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.

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.

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.

Application of pesticide application measures to reduce residue based on the metabolic transfer law of imidacloprid in banana leaves and soil.

An investigation of the metabolism and transfer of imidacloprid (IMI) in banana plants and soil was performed using high-resolution mass spectrometry. Results indicated the presence of eight IMI metabolites in soil and leaves that resulted from hydroxylation of the imidazolidine ring, the reduction and loss of nitro groups, and oxidative cleavage of methylene bridges. Six metabolites, including 4/5-hydroxy IMI (4/5-hydroxy), IMI olefin (olefin), and 6-chloronicotinic acid (6-CNA), were detected in the fruits following leaf treatment, while only three were detected after soil treatment. Quantitative analysis showed that the total amount of imidacloprid and its metabolites transferred from leaves to fruits was higher than that transferred from soil to fruits. Therefore, leaf transfer was considered the main means by which IMI and its metabolites transferred to banana fruits. We found that adjuvants tank-mixed with IMI could reduce the total concentration of pesticide transfer from leaves to fruits, especially reducing the amount of metabolites transformed from the reduction and loss of nitro groups and oxidative cleavage of methylene bridges, thus reducing the pesticide residue in fruits and achieving the purpose of reducing the safety risk.

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.

A critical review on the accumulation of neonicotinoid insecticides in pollen and nectar: Influencing factors and implications for pollinator exposure.

Neonicotinoids are a class of neuro-active insecticides widely used to protect major crops, primarily because of their broad-spectrum insecticidal activity and low vertebrate toxicity. Owing to their systemic nature, plants readily take up neonicotinoids and translocate them through roots, leaves, and other tissues to flowers (pollen and nectar) that serve as a critical point of exposure to pollinators foraging on treated plants. The growing evidence for potential adverse effects on non-target species, especially pollinators, and persistence has raised serious concerns, as these pesticides are increasingly prevalent in terrestrial and aquatic systems. Despite increasing research efforts, our understanding of the potential toxicity of neonicotinoids and the risks they pose to non-target species remains limited. Therefore, this critical review provides a succinct evaluation of the uptake, translocation, and accumulation processes of neonicotinoids in plants and the factors that may affect the eventual build-up of neonicotinoids in pollen and nectar. The role of plant species, as well as the physicochemical properties and application methods of neonicotinoids is discussed. Potential knowledge gaps are identified, and questions meriting future research are suggested for improving our understanding of the relationship between neonicotinoid residues in plants and exposure to pollinators.

Behavioral and physiological response of the passerine bird Agelaioides badius to seeds coated with imidacloprid.

Neonicotinoids are globally used insecticides, and there are increasing evidence on their negative effects on birds. This study is aimed at characterizing the behavioral and physiological effects of the neonicotinoid imidacloprid (IMI) in a songbird. Adults of Agelaioides badius were exposed for 7 days to non-treated peeled millet and to peeled millet treated with nominal concentrations of 75 (IMI1) and 450 (IMI2) mg IMI/kg seed. On days 2 and 6 of the trial, the behavior of each bird was evaluated for 9 min by measuring the time spent on the floor, the perch, or the feeder. Daily millet consumption, initial and final body weight, and physiological, hematological, genotoxic, and biochemical parameters at the end of exposure were also measured. Activity was greatest on the floor, followed by the perch and the feeder. On the second day, birds exposed to IMI1and IMI2 remained mostly on the perch and the feeder, respectively. On the sixth day, a transition occurred to sectors of greater activity, consistent with the disappearance of the intoxication signs: birds from IMI1 and IMI2 increased their time on the floor and the perch, respectively. Control birds always remained most of the time on the floor. IMI2 birds significantly decreased their feed intake by 31% the first 3 days, compared to the other groups, and significantly decreased their body weight at the end of the exposure. From the set of hematological, genotoxic, and biochemical parameters, treated birds exhibited an alteration of glutathione-S-transferase activity (GST) in breast muscle; the minimal effects observed are probably related to the IMI administration regime. These results highlight that the consumption of less than 10% of the bird daily diet as IMI-treated seeds trigger effects at multiple levels that can impair bird survival.

Changing on the Concentrations of Neonicotinoids in Rice and Drinking Water through Heat Treatment Process.

