Effect of vine leaves processing on Azoxystrobin, Fenazaquin and Indoxacarb residues dissipation: processing factors and consumer safety assessment.

The effect of vine leaves processing techniques on Azoxystrobin, Fenazaquin, and Indoxacarb residues was investigated. Residue extraction following field application of pesticides and leaf processing was carried out using the QuEChERS method, with analysis conducted by LC-MS/MS. In dry conservation, Azoxystrobin's half-life was estimated to exceed a year, Fenazaquin's was 18 days, and Indoxacarb's was 142 days. Azoxystrobin had a half-life of 261 days, Fenazaquin had a half-life of 9 days, and Indoxacarb's half-life exceeded a year in brine conservation. It is recommended to use dry conservation because it results in an average 60 % reduction in residue levels for the three pesticides. Boiling water significantly reduced pesticide residues (Azoxystrobin -40.3 %, Indoxacarb -22.4 %, and Fenazaquin -28.8 %). It is recommended to use boiling water for washing, as it shows an average removal rate of approximately 30 %. The health risk assessment indicated that consuming vine leaves posed no health risk for consumers, but overall exposure to residues must be considered.

Pesticides in surface water of the Ondas river watershed, western Bahia, Brazil: Spatial-seasonal distribution and risk assessment.

This study investigated the occurrence and seasonal distribution of different classes of pesticides in surface waters of the Ondas River Watershed, as well as potential risks to the aquatic health and human water consumption in the western region of Bahia state, Brazil. Two gas chromatography-mass spectrometry analytical methods were applied to monitor 34 pesticides in water samples collected during both the dry and rainy seasons at 17 sites. Upon individual analysis, only γ-HCH, methoxychlor, demeton-S, methyl parathion, fenitrothion, chlorpyrifos, and azoxystrobin exhibited statistically significant differences between seasons. During rainy season, concentration medians of residues were higher for γ-HCH (74.7 ng L-1), methoxychlor (25.1 ng L-1), and azoxystrobin (47.2 ng L-1), potentially linked to historical contamination or illegal use. Conversely, pesticides like methyl parathion, fenitrothion, and chlorpyrifos, belonging to the organophosphate class, showed higher concentration medians in the dry period, measuring 75.1, 5.50, and 10.8 ng L-1, respectively, probably due to region crop activities. The risk quotient (RQ) assessment for aquatic life indicated that 59.0% of the samples in the dry season and 76.0% in the rainy season had RQ values greater than one, signifying a critical scenario for species conservation. Regarding human consumption, elevated risks were observed for heptachlor in both sampling periods and for azoxystrobin during the rainy season, surpassing RQ levels above 1, indicating danger in untreated water ingestion. Additionally, 24.0% and 53.0% of the samples in the dry and rainy seasons, respectively, contained at least one pesticide exceeding the EU resolution limit (100 ng L-1). Therefore, considering this information, implementing mitigation measures to avoid the river's contamination becomes imperative.

Assessment of Mitochondrial Function in the AmE-711 Honey Bee Cell Line: Boscalid and Pyraclostrobin Effects.

There is a growing concern that chronic exposure to fungicides contributes to negative effects on honey bee development, life span, and behavior. Field and caged-bee studies have helped to characterize the adverse outcomes (AOs) of environmentally relevant exposures, but linking AOs to molecular/cellular mechanisms of toxicity would benefit from the use of readily controllable, simplified host platforms like cell lines. Our objective was to develop and optimize an in vitro-based mitochondrial toxicity assay suite using the honey bee as a model pollinator, and the electron transport chain (ETC) modulators boscalid and pyraclostrobin as model fungicides. We measured the effects of short (~30 min) and extended exposures (16-24 h) to boscalid and pyraclostrobin on AmE-711 honey bee cell viability and mitochondrial function. Short exposure to pyraclostrobin did not affect cell viability, but extended exposure reduced viability in a concentration-dependent manner (median lethal concentration = 4175 µg/L; ppb). Mitochondrial membrane potential (MMP) was affected by pyraclostrobin in both short (median effect concentration [EC50] = 515 µg/L) and extended exposure (EC50 = 982 µg/L) scenarios. Short exposure to 10 and 1000 µg/L pyraclostrobin resulted in a rapid decrease in the oxygen consumption rate (OCR), approximately 24% reduction by 10 µg/L relative to the baseline OCR, and 64% by 1000 µg/L. Extended exposure to 1000 µg/L pyraclostrobin reduced all respiratory parameters (e.g., spare capacity, coupling efficiency), whereas 1- and 10-µg/L treatments had no significant effects. The viability of AmE-711 cells, as well as the MMP and cellular respiration were unaffected by short and extended exposures to boscalid. The present study demonstrates that the AmE-711-based assessment of viability, MMP, and ETC functionality can provide a time- and cost-effective platform for mitochondrial toxicity screening relevant to bees. Environ Toxicol Chem 2024;43:976-987. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Biodegradation of the strobilurin fungicide pyraclostrobin by Burkholderia sp. Pyr-1: Characteristics, degradation pathway, water remediation, and toxicity assessment.

