Non-target influence of imidacloprid residues on grape global metabolome and berry quality with the identification of metabolite biomarkers.

This paper illustrates the non-target impact of imidacloprid (IM) residues on the grape global metabolome and biomarker identification with high-resolution mass spectrometry. IM was applied at the recommended dose (SD), and ten times SD (10 RD). The global metabolome analysis revealed that 21 metabolites were up- and down-regulated with IM SD treatment. In 10 RD, 9 metabolites were upregulated, and 28 were downregulated. Pathway enrichment analysis revealed the primary and secondary pathway disruption in grapes. Berry quality was affected with decrease in flavonoids by 32.97% in 10 RD; phenols were reduced by 53.93 in SD, 50.8% in 10 RD. The non-target and target study revealed the degradation of IM in grapes to desnitro-IM and IM-urea which were identified as a potential biomarker for IM residues in grapes, which would benefit the authentication of organic product. Overall, imidacloprid showed a significant impact on the grape metabolome and quality.

Identification of key factors affecting neonicotinoid residues in crops and risk of dietary exposure.

Neonicotinoids, widely used on farmland, are ubiquitous in food; however, their distribution among various crops and associated exposure risks at the provincial level in China remain unclear. We collected 19 types of crop samples (fruits, vegetables, and tea) from farmland in nine prefectural cities in Zhejiang Province, China. We analyzed nine commonly used neonicotinoids in the edible portions of these crops. A notable detection rate (42.1 %-82.9 %) and high residual neonicotinoid concentrations (278 ± 357 ng/g) were observed. Tea exhibited the highest residue, followed by fruits, and vegetables showed the lowest (P < 0.05). Neonicotinoid ratios in crops to soil (R_C/S) and soil to water (R_S/W) were defined to discern insecticide distribution across different environments. Increased water solubility leads to increased migration of neonicotinoids (R_S/W) from agricultural soils to water through runoff, thereby increasing the relative contribution of nitenpyram and dinotefuran in water. In comparison with other studied compounds, all crops demonstrated the strongest soil uptake of thiamethoxam, denoted by the highest R_C/S value. Elevated R_C/S values in tea, pickled cabbage, and celery suggest increased susceptibility of these crops to neonicotinoid absorption from the soil (P < 0.05). Estimated dietary intake for teenagers, adults and elders was 8.9 ± 0.5, 8.9 ± 0.6, and 8.8 ± 0.3 µg/kg/d, respectively, below the reference dose (57 µg/kg/d). Teenagers, compared to adults and elders, exhibited significantly higher neonicotinoid exposure through fruit consumption, emphasizing the need for increased attention to neonicotinoid exposure among vulnerable populations.

Neonicotinoid insecticides in plant-derived Foodstuffs: A review of separation and determination methods based on liquid chromatography.

Neonicotinoids (NEOs) are the most widely used insecticides globally. They can contaminate or migrate into foodstuffs and exert severe neonic toxicity on humans. Therefore, lots of feasible analytical methods were developed to assure food safety. Nevertheless, there is a lack of evaluation that the impacts of food attributes on the accurate determination of NEOs. This review aims to provide a comprehensive overview of sample preparation methods regarding 6 categories of plant-derived foodstuffs. Currently, QuEChERS as the common strategy can effectively extract NEOs from plant-derived foodstuffs. Various enrichment technologies were developed for trace levels of NEOs in processed foodstuffs, and multifarious novel sorbents provided more possibility for removing complex matrices to lower matrix effects. Additionally, detection methods based on liquid chromatography were summarized and discussed in this review. Finally, some limitations were summarized and new directions were proposed for better advancement.

Comprehensive analysis of neonicotinoids in Chinese commercial honey and pollen: A corresponding health risk assessment for non-targeted organisms.

