Dissipation behavior and risk assessment of imidacloprid and its metabolites in apple from field to products.

Pesticides play vital roles in controlling pests and boosting crop yields. Imidacloprid is widely used all over the world and may form in agricultural products. The presence of pesticide residues in apples raises serious health concerns. Understanding the residual fate of imidacloprid is critical for food safety and human health. In this study, the dissipation behavior, metabolism, household processing and risk assessment of imidacloprid and its metabolites in apple were investigated from filed to products. Field experiment results suggested that the half-lives of imidacloprid at 5 times the recommended dosage was 1.5 times that of the standard dosage. And the final residues of imidacloprid were less than the established maximum residue limits (MRLs). Clarification and simmering had little effect on the reduction the residues of imidacloprid and its metabolites. The calculated processing factors were lower than 1 for imidacloprid and its metabolites, implying that the residual ratios of imidacloprid and its metabolites in each steps of the food processing were reduced. The risk quotients were <1 for all Chinese people, indicating that acceptable risks associated with dietary exposure to imidacloprid in apple. However, the higher risks were observed in young people than adults, and females faced higher risks than males. Given high residue levels in pomace, imidacloprid and its metabolites should be further studied in commercial byproducts.

CYP4CS5-mediated thiamethoxam and clothianidin resistance is accompanied by fitness cost in the whitefly Bemisia tabaci.

BACKGROUND: Understanding the trade-offs between insecticide resistance and the associated fitness is of particular importance to sustainable pest control. One of the most devastating pest worldwide, the whitefly Bemisia tabaci, has developed resistance to various insecticides, especially the neonicotinoid group. Although neonicotinoid resistance often is conferred by P450s-mediated metabolic resistance, the relationship between such resistance and the associated fitness phenotype remains largely elusive. By gene cloning, quantitative reverse transcription (qRT)-PCR, RNA interference (RNAi), transgenic Drosophila melanogaster, metabolism capacity in vitro and 'two sex-age stage' life table study, this study aims to explore the molecular role of a P450 gene CYP4CS5 in neonicotinoid resistance and to investigate whether such resistance mechanism carries fitness costs in the whitefly. RESULTS: Our bioassay tests showed that a total of 13 field-collected populations of B. tabaci MED biotype displayed low-to-moderate resistance to thiamethoxam and clothianidin. Compared to the laboratory susceptible strain, we then found that an important P450 CYP4CS5 was remarkably upregulated in the field resistant populations. Such overexpression of CYP4CS5 had a good match with the resistance level among the whitefly samples. Further exposure to the two neonicotinoids resulted in an increase in CYP4CS5 expression. These results implicate that overexpression of CYP4CS5 is closely correlated with thiamethoxam and clothianidin resistance. RNAi knockdown of CYP4CS5 increased mortality of the resistant and susceptible populations after treatment with thiamethoxam and clothianidin in bioassay, but obtained an opposite result when using a transgenic line of D. melanogaster expressing CYP4CS5. Metabolic assays in vitro revealed that CYP4CS5 exhibited certain capacity of metabolizing thiamethoxam and clothianidin. These in vivo and in vitro assays indicate an essential role of CYP4CS5 in conferring thiamethoxam and clothianidin resistance in whitefly. Additionally, our life-table analysis demonstrate that the field resistant whitefly exhibited a prolonged development time, shortened longevity and reduced fecundity compared to the susceptible, suggesting an existing fitness cost as a result of the resistance. CONCLUSION: Collectively, in addition to the important role of CYP4CS5 in conferring thiamethoxam and clothianidin resistance, this resistance mechanism is associated with fitness costs in the whitefly. These findings not only contribute to the development of neonicotinoids resistance management strategies, but also provide a new target for sustainable whitefly control. © 2023 Society of Chemical Industry.

Single and joint toxicity assessment of acetamiprid and thiamethoxam neonicotinoids pesticides on biochemical indices and antioxidant enzyme activities of a freshwater fish Catla catla.

