, and soil matrices using QuEChERS pretreatment coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The residue levels and dissipation kinetics of PYR were determined under greenhouse conditions. The recoveries ranged from 89.8 to 103.6% with relative standard deviations (RSDs) of 3.6-7.5% at three spiking levels. The results demonstrated that PYR dissipated quickly in the cucumber field with half-lives (DT50) of 2.14-4.17 days on different sites and in different matrices. The residue of its metabolite BF 500-3 was very low and showed a trend of first increasing and then decreasing. The degradation rate of PYR in soil was the fastest, followed by that on cucumber fruits and leaves. The terminal residue of PYR at an application rate of 150 g a.i. ha-1 (the maximum recommended rate) in cucumber fruits was below the maximum residue limit (MRL) of 0.5 mg/kg established in China. However, the application of the fungicide at 225 g a.i. ha-1 (1.5× the maximum recommended rate) resulted in residues that were above the MRL 1 day after the final application, which is an unacceptable risk. Therefore, the application dosage of PYR at the recommended rates was safe to human beings and animals.

Study on stereoselective bioactivity, acute toxicity, and degradation in cucurbits and soil of chiral fungicide famoxadone.

The chiral pesticide famoxadone is mainly applied to control fungal diseases on fruiting vegetables. The fungicidal activity, ecotoxicological effects, and degradation behavior of famoxadone enantiomers are less well known. In this study, a systemic assessment of the stereoselectivity of famoxadone was performed in cucurbits and soil. Famoxadone enantiomers presented distinct inhibitory activities among different fungal species. The bioactivities of R-(-)-famoxadone were 2.7-178 times higher than S-(+)-famoxadone toward five phytopathogens. Based on the obtained LC50 values, famoxadone was super toxic to Eisenia foetida (E. foetida). Moreover, the acute toxicity of R-(-)-famoxadone presented 167 times greater to E. foetida than that of S-(+)-famoxadone, indicating that R-(-)-famoxadone showed higher bioactivity toward target organisms and non-target organisms than S-(+)-famoxadone. In addition, a simple high-performance liquid chromatography (HPLC) method was established to determine the stereoselective degradation of famoxadone in two species of cucurbits (cucumber and chieh-qua) and in field soil. The half-life values of famoxadone degradation were from 5.4 to 14.1 days, indicating that famoxadone was easily degraded. Additionally, no stereoselective degradation was found in cucurbits and soil. The results may provide promising implications for comprehensive environmental and ecological risk assessments of famoxadone.

Evaluation of hematological parameters, oxidative stress and DNA damage in the cichlid Australoheros facetus exposed to the fungicide azoxystrobin.

Azoxystrobin (AZX) is a broad-spectrum systemic fungicide massively used worldwide. Its mode of action consists in the inhibition of mitochondrial respiration decreasing the synthesis of ATP and leading to oxidative stress in the target fungus. However, whether this effect occurs in non target organisms has been scarcely studied. The objectives of this work were (1) to evaluate biomarkers of oxidative stress, hematological, physiological and of genotoxicity in the native cichlid fish Australoheros facetus exposed to environmentally relevant concentrations of AZX and (2) to compare these biomarkers in different developmental stages using juvenile and adult fish (n = 6) exposed during 48 h. The exposure concentrations were 0 (negative control, C (-)), 0.05, 0.5, 5 and 50 µg/L AZX of the commercial formulation AMISTAR®. Blood was drawn to evaluate hematology, and DNA damage through the comet assay (CA) and micronucleus test (MN). Genotoxicity was observed by mean of both biomarkers in juvenile and adult fish at 50 µg/L AZX. Samples of liver and gills were used to determine antioxidant enzymes activity, hydrogen peroxide (H2O2) and malondialdehyde (MDA) contents. In juvenile fish inhibition of superoxide dismutase (SOD) was observed in liver at 0.05, 5 and 50 µg/L AZX and in gills at 5 and 50 µg/L AZX. Glutathione- S- transferases (GST) activity increased in gills at all AZX concentrations tested. In adult fish, increase of hepatic catalase (CAT) activity at 0.5 and 50 µg/L AZX and MDA content at 50 µg/L AZX were observed. In gills only H2O2 content showed changes at 50 µg/L AZX. The sensitivity showed by gills constitutes the first report about AZX toxicity in this organ. All these negative effects were observed in the range of realistic AZX concentrations, which warns of the possible consequences that it may have on the health of aquatic biota. Differences between juvenile and adult fish demonstrate the relevance of considering the developmental stage on the evaluation of biomarkers.

