Residues determination, risk assessment, and dissipation behavior of myclobutanil formulation on apple.

This study aimed to investigate the dissipation pattern, risk assessment, and waiting period of myclobutanil on apple fruit (Malus domestica Borkh.) under temperate conditions in Kashmir, India. The study involved the application of myclobutanil 10 WP at a single recommended dosage (125 g a.i. ha-1) and double dosage (250 g a.i. ha-1) on Red Velox apple trees, 2 months before harvest. GC equipped with an electron capture detector was used to analyze myclobutanil residues in fruit samples. The study revealed that myclobutanil, at both recommended and double recommended doses, dissipated rapidly and became nondetectable after 55 and 60 days, respectively. The waiting period for myclobutanil application was determined to be 12.41 days for the single dose and 25.58 days for the double dose, respectively. These waiting periods were based on the maximum residue limit of 0.6 ppm as prescribed by the Codex Alimentarius Commission, Food Safety and Standards Authority of India, and European Commission. The study concludes that myclobutanil 10 WP is safe for consumers at both recommended and double recommended doses when applied 2 months before harvest. Risk assessment, considering the average daily apple consumption in India and theoretical maximum residue contributions (TMRCs), indicates negligible health hazards even at double the recommended dosage. The calculated TMRC values at Day 0 were significantly below the maximum permissible intake. For average and maximum myclobutanil residues at single and double doses, the TMRC values were found to be 0.0069 and 0.0070 mg day-1 person-1 and 0.0105 and 0.0106 mg day-1 person-1, respectively. These results indicate that myclobutanil, when used according to recommended dosages and waiting periods, poses minimal health risks to consumers. The study emphasizes the importance of prudent fungicide use to minimize fungicide residues on fruits, thereby ensuring their safety for consumption.

Antifungal Activity of 2-Allylphenol Derivatives on the Botrytis cinerea Strain: Assessment of Possible Action Mechanism.

Botrytis cinerea is a phytopathogenic fungus that causes serious damage to the agricultural industry by infecting various important crops. 2-allylphenol has been used in China as a fungicide for more than a decade, and it has been shown that is a respiration inhibitor. A series of derivatives of 2-allylphenol were synthesized and their activity against B. cinerea was evaluated by measuring mycelial growth inhibition. Results indicate that small changes in the chemical structure or the addition of substituent groups in the aromatic ring induce important variations in activity. For example, changing the hydroxyl group by methoxy or acetyl groups produces dramatic increases in mycelial growth inhibition, i.e., the IC50 value of 2-allylphenol decreases from 68 to 2 and 1 µg mL-1. In addition, it was found that the most active derivatives induce the inhibition of Bcaox expression in the early stages of B. cinerea conidia germination. This gene is associated with the activation of the alternative oxidase enzyme (AOX), which allows fungus respiration to continue in the presence of respiratory inhibitors. Thus, it seems that 2-allylphenol derivatives can inhibit the normal and alternative respiratory pathway of B. cinerea. Therefore, we believe that these compounds are a very attractive platform for the development of antifungal agents against B. cinerea.

Drug repurposing strategy II: from approved drugs to agri-fungicide leads.

Epidemic diseases of crops caused by fungi deeply affected the course of human history and processed a major restriction on social and economic development. However, with the enormous misuse of existing antimicrobial drugs, an increasing number of fungi have developed serious resistance to them, making the diseases caused by pathogenic fungi even more challenging to control. Drug repurposing is an attractive alternative, it requires less time and investment in the drug development process than traditional R&D strategies. In this work, we screened 600 existing commercially available drugs, some of which had previously unknown activity against pathogenic fungi. From the primary screen at a fixed concentration of 100 µg/mL, 120, 162, 167, 85, 102, and 82 drugs were found to be effective against Rhizoctonia solani, Sclerotinia sclerotiorum, Botrytis cinerea, Phytophthora capsici, Fusarium graminearum and Fusarium oxysporum, respectively. They were divided into nine groups lead compounds, including quinoline alkaloids, benzimidazoles/carbamate esters, azoles, isothiazoles, pyrimidines, pyridines, piperidines/piperazines, ionic liquids and miscellaneous group, and simple structure-activity relationship analysis was carried out. Comparison with fungicides to identify the most promising drugs or lead structures for the development of new antifungal agents in agriculture.

