Large-scale field trials with various dose gradients and application frequencies of iprodione took place at 37 experimental sites on 11 types of specialty fruits and vegetables across China, to accurately portray the environmental fate and comprehensively evaluate its associated exposure risks in typical agricultural system. The initial deposition of iprodione was high as 125.0 mg/kg and final residue levels of chives and lettuce leaves exceeded the maximum residue limit in China after the preharvest intervals (PHIs) application. This should be of significant concern. The bi-exponential model selected through model comparison further revealed that the half-lives of iprodione in crops ranged from 0.8 to 9.4 d under open field cultivation, which were prolonged up to 6.5 times in greenhouse environments. The acute exposure risks in order were dark-colored vegetables, light-colored vegetables, shallots and melons, with certain crops like cos lettuce (324.5%) and green garlic (135.0%) in 1-6 years children exceeding safety thresholds. An integrated deterministic and probabilistic risk assessment model was employed to evaluate total risk quotient (RQt, 132.6%–247.2%) and total hazard quotient (HQt, 142.9%–340.0%), where chives contribute the most and shallots come next. The exposure risks of iprodione for rural populations was significantly higher than that for urban populations at a 95% probability level (P < 0.05), with no significant difference between genders. The findings provide a critical scientific foundation for the targeted management and regulatory oversight of iprodione, with specific emphasis on protecting vulnerable populations and mitigating exposure from high-risk crops.

In this study, the residue dynamics of cyflumetofen (CYF) and its metabolite 2-trifluoromethylbenzoic acid (B-1) throughout strawberry cultivation and processing were investigated using high-performance liquid chromatography-tandem mass spectrometry. This technique enabled precise separation and identification of cyflumetofen (CYF, 2.12 min) and its metabolite B-1 (1.35 min), with LOQs of 0.001 mg/kg for both. CYF and B-1 remained stable under frozen and dark storage conditions, persisting in strawberry tissues for up to 59 days. Affected by climate, environment, and strawberry variety, initial CYF residues during cultivation were 0.20-0.46 mg/kg (degradation half-life:1.92-7.07 days), with final residues stabilizing at 0.03-0.36 mg/kg. Additionally, 0.87-50.0% of CYF metabolized into B-1, both showing toxicological effects. Washing reduced their residues in fresh strawberries. Dietary risk assessments (deterministic models) showed processing significantly reduced the dietary risk of strawberry jam to 0.0013-0.0094%.

Elucidating the degradation fate and risk characteristics of chlorfluazuron, chlorfenapyr, and its metabolite in chives in both open-field and greenhouse cultivations is crucial for safeguarding the ecosystem and humans from their hazardous effects. This study shows that the dissipation pattern and concentration variations of these pesticides are governed by multiple factors, including cultivation patterns and climatic conditions. A biexponential model revealed that the half-lives of chlorfluazuron and chlorfenapyr were 5.4–11.8 d and 3.3–11.6 d in chives, respectively, as indicated by lower akaike information criterion values and the residual mass closer to zero. Additionally, 0.2%–7.9% of chlorfenapyr was metabolized to tralopyril effects after application. A novel risk assessment framework was developed by integrating deterministic modeling with probabilistic Monte Carlo simulation.