Fate, residues and dietary risk assessment of the fungicides epoxiconazole and pyraclostrobin in wheat in twelve different regions, China.

The fungicides epoxiconazole and pyraclostrobin have been widely used to control wheat fusarium head blight. This study was designed to investigate the dissipation behaviors in different climate regions and provide data for the modification of maximum residue limits of the two fungicides. Wheat samples were collected from field sites in twelve different regions, China and analyzed with an HPLC-MS/MS method for simultaneous detection of epoxiconazole and pyraclostrobin in wheat. The average recoveries of epoxiconazole and pyraclostrobin in wheat matrix were 87-112% and 85-102%, respectively, with the relative standard deviations ≤8.1%. The limits of quantification of epoxiconazole and pyraclostrobin in grain and straw were both 0.01 mg/kg. The dissipations of epoxiconazole and pyraclostrobin followed first-order kinetics, with the half-lives of 10.3 days and 7.6 days, respectively. The terminal residues of epoxiconazole and pyraclostrobin in grain were below 0.034 and 0.028 mg/kg, separately, both lower than the maximum residue limits recommended by China. Based on Chinese dietary pattern and terminal residue distributions, the risk quotients of epoxiconazole and pyraclostrobin were 13.9% and 65.9%, respectively, revealing the evaluated wheat exhibited an acceptably low dietary risk to consumers.

Statistical evaluation of analytical curves for quantification of pesticides in bananas.

The aim of this paper is to statistically validate the analytical curves of a chromatography method to identify and quantify azoxystrobin, difenoconazole and propiconazole residues in banana pulp, using QuEChERS and GC-SQ/MS. A matrix-matched calibration was used and analytical curves were estimated by weighted least squares regression (WLS), confirming heteroscedasticity for all compounds. Statistical tests were performed to confirm the quality adjustment of the proposed linear model. The correlation coefficient for azoxystrobin, difenoconazole and propiconazole were, respectively, 0.9985, 0.9966 and 0.9997 (concentration range: 0.05 and 2.0 mg kg-1). The limits of detection and quantification were, respectively, between 0.007 and 0.066 mg kg-1, and between 0.022 and 0.199 mg kg-1, below the maximum limits stipulated by Brazilian, American, and European legislation. Only difenoconazole had an insignificant matrix effect (6.8%). Thus, the weighted least squares method is shown to be a safe linear regression model, providing greater reliability of the results.

Determination of pyraclostrobin dynamic residual distribution in tilapia tissues by UPLC-MS/MS under acute toxicity conditions.

As a lipophilic fungicide, pyraclostrobin is highly toxic to aquatic organisms, especially to fish. In recent years, research has mainly focused on the pyraclostrobin residue in fish tissues under chronic toxicity, but less is known about its distribution in fish tissues under acute toxicity conditions. In this study, the distribution of pyraclostrobin in fish tissues (blood, liver, muscle and gill) was determined by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The purification effects of different purification materials [1) mixtures of PSA, C18 and MgSO4; 2) QuEChERS-PC; and 3) Oasis HLB SPE] were compared for the detection of pyraclostrobin in fish tissues. Finally, the quick and easy clean-up tool of the Oasis HLB SPE procedure was selected. Under optimum conditions, the linearities had a good relationship (determination coefficient R2 > 0.999). The mean recoveries of the analyte for all tested concentrations ranged from 86.94% to 108.81% with RSDs of 0.7%-4.9%. The pyraclostrobin residue amount was much different in fish tissues. Furthermore, the pyraclostrobin residue in different fish tissues increased initially and then decreased gradually. The concentrations in each tissue were initially ranked before 120 min in the following order: gill > liver > blood > muscle. These phenomena may be attributed to the stress response of fish under acute poisoning. This is the first study to document the distribution of pyraclostrobin in fish tissues under acute toxicity conditions, and it provides reference for the management of agrochemicals in terms of aquatic ecological risks.