Neonicotinoids are broad-spectrum and highly effective insecticides that work by affecting neural activity in insects. Neonicotinoids are systemic pesticides that are absorbed by plants, transported, and accumulated in plant tissues, including nectar and pollen. Currently, there is a lack of a comprehensive assessment of the level of neonicotinoid contamination and the associated health risks to non-targeted organisms in commercial honey and pollen produced in China. This study collected 160 batches of honey and 26 batches of pollen from different regions and plant sources in China, analyzed the residue patterns of neonicotinoid pesticides, and comprehensively evaluated the exposure risks to non-targeted organisms including bees (adults and larvae) and humans. Furthermore, this study addresses this imperative by establishing a high-throughput, rapid, and ultra-sensitive indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) based on broad-spectrum monoclonal antibodies to detect and quantify neonicotinoids, with validation conducted using the LC-MS/MS method. The findings indicated that 59.4 % of honey samples contained at least one of eight neonicotinoids, and the ic-ELISA rapid detection and calculation method could detect all the samples containing neonicotinoids. Additionally, the dietary risk assessment for humans and honeybees indicates that the consumption of a specific quantity of honey may not pose a health risk to human due to neonicotinoid intake. However, the Risk Quotient values for imidacloprid to adult bees and bee larvae, as well as clothianidin to bee larvae, were determined to be 2.22, 5.03, and 1.01, respectively-each exceeding 1. This highlights the elevated risk of acute toxicity posed by imidacloprid and clothianidin residues to honey bees. The study bears significant implications for the safety evaluation of non-targeted organisms in the natural food chain. Moreover, it provides scientific guidance for protecting the diversity and health of the ecosystem.

Assessing neonicotinoid accumulation and ecological risks in the aquatic environment of Yangtze River Basin, China.

Neonicotinoids (NNIs) constitute commonly used pesticides across various regions, however, the lack of research and data on its long-term effects and threshold levels within specific ecosystems have left an important knowledge gap. This study aimed to comprehensively examine NNI concentrations and their potential impacts on human health and aquatic organisms in the region of the Yangtze River Basin (YRB). The study employed datasets on seven commonly applied NNIs across 244 surface water samples collected from 12 distinct geographic sites within the YRB. The relative potency factor was used to evaluate human exposure risks, while the species sensitivity distribution could estimate acute and chronic hazardous concentrations for 5% of species (HC5) for NNIs impacting aquatic organisms. Analysis revealed varying NNI concentrations across the sampled sites, with thiacloprid recording the lowest concentration at 0.1 ng L-1, and dinotefuran recording a high concentration of 408 ng L-1. The observation indicated NNI concentration declined at sampling sites downstream of the YRB. Infants were identified as the most vulnerable to NNI exposure, with an estimated daily intake of 40.8 ng kg-1 bw d-1. The acute HC5 was determined at 946 ng L-1 and a chronic HC5 at 338 ng L-1, to NNI hazards. These findings highlight the urgent need for a more comprehensive understanding of the ecological implications and hazards posed by NNIs within the YRB. Variations in NNI concentrations across sites, potential risks to human health, and increased vulnerability of aquatic organisms from this study underscore the necessity for further research and concerted efforts to mitigate these ecological threats in the region.

Residual behavior of dinotefuran and its metabolites during Huangjiu fermentation and their effects on flavor.

Yellow rice wine (Huangjiu) is a traditional Chinese alcoholic beverage. However, there is a risk of pesticide residues in Huangjiu due to pesticide indiscriminate use. In this study, the residues of dinotefuran and its metabolites during Huangjiu fermentation and their effects on flavor substances were studied. The initial concentrations of dinotefuran ranged from 856.3 to 1874.9 µg/L, and its half-life was no more than 3.65 d. At 24 d of Huangjiu fermentation, the terminal residues of dinotefuran, 1-methyl-3-(tetrahydro-3-furylmethyl)urea (UF) and 1-methyl-3-(tetrahydro-3-furylmethyl)guanidine (DN) were 195.1-535.3 µg/L, 38.33-48.70 µg/L and 37.8-74.1 µg/L, respectively. Twenty potential degradation compounds were identified by ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS), and their toxicity was evaluated. Finally, the effect of dinotefuran on physicochemical properties and total phenol content of Huangjiu were analyzed. The risk of rancidity was significantly increased and bitter amino acids were formed. These findings provide a guidance and the safe production of Huangjiu.

Aquatic ecological risk assessment of imidacloprid and thiacloprid in an urban river of Qingdao, China.