Neonicotinoids pesticides are extensively used in many countries due to their high insect selectivity. Acetamiprid and thiamethoxam are the neonicotinoids most commonly detected in the aquatic environment. This work examined the single and joint toxicity of acetamiprid and thiamethoxam in a freshwater fish Catla catla. Fish were exposed to acetamiprid (0.5 mg/L and 1 mg/L), thiamethoxam (0.01 mg/L and 0.5 mg/L) and their binary mixtures (0.5 mg/L of acetamiprid and 0.01 mg/L of thiamethoxam) for 96 h. The stress biomarkers such as glucose, protein, electrolytes, Na+/K+ -ATPase and oxidative stress were evaluated. Among the biochemical parameters, plasma protein, electrolytes (sodium, potassium and chloride) and gill ATPase activity were decreased in response to individual and binary mixtures treatments. In contrast, blood glucose level showed significant increase in all the treatments. Exposure to various concentrations of acetamiprid and thiamethoxam resulted in significant decrease in superoxide dismutase (SOD) activity in the gill tissue. However, SOD activity was significantly elevated during binary mixtures treatment. Glutathione peroxidase (GPx), catalase (CAT), glutathione-S-transferase (GST) and reduced glutathione (GSH) levels in gills were decreased significantly after individual and binary mixtures treatments. Fish exposed at individual and binary mixtures significantly elevated the level of LPO in gill tissue. Our findings suggest that multi-biomarker approach can be effectively used to assess the effects of joint toxicity of pesticides and to monitor the neonicotinoids pesticides in the aquatic environment.

Monitoring residue levels and dietary risk assessment of thiamethoxam and its metabolite clothianidin for Chinese consumption of Chinese kale.

BACKGROUND: Thiamethoxam is widely used to control pests in Chinese kale, popularly consumed leafy vegetables. The potential risk to the environment and human health has aroused much public concern. Therefore, it is important to investigate the degradation behavior, residue distribution and dietary risk assessment of thiamethoxam in Chinese kale. RESULTS: A sensitive analytical method for determination of thiamethoxam and its metabolite clothianidin residue in Chinese kale was established and validated through a quick, easy, cheap, effective, rugged, and safe (QuEChERS) technique with ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The recoveries were 85.4-101.2% for thiamethoxam and 79.5-108.1% for clothianidin, with the relative standard deviations (RSDs) of 0.9-10.2% and 1.8-6.0%, respectively. For the dissipation kinetics, the data showed that thiamethoxam in Chinese kale was degraded with the half-lives of 4.1 to 4.5 days. In the terminal residue experiments, the residues of thiamethoxam were 0.017-0.357 mg kg-1 after application 2-3 times with a preharvest interval (PHI) of 7 days under the designed dosages. The chronic and acute dietary exposure assessment risk quotient (RQ) values of thiamethoxam in Chinese kale for different Chinese consumers were 0.08-0.19% and 0.05-0.12%, respectively, and those of clothianidin were 0.01-0.04% and 0.02-0.04%, respectively, all of the RQ values were lower than 100%. CONCLUSION: Thiamethoxam in Chinese kale was rapidly degraded following first-order kinetics models. The dietary risk of thiamethoxam and clothianidin through Chinese kale was negligible to consumers. The results from this study are important reference for Chinese governments to developing criteria for the safe and rational use of thiamethoxam, setting maximum residue levels (MRLs), monitoring the quality safety of agricultural products and protecting consumer health. © 2021 Society of Chemical Industry.

Residue behavior, transfer and risk assessment of tolfenpyrad, dinotefuran and its metabolites during tea growing and tea brewing.

BACKGROUND: Tolfenpyrad and dinotefuran are two representative pesticides used for pest control in tea gardens. Their application may bring about a potential risk to the health of consumers. Therefore, it is essential to investigate the residue behavior, transfer and risk assessment of tolfenpyrad, dinotefuran and metabolites from tea garden to teacup. RESULTS: An effective analytical method was established and validated to simultaneously determine tolfenpyrad, dinotefuran and its metabolites (DN and UF) in tea. The average recoveries of tolfenpyrad, dinotefuran, DN and UF were in the range 72.1-106.3%, with relative standard deviations lower than 11.8%. On the basis of the proposed method, the dissipation of tolfenpyrad and dinotefuran in fresh tea leaves followed first-order kinetics models with half-lives of 4.30-7.33 days and 4.65-5.50 days, respectively. With application amounts of 112.5-168.75 g a.i. ha-1 once or twice, the terminal residues of tolfenpyrad and total dinotefuran in green tea were lower than 19.6 and 7.13 mg kg-1 , respectively, and below their corresponding maximum residue limits . The leaching rates of tolfenpyrad and total dinotefuran during the tea brewing were in the ranges 1.4-2.3% and 93.7-98.1%, respectively. CONCLUSION: Tolfenpyrad and dinotefuran in tea were easily degraded. The RQc and RQa values for tolfenpyrad were 37.6% and 5.4%, which were much higher than for dinotefuran at 24.7% and 0.84%, respectively. The data indicated that there was no significant health risk in tea for consumers at the recommended dosages. The results provide scientific data regarding the reasonable use of tolfenpyrad and dinotefuran aiming to ensure safe tea consuption. © 2021 Society of Chemical Industry.