Pice quality is often required to monitor the routine pesticide residues.However,there are matrix sensitivity variations during operation.In this study,the UHPLC-MS/MS approach was developed to simultaneously determine the thiodicarb and methomyl in spices(chili,pepper,and spearmint).A systematic optimization of the chromatographic system was undertaken for the optimal separation,sensitivity,and robustness.Sample preparation was commenced with the acetonitrile extraction of the homogenized spice samples,followed by a clean-up step using a modified QuEChERS-based dispersive solid-phase extraction(d-SPE)procedure.Specifically,the materials were also employed as the 50 mg of primary secondary amine(PSA),10 mg of graphitized carbon black(GCB),and 150 mg of anhydrous magnesium sulfate per 1.5mL of the extract.Three analytical columns with the stationary phases were evaluated after optimization under chromatographic conditions:A BEH C18 column(1.7 μm,100 mm×2.1 mm),a BEH HILIC column(1.7 μm,100 mm×2.1 mm),and an HSS T3 column(1.8 μm,100 mm×2.1 mm).The HSS T3 column was specifically designed to retain the polar compounds,indicating the markedly superior performance,thus providing for the excellent peak shape and sufficient retention for both analytes.Subsequent optimization was focused on the mobile phase composition.Four systems were compared:acetonitrile with 0.05％formic acid in water,methanol with 0.05％formic acid in water,pure acetonitrile with water,and pure methanol with water.The optimal methanol-water system was selected without the acid modification.There was a significant increase in the peak area,approximately 57％higher for the thiodicarb.The methomyl was improved to maintain the excellent peak symmetry,compared with the acidified systems.The flow rate was optimized in a range from 0.15 to 0.55 mL/min.A flow rate of 0.35 mL/min was identified as the ideal compromise,indicating a significant enhancement in the peak area,compared with the higher flow rates.The total time was also maintained.The column temperature was examined from 25℃ to 65℃.A temperature of 55℃ was found to maximize the detector response for both compounds.The thiodicarb shared a particularly significant 31.4％increase in the peak area,compared with 25℃.The injection volume was 2 μL,as the excessive volume compromised the chromatographic integrity.Mass spectrometric detection was performed using electrospray ionization in the positive mode(ESI+)with multiple reaction monitoring(MRM).The optimal performance was achieved by the effective separation of the thiodicarb and methomyl within 3 min,with the reproducible retention times of 2.68 and 2.10 min,respectively.The slope ratio of the matrix-matched versus solvent-based calibration curves revealed that there was extreme signal enhancement in the significant matrix,particularly for the methomyl in chili(ME=1815.6％).Matrix-matched calibration was therefore essential for the accurate quantification.There was excellent linearity from 0.001 to 1 mg/L in all spice matrices,with the correlation coefficients(r)≥0.9980.The accuracy and precision were validated after recovery tests at three fortification levels(0.002,0.01,and 0.5 mg/kg)with five replicates.Mean recoveries ranged from 84.3％to 107.7％,with the CV of 3.0％-8.8％.The high sensitivity was obtained with an LOQ of 0.002 mg/kg and LOD of 0.16×10-3 μg/kg,below the regulatory limits.The optimal,sensitive,and robust UHPLC-MS/MS can be expected to simultaneously quantify the thiodicarb and methomyl in the complex spice matrices.The systematic optimization of the chromatographic system,particularly the selection of the HSS T3 column and the methanol-water mobile phase,effectively mitigated the analytical challenges and detection sensitivity.Its suitability was also verified for the routine application in the regulatory monitoring and quality control laboratories,thereby strengthening the safety of the spices in the global food supply chain.

Procymidone (PRM), a widely used amide-type fungicide in vegetables, poses potential health risks due to its high detection rate. This study introduces a pretreatment device and an intelligent quantification method for PRM in Chinese leek, cowpea, and celery using a lateral flow immunoassay (LFIA) integrated with a smartphone. The whole pretreatment and detection process can be achieved within 21 min. Recovery rates were 76.7%- 100.7% with an RSD of <12.6%, and the limit of quantification was 7.54-13.01 ng/g. Dietary risk assessment on 122 real samples from nine cities revealed that the chronic risk of PRM was all acceptable among different population group. However, the acute dietary in Chinese leek was unacceptable for children, with %ARfD of 125.20% at 97.5th percentiles. This work developed a convenient platform for on-site and rapid PRM detection, and provided scientific basis to protect human health from hazards of PRM.

Emamectin benzoate (EB) is frequently used against various pests in Allium tuberosum Rottler and Dendrobium officinale, but its residue levels and safety to public health are still unclear after field application. This study conducted field residue trials of EB in Allium tuberosum Rottler and Dendrobium officinale and assessed the long-term and short-term dietary risks of EB through a dietary risk assessment model. Based on LC-MS/MS, an enhanced residue analytical method of EB was established with excellent linearity (R2 > 0.9990), accuracy (recoveries ranging from 99% to 107%) and precision (standard deviations from 1.4% to 4.7%). After EB applications, the residues in Allium tuberosum Rottler leaves were less than 0.01 mg/kg (the limit of quantification) at 5 d, while in fresh and dried stems of Dendrobium officinale, they were 0.001-0.13 mg/kg at 14 d. The long-term RQ is 79.1%, and the short-term RQ ranges from 0.0365% to 0.1248%, ensuring accuracy, indicating highly unlikely to pose significant public health concerns. The results of this study can provide a reference for the safe application of EB in Allium tuberosum Rottler and Dendrobium officinale.