Imidacloprid and thiacloprid, two neonicotinoid insecticides that are extensively used in urban areas, are potentially toxic to non-target aquatic organisms. In this study, the concentrations of imidacloprid and thiacloprid in surface runoff after rainfall were 20.79-43.77 ng/L and 25.13-63.84 ng/L, respectively, whereas the levels for the Licun River were 10.78-41.70 ng/L and 2.66-39.68 ng/L, respectively. The acute and chronic criteria for imidacloprid and thiacloprid are 0.865, 0.006, 0.83, and 0.012 µg/L, respectively. Tiered ecological risk assessments revealed the chronic ecological risks of these micropollutants to local aquatic species. There was a moderate chronic toxicity risk associated with imidacloprid and thiacloprid in the Licun River, and the joint probability curves showed a probability of chronic ecological risk to 5 % of the aquatic organisms at 68 %-97 %. The results provide evidence of urban surface runoff transporting micropollutants from surface into rivers and estuaries, highlighting the ecological risks to aquatic ecosystems.

Covalent organic framework-sodium alginate-Ca2+-polyacrylic acid composite beads for convenient dispersive solid-phase extraction of neonicotinoid insecticides in fruit and vegetables.

Neonicotinoids, the fastest-growing class of insecticides, have posed a multi-media residue problem with adverse effects on environment, biodiversity and human health. Herein, covalent organic framework-sodium alginate-Ca2+-polyacrylic acid composite beads (CACPs), facilely prepared at room temperature, were used in convenient dispersive solid-phase extraction (dSPE) and combined with high-performance liquid chromatography (HPLC) for the detection of five neonicotinoid insecticides (thiamethoxam, acetamiprid, dinotefuran, clothianidin, imidacloprid). CACPs can be completely separated within 1 min without centrifugation. After seven adsorption/desorption cycles, it maintained high extraction efficiencies (>90%). The developed method exhibited a wide linear range (0.01 âˆ¼ 10 µg mL-1), low limits of detection (LODs, 0.0028 âˆ¼ 0.0031 mg kg-1), and good repeatability (RSD ≤ 8.11%, n = 3). Moreover, it was applied to the determination of five neonicotinoids in fruit and vegetables (peach, pear, lettuce, cucumber, tomato), and recoveries ranged from 73.6% to 116.2%.

Photolysis of dinotefuran in aqueous solution: Kinetics, influencing factors and photodegradation mechanism.

The environmental behaviour of neonicotinoid insecticides (NNIs) is of momentous concern due to their frequent detection in aquatic environment and their biotoxicity for non-target organisms. Phototransformation is one of the most significant transformation processes, which is directly related to NNIs exposure and environmental risks. In this study, the photodegradation of dinotefuran (DIN, 1-Methyl-2-nitro-3-(tetrahydro-3-furanylmethyl)-guanidine), one of the most promising NNIs, was conducted under irritated light in the presence of Cl-, DOM along with the effect of pH and initial concentration. The findings demonstrated that in ultra-pure (UP) water, the photolysis rate constants (k) of DIN rose with increasing initial concentration. Whereas, in tap water, at varied pH levels, and in the presence of Cl-, the outcomes were reversed. At the same time, lower concentration of DOM promoted DIN photolysis processes due to the production of reactive oxygen species, while higher concentrations of DOM inhibited the photolysis by the predominance of light shielding effects. The singlet oxygen (1O2) was produced in the photolysis processes of DIN with Cl- and DOM, which was confirmed by electron spin resonance (EPR) analysis. Four main photolysis products and three intermediates were identified by UPLC-Q-Exactive Orbitrap MS analysis. The possible photodegradation pathways of DIN were proposed including the oxidation by 1O2, reduction and hydrolysis after the removal of nitro group from parent compounds. This study expanding our understanding of transformation behavior and fate of NNIs in the aquatic environment, which is essential for estimating their environmental risks.

Maternal serum neonicotinoids during early-mid pregnancy and congenital heart diseases in offspring: An exploratory study.

Experimental evidence has indicated a correlation between in-utero exposure to neonicotinoid pesticides (NEOs) and adverse birth outcomes in mammals. However, the distribution of NEO exposure during human pregnancy, as well as its association with congenital heart diseases (CHDs), the most common birth defects, are unclear. Our purpose was to explore the distribution of and contributing factors to NEO exposure in pregnant women during early-mid pregnancy and to assess the associations between NEOs and CHDs. This nested case-control study was conducted within an ongoing prospective birth cohort study and enrolled 141 CHD singletons and their 282 individually matched controls. Six "parent" NEOs and three NEO metabolites were measured in maternal serum collected at an average gestational age of 16 weeks, using liquid chromatography-tandem mass spectrometry. Logistic regression was used to quantify the NEOs-CHDs associations and explore potential contributing factors to serum NEO levels in controls. N-desmethyl acetamiprid (N-dm-ACE) and imidacloprid (IMI) were the most frequently detected NEOs, found in 100% and 20% of maternal sera, respectively. We did not find a statistically significant association between total NEOs and overall CHDs. However, there was a trend towards a higher risk of septal defects with greater serum NEOs (ORs ranged from 1.80 to 2.36), especially nitro-containing NEOs represented by IMI. Pregnant women with lower education had elevated serum total NEOs compared to women with higher education (OR = 48.39, 95% CI: 23.48-99.72). Pregnant women were primarily exposed to N-dm-ACE and IMI during early-mid pregnancy. Gestational exposure to NEOs may be associated with an increased risk of septal defects, but the evidence is limited at present. Education is a potential contributing factor to NEO exposure in pregnant women. Larger and more precise studies with longitudinal biospecimen collection, are recommended to validate our exploratory findings.