Neonicotinoids (NEOs) have become the most widely used insecticides in the world since the mid-1990s. According to Chinese dietary habits, rice and water are usually heated before being consumed, but the information about the alteration through the heat treatment process is very limited. In this study, NEOs in rice samples were extracted by acetonitrile (ACN) and in tap water, samples were extracted through an HLB cartridge, then, a high-performance liquid chromatography system and a triple quadrupole mass spectrometry (HPLC-MS/MS) were applied for target chemical analysis. The parents of NEOs (p-NEOs) accounted for >99% of the total NEOs mass (∑NEOs) in both uncooked (median: 66.8 ng/g) and cooked (median: 41.4 ng/g) rice samples from Guangdong Province, China, while the metabolites of NEOs (m-NEOs) involved in this study accounted for less than 1%. We aimed to reveal the concentration changes of NEOs through heat treatment process, thus, several groups of rice and water samples from Guangdong were cooked and boiled, respectively. Significant (p < 0.05) reductions in acetamiprid, imidacloprid (IMI), thiacloprid, and thiamethoxam (THM) have been observed after the heat treatment of the rice samples. In water samples, the concentrations of THM and dinotefuran decreased significantly (p < 0.05) after the heat treatment. These results indicate the degradation of p-NEOs and m-NEOs during the heat treatment process. However, the concentrations of IMI increased significantly in tap water samples (p < 0.05) after heat treatment process, which might be caused by the potential IMI precursors in those industrial pesticide products. The concentrations of NEOs in rice and water can be shifted by the heat treatment process, so this process should be considered in relevant human exposure studies.

Climate warming inhibits neonicotinoid photodegradation on vegetable leaves: Important role of the olefin group in leaf wax.

Neonicotinoid photodegradation is seldom considered in different vegetable leaves after spraying under climate warming. This study investigated the effect of elevated cultivated temperature from 15/10 °C to 21/16 °C on the photodegradation of dinotefuran, thiamethoxam, acetamiprid, and thiacloprid on four vegetable leaves under simulated sunlight irradiation. The photodegradation rates of neonicotinoids on spinach leaves were 1.1-1.6, 1.1-2.0, and 1.4-2.4 times higher than those on pak choi, Chinese cabbage, and radish leaves, respectively. The higher production concentrations of hydroxyl radicals (•OH) and superoxide radicals in spinach leaf wax may contribute to the fastest photodegradation among four vegetables. When the cultivated temperature increased from 15/10 °C to 21/16 °C, neonicotinoid photodegradation rates decreased by 1.4-2.8 times on the four vegetables. Elevated cultivated temperature decreased the polarity of wax, which reduced the contact probability of neonicotinoids with reactive species on vegetable leaves and photodegradation rates. A positive linear correlation was found between the content of CHCH groups in wax determining •OH generation and the neonicotinoid photodegradation rates on four vegetable leaves cultivated at three temperatures (R2 = 0.67-0.94). Insights into neonicotinoid photodegradation on edible vegetables under climate warming are of great significance for better evaluating human exposure to neonicotinoids through the dietary pathway.

Imidacloprid exposure is detectable in over one third of wild bird samples from diverse Texas ecoregions.

Avian decline is occurring globally with neonicotinoid insecticides posed as a potentially contributing factor. Birds can be exposed to neonicotinoids through coated seeds, soil, water, and insects, and experimentally exposed birds show varied adverse effects including mortality and disruption of immune, reproductive, and migration physiology. However, few studies have characterized exposure in wild bird communities over time. We hypothesized that neonicotinoid exposure would vary temporally and based on avian ecological traits. Birds were banded and blood sampled at eight non-agricultural sites across four Texas counties. Plasma from 55 species across 17 avian families was analyzed for the presence of 7 neonicotinoids using high performance liquid chromatography-tandem mass spectrometry. Imidacloprid was detected in 36 % of samples (n = 294); this included quantifiable concentrations (12 %; 10.8-36,131 pg/mL) and concentrations that were below the limit of quantification (25 %). Additionally, two birds were exposed to imidacloprid, acetamiprid (18,971.3 and 6844 pg/mL) and thiacloprid (7022.2 and 17,367 pg/mL), whereas no bird tested positive for clothianidin, dinotefuran, nitenpyram, or thiamethoxam, likely reflecting higher limits of detection for all compounds compared to imidacloprid. Birds sampled in spring and fall had higher incidences of exposure than those sampled in summer or winter. Subadult birds had higher incidences of exposure than adult birds. Among the species for which we tested more than five samples, American robin (Turdus migratorius) and red-winged blackbird (Agelaius phoeniceus) had significantly higher incidences of exposure. We found no relationships between exposure and foraging guild or avian family, suggesting birds with diverse life histories and taxonomies are at risk. Of seven birds resampled over time, six showed neonicotinoid exposure at least once with three showing exposures at multiple time points, indicating continued exposure. This study provides exposure data to inform ecological risk assessment of neonicotinoids and avian conservation efforts.