Assessment of the Effects of Triticonazole on Soil and Human Health.

Triticonazole is a fungicide used to control diseases in numerous plants. The commercial product is a racemate containing (R)- and (S)-triticonazole and its residues have been found in vegetables, fruits, and drinking water. This study considered the effects of triticonazole on soil microorganisms and enzymes and human health by taking into account the enantiomeric structure when applicable. An experimental method was applied for assessing the effects of triticonazole on soil microorganisms and enzymes, and the effects of the stereoisomers on soil enzymes and human health were assessed using a computational approach. There were decreases in dehydrogenase and phosphatase activities and an increase in urease activity when barley and wheat seeds treated with various doses of triticonazole were sown in chernozem soil. At least 21 days were necessary for the enzymes to recover the activities. This was consistent with the diminution of the total number of soil microorganisms in the 14 days after sowing. Both stereoisomers were able to bind to human plasma proteins and were potentially inhibitors of human cytochromes, revealing cardiotoxicity and low endocrine disruption potential. As distinct effects, (R)-TTZ caused skin sensitization, carcinogenicity, and respiratory toxicity. There were no significant differences in the interaction energies of the stereoisomers and soil enzymes, but (S)-TTZ exposed higher interaction energies with plasma proteins and human cytochromes.

Dissipation and Residue of Metalaxyl-M and Azoxystrobin in Scallions and Cumulative Risk Assessment of Dietary Exposure to Hepatotoxicity.

Metalaxyl-M and azoxystrobin have been used to control various fungal diseases on scallion and other crops. In view of the adverse toxic effects of both on the mammalian liver, it is necessary to conduct a cumulative risk assessment of their dietary exposure to consumers. The residues of metalaxyl-M and azoxystrobin on scallion were determined by a quick, easy, cheap, effective, rugged, and safe method (QuEChERS) combined with high-performance liquid chromatography tandem mass spectrometry (LC-MS/MS). The half-lives were about 1.15 and 3.89 days, respectively, and the final residues after a seven-day harvest interval were <0.001−0.088 mg/kg and 0.190−4.687 mg/kg, respectively. The cumulative dietary risk quotient of the two fungicides to Chinese consumers calculated by the probability model is 13.94%~41.25%. According to the results of the contribution analysis, the risk posed by azoxystrobin is much greater than that of metalaxyl-M. Although metalaxyl-M and azoxystrobin do not pose a cumulative risk to Chinese consumers, the risk to children and adolescents is significantly higher than that to adults. This suggests that in future research, more consideration should be given to the cumulative risk of compounds to vulnerable groups.

Photodegradation of enestroburin in water by simulated sunlight irradiation: Kinetics, isomerization, transformation products identification and toxicity assessment.

Enestroburin is the first strobilurin fungicide developed by China and has been widely used to control fungal disease for 15 years. Investigation of its photolytic behaviour is essential for the comprehensive evaluation of its ecological risk. The effects of solution pH, humic acid (HA) and Fe(III) ions on photolysis were studied. The direct photolysis rates of enestroburin in the acidic solution (pH = 4) was faster than that in the basic (pH = 7) or neutral condition (pH = 9). HA and Fe3+ ions inhibited photolysis by the light screening effect. The photolysis of enestroburin was very fast due to the generation of photo-isomers. Seven isomeric products of enestroburin were observed using SFC-MS/MS, and the reaction mechanism for photo-induced isomers was proposed. The reaction occurred on three double bonds, including tautomerism of enol ether and oxonium and the triplet energy transfer of the CC and CN double bond. 12 transformation products (TPs) were identified by screening suspect compounds and non-target compounds, and one product (M-381) was synthesized for confirmation and quantification. A probable transformation mechanism was suggested based on the identified TPs and DFT calculations. The main transformation reactions included hydration, hydrolysis, oxidation, reduction and decarboxylation. Finally, the toxicities of the identified TPs and parent compound to aquatic organisms were predicted using ECOSAR software, and the toxicities of enestroburin and M-381 to daphnia magna were tested in the laboratory. The toxicity classification proposed by ECOSAR is reliable to a certain extent. Enestroburin and 2 TPs (M-313 and M-327) were classified as "very toxic", which may pose a potential threat to aquatic ecosystems.