Pyraclostrobin, a widely used fungicide, poses significant risks to both the environment and human health. However, research on the microbial degradation process of pyraclostrobin was scarce. Here, a pyraclostrobin-degrading strain, identified as Burkholderia sp. Pyr-1, was isolated from activated sludge. Pyraclostrobin was efficiently degraded by strain Pyr-1, and completely eliminated within 6 d in the presence of glucose. Additionally, pyraclostrobin degradation was significantly enhanced by the addition of divalent metal cations (Mn2+ and Cu2+). The degradation pathway involving ether bond and N-O bond cleavage was proposed by metabolite identification. The sodium alginate-immobilized strain Pyr-1 had a higher pyraclostrobin removal rate from contaminated lake water than the free cells. Moreover, the toxicity evaluation demonstrated that the metabolite 1-(4-chlorophenyl)-1H-pyrazol-3-ol significantly more effectively inhibited Chlorella ellipsoidea than pyraclostrobin, while its degradation products by strain Pyr-1 alleviated the growth inhibition of C. ellipsoidea, which confirmed that the low-toxic metabolites were generated from pyraclostrobin by strain Pyr-1. The study provides a potential strain Pyr-1 for the bioremediation in pyraclostrobin-contaminated aquatic environments.

Residue analysis and dietary risk assessment of picoxystrobin in potato (Solanum tuberosum), citrus fruit (Citrus reticulata Blanco), and Dendrobium officinale Kimura et Migo.

Picoxystrobin is a systemic fungicide widely used on potato, citrus fruit, and Dendrobium officinale. To provide information for the risk assessment of potato, citrus, and Dendrobium officinale, field experiments combined with QuEChERS and HPLC-MS/MS were performed to detect picoxystrobin. Picoxystrobin had good linearity (R2 > 0.99), the average recovery rate was 75 - 102%, and the relative standard deviation was 1 - 11%. Picoxystrobin was utilized as the test agent in field experiments, and samples were evaluated and analyzed at various times after the final application utilizing random sampling. The results showed that picoxystrobin residuals in potato and citrus (orange meat) were ˂ 0.01 mg kg-1, whereas those in citrus whole fruit, D. officinale (fresh), and D. officinale (dried) were < 0.05 - 0.084, 0.16 - 3.82, and 0.34 - 9.05 mg kg-1, respectively. Based on these results, both the acute risk quotient (2.77%) and chronic risk quotient (8.7%) were ˂100%, and the dietary risk assessment indicated that the intake of picoxystrobin residues in potato, citrus fruit, and D. officinale did not pose a health risk. This study can guide the reasonable use of picoxystrobin in potato, citrus fruit, and D. officinale.

Investigations into Economic Returns Resulting from Foliar Fungicides and Application Timing on Management of Tar Spot in Indiana Hybrid Corn.

Tar spot, caused by Phyllachora maydis, is the most significant yield-limiting disease of corn (Zea mays L.) in Indiana. Currently, fungicides are an effective management tool for this disease, and partial returns from their use under different disease severity conditions has not previously been studied. Between 2019 and 2021, two separate field experiments were conducted in each year in Indiana to assess the efficacy of nine foliar fungicide products and nine fungicide application timings based on corn growth stages on tar spot symptoms and stromata, canopy greenness, yield, and influence on partial returns. All fungicides evaluated significantly suppressed tar spot development in the canopy and increased canopy greenness over the nontreated control. Additionally, applications of mefentrifluconazole + pyraclostrobin, metconazole + pyraclostrobin, cyproconazole + picoxystrobin at tassel, and propiconazole + benzovindiflupyr + azoxystrobin between the tassel and dough growth stages were the most effective at significantly reducing disease severity, increasing canopy greenness, protecting yield, and offered the greatest partial return. Fungicide products varied in their ability to protect yield under low and high disease severity conditions relative to the nontreated control. Consistently, positive yield increases were observed when disease severity was high, which translated to greater profitability relative to low severity conditions. On average, the yield increases across foliar fungicide products and timed application treatments were 544.6 and 1,020.7 kg/ha greater, and partial returns using a grain value of $0.17/kg were $92.6/ha and $173.5/ha greater, respectively, when high severity conditions occurred. This research demonstrates that foliar fungicides and appropriately timed fungicide applications can profitably be used to manage tar spot in Indiana under high disease severity conditions.