Occurrence, distribution and potential risk to infants of neonicotinoids in breast milk: A case study in Hangzhou, China.

The pervasive use of neonicotinoid insecticides (neonics) has led to increasing concerns regarding the potential health risks associated with them. Breast milk is the main food source of infants, and thus, the presence of chemicals in breast milk has a greater impact on infant health. However, there have only been few reports regarding the presence of neonics in breast milk. Herein, eight neonics were detected in breast milk samples using ultraperformance liquid chromatography-mass spectrometry and their Pearson correlation was analyzed. The potential health risks of neonics to infants were assessed using the relative potency factor (RPF) method. The results revealed that neonics were widely detected in the breast milk samples from Hangzhou, with at least one neonics being detected in >94 % of the breast milk samples. The most frequently detected neonics included thiamethoxam (70.8 %) followed by imidacloprid (IMI) (62.0 %) and clothianidin (46.0 %). The residual concentrations of neonics in the breast milk samples ranged from

Multi-omics approach reveals elevated potential of bacteria for biodegradation of imidacloprid.

The residual imidacloprid, a widely used insecticide is causing serious environmental concerns. Knowledge of its biodegradation will help in assessing its residual mass in soil. In view of this, a soil microcosm-based study was performed to test the biodegradation potential of Agrobacterium sp. InxBP2. It achieved ∼88% degradation in 20 days and followed the pseudo-first-order kinetics (k = 0.0511 day-1 and t1/2=7 days). Whole genome sequencing of Agrobacterium sp. InxBP2 revealed a genome size of 5.44 Mbp with 5179 genes. Imidacloprid degrading genes at loci K7A42_07110 (ABC transporter substrate-binding protein), K7A42_07270 (amidohydrolase family protein), K7A42_07385 (ABC transporter ATP-binding protein), K7A42_16,845 (nitronate monooxygenase family protein), and K7A42_20,660 (FAD-dependent monooxygenase) having sequence and functional similarity with known counterparts were identified. Molecular docking of proteins encoded by identified genes with their respective degradation pathway intermediates exhibited significant binding energies (-6.56 to -4.14 kcal/mol). Molecular dynamic simulation discovered consistent interactions and binding depicting high stability of docked complexes. Proteome analysis revealed differential protein expression in imidacloprid treated versus untreated samples which corroborated with the in-silico findings. Further, the detection of metabolites proved the bacterial degradation of imidacloprid. Thus, results provided a mechanistic link between imidacloprid and associated degradative genes/enzymes of Agrobacterium sp. InxBP2. These findings will be of immense significance in carrying out the lifecycle analysis and formulating strategies for the bioremediation of soils contaminated with insecticides like imidacloprid.

Meta-analysis of neonicotinoid insecticides in global surface waters.