Dissipation Residue Behaviors and Dietary Risk Assessment of Boscalid and Pyraclostrobin in Watermelon by HPLC-MS/MS.

Fungicides containing active ingredients of boscalid and pyraclostrobin have been widely applied in watermelon disease control. To provide data for avoiding health hazards caused by fungicides, we investigated its terminal residues and evaluated the dietary risk. In this work, watermelon samples were collected from field sites in six provinces and analyzed with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The average recoveries of boscalid and pyraclostrobin in the watermelon matrix were 97-108% and 93-103%, respectively, with the relative standard deviations (RSDs) ≤ 9.1%. The limits of quantifications (LOQs) were 0.01 and 0.005 mg/kg for boscalid and pyraclostrobin. Twenty-one days after applying the test pesticide with 270 g a.i./ha, the terminal residues of boscalid and pyraclostrobin were all below 0.05 mg/kg and below the maximum residue limits (MRLs) recommended by European Food Safety Authority (EFSA). According to the national estimated daily intake (NEDI), the risk quotients (RQs) of boscalid and pyraclostrobin were 48.4% and 62.6%, respectively. That indicated the pesticide evaluated in watermelon exhibited a low dietary risk to consumers. All data provide a reference for the MRL establishment of boscalid in watermelon for China.

Evaluation of Chiral Fungicide Penflufen in Legume Vegetables: Enantioseparation and Its Mechanism, Enantioselective Behaviors, and Risk Assessment.

Illustrating the enantioselective behaviors of the novel chiral fungicide penflufen was extremely important for ecological safety and human health. For penflufen enantiomers, an excellent separation method including a short analysis time (4 min), a high sensitivity (2 ng/g), and lesser consumption of an organic solvent was first established through supercritical fluid chromatography-tandem mass spectrometry. The enantioseparation mechanism was explained by computational chemistry, and the stronger binding ability of S-(+)-penflufen with cellulose tris-(3-chloro-4-methylphenylcarbamate) (the chiral stationary phase OZ-3 column) contributed to the posterior elution. In legume vegetables, penflufen dissipation was the fastest in Pisum sativum Linn plants (half-life, 1 day) and the slowest in Glycine max plants (half-lives, 11.3-12.9 days). After 30, 50, and 40 days, the rac-penflufen residues were lower than the maximum residue level value in the Electronic Code of Federal Regulations (10 ng/g) in G. max, P. sativum Linn, and Vigna unguiculata, respectively. Abundant S-(+)-penflufen was found in these plants with stereoisomeric excess (se) changes being >10% in the initial stage, so the risk assessment might be driven by S-(+)-penflufen. However, the se changes were <10% in V. unguiculata plants, and the risk assessment might be calculated based on rac-penflufen. Moreover, penflufen enantiomers could be transferred from legume vegetables to soils, and the concentrations increased with time. The high persistence and medium mobility of penflufen in soils might lead to potential groundwater contamination, which was noteworthy. These results could contribute to a more accurate risk assessment of penflufen in legume vegetables.

Determination, dissipation dynamics, terminal residues and dietary risk assessment of thiophanate-methyl and its metabolite carbendazim in cowpeas collected from different locations in China under field conditions.

BACKGROUND: 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. RESULTS: 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 (R2 > 0.998) was obtained, and the recoveries and relative standard deviations were 80.0-104.7% and 1.4-5.2%, respectively. The dissipation rates of thiophanate-methyl, carbendazim and total carbendazim were high (half-lives of 1.61-2.46 days) and varied in the field cowpea samples because of the different weather conditions and planting patterns. Based on the definition of thiophanate-methyl, the terminal residues of total carbendazim in cowpea samples were below the maximum residue limits set by Japan for other legumes. The acute and chronic risk quotients of three analytes were 0.0-27.6% in cowpea samples gathered from all terminal residue treatments, which were below 100%. CONCLUSION: 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.