To investigate the expression of micro RNAs (miRNA) at the transcriptome level in interactions between maize (Zea mays) and the Asian corn borer (Ostrinia furnacalis), four miRNA libraries were constructed based on four groups of samples: fresh, uneaten maize leaves; maize leaves eaten by Asian corn borer larvae; Asian corn borer larvae that had eaten maize leaves; and Asian corn borer reared on an artificial diet). Through second-generation sequencing technology, 810 known miRNAs and 132 new miRNAs were identified and analyzed. In specific miRNA comparisons, five new plant-derived miRNAs were found in the Asian corn borer larvae, of which one was differentially expressed because of its diet. Expression levels of all differentially expressed miRNAs were validated using qRT PCR. Because of biotic stress and differences in food types, miRNAs with cross-kingdom transfer were regulated by their target genes to express metabolic factors such as transcription factors (e.g., growth hormone response factors (ARF6, ARF8), inorganic phosphate transporters (Pht10), and phosphate transporters (Pht7, Pht9)). We improve understanding of the roles of microRNAs in plant–insect interactions, and establish a foundation upon which new maize varieties with resistance to Asian corn borer larvae can be developed through genetic engineering.

Elucidating the environmental fate and exposure risk of lufenuron is crucial to ensure food safety and protect human health. In this study, we developed a rapid and sensitive analytical method for tracing lufenuron in cabbages using ultra-high-performance liquid chromatography-tandem mass spectrometry. The occurrence, pharmacokinetic dissipation, and concentration variation of lufenuron were characterized by primary concentrations (0.009-0.420 mg/kg), half-lives (0.3 d-11.7 d), and final magnitude (<LOQ-0.320 mg/kg). A probabilistic model was introduced to assess dietary risks and presented a comprehensive picture of the risk at multi-probabilities. The chronic dietary risk (ADI%) of lufenuron were 1.074-5.609 % from the 50th to the 99.9th percentile. This was compared with deterministic models, which yielded ADI% values ranging from 0.177 % to 0.500 %, both of which were acceptable. The exposure risks of rural females aged 4-6 years were significantly higher than those of the other groups (P < 0.05), which should be taken seriously with the increasing requirement of lufenuron in actual agricultural production.

Elucidating the combined exposure of agrochemicals is essential for safeguarding human health and agroecosystem safety. A rapid and high-sensitivity UHPLC-MS/MS method was developed for simultaneous quantification of nine compounds in sorghum by an assembly-line optimization process with a limit of quantitation of 0.001 mg/kg. The concentration variation of atrazine, quinclorac, fluroxypyr-meptyl and metabolites was reflected by terminal magnitudes of <= 0.0665 mg/kg. Additionally, atrazine was dealkylated to deethyl atrazine and desethyl desisopropyl atrazine at concentrations of 0.0014-0.0058 mg/kg during the sorghum harvest. Acceptable health hazardous of atrazine and quinclorac for all life cycle populations were comparatively assessed via deterministic and probabilistic models, in which atrazine gained an 83.55 % share of cumulative dietary risks. Rural residents had significantly higher risks than urban residents, and children were the most sensitive group. Despite the low health risks, combined exposure to herbicides and their metabolites should be continuously stressed, given their cumulative amplification effects.

Understanding the negative effects of agrochemicals on the environment and human health is indispensable for achieving green agriculture. In this study, the optimized UHPLC-MS/MS method achieved a highly sensitive quantification of tolfenpyrad in cabbage within 4.04 min. The occurrence, dissipation, and concentration variation of tolfenpyrad were reflected by the initial deposition of 0.250-2.045 mg/kg, half-lives (T1/2) of 2.4-10.2 d, and terminal magnitudes within 1.134 mg/kg. Furthermore, the fates of tolfenpyrad during processing were elucidated, with processing factors (Pfs) of 0.561-1.282. Among the different processing procedures, soaking in tap water (25 °C) for 5 min removed 43.9 % of tolfenpyrad and was recommended for initial processing. The multidimensional dietary assessment revealed unacceptable levels of short-term risks from tolfenpyrad in children (%ARfD, 160.519-688.725 %) using deterministic and probabilistic models. Fortunately, the risks were minimized to negligible levels (%ARfD, 69.665-98.719 %) through washing and heat processing. Despite the long-term risks (%ADI, 3.310-9.371 %) being within the safety threshold, the cumulative effect of tolfenpyrad in multiple crops (%ADIt, 46.407-121.472 %) and regional differences (p < 0.05) should be emphasized. Our investigation shed light on the fates of tolfenpyrad in raw to processed cabbage with the aim of achieving sustainable agriculture and alerting to the agricultural pollutant's danger to children.

