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.

Determination of pesticide residual levels in strawberry (Fragaria) by near-infrared spectroscopy.

BACKGROUND: In this study, an infrared-based prediction method was developed for easy, fast and non-destructive detection of pesticide residue levels measured by reference analysis in strawberry (Fragaria × ananassa Duch, cv. Albion) samples using near-infrared spectroscopy and demonstrating its potential alternative or complementary use instead of traditional pesticide determination methods. Strawberries of Albion variety, which were supplied directly from greenhouses, were used as the study material. A total of 60 batch sample groups, each consisting of eight strawberries, was formed, and each group was treated with a commercial pesticide at different concentrations (26.7% boscalid + 6.7% pyraclostrobin) and varying residual levels were obtained in strawberry batches. The strawberry samples with pesticide residuals were used both to collect near-infrared spectra and to determine reference pesticide levels, applying QuEChERS (quick, easy, cheap, rugged, safe) extraction, followed by liquid chromatographic-mass spectrometric analysis. RESULTS AND CONCLUSION: Partial least squares regression (PLSR) models were developed for boscalid and pyraclostrobin active substances. During model development, the samples were randomly divided into two groups as calibration (n = 48) and validation (n = 12) sets. A calibration model was developed for each active substance, and then the models were validated using cross-validation and external sets. Performance evaluation of the PLSR models was evaluated based on the residual predictive deviation (RPD) of each model. An RPD of 2.28 was obtained for boscalid, while it was 2.31 for pyraclostrobin. These results indicate that the developed models have reasonable predictive power. © 2019 Society of Chemical Industry.

Simultaneous determination and risk assessment of metalaxyl and azoxystrobin in potato by liquid chromatography with tandem mass spectrometry.

A liquid chromatography with tandem mass spectrometry method was developed and validated to simultaneously determine metalaxyl and azoxystrobin in soil, potato, and potato foliage samples. The samples were extracted by 20 mL of acetonitrile and purified with dispersive solid-phase extraction using octadecyl silane as sorbent. The method showed good linearity (determination coefficients ≥ 0.9926) for metalaxyl (2.5-500 ng/mL) and azoxystrobin (5-1000 ng/mL). The limits of detection and quantification for both fungicides were 1.5-20 µg/kg. The average recoveries in soil, potato, and potato foliage were 83.07-92.87% for metalaxyl and 82.71-98.53% for azoxystrobin. The intra- and inter-day relative standard deviations were all less than 9%. The method was successfully applied on the residual analysis of metalaxyl and azoxystrobin in field trial samples. The results showed that the concentrations of metalaxyl and azoxystrobin in potato samples collected from Guizhou and Hunan were below 50 and 100 µg/kg (maximum residue limit set by China), respectively, at 5 days after the last application. When following the recommended application manual, metalaxyl and azoxystrobin do not present health concerns to the population because the risk quotients are far below 100%. All the above data could help and promote the safe and proper use of metalaxyl and azoxystrobin in potato.

Dynamic residual pattern of azoxystrobin in Swiss chard with contribution to safety evaluation.

This study aimed at quantifying the residual amount of azoxystrobin in Swiss chard samples grown under greenhouse conditions at two different locations (Gwangju and Naju, Republic of Korea). Samples were extracted with acetonitrile, separated by salting out, and subjected to purification by using solid-phase extraction. The analyte was identified using liquid chromatography-ultraviolet detection. The linearity of the calibration range was excellent with coefficient of determination 1.00. Recovery at three different spiking levels (0.1, 0.5, and 4 mg/kg) ranged between 82.89 and 109.46% with relative standard deviation <3. The limit of quantification, 0.01 mg/kg, was considerably much lower than the maximum residue limit (50 mg/kg) set by the Korean Ministry of Food and Drug Safety. The developed methodology was successfully used for field-treated leaves, which were collected randomly at 0-14 days following azoxystrobin application. The rate of disappearance in/on Swiss chard was ascribed to first-order kinetics with a half-life of 8 and 5 days, in leaves grown in Gwangju and Naju greenhouses, respectively. Risk assessments revealed that the acceptable daily intake percentage is substantially below the risk level of consumption at day 0 (in both areas), thus encouraging its safe consumption.

Dissipation kinetics and safety evaluation of tebuconazole and trifloxystrobin in tea under tropical field conditions.

Dissipation kinetics of tebuconazole, trifloxystrobin and its acid metabolite residues were studied in tea under tropical field conditions using GC-MS (SIM). The average recoveries ranged from 80.7% to 105.8%, with a RSD of <9.3%. Dissipation rate for both doses applied followed first-order kinetics, with half-lives in green leaves in the range of 2.8-3.3 and 2.9-3.3 days; ranges in processed tea were 2.7-3.6 days for trifloxystrobin and 3.0-3.1 days for tebuconazole. The trifloxystrobin residues were not transferred into the tea infusion during the infusion process; tebuconazole did transfer, in the range of 14.3-18.9%. As the theoretical maximum residue contributions on tea from initial deposits were found to be less than the maximum permissible intake values, at the recommended application dose a withdrawal period of 23 days before consumption should be applied to reduce risk.

Persistence in and Release of 2,4-D and Azoxystrobin from Turfgrass Clippings.

Research has shown that pesticide residue in clippings from previously treated turfgrass may become bioavailable as grass decomposes, adversely affecting off-target organisms. We conducted a field study to quantify 2,4-D (2,4-dichlorophenoxyacetic acid) and azoxystrobin (methyl(E)-2-{2[6-(2-cyanophenoxy)pyrmidin-4-yloxy]phenyl}-3-methoxyacrylate) residues in turfgrass clippings collected from hybrid bermudagrass [ (L.) Pers. × Burtt-Davy], tall fescue [ (Schreb.) S.J. Darbyshire], and zoysiagrass ( Steud.). A subsequent greenhouse experiment was conducted to measure pesticide release from clippings into water. 2,4-D (1.6 kg a.i. ha) and azoxystrobin (0.6 kg a.i. ha) were applied to field plots at 32, 16, 8, 4, 2, 1, or 0 d before collection of the clippings. Clippings were collected from each experimental unit to quantify pesticide release from clippings into water. Both 2,4-D and azoxystrobin were detected when turfgrass was treated over the 32-d experimental period, suggesting that clipping management should be implemented for an extended period of time after application. Pesticide residue was detected in all water samples collected, confirming 2,4-D and azoxystrobin release from turfgrass clippings; however, pesticide release varied between compounds. Two days after clippings were incorporated in water, 39 and 10% of 2,4-D and azoxystrobin were released from clippings, respectively. Our research supports the currently recommended practice of returning clippings to the turfgrass stand when mowing because removal of 2,4-D and azoxystrobin in clippings may reduce pest control and cause adverse off-target impacts.