Simultaneous Quantification of Two Neonicotinoids Using QuEChERS-LC-MS/MS in Moroccan Spearmint (Mentha Spicata.L): Qualimetry of the Method by Uncertainty Estimation Using Generalized Pivotal Quantities Approach and Monte Carlo Simulation.

BACKGROUND: Neonicotinoids (NEOs) are used for the phytosanitary treatment of Mentha Spicata.L crops, and this practice requires precise control of these harmful substances at very low concentrations. OBJECTIVE: The objective of this study is to apply an approach allowing simultaneously validation and evaluation of measurement uncertainty based on total error methodology, in order to accurately quantify the presence of two NEOs in Mentha Spicata.L utilizing a Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS)-LC-MS/MS methodology. METHODS:  The quantification of imidacloprid and acetamiprid employing a QuEChERS extraction method, coupled with LC-MS/MS, ensuring the accuracy of the analytical method and managing the risks associated with its routine use. A complete and exhaustive validation approach based on the "ß-content, γ-confidence" tolerance interval was used for the uncertainty assessment, using the generalized pivot quantity (GPQ) concept and Monte Carlo simulation, which avoids the need for additional data while achieving intermediate precision for each concentration level within predetermined acceptable limits. RESULTS: The validation procedure is based on the choice of a quadratic model for the two NEOs, allowing the validation of acetamiprid and imidacloprid by LC-MS/MS assay within the range of working concentration. The flexibility of the uncertainty profile intervals was demonstrated with a variation in ß-content values (66.7, 80, and 90%) and risk values (10 and 5%), which remained within the acceptability limits of 20%, and the relative expanded uncertainty did not exceed 15 and 11%. CONCLUSION: A QuEChERS-LC-MS/MS method for the analysis of two NEOs has been successfully fully validated using the uncertainty profile strategy. HIGHLIGHTS: Implementation of an overall validation strategy, which involves both the validation and uncertainty assessment known as the uncertainty profile, for the quantification of two important NEOs in Mentha Spicata.L using QuEChERS-LC-MS/MS. This qualimetric approach has been conducted by computing the measurement uncertainty of the method utilizing data from analytical validation under conditions of intermediate precision at each level of concentration without additional effort. After that we have demonstrated the flexibility of this strategy for the LC-MS/MS quantification of acetamiprid and imidacloprid, using a decision tool that enables the choice and modification of ß-content and γ-confidence values.

Pesticide residues in adults living near a bioenergy plant with 85,000 tons of contaminated wetcake.

Neonicotinoid insecticide use is on the rise worldwide due to its broad-spectrum insecticidal action and exclusive approach of neurotoxic action. Besides application during the cultivation of several crops, all seed companies coat their seeds with neonicotinoids to have increased protection against insects during germination. Despite reduced mammalian toxicity, neonicotinoids have harmful effects on non-target non-mammalian organisms such as bees, an essential part of maintaining the ecosystem. In addition, epidemiologic studies have linked human exposure to neonicotinoids with poor developmental and neurological outcomes. Starting in 2015, the AltEn bioenergy plant near Mead, Nebraska, USA, used coated seeds for their ethanol production and failed to properly dispose of byproducts, causing environmental contamination that still exists. This pilot study reports the human urinary levels of neonicotinoids in samples collected during 2022-2023 in the population living in areas close to this now-closed bioenergy plant. Our results show that approximately 30% of the urine samples are contaminated with at least one of the targeted neonicotinoids or their transformed products. The most frequently detected parent neonicotinoid was clothianidin, which accounts for 13% of the samples. However, 5-hydroxy-imidacloprid, the transformed imidacloprid product, is detected in 27% of the samples, ranging from 1.2 to 42 ng/mL. In conclusion, the environmental contamination near Mead, Nebraska, due to improper storage and disposal of highly contaminated byproducts, puts the nearby population at risk from continuous exposure to neonicotinoids through air and dust particles and possible water contamination.