Study on degradation behaviour, residue distribution, and dietary risk assessment of propiconazole in celery and onion under field application.

BACKGROUND: Propiconazole is widely used to control fungal diseases in field crops, including celery and onion. The potential risk to the environment and human health has aroused much public concern. Therefore, it is significant to investigate the degradation behaviour, residue distribution, and dietary risk assessment of propiconazole in celery and onion. RESULTS: A sensitive analytical method for determination of propiconazole residue in celery and onion was established and validated through high-performance liquid chromatography tandem mass spectrometry. The average recovery rate of propiconazole ranged from 85.7% to 101.8%, with a relative standard deviation of 2.1-6.3%. For the dissipation kinetics, the data showed that propiconazole in celery and onion was degraded, with half-lives of 6.1-6.2 days and 8.7-8.8 days respectively. In the terminal residue experiments, the residues of propiconazole were below 4.66 mg kg-1 in celery after application two or three times and were below 0.029 mg kg-1 in onion after application of three or four times with an interval of 14 days under the designed dosages. The chronic and acute dietary exposure assessments for propiconazole were valued by risk quotient, with all values being lower than 100%. CONCLUSION: Propiconazole in celery and onion was rapidly degraded following first-order kinetics models. The dietary risk of propiconazole through celery or onion was negligible to consumers. The study not only offers a valuable reference for reasonable usage of propiconazole on celery and onion, but also facilitates the establishment of maximum residue limits in China. © 2020 Society of Chemical Industry.

Hazard assessment using an in-silico toxicity assessment of the transformation products of boscalid, pyraclostrobin, fenbuconazole and glyphosate generated by exposure to an advanced oxidative process.

Agricultural pesticide use is ongoing and consumer concern regarding the safety of pesticide residues on produce has generated interest in techniques that can safely reduce residues post-harvest. Recently an advanced oxidative process has shown promise in substantial residue reduction on the surface of produce. Given the potential for oxidative transformation of pesticides to generate transformation products with greater toxicity than the parent residue, take for example the oxon products of the organophosphorus insecticides, it is important to consider what transformation products are generated by pesticide exposure to an oxidative process and their potential toxicity. In this study, previously published transformation products of boscalid, pyraclostrobin, fenbuconazole and glyphosate were identified after exposure to 3% hydrogen peroxide, UV-C irradiation or their combination in an advanced oxidative process on glass, their oral toxicity, carcinogenicity and developmental toxicity were identified in-silico and an initial tier hazard assessment was conducted. Of the 87 total structures that were searched for, 53 were detected by UPLC-QTOF-MS and identified by mass spectra: 15, 13, 22 and 3 structures for boscalid, pyraclostrobin, fenbuconazole and glyphosate respectively, including the parent residues. Oral toxicity of the transformation products of pyraclostrobin and glyphosate was similar to or lower than the parent residue. Several transformation products of boscalid and fenbuconazole were estimated to be significantly more orally toxic than their parent residues. While the majority of the transformation products of boscalid, pyraclostrobin and fenbuconazole were predicted to be carcinogenic there were 11 that were consistently identified to have carcinogenic potential by several assessments. 29 of the 53 molecules were predicted to be probable developmental toxicants. An initial tier hazard assessment was conducted for Cramer rules classification and mutagenicity using the threshold of toxicological concern approach and predicted rat oral LD50. Two exposure scenarios were considered, one highly protective considering each transformation product to be at the highest maximum residue limit (MRL) for the pesticide and whole produce consumption at the highest consumption rate from the USEPA Exposures Handbook, the other considering only apple consumption with the relevant MRL. As indicated by the hazard assessment, several transformation products of boscalid, pyraclostrobin and fenbuconazole should be strongly considered for further testing, either by quantifying their production or in-vivo and in-vitro toxicity tests due to their predicted toxicity and associated hazard.

Residue Monitoring and Risk Assessment of Cyazofamid and Its Metabolite in Korean Cabbage Under Greenhouse Conditions.