Incorporating climate projections in the environmental risk assessment of pesticides in aquatic ecosystems.

Global climate change will significantly impact the biodiversity of freshwater ecosystems, both directly and indirectly via the exacerbation of impacts from other stressors. Pesticides form a prime example of chemical stressors that are expected to synergize with climate change. Aquatic exposures to pesticides might change in magnitude due to increased runoff from agricultural fields, and in composition, as application patterns will change due to changes in pest pressures and crop types. Any prospective chemical risk assessment that aims to capture the influence of climate change should properly and comprehensively account for the variabilities and uncertainties that are inherent to projections of future climate. This is only feasible if they probabilistically propagate extensive ensembles of climate model projections. However, current prospective risk assessments typically make use of process-based models of chemical fate that do not typically allow for such high-throughput applications. Here, we describe a Bayesian network model that does. It incorporates a two-step univariate regression model based on a 30-day antecedent precipitation index, circumventing the need for computationally laborious mechanistic models. We show its feasibility and application potential in a case study with two pesticides in a Norwegian stream: the fungicide trifloxystrobin and herbicide clopyralid. Our analysis showed that variations in pesticide application rates as well as precipitation intensity lead to variations in in-stream exposures. When relating to aquatic risks, the influence of these processes is reduced and distributions of risk are dominated by effect-related parameters. Predicted risks for clopyralid were negligible, but the probability of unacceptable future environmental risks due to exposure to trifloxystrobin (i.e., a risk quotient >1) was 8%-12%. This percentage further increased to 30%-35% when a more conservative precautionary factor of 100 instead of 30 was used. Integr Environ Assess Manag 2024;20:384-400. © 2023 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Abiotic transformation of kresoxim-methyl in aquatic environments: Structure elucidation of transformation products by LC-HRMS and toxicity assessment.

In this study, abiotic transformation of an important strobilurin fungicide, kresoxim-methyl, was investigated under controlled laboratory conditions for the first time by studying its kinetics of hydrolysis and photolysis, degradation pathways and toxicity of possibly formed transformation products (TPs). The results indicated that kresoxim-methyl showed a fast degradation in pH9 solutions with DT50 of 0.5 d but relatively stable under neutral or acidic environments in the dark. It was prone to photochemical reactions under simulated sunlight, and the photolysis behavior was easily affected by different natural substances such as humic acid (HA), Fe3+and NO3-which are ubiquitous in natural water, showing the complexity of degradation mechanisms and pathways of this chemical compound. The potential multiple photo-transformation pathways via photoisomerization, hydrolyzation of methyl ester, hydroxylation, cleavage of oxime ether and cleavage of benzyl ether were observed. 18 TPs generated from these transformations were structurally elucidated based on an integrated workflow combining suspect and nontarget screening by high resolution mass spectrum (HRMS), and two of them were confirmed with reference standards. Most of TPs, as far as we know, have never been described before. The in-silico toxicity assessment showed that some of TPs were still toxic or very toxic to aquatic organisms, although they exhibit lower aquatic toxicity compared to the parent compound. Therefore, the potential hazards of the TPs of kresoxim-methyl merits further evaluation.

Safe Application of 75% Trifloxystrobin-Tebuconazole as Water-Dispersible Granules in Paddy Based on Residue and Dietary Risk Assessment.

The present study describes the development of a highly effective approach for determining the residue distribution and dissipation of trifloxystrobin and tebuconazole, and their risk assessment in brown rice, husk, straw, and grain using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The current study provides considerable novel information regarding the safe utilization of a mixture of trifloxystrobin and tebuconazole in paddy production. The samples demonstrated a range of mean recoveries between 72% and 86%, with a 1.1-9.2% relative standard deviation (RSD). The limits of quantification (LOQ) and half-lives (t1/2) for brown rice, husk, straw, and grain were, respectively, established to be 0.001-0.01 mg/kg and 4.1-7.7 days. The concentrations of terminal residues in the brown rice, husk, straw, and grain were, respectively, found to be 0.02-0.05, 0.03-0.11, 0.02-0.07, and 0.02-0.05 mg/kg after being treated twice at 168.75 g a.i./ha with 21 and 28 days of pre-harvest intervals (PHIs). Trifloxystrobin and tebuconazole presented a non-negligible chronic risk to human subjects, as evidenced by a risk quotient (RQ) value of less than 1.