To evaluate the potential ecotoxicity of ethiprole and early warning to earthworms (Eisenia fetida), different concentrations (0 mg·kg−1, 416 mg·kg−1, 625 mg·kg−1, and 1000 mg·kg−1) of ethiprole were added to artificial soil. The key bioindicators were measured and screened at 3 days, 7 days, 14 days, 21 days, and 28 days. The results show that the activity of catalase (CAT) was inhibited for all treatments during the whole exposure period. Besides, the olive tail moment (OTM) value increased gradually as the concentration got higher, which exhibited a dose-time-dependent relationship. Superoxide dismutase (SOD) gene reached the maximum on the 7th day. Mitochondrial large ribosomal RNA (l-rRNA) subunit gene was always in a downregulated state as the concentration increased. Our results show that different concentrations of ethiprole induced certain oxidative stress, DNA damage, and genotoxicity in earthworms. The CAT activity, OTM, and SOD gene could be the most sensitive biomarkers to monitor the toxicity of ethiprole in the soil.

The pesticide application method is one of the important factors affecting its effectiveness and residues, and the risk of pesticides to non-target organisms. To elucidate the effect of application methods on the efficacy and residue of cyenopyrafen, and the toxic effects on pollinators honeybees in strawberry cultivation, the efficacy and residual behavior of cyenopyrafen were investigated using foliar spray and backward leaf spray in field trials. The results showed that the initial deposition of cyenopyrafen using backward leaf spray on target leaves reached 5.06-9.81 mg/kg at the dose of 67.5-101.25 g a.i./ha, which was higher than that using foliar spray (2.62-3.71 mg/kg). The half-lives of cyenopyrafen in leaves for foliar and backward leaf spray was 2.3-3.3 and 5.3-5.9 d, respectively. The residues (10 d) of cyenopyrafen in leaves after backward leaf spray was 1.41-3.02 mg/kg, which was higher than that after foliar spraying (0.25-0.37 mg/kg). It is the main reason for the better efficacy after backward leaf spray. However, the residues (10 d) in strawberry after backward leaf spray and foliar spray was 0.04-0.10 and < 0.01 mg/kg, which were well below the established maximum residue levels of cyenopyrafen in Japan and South Korea for food safety. To further investigate the effects of cyenopyrafen residues after backward leaf spray application on pollinator honeybees, sublethal effects of cyenopyrafen on honeybees were studied. The results indicated a significant inhibition in the detoxification metabolic enzymes of honeybees under continuous exposure of cyenopyrafen (0.54 and 5.4 mg/L) over 8 d. The cyenopyrafen exposure also alters the composition of honeybee gut microbiota, such as increasing the relative abundance of Rhizobiales and decreasing the relative abundance of Acetobacterales. The comprehensive data on cyenopyrafen provide basic theoretical for environmental and ecological risk assessment, while backward leaf spray proved to be effective and safe for strawberry cultivation.

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 (R-2 > 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.

Elucidating exposure risks associated with the most widely used agrochemicals and their metabolites in celery agrosystems are vital for food safety and human health. The occurrence, distribution, dissipation and metabolism of imidacloprid (IMI), acetamiprid (ACE), thiamethoxam (THM) and difenoconazole (DIF) in celery tissues reflected by initial depositions, uptake characteristics, half-lives, concentration variations. DIF exhibited unacceptable ecological risk to soil organisms under multi-risk evaluation models, including toxicity exposure ratio, risk quotient, and BITSSD model. The joint dietary risks of target pesticides were 37.273-647.454% and 0.400-2522.016% based on deterministic and probabilistic models, with non-carcinogenic risks of 30.207-85.522% and 1.229-2524.662%, respectively. Children aged 1-6 years suffered the highest exposure, with the leaves posing higher risk than other tissues. Long-term exposure risks should be continuously assessed for ecological sustainability and human health, given the widespread usage and cumulative effects of target pesticides, especially for rural children.