Neonicotinoids (NEOs) are a class of insecticides that have high insecticidal activity and are extensively used worldwide. However, increasing evidence suggests their long-term residues in the environment and toxic effects on nontarget organisms. NEO residues are frequently detected in water and consequently have created increasing levels of pollution and pose significant risks to humans. Many studies have focused on NEO concentrations in water; however, few studies have focused on global systematic reviews or meta-analyses of NEO concentrations in water. The purpose of this review is to conduct a meta-analysis on the concentration of NEOs in global waters based on published detections from several countries to extend knowledge on the application of NEOs. In the present study, 43 published papers from 10 countries were indexed for a meta-analysis of the global NEO distribution in water. Most of these studies focus on the intensive agricultural area, such as eastern Asia and North America. The order of mean concentrations is identified as imidacloprid (119.542 ± 15.656 ng L-1) > nitenpyram (88.076 ± 27.144 ng L-1) > thiamethoxam (59.752 ± 9.068 ng L-1) > dinotefuran (31.086 ± 9.275 ng L-1) > imidaclothiz (24.542 ± 2.906 ng L-1) > acetamiprid (23.360 ± 4.015 ng L-1) > thiacloprid (11.493 ± 5.095 ng L-1). Moreover, the relationships between NEO concentrations and some environmental factors are analyzed. NEO concentrations increase with temperature, oxidation-reduction potential, and the percentage of cultivated crops but decrease with stream discharge, pH, dissolved oxygen, and precipitation. NEO concentrations show no significant relations to turbidity and conductivity.

The fate, acute, and subchronic risks of dinotefuran in the water-sediment system: A systematic analysis at the enantiomer level.

Environmental risks associated with neonicotinoid insecticides have attracted considerable attention. This study systematically investigated the stereoselective behavior of dinotefuran in a water-sediment system. The results showed that S-dinotefuran accumulated more easily in sediment and zebrafish. Although dinotefuran enantiomers and metabolites present a low risk to aquatic organisms, the risk of dinotefuran enantiomers to sediment organisms should be considered. Additionally, S-dinotefuran induced more remarkable oxidative damage in zebrafish than that of R-dinotefuran. Nevertheless, R-dinotefuran remarkably activated antioxidant and detoxifying enzymes. Multi-omics analyses revealed that S-dinotefuran induced more differentially expressed genes (DEGs) and differentially expressed proteins (DEPs) in zebrafish. In particular, S-dinotefuran inhibited the expression of ribosome- and proteasome-related genes and proteins, affecting the synthesis and degradation of proteins in zebrafish. R-dinotefuran remarkably activated peroxisome-related genes and proteins, thereby enhancing antioxidant and detoxification abilities of zebrafish. The stereoselective interactions between dinotefuran enantiomers and key DEPs were elucidated using AlphaFold2 modeling and molecular docking techniques, which may serve as the main reason for stereoselective subchronic toxicity. The present study is beneficial for the correct use of dinotefuran and provides an effective means for elucidating the mechanism of the stereoselective behavior of chiral compounds.

Integrated exposure assessment and potential risks of neonicotinoids in vegetables from three different sources in Zhejiang, China (2018-2020).

Dietary exposure is the primary route of human exposure to neonicotinoids (neonics), and vegetables are essential foods in people's daily diet. However, the residues and potential health risks of neonics in vegetables from different sources have not been well examined. In this study, we collected 1588 samples of vegetables from organic vegetable bases, farmer's markets, and supermarkets in Zhejiang, China. Three frequently used neonics, acetamiprid, imidacloprid, and thiamethoxam, were selected and analyzed. We investigated the residue, temporal and spatial distribution, and potential health risks. Cowpea was detected with the highest mean imidacloprid-equivalent total neonics (IMIRPF) by value of 655 µg/kg. Vegetable samples from farmer's markets were detected with the highest mean IMIRPF by value of 168 µg/kg, followed by supermarkets (134 µg/kg) and the lowest in organic vegetable bases (76.9 µg/kg). The outcomes of integrated risk assessment for dietary intake of those three neonics in vegetables were all within the safety.

Comparing imidacloprid, clothianidin, and azoxystrobin runoff from lettuce fields using a soil drench or treated seeds in the Salinas Valley, California.