Characterization of Environmental Levels of Pesticide Residues in Household Air and Dust Samples near a Bioenergy Plant Using Treated Seed as Feedstock.

Exposure to neonicotinoid insecticides is associated with adverse human health outcomes. There is environmental contamination in Saunders County, Nebraska, due to the accumulation of fungicides and insecticides from a now-closed ethanol plant using seed corn as stock. A pilot study quantified environmental contamination in nearby houses from residual pesticides by measuring dust and air (indoor/outdoor) concentrations of neonicotinoids and fungicides at the study site (households within two miles of the plant) and control towns (20-30 miles away). Air (SASS® 2300 Wetted-Wall Air Sampler) and surface dust (GHOST wipes with 4 × 4-inch template) samples were collected from eleven study households and six controls. Targeted analysis quantified 13 neonicotinoids, their transformation products and seven fungicides. Sample extracts were concentrated using solid phase extraction (SPE) cartridges, eluted with methanol and evaporated. Residues were re-dissolved in methanol-water (1:4) prior to analysis, with an Acquity H-Class ultraperformance liquid chromatograph (UPLC) and a Xevo triple quadrupole mass spectrometer. We compared differences across chemicals in air and surface dust samples at the study and control sites by dichotomizing concentrations above or below the detection limit, using Fisher's exact test. A relatively higher detection frequency was observed for clothianidin and thiamethoxam at the study site for the surface dust samples, similarly for thiamethoxam in the air samples. Our results suggest airborne contamination (neonicotinoids and fungicides) from the ethanol facility at houses near the pesticide contamination.

Exploratory analysis of the associations between neonicotinoids insecticides and serum lipid profiles among US adults: A cross-sectional, population-based study.

Neonicotinoid insecticides (NNIs) are widely used in agriculture, horticulture, forestry, and household environment, but their potential impact on human health remains a subject of concern. This study aimed to investigate the relationship between NNIs and their metabolites in urine with serum lipid profiles in adults using data from the National Health and Nutrition Examination Survey (NHANES) 2015-2016. The study included 1192 participants aged over 20 years with urinary NNIs levels, serum lipid parameter levels and potential confounders. Urinary concentrations of NNIs, including imidacloprid, acetamiprid, clothianidin, thiacloprid, N-desmethyl-acetamiprid, and 5-hydroxy-imidacloprid, were quantified. Serum lipids profiles, such as total cholesterol (TC), triglyceride (TG), high-density lipoprotein cholesterol (HDL-C), low-density lipoprotein cholesterol (LDL-C) and apolipoprotein B (Apo-B), were assessed. Considering the effects of lipid-lowering medications, the censored normal regression model was used to explore the associations between urinary NNIs and TC, TG, HDL-C, LDL-C and Apo-B levels. The results revealed a significant increase of 9.0 mg/dL (95%CI: 2.0, 16.1) in TC levels among participants with detectable N-desmethyl-acetamiprid compared to those with undetectable levels. Stratified analysis indicated that the association between N-desmethyl-acetamiprid and HDL-C levels was more pronounced among participants aged ≥ 46 years compared to those aged between 20 and 45 years with undetectable N-desmethyl-acetamiprid (pinteraction=0.044). Additionally, there were marginal effect modification of BMI on the association between N-desmethyl-acetamiprid and LDL-C (pinteraction=0.097) and Apo-B (pinteraction=0.052) levels. Specifically, participants with BMI ≥ 25 kg/m² and detectable N-desmethyl-acetamiprid tended to have higher LDL-C and Apo-B levels compared to those with BMI < 25 kg/m² and undetectable N-desmethyl-acetamiprid. However, no significant associations were observed between other NNIs and lipid profiles in the present study. To validate these findings, further longitudinal studies with larger sample sizes should be conducted, particularly within populations characterized by a high detection rate of NNIs.

Dissipation kinetics, decontamination, consumer risk assessment and monitoring of flonicamid and imidacloprid residues in capsicum under open field and polyhouse condition.