The residual characteristics and risk assessment with respect to cyazofamid and its metabolite 4-chloro-5-p-tolylimidazole-2-carbonitrile were monitored in case of Korean cabbage at different preharvest intervals during a greenhouse trial. The 0.02 kg a.i/ha of cyazofamid was sprayed twice on seven-day intervals (i.e., on day 0, 7, 14, and 21 before harvest). The liquid chromatography-tandem mass spectrometry analysis was used to monitor the residual amount of fungicide. The matrix-matched calibration curves with respect to the cyazofamid in Korean cabbage exhibited good linearity (R2 ≥ 0.999) and acceptable recoveries of 84.1%-114.9%. The biological half-life of cyazofamid in Korean cabbage was 3.18 days. During the treatment, the preharvest residue of cyazofamid in Korean cabbage 14 days before harvest (0.80 mg/kg) was lower than that specified by the MFDS-MRL (Ministry of Food and Drug Safety-Maximum Residue Limit, 2.0 mg/kg) and should be recommended as the safe preharvest-interval application limit. The hazard quotient showed low toxicity (70.58%) during the risk assessment study of cyazofamid.

Assessment of Mint, Basil, and Lavender Essential Oil Vapor-Phase in Antifungal Protection and Lemon Fruit Quality.

There is an increasing interest in developing natural methods to replace the current chemicals used for maintaining postharvest quality of citrus fruits. The essential oil antifungal activity of mint (MEO), basil (BEO), and lavender (LEO) acting as the vapor-phases was tested against Penicillium digitatum. The minimum doses with fungistatic and fungicidal effect, in vitro, acting as the vapor-phases, were set up. The minimum fungicidal dose was 300 µL for BEO and 350 µL LEO, while for MEO only minimal dose with fungistatic effect was reached. The IC50 values were calculated and used (v/v) for testing preservation of lemon fruits, in close space enriched in vapor oil. For this purpose, the following two independent in vivo experiments were carried out: experiment 1, inoculated lemons with P. digitatum stored without chemical treatments 7 days, at 22 ± 2 °C, at two concentrations (C1-IC50 equivalent; C2-half of C1); and experiment 2, the non-inoculated lemons kept under the same conditions and concentrations of EO vapor served to evaluate the lemon quality properties. The results showed that antifungal protective effect was provided in the order of LEO-C1 > BEO-C1 > MEO-C1 > BEO-C2 > MEO-C2 > LEO-C2. The quality indicators like weight loss, pH, and firmness were not negatively influenced.

Chitin/Chitosan and Its Derivatives: Fundamental Problems and Practical Approaches.

In this review, we present the data on the natural occurrence of chitin and its partially or fully deacetylated derivative chitosan, as well as their properties, methods of modification, and potential applications of derivatives with bactericidal, fungicidal, and antioxidant activities. The structure and physicochemical characteristics of the polymers, their functions, and features of chitin microbial synthesis and degradation, including the processes occurring in nature, are described. New data on the hydrolytic microorganisms capable of chitin degradation under extreme conditions are presented. Special attention is focused on the effect of physicochemical characteristics of chitosan, including molecular weight, degree of deacetylation, polydispersity index, and number of amino group derivatives (quaternized, succinyl, etc.) on the antimicrobial and antioxidant properties of modified polymers that can be of particular interest for biotechnology, medicine, and agriculture. Analysis of the available literature data confirms the importance of fundamental research to broaden our knowledge on the occurrence of chitin and chitosan in nature, their role in global biosphere cycles, and prospects of applied research aimed at using chitin, chitosan, and their derivatives in various aspects of human activity.

Design, Synthesis, and Antifungal Evaluation of Neocryptolepine Derivatives against Phytopathogenic Fungi.