Elaborating on the fate profiling and risk magnitude of butralin during large-scale applications was conducive to agroecosystems sustainability and dietary rationality. Occurrence, dissipation and concentration variation of butralin were elucidated from garlic cultivation to household processing by tracing UHPLC-MS/MS within 2 min, with regard to original depositions, half-lives, and terminal magnitude in typical origins of garlic. The processing factors (Pfs) of butralin were further clarified among washing, stir-frying and pickling of garlic crops, and pickling was the most effec-tive way for butralin removal with a Pf of 0.092. A probabilistic model with Pfs was further introduced for the compre-hensive risk estimations, by reduction factors of 3.1-10.9 from raw garlic crops to processed products. The short-term risks of butralin from green garlic were greater than those between garlic shoot and garlic, with the %ARfDs of 0.030 %-6.323 % from 50th to 99.9th percentiles. The long-term risks were inversely correlated to the age of the pop-ulation, whose location in rural (%ADIs, 0.256 %-0.768 %) suffered more serious exposures than in urban (%ADIs, 0.231 %-0.699 %). High potential risk amplification should be continuously emphasized given the increasing applica-tions and persistent fate of butralin, especially for vulnerable rural children.

蚯蚓是监测土壤污染物的重要指示生物.为探明手性农药乙虫腈对映体在蚯蚓体内是否存在对映选择性体累积行为,首先建立了一种快速、便捷的乙虫腈对映体在蚯蚓、土壤中的手性检测方法,在此基础上,采用人工土壤法,研究了不同浓度(0.5、5.0、12.5 mg·kg-1)处理下,赤子爱胜蚓体内乙虫腈对映体的选择性累积行为.结果表明:蚯蚓体内乙虫腈的EF值低于0.5,BSAF值在0.04～0.23之间,说明蚯蚓对乙虫腈对映体的吸收存在对映体选择性,但乙虫腈两对映体在蚯蚓体内均不存在累积行为.该研究结果可为乙虫腈环境风险评估提供数据支撑.

Pymetrozine is used on potato (S. tuberosum) and Chrysanthemum morifolium (C. morifolium) to obtain greater yield and quality. However, pesticide use carries the potential for residues to remain and be detected on harvested crops. Therefore, the aim of this study was to estimate pesticide residues in S. tuberosum and C. morifolium products that are commercially available for human consumption and to assess the associated dietary risks. For this study, a total of 340 samples (200 S. tuberosum samples and 140 C. morifolium samples) were collected randomly from supermarkets and farmer's markets. Residues of pymetrozine in S. tuberosum and C. morifolium were detected by using an established and validated QuECHERS-HPLC-MS / MS method, while a dietary risk assessment of pymetrozine in S. tuberosum and C. morifolium was performed using these data. The detection rates of pymetrozine in S. tuberosum and C. morifolium samples were 92.31% and 98.17%, respectively, with residues not more than 0.036 and 0.024 mg/kg, respectively. Based on these results, the dietary risk assessment indicated that the intake of pymetrozine residues in S. tuberosum and C. morifolium does not pose a health risk. This work improved our understanding of the potential exposure risk of pymetrozine in S. tuberosum and C. morifolium.

The risk assessment of dietary exposure to pesticide residues is a great concern in the fields of chemical risk management, food safety and human health. Effective quantitative risk assessment models are basic tools for assessing dietary exposure to pesticide residues. Based on a review of recent progress in the risk assessment of dietary exposure to pesticide residues, this paper summarizes the risk assessment models for dietary exposure to pesticide residues, including the deterministic assessment models, the probabilistic assessment models and the cumulative assessment models. The advantages and disadvantages of these models are compared in terms of their evolution, the situations to which they apply and the assessment demand, and the key factors such as model uncertainty, assessment software and database application are discussed. Based on the current status of the dietary risk assessment of pesticide residues in China, we highlight the urgency and importance of integrating model parameters, which will provide a scientific basis for improving the construction of risk assessment systems for dietary exposure to pesticide residues.