Liquid chromatography mass spectrometry (LC-MS)-based detection of flonicamid, imidacloprid and 6-chloronicotinic acid residues was validated and analysed in capsicum fruit, processed products and soil. The standard concentrations (0.0025 to 0.25 µg mL-1) of insecticides had a good linear curve (r2>0.99). Limit of detection and limit of quantification values were 0.0025 and 0.01 mg kg-1, respectively. The accuracy (80.53 to 100.33 %) of capsicum matrices and soil (89.41 to 100.52 %) and precision (RSD <10%) were established. Dissipation of imidacloprid (20 and 40 g a.i. ha-1) and flonicamid (75 and 150 g a.i. ha-1) at single (X) and double dose (2X) was studied under open field and polyhouse conditions. Under open field conditions, the flonicamid and imidacloprid residues persisted with half-life of 1.98, 2.90 days (X) and 2.80, 3.14 (2X) days, respectively. While under polyhouse conditions, the flonicamid and imidacloprid residues persisted with a half-life of 2.84, 3.66 (X) and 3.24, 3.97 (2X) days, respectively. The metabolite, 6-CNA, was not detected in any samples under open field and polyhouse condition. Among decontamination treatments, cooking in boiling water for 10 minutes reduced 78 to 81.60 percent of imidacloprid and flonicamid residues in both doses. The estimated dietary risk assessment of imidacloprid and flonicamid residues (RQ <1) indicated that the risk is within the acceptable limit. In farmgate capsicum samples, residues of flonicamid (7 samples) and imidacloprid (11 samples) were detected. Market samples of capsicum products (powder, flakes and sauce) were not detected with residues of selected insecticides.

A salting-out assisted liquid-liquid extraction method for 25 emerging pesticides in follicular fluid.

Emerging pesticides of neonicotinoids (NEOs) and "Universal Pesticides" (UPs) are a growing global concern due to their growing commercial importance and potential risks to human health. The currently available analytical methods for these pesticides in biomonitoring were usually tailored for limited number of analytes, or were time consuming and costly. In this study, an efficient and sensitive method for the analysis of 16 NEOs and nine UPs in human follicular fluid (FF) was developed by using a salting-out assisted liquid-liquid extraction (SALLE) method and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Method performance was evaluated by calibration linearity (r > 0.99), sensitivity at limits of quantification (0.01-0.50 ng/mL), accuracy at relative recoveries (81-117%) and precision at relative standard deviations (≤16%). The developed method was further validated by analyzing 21 human FF samples that were collected from a hospital in Guangzhou, China. Among the 25 study analytes, two NEOs and six UPs had their detection rates over 85% and medians at 0.048-0.808 ng/mL in the FF samples. Considering the well-known toxicity of these pesticides and their metabolites, it is urgent to figure out exposure profiles of study pesticides and potential reproductive risk for women. To the best of our knowledge, this study is the first to develop and apply the SALLE method in the extraction of 16 NEOs and nine UPs simultaneously in human FF.

Behavioral and physiological changes in the passerine Agelaioides badius following the ingestion of coated seeds with imidacloprid in a 30-day experiment.

The wide use of neonicotinoid seed treatment represents a hazard for farmland birds that feed on treated seeds. This study aimed to characterize the long-term effects of the neonicotinoid imidacloprid (IMI) in the passerine grayish baywing (Agelaioides badius). The birds were fed ad libitum for 32 days only with seeds treated with 53.1 (Low, 11 % of LD50) and 514 (High, (112 % of LD50) mg IMI/kg seed; these concentrations representing respectively, 1.8 and 17.1 % of 3 g IMI/kg, an average application rate used to treat crop seeds in Argentina. The effects exerted by IMI on birds were evaluated at behavioral, physiological, hematological, genotoxic, and biochemical levels. No differences in food consumption were observed between Control and Low treatments birds, indicating a lack of aversion to treated seeds. High treatment birds only decreased their food consumption by 20 % in the first 3 days of exposure. Birds from High treatment experienced an early loss of body weight, reduction in their mobility, lack of response to threats (i.e., predator call and approaching person), and altered their use of the cage. On the contrary, birds from Low treatment experienced a delay in the onset of effects like reduction in mobility, lack of response to threats, and a tendency to reduce their body weight. At the end of exposure, glutathione S transferase activity in the plasma of treated birds decreased, and cholinesterase activity increased in the liver of treated birds. This study highlights that consumption equivalent to 1.8 % of the daily diet of baywings as IMI-treated seeds, is sufficient to generate behavioral and physiological alterations and death. In the wild, these effects may have ecological consequences, by impairing the survival of birds, representing a risk to farmland bird populations.