Neocryptolepine is an alkaloid isolated from traditional African herbal medicine Cryptolepis sanguinolenta, and its broad spectrum of biological activities has been illuminated in past decades. In this study, neocryptolepine and its derivatives (1-49) were designed and synthesized from economical and readily available starting materials. Their structures were confirmed by proton nuclear magnetic resonance, carbon nuclear magnetic resonance, and mass spectrometry. The synthesized compounds were screened for their antifungal profile against six agriculturally important fungi Rhizoctonia solani, Botrytis cinerea (B. cinerea), Fusarium graminearum, Mycosphaerella melonis, Sclerotinia sclerotiorum, and Magnaporthe oryzae. The results of in vitro assay revealed that compounds 5, 21, 24, 35, 40, 45, and 47 presented remarkable antifungal activity against the fungi tested with EC50 values lower than 1 µg/mL. Significantly, compound 24 displayed the most effective inhibitory potency against B. cinerea (EC50 = 0.07 µg/mL), and the data from in vivo experiments revealed that compound 24 demonstrated comparable protective activity with the positive control boscalid. Preliminary mechanism studies indicated that compound 24 showed impressive spore germination inhibitory effectiveness and lower cytotoxicity than azoxystrobin, imparted on normal function of the cell membrane and cell wall, and arrested the normal function of the nucleus. Besides the excellent inhibitory activity against agriculturally important phytopathogenic fungi tested, the designed assemblage possesses several benefits with a high profile of variation in synthesized molecules, the ease of synthesis, and good cost-effectiveness of commercially available synthetic reagents, all of these have highlighted the potential worth of compound 24 as a new and highly efficient agricultural fungicide.

Dissipation and Risk Assessment of Multiresidual Fungicides in Grapes under Field Conditions.

Grapes are among the most popular fruits globally, and various fungicides are widely applied to grape crops. As such, the presence of multiple fungicide residues and dietary risks in grapes has become the focus of significant attention. In this study, an easy-to-implement and sensitive UPLC-MS/MS approach was developed to simultaneously determine pyraclostrobin, dimethomorph, cymoxanil, cyazofamid and its metabolite CCIM in grapes via QuEChERS. This approach achieved 78.1-106.0% recovery and a 0.01 mg kg-1 limit of quantitation (LOQ). Field trials revealed that these compounds had degradation half-lives ranging from 0.9 to 13.3 days. And their terminal residues ranging from < LOQ to 1.36 mg kg-1 were below the official maximum residue limit (MRL) in China. The short-term risk for each tested fungicide was below 54%. The long-term risk of individual chemicals ranged from 0.0086% to 3.1%, and their cumulative risk was 4.4%. Results indicated that the dietary risk of these fungicides in grapes was minor.

Dissipation behavior, residue distribution and risk assessment of three fungicides in pears.

BACKGROUND: Fungicides are often applied to pears before they are kept in storage facilities. The scientific application of pesticides can reduce unnecessary exposure, which in turn could benefit both humans and the environment. RESULTS: We investigated dissipation behavior and residue distribution, and conducted risk assessments for prochloraz, pyraclostrobin, and tebuconazole in pears stored under different conditions using ultra-performance liquid chromatography (UPLC). The recoveries of the three fungicides ranged from 76.5% to 114.5%, and the coefficients of variation were 1.0%-8.5%. The half-life (t1/2 ) ranges for degradation of the three fungicides in Dangshan Su pear peel were 8.8-13.9 days after storage at 25 °C and 99.0-346.6 days after storage at 2 °C. Among the three fungicides, tebuconazole had the lowest residue concentration in pear pulp (maximum of 0.226 mg·kg-1 ) and the longest half-life (≥ 231.0 days). Accordingly, among these fungicides, tebuconazole is the most suitable for the preservation of Dangshan Su pears during storage. Finally, we analyzed samples of six pear varieties from markets in China and found that the residue concentrations of the three fungicides in pear pulp and fruit met Chinese standards. CONCLUSION: The results provide a scientific basis for rationalizing the use of prochloraz, pyraclostrobin, and tebuconazole, and improving the safety of pears for eating. © 2019 Society of Chemical Industry.

Residue behaviours, dissipation kinetics and dietary risk assessment of pyaclostrobin, cyazofamid and its metabolite in grape.