Determination of pesticide residues in edible snails with QuEChERS coupled to GC-MS/MS.

A QuEChERS multi-residue GC-MS/MS method was developed for determining 160 pesticides in fresh edible snails. The method was validated according to the EU guidance SANTE/12682/2019. Twenty-seven different pesticides were quantified in the 824 samples analysed. Of these, 22.09% contained pesticide residues; in one case six different pesticides. The most frequently quantified pesticides were chlorpyrifos (108 samples), cypermethrin (50), difenoconazole (24), oxyfluorfen (13), lambda-cyhalothrin (12), tetraconazole and azoxystrobin (7). Other pesticides were found in <5 samples. Of the samples containing residues, 154 exceeded the EU legal limit. However, the estimated daily intake of pesticide residues showed that snail consumption does not represent appreciable risks to consumer health.

Simultaneous determination of strobilurin fungicides residues in bean samples by HPLC-UV-AD using boron-doped diamond electrode.

The aim of this paper was the development of a method for the determination of six strobilurins (fungicides) using boron-doped diamond (BDD) electrode with amperometric detection (AD) homemade coupled to high performance liquid chromatography (HPLC/UV-Vis). HPLC separation of fungicides was performed in a C18 reverse phase column using both UV and AD detectors at 200 mn and 1.9 V, respectively. The linear range for each strobilurin was from 5 to 15 mg L-1 and the correlation coefficients for all the compounds were above 0.997. Both detectors presented adequate detectability (LOD ranging from 1.33 to 1.57 µg kg-1) respecting the limits pre-established by regulatory agencies. The method was validated presenting good values of recovery and accuracy. In the spiked samples the recoveries ranged from 61.6% (trifloxystrobin) to 98.8% (azoxystrobin) for UV and 62.3% (trifloxystrobin) to 95.2% (azoxystrobin) for AD. In blanks spikes the recovery varied from 77.8% (picoxystrobin) to 88.4% (kresoxim-methyl) for UV and 76.7% (picoxystrobin) to 87.1% (dimoxystrobin) for AD. The method showed good precision (RSD < 10%). The results obtained by amperometric and UV detections were statistically comparable. Seven bean samples were analyzed to detect fungicide residues.

Dispersive liquid-liquid microextraction based on the solidification of floating organic droplets for HPLC determination of three strobilurin fungicides in cereals.

In this paper, a dispersive liquid-liquid microextraction method based on the solidification of floating organic droplets, combined with high-performance liquid chromatography (DLLME-SFOD-HPLC), was developed for the detection of strobilurin fungicides (azoxystrobin, pyraclostrobin, and trifloxystrobin) in cereals. Natural fatty acids were used as an extractant and have low toxicity, density, and freezing point. The extractant nonanoic acid was evenly dispersed as droplets in sample solution and was then solidified in the upper layer of sample solution after centrifugation and ice bath, which improved the extraction and collection efficiency. The dispersive liquid-liquid microextraction procedure was optimised by univariate analysis and the Box-Behnken response surface methodology. Optimum conditions were as follows: the volume of nonanoic acid was 82 µL, the volume of acetonitrile was 620 µL, and the amount of salt was 256 mg. Under optimised conditions, the method had good linearity with a correlation coefficient higher than 0.997, and the limit of detection was 2.57-4.87 µg kg-1. The recoveries of azoxystrobin, pyraclostrobin, and trifloxystrobin in rice, corn, and wheat were 82.0%-93.2%, and the relative standard deviations were 1.6%-7.4%. Therefore, the method was successfully applied to detect target fungicides in cereals.