Neonicotinoid insecticide use has increased over the last decade, including as agricultural seed treatments (application of chemical in a coating to the seed prior to planting). In California, multiple crops, including lettuce, can be grown using neonicotinoid treated seeds or receive a direct neonicotinoid soil application (drenching) at planting. Using research plots, this study compared pesticide runoff in four treatments: (1) imidacloprid seed treatment; (2) clothianidin seed treatment; (3) imidacloprid drench and an azoxystrobin seed treatment; and (4) a control with no pesticidal treatment. Neonicotinoid and azoxystrobin concentrations were measured in surface water runoff during six irrigations events in the 2020 growing seasons. Results showed runoff concentrations up to 1308 (±1200) ng L-1 for imidacloprid drench treatment, 431 (±100) ng L-1 for clothianidin seed treatment, 135 (±60) ng L-1 for imidacloprid seed treatment, and 13 (±10) ng L-1 for azoxystrobin seed treatment (treatments averaged). The percent of applied mass in runoff over the entire sampling period varied by compound; the imidacloprid seed treatment and drench were similar (0.015 and 0.019%, respectively) to the clothianidin seed treatment (0.036%) while the azoxystrobin seed treatment was much higher (15%). Although the proportion of imidacloprid in runoff was similar for imidacloprid treatments, the mass applied during soil drench was > 4x the amount applied from the imidacloprid seed treatment. Surface soils were collected before planting and at the end of the trial. The neonicotinoids were detected in soil throughout the study and average maximum concentrations were 9-13 ng g-1; azoxystrobin was detected in only two soils at concentrations up to 0.57 ng g-1. These results elucidate the comparative mass runoff resulting from planting treated seed and soil drench applications and highlight the value of additional work to characterize off-site transport from the many commodities that may be utilizing treated seeds.

Neonicotinoids residues in the honey circulating in Chinese market and health risk on honey bees and human.

China is the largest beekeeping and honey consumption country globally. Neonicotinoids in honey can pose adverse effects on honey bees and human, but data on neonicotinoids residues in honey and its health risk remain limited in China. A total of 94 honey samples were selected from Chinese market based on production region and sale volume in 2020. Eight neonicotinoids and four metabolites were determined by liquid chromatography coupled to mass spectrometry. Health risk of neonicotinoids in honey on honey bees and human was assessed by hazard quotient (HQ) and hazard index (HI). Neonicotinoids and their metabolites were overall detected in 97.9% of honey samples. Acetamiprid, thiamethoxam, and imidacloprid were top three dominant neonicotinoids in honey with the detection frequencies of 92.6%, 90.4%, and 73.4%, respectively. For honey bees, 78.7% of honey samples had a HI larger than one based on the safety threshold value of sublethal effects. Top three neonicotinoids with the highest percent proportion of HQ larger than one for honey bees were acetamiprid (43.6%), imidacloprid (31.9%), and thiamethoxam (24.5%) and their maximum HQs were 420, 210, and 41, respectively. Based on oral median lethal doses for honey bees, both HQ and HI were lower than one in all honey samples. For human, both HQ and HI were lower than one based on acceptable daily intakes in all honey samples. Neonicotinoids concentrations and detection frequencies in honey samples and its health risk varied with production region, commercial value of nectariferous plants, number of nectariferous plants, and sale price. The results suggested extensive residues of neonicotinoids in honey in Chinese market with a variation by the characteristics of honey. The residues were likely to affect the health of honey bees, but showed no detectable effect on human health.

Emissions and light absorption of PM2.5-bound nitrated aromatic compounds from on-road vehicle fleets.

Vehicle emissions are an important source of nitrated aromatic compounds (NACs) in particulate size smaller 2.5 µm (PM2.5), which adversely affect human health and biodiversity, especially in urban areas. In this study, filter-based PM2.5 samples were collected during October 14-19, 2019, in a busy urban tunnel (approximately 35,000 vehicles per day) in south China to identify PM2.5-bound NACs. Among them, 2,8-dinitrodibenzothiophene, 3-nitrodibenzofuran and 2-nitrodibenzothiophene were the most abundant nitrated polycyclic aromatic hydrocarbons (NPAHs), while 2-methyl-4-nitrophenol, 2,4-dinitrophenol, 3-methyl-4-nitrophenol and 4-nitrophenol were the most abundant nitrophenols (NPs). The observed mean fleet emission factors (EFs) of NPAHs and NPs were 2.2 ± 2.1 and 7.7 ± 4.1 µg km-1, and were 2.9 ± 2.7 and 10.2 ± 5.4 µg km-1 if excluding electric and liquefied petroleum gas vehicles, respectively. Regression analysis revealed that diesel vehicles (DVs) had NPAH-EFs (55.3 ± 5.3 µg km-1) approximately 180 times higher than gasoline vehicles (GVs) (0.3 ± 0.2 µg km-1), and NP-EFs (120.6 ± 25.8 µg km-1) approximately 30 times higher than GVs (4.1 ± 0.2 µg km-1), and thus 89% NPAH emissions and 56% NP emissions from the onroad fleets were contributed by DVs although DVs only accounted for 3.3% in the fleets. Methanol solution-based light absorption measurements demonstrated that the mean incremental light absorption for methanol-soluble brown carbon at 365 nm was 6.8 ± 2.2 Mm-1, of which the 44 detected NACs only contributed about 1%. The mean EF of the 7 toxic NACs was approximately 3% that of the 16 priority PAHs; However, their benzo(a)pyrene toxic equivalence quotients (TEQBaP) could reach over 25% that of the PAHs. Moreover, 6-nitrochrysene mainly from DVs contributed 93% of the total TEQBaP of the NACs. This study demonstrated that enhancing DV emission control in urban areas could benefit the reduction of exposure to air toxins such as 6-nitrochrysene.