BACKGROUND: Grape is an important fruit consumed either fresh or processed, therefore, fungicide misuse of grape has become an issue of global food safety and human health. Pyraclostrobin, and cyazofamid have been applied to grape frequently. RESULTS: Here a simple QuEChERS (quick, easy, cheap, effective, rugged, and safe) liquid chromatography mass spectrometry technique has been developed and validated for the determination of pyraclostrobin, cyazofamid and its metabolite CCIM in open field grape samples. The recoveries of these three in the range of 0.01 to 5 mg kg-1 (n = 5) ranged from 73.1% to 97.9%. The relative standard deviations (RSDs) were below 12% for all cases. The limits of quantitation of each analyte was 0.005 mg kg-1 , which was lower than maximum residue limits of not only pyraclostrobin but also cyazofamid. Not only dissipation kinetics but also residue determination was obtained in grape for those three pesticides. Furthermore, their half-lives in grapes were 10.7-30.1 days, recommending the pre-harvest intervals for these three of 14 days. The calculated hazard quotient and acute hazard index lower than 100% illustrated the safety of intake of grape for the Chinese population for not only long-term but also short-term dietary risk assessment. CONSLUSIONS: The less than 30 day half-life illustrated that pyraclostrobin and cyazofamid could degrade relatively easily in the environment. The long-term and short-term dietary risk assessment also illustrated the intake safety of these three. Thus, a 14 day pre-harvest interval was safe and recommended. The results of this study contributed to environmental protection, food safety and human health. © 2019 Society of Chemical Industry.

Dissipation of Prothioconazole and Its Metabolite Prothioconazole-Desthio in Rice Fields and Risk Assessment of Its Dietary Intake.

Rice is an important food crop, with a long history of cultivation in China, and is one of the important staple foods for Chinese today. However, the occurrence of rice diseases has had a substantial impact on its yield. At present, chemical control is the main means of prevention and control of rice diseases. As a high-efficacy and broad-spectrum fungicide, prothioconazole shows an ideal effect on the prevention and control of common rice diseases, but the residuals that remain after its use may have an impact on human health. In this paper, ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was used to develop a residue analysis method and explore the dissipation of prothioconazole and its metabolite prothioconazole-desthio in rice grain, rice husk, and rice plants, and the risks of chronic and acute dietary intake of prothioconazole in different Chinese populations were evaluated. The results showed that at a concentration range of 0.005-5.0 µg/mL, prothioconazole and its metabolites showed good linear correlations, and the correlation coefficients were all above 0.9992. The average recoveries of prothioconazole in three matrixes ranged from 80.0% to 99.7%, the RSD was between 1.54% and 11.0%, and the limit of quantitation was less than 0.01 µg/g. The sensitivity, accuracy, and precision of the established method all met the measurement requirements. The dissipation experimental results showed that the parent compound prothioconazole was rapidly metabolized to prothioconazole-desthio in the rice field environment, and the dissipation half-life in rice plants after application was 2.5-10.1 d. According to the results of dietary risk assessment, under the standardized residue test conditions, the residual level of rice at the sampling interval of 7 days was within the acceptable range for the chronic and acute dietary risks of different populations in China. Our research is important for directing the scientific application of pesticides in China.

The biological activities of prothioconazole enantiomers and their toxicity assessment on aquatic organisms.

Chiral fungicide prothioconazole has a wide range of antifungal spectrum; however, little research has been conducted to evaluate prothioconazole on an enantiomeric level. Five target pathogens and three common aquatic organisms were tested for the enantioselective bioactivity and toxicity of prothioconazole in this work. The antifungal activity of the enantiomers against wheat phytoalexin, rice blast fungus, exserohilum turcicum, Alternaria triticina, and Fusarium avenaceum was determined, and it was found that (-)-prothioconazole were 85 to 2768 times more active than (+)-prothioconazole toward these target organisms. In order to reflect the risk to aquatic ecosystem, the acute toxicity of the enantiomers to Daphnia magna, Chlorella pyrenoidosa, and Lemna minor L. was assessed. It was observed that the toxicity of (-)-prothioconazole to D. magna was 2.2 times higher than (+)-prothioconazole, but it was lower to C. pyrenoidosa and L. minor L. The toxicities of (+)-enantiomer and (-)-enantiomer to D. magna and C. pyrenoidosa were synergy, indicating that the racemate had higher threat to the organisms. It could be concluded that the effects of prothioconazole on target organisms and the acute toxicity to nontarget species were enantioselective with (-)-enantiomer possessing higher efficiency and lower toxicity. Such enantiomeric differences should be taken into consideration when assessing the performance of prothioconazole.