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 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.

Neurotoxicity assessment of QoI strobilurin fungicides azoxystrobin and trifloxystrobin in human SH-SY5Y neuroblastoma cells: Insights from lipidomics and mitochondrial bioenergetics.

Strobilurin fungicides are quinone outside inhibitors (QoI) used to treat fungal pathogens for agricultural and residential use. Here, we compared the potential for neurotoxicity of the widely used strobilurins, azoxystrobin (AZS) and trifloxystrobin (TFS), in differentiated human SH-SY5Y cells. Fungicides did not include cytotoxicity up to 200 µM but both induced loss of cell viability at 48 h, with TFS showing slightly higher toxicity that AZS. Caspase 3/7 activity was induced in SH-SY5Y cells by both fungicides at 48 h (50 µM for AZS and 25 µM for TFS). ATP levels were reduced following a 24-hour exposure to > 25 µM AZS and > 6.25 µM TFS and both fungicides rapidly impaired oxidative respiration (~12.5 µM for AZS and ~3.125 µM TFS) and decreased oligomycin-induced ATP production, maximal respiration, and mitochondrial spare capacity. AZS at 100 µM showed a continual impairment of mitochondrial membrane potential (MMP) between 4 and 48 h while TFS at > 50 µM decreased MMP at 24 h. Taken together, TFS exerted higher mitochondrial toxicity at lower concentrations compared to AZS in SH-SY5Y cells. To discern toxicity mechanisms of strobilurin fungicides, lipidomics was conducted in SH-SY5Y cells following exposure to 6.25 µM and 25 µM AZS, and a total of 1595 lipids were detected, representing 49 different lipid classes. Lipid classes with the largest proportion of lipids detected in SH-SY5Y cells included triglycerides (17%), phosphatidylethanolamines (8%), ether-linked triglycerides (8%), phosphatidylcholines (7%), ether-linked phosphatidylethanolamines (6%), and diacylglycerols (5%). Together, these 5 lipid classes accounted for over 50% of the total lipids measured in SH-SY5Y cells. Lipids that were increased by AZS included acyl carnitine, which plays a role in long chain fatty acid utilization for mitochondrial ß-oxidation, as well as non-modified, ether linked, and oxidized triacylglycerols, suggesting compensatory upregulation of triglyceride biosynthesis. The ceramide HexCer-NS, linked to neurodegenerative diseases, was decreased in abundance following AZS exposure. In summary, strobilurin fungicides rapidly inhibit mitochondrial oxidative respiration and alter the abundance of several lipids in neuronal cells, relevant for understanding environmental exposure risks related to their neurotoxicity.

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).

Residue Behavior and Risk Assessment of Pyraclostrobin and Thifluzamide in Cowpea.

A rapid and sensitive analytical method for determination of pyraclostrobin and thifluzamide in cowpea was established based on QuEChERS sample preparation and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Average recoveries of pyraclostrobin and thifluzamide on cowpea were 100%-105% and 99%-105% with RSDs of 1%-5% and 2%-6%, respectively. The storage stability tests showed degradation rates of < 20% for samples stored at - 18℃ within 12 weeks. The field trials at eight locations in China showed that the residues of pyraclostrobin in cowpea at 3 and 5 days after spraying were 0.081-0.49 mg/kg and 0.029-0.48 mg/kg, and the residues of thifluzamide were 0.12-0.46 mg/kg and 0.047-0.50 mg/kg, respectively, which were all lower than the corresponding maximum residue limits in China. The dissipation of both pyraclostrobin and thifluzamide in cowpea were fast with half-lives (T1/2) of 1.5-2.3 days and 1.7-2.4 days. This study provided risk assessment data for establishment of good agricultural practice in cowpea plant.

Estimation of residue levels and dietary risk assessment of cyproconazole and azoxystrobin in cucumber after field application in China.