Trace determination of imidacloprid and its major metabolites in wheat-soil system.

Trace analysis method is a reliable basis for studying the translocation and metabolism of imidacloprid used as an insecticide in wheat, and it clarifies whether biologically active metabolites including residual imidacloprid, have long-lasting insecticidal potency against wheat aphids under seed treatment during the entire growth period. In this study, a highly sensitive analytical method was established to determine the residues of imidacloprid and its six metabolites (5-hydroxy imidacloprid, imidacloprid olefin, imidacloprid guanidine, imidacloprid urea, 6-chloronicotinic acid, and imidacloprid nitrosimine) in wheat-soil systems, such as in wheat leaves, wheat ears, wheat grains, roots, and soil. All the compounds were extracted using an ACN:water (8:2, v/v) mixture and purified by dispersive solid-phase extraction. The average recoveries ranged from 74.4% to 109.5% for all matrices, with intra- and inter-day variations of less than 14.9%. The limit of quantitation was in the range of 0.001-0.005 mg/kg. The method is demonstrated to be sensitive and accurate for monitoring imidacloprid and its metabolites at trace levels during the entire growth period under field conditions.

Chemical composition, sources and optical properties of nitrated aromatic compounds in fine particulate matter during winter foggy days in Nanjing, China.

Functionalized aromatic compounds are one of the most important light-absorbing organic chromophores - so-called brown carbon (BrC) - in fine particulate matter (PM2.5). In this study, we conducted a wintertime field campaign to measure eight nitrated aromatic compounds (NACs) in PM2.5 with offline analysis techniques, including liquid chromatograph mass spectrometer (LC-MS) and aerodyne high-resolution aerosol mass spectrometer (AMS) measurements, during foggy and nonfoggy days in suburban Nanjing in the Yangtze River Delta region, China. On average, 4-nitrophenol could be one of the most important light absorbing materials in the observed BrC, which accounted for over 40% of the mass concentration of identified chromophores. The mass concentration of 2-methyl-4-nitrophenol and 2,6-dimethyl-4-nitrophenol were evidently increased during foggy days, contribution of which to total NACs were increased by 10% and 5%, respectively. Positive matrix factorization analysis of combining LC-MS and AMS dataset was performed to identify the primary and secondary sources of NACs. Primary sources, e.g., traffic and solid-fuel combustion, accounted for 71% of the sum of 4-nitrophenol, 2,6-dimethyl-4-nitrophenol and 3-nitrosalicylic acid, suggesting important contribution of primary emissions to these NACs. The contribution of secondary sources, associated with two oxygenated organic aerosols, could contribute 66% to 4-nitrophenol, reflecting the link of such nitrated aromatic compounds to secondary organic aerosol source. Together with optical measurements, 4-nitrophenol presented a high contribution (>50%) to the identified BrC absorbance in the light range 250 and 550 nm was observed. This could highlight an important role of such NACs in ambient BrC light absorption, despite its mass contribution to total organic carbon was negligible. Our work could improve the understanding of the links between optical properties and chemical composition of BrC, and the difference between BrC chromophores from nonfoggy days and foggy days under the typical polluted atmospheric conditions.