Residual behavior and dietary intake risk assessment of flonicamid, dinotefuran and its metabolites on peach trees.

BACKGROUND: Flonicamid and dinotefuran are widely applied to control pests and diseases in various economic crops arousing much public concerns about the potential risk to human health. In this study, the multi-determination and residual behavior of flonicamid-dinotefuran mixture on peach trees were investigated. The chronic risk of long-term dietary intake for Chinese consumers was evaluated. RESULTS: An optimized QuEChERS method combined with ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) analysis for simultaneous determination of flonicamid, dinotefuran and its metabolites was established to analyze the residual dissipation and terminal residues in peach matrices. The results demonstrated that (i) a satisfactory linearity relationship with the detector response and the correlation coefficient R2 > 0.999, the average recoveries of these four analytes ranged from 94 to 108%, the relative standard deviation was between 1.0% and 8.8%, and the limit of the quantitation was 0.02 mg kg-1 ; (ii) the dissipation behaviors of flonicamid and dinotefuran followed with the first-order dynamic kinetics model, and the half-lives were 6.9-12.4 days and 8.1-15.1 days, respectively; (iii) the recommended preharvest interval (PHI) was 21 days, the risk quotient (RQ) values of flonicamid and dinotefuran were 16.6 and 20.7%, respectively, which were significantly less than 100%. CONCLUSION: The established analytical method met the detection requirement in terms of sensitivity, accuracy, and precision. Additionally, the results indicated that the potential dietary intake risk of the flonicamid-dinotefuran mixture on peach trees was negligible. This work can be utilized in the safe and responsible use of flonicamid-dinotefuran mixture and provide guidance for establishing its maximum residue limit (MRL) in China. © 2021 Society of Chemical Industry.

Imidacloprid dissipation, metabolism and accumulation in Agaricus bisporus fruits, casing soil and compost and dietary risk assessment.

An improved understanding of imidacloprid (IMI) metabolism and accumulation in casing soil or compost-mushroom systems will help to optimise the safe use of IMI for agricultural pest control in Agaricus bisporus cultivation. In this study, the dissipation, metabolites and accumulation of IMI in casing soil or compost-A. bisporus systems were investigated. The results show that the IMI dissipation half-lives at doses of 10 and 50 mg kg-1 were 65 d and 59 d in casing soil and 6.6 d and 6.2 d in compost, respectively during the cultivation period. Three IMI metabolites were observed in casing soil during cultivation of mushrooms. Urea-imidacloprid (IMI-urea) was a major metabolite, accounting for more than 59%. In compost, the main metabolite in the first 5 days was IMI-urea, from 5 to 10 days olefin-imidacloprid (IMI-ole) and 6-chloronicotinic acid (6-CNA) were both the most prominent compounds, and after 10 days 6-CNA alone. At 50 mg kg-1 dose, IMI and the metabolites (IMI-urea, IMI-ole) were detected in the fruiting body with IMI applied to casing soil and only the metabolite 6-CNA was detected in fruiting body with IMI applied to compost. The bio concentration factors (BCFs) of IMI-ole and IMI-urea were higher than of IMI and 6-CNA, and the BCFs had no obvious relationship with log Kow. Furthermore, the potential dietary risk of IMI in A. bisporus was acceptable when application rates in casing soil or compost was up to 50 mg kg-1. Our study supports a safe use of IMI as agricultural pest control in A. bisporus cultivation.