Salting-Out Assisted Liquid-Liquid Microextraction and Reverse-Phase Chromatographic Quantification of Two Neonicotinoid Insecticides from Fruits and Vegetables.

The present monograph describes the salting-out assisted liquid-liquid microextraction (SALLME) and reverse-phase high-performance liquid chromatography with diode array detector (RP-HPLC-DAD) based quantification of two frequently applied neonicotinoid insecticides, i.e., acetamiprid (ACE) and imidacloprid (IMD), from selected tropical fruits (citrus and guava) and vegetables (tomato, okra and cauliflower). The SALLME conditions like pH, liquid/solid ratio and salt ratio (NaCl/Na2SO4) were varied over a wide range of conditions for the enhanced recovery of IMD and ACE from spiked quality control (low, high and medium) of fruits and vegetables. Meanwhile, RP-HPLC-DAD quantification of IMD and ACE was found to be linear over 1-100 µg/L with the coefficient of determination (R2) value ≥0.997 and slope of the calibration curve (sensitivity) ≥2.3 × 104 peak area unit (µAu). The analysis of selected fruits and vegetables after 0 (1 h), 1, 3, 7, 10 and 14 days of foliar application revealed the presence of IMD and ACE residues in okra and guava higher than maximum residual limits set by the Codex Alimentarius Commission until the third day of spray. Overall, the SALLME-RP-HPLC-DAD was found to be a rapid, selective and expedient choice for the routine analysis of neonicotinoids in environmental and food commodities.

Neuron-Inspired Nanofluidic Biosensors for Highly Sensitive and Selective Imidacloprid Detection.

Pesticides have caused concerns about food safety due to their residual effects in vegetables and fruits. Imidacloprid, as the frequently used neonicotinoid pesticide, could harm cardiovascular and respiratory function and cause reproductive toxicity in humans. Therefore, reliable methods for portable, selective, and rapid detection are desirable to develop. Herein, we report a neuron-inspired nanofluidic biosensor based on a tyrosine-modified artificial nanochannel for sensitively detecting imidacloprid. The functional tyrosine is modified on the outer surface of porous anodic aluminum oxide to rapidly capture imidacloprid through π-π interactions and hydrogen bonds. The integrated nanofluidic biosensor has a wide concentration range from 10-8 to 10-4 g/mL with an ultralow detection limit of 6.28 × 10-9 g/mL, which outperforms the state-of-the-art sensors. This work provides a new perspective on detecting imidacloprid residues as well as other hazardous pesticide residues in environmental and food samples.

Neonicotinoids in tea leaves and infusions from China: Implications for human exposure.

The ingestion of contaminated tea involves the risk of human exposure to residues of neonicotinoids (NEOs). Nevertheless, there is little empirical research about this topic; to bridge the current knowledge gap, we collected 220 samples of various tea products from four geographical areas in China, including unfermented green tea, semi-fermented white tea and oolong tea, completely fermented black tea, and post-fermented dark tea. A total of six NEOs were detected from the tea leaves and infusions, namely, dinotefuran (DIN), thiamethoxam (THM), clothianidin (CLO), imidacloprid (IMI), acetamiprid (ACE), and thiacloprid (THI). The detection frequencies (DFs) and concentrations of all target NEOs were relatively high across the investigated tea samples, and the DIN, IMI and ACE residues measured in some samples exceeded the maximum residue level (MRL) standards for the European Union. Samples representing the Jiangnan area exhibited greater levels of total target NEOs (∑6NEOs) than samples representing the Jiangbei area (p < 0.001). Moreover, dark tea samples were found to have far higher levels of NEO residues than green (p < 0.001), white (p < 0.05), or oolong (p < 0.001) samples. The health risks associated with exposure to NEO residues via tea were small for both children and adults in terms of acute, chronic, and cumulative dietary exposure risk assessments. The transfer rates (TRs) of NEOs observed in white, black, and dark tea infusions gradually decreased after the third brewing time. As such, it is recommended to only consume tea that has been brewed at least three times. The presented results not only describe the extent of NEO contamination in Chinese tea leaves and infusions, but also provide tea drinking guidelines for consumers.