Residue field trials in cucumber were conducted for the safe use of a commercial formulation of cyproconazole·azoxystrobin 28% suspension concentrate (SC 294 g a.i. ha-1, three applications at a 7-day interval) in the year 2018, in China. To determine the residues of cyproconazole and azoxystrobin in cucumber, a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was developed using high-performance liquid chromatography coupled with tandem mass spectrometry. This validated method was applied to analyze cucumber samples collected from 12 specified regions. At the 3-day interval to harvest, the highest residue (HR) of azoxystrobin was 0.150 mg kg-1, which was lower than the maximum residue limit (MRL; 0.5 mg kg-1) permitted in China, and the HR of cyproconazole was 0.084 mg kg-1, for which no MRL value has been set in China. The chronic risk quotient values of cyproconazole and azoxystrobin for Chinese adults at a 3-day interval to harvest were 2.56% and 13.72%, respectively. The acute risk quotient values of cyproconazole in cucumber were specified as 5.52% for children (1-6 years old) and 2.83% for the adults (> 18 years old) in China. These results indicate that cyproconazole·azoxystrobin 28% SC sprayed on cucumber at the pre-harvest interval of 3 days has no significant potential risk for Chinese consumers.

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.

Azole and strobilurin fungicides in source, treated, and tap water from Wuhan, central China: Assessment of human exposure potential.

Fungicides are widely used in agriculture worldwide. However, data on the occurrence of fungicides in drinking water are scarce. This study aimed to determine the occurrence of 12 selected fungicides in drinking water, the removal efficiency of conventional water treatment processes for fungicides, and the risk of fungicide exposure. In this study, source water (February and July), treated water (February and July), and tap water samples (February, April, July, and October) were collected from Wuhan, central China, in 2019. Seven of the twelve selected fungicides were 100% detected in the three types of water samples; tricyclazole was found with the highest concentrations in the source water phase (median: 15.2 ng/L; range: 4.21-67.9 ng/L). The concentrations of the 12 selected fungicides remaining in the treated water samples (median proportion of the remaining content: 77.5%) revealed that most of the target analytes may not be removed efficiently by conventional water treatment processes, though they could be removed efficiently by advanced treatment. Higher concentrations of the fungicides were observed in samples collected in July (median: 38.7 ng/L; range: 12.5-85.8 ng/L), followed by those in October (median: 21.8 ng/L; range: 10.2-58.8 ng/L), February (median: 9.82 ng/L; range: 5.63-93.3 ng/L), and April (median: 7.13 ng/L; range: 6.23-91.1 ng/L). The health risk assessment implied that estimated daily intake of these fungicides through tap water ingestion might pose a low risk to consumers, though risk associated with infant exposure to the fungicides requires further attention. This study provides baseline data on the occurrence, removal efficiencies, and seasonal variations of the selected fungicides in tap water from central China.

COMPARATIVE HYGIENIC ASSESSMENT OF WORKING CONDITIONS AND OCCUPATIONAL RISK IN THE APPLICATION OF PESTICIDES (ON THE EXAMPLE OF FUNGICIDE AMISTAR EXTRA 280, SC) USING DIFFERENT TYPES OF SPRAYERS.

OBJECTIVE: The aim: Was a comparative hygienic assessment of working conditions and occupational risk in the application of fungicide Amistar Extra 280, SC using slotted and injector sprayers. PATIENTS AND METHODS: Materials and methods: Sprayers Super Poly 110-04 (variant №1) and Guardian Air GA110-04 (variant № 2), and certified equipment were used. The occupational risk was assessed in accordance with the methodological recommendations proposed by the L.I. Medvedia Scientific Center for Preventive Toxicology, Food and Chemical Safety specialists. RESULTS: Results: When using the slotted sprayer Super Poly 110-04 in the air of the working zone of the tractor driver the content of azoxystrobin was 0.0015 ± 0.0001 mg/m3, cyproconazole - 0.085 ± 0.002 mg/m3, at a distance of 10 m from the edge of the field on the leeward side - 0.003 ± 0.001 and 0.11 ± 0.02 mg/m3, respectively. Visual analysis of water-sensitive cards after using slotted sprayers showed the presence of single drops of pesticide working solution in the wear zone. When applying the pesticide using a Guardian Air GA110-04 injector sprayer in the air of the working zone of the tractor driver, areas of possible wear (10 and 100 m), theconcentration of the active substances of Amistar Extra 280, SC formulation was below the limit of quantification of the method. When assessing the complex risk for tractor drivers, a statistically significant difference was found for azoxystrobin (p = 0.002) and cyproconazole (p = 0.001) when using a slotted sprayer Super Poly 110-04 and injector Guardian Air GA110-04. CONCLUSION: Conclusions: Values of the combined complex risk of application of the Amistar Extra 280, SC formulation for tractor drivers of variant №2 application were significantly lower than those for tractor drivers of variant №1.