Neonicotinoid residues in fruits and vegetables in Shenzhen: Assessing human exposure and health risks.

The extensive use of neonicotinoids (NEOs) in agricultural production has led to their pervasive presence in various environmental matrices, including human samples. Given the central role of fruits and vegetables in daily human diets, it is crucial to evaluate the levels of NEOs residues and their potential health risks. In this study, 3104 vegetable samples and 1567 fruit samples from the Shenzhen city were analyzed. Using the relative potency factor (RPF) method, the residue levels of six representative neonicotinoids, including imidacloprid (IMI), acetamiprid (ACE), thiamethoxam (THM), dinotefuran (DIN), clothianidin (CLO), thiacloprid (THI), were systematically evaluated. The estimated daily intake (EDI), hazard quotient (HQ), and hazard index (HI) for both children and adults were calculated to gauge the prevalence and potential health risks of NEOs in fruits and vegetables. Acetamiprid (ACE) was the most frequently detected NEO in vegetables (69.4%) and fruits (73.9%), making it the predominant contributor to total residues. Further analyses indicated notably higher levels of imidacloprid-equivalent total neonicotinoids (IMIRPF) in root and tuber vegetables (3025 µg/kg) and other fruits (243 µg/kg). A significant strong positive correlation (r = 0.748, P < 0.05) was observed between thiamethoxam (THM) and clothianidin (CLO), possibly due to their shared metabolic pathways. Although the mean HI values for adults and children from daily fruit (adults: 0.02, children: 0.01) and vegetable (adults: 0.02, children: 0.03) intake were generally below safety thresholds, some maximum HI values exceeded these limits, indicating that the potential health risks associated with NEOs exposure should not be overlooked.

[Determination of eight neonicotinoid pesticides in wastewater by solid phase extraction combined with liquid chromatography-tandem mass spectrometry].

Neonicotinoid pesticides are a relatively new class of pesticides that have garnered significant attention owing to their potential ecological risks to nontarget organisms. A method combining solid phase extraction with liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) was developed for the rapid and accurate detection of eight neonicotinoid pesticides (dinotefuran, E-nitenpyram, thiamethoxam, clothianidin, imidacloprid, imidaclothiz, acetamiprid, and thiacloprid) in wastewater. The chromatographic mobile phase and MS parameters were selected, and a single-factor method was used to determine the optimal column type, extraction volume, sample loading speed, and pH for SPE. The optimal parameters were as follows: column type, HLB column (500 mg/6 mL); sample extraction volume, 500 mL; sample loading speed, 10 mL/min; and sample pH, 6-8. The matrix effects of the wastewater samples were reduced by optimizing the chromatographic gradient-elution program, examining the dilution factor of the samples, and using the isotope internal standard calibration method. Prior to analysis, the wastewater samples were diluted 5-fold with ultrapure water for pretreatment. Subsequently, 2 mmol/L ammonium acetate aqueous solution containing 0.1% (v/v) formic acid and methanol was used as mobile phases for gradient elution on a ZORBAX Eclipse Plus C18 column (100 mm×2.1 mm, 1.8 µm). The samples were quantified using positive-ion multiple reaction monitoring (MRM) mode for 10 min. Imidacloprid-d4 was used as the isotope internal standard. The SPE process was further optimized by applying response surface methodology to select the type and mass of rinsing and elution solvents. The optimal pretreatment of the SPE column included rinsing with 10% methanol aqueous solution and elution with methanol-acetonitrile (1∶1, v/v) mixture (7 mL). The eight neonicotinoid pesticides showed satisfactory linearity within the relevant range, with linear correlation coefficients (r) all greater than 0.9990. The method detection limits (MDLs) ranged from 0.2 to 1.2 ng/L, and the method quantification limits (MQLs) ranged from 0.8 to 4.8 ng/L. The average recoveries of the eight neonicotinoid pesticides were in the range of 82.6%-94.2% at three spiked levels, with relative standard deviations (RSDs) ranging from 3.9% to 9.4%. Finally, the optimized method was successfully applied to analyze wastewater samples collected from four sewage treatment plants. The results indicated that the eight neonicotinoid pesticides could be generally detected at concentrations ranging from not detected (ND) to 256 ng/L. The developed method has a low MDL and high accuracy, rendering it a suitable choice for the trace detection of the eight neonicotinoid pesticides in wastewater when compared with other similar methods. The proposed method can be utilized to monitor the environmental impact and assess the potential risks of neonicotinoid pesticides in wastewater, thus promoting the protection of nontarget organisms and the sustainable use of these pesticides in agriculture.

Potential exposure of honey bees to neonicotinoid seed treatments in US rice.

Neonicotinoid insecticide seed treatments are commonly used in rice (Oryza sativa) production to control rice water weevil (Lisorhoptrus oryzophilus). With the use of neonicotinoid seed treatments, there is potential that honey bees (Apis mellifera) could be exposed to neonicotinoids through translocation to the pollen. Studies were conducted in 2015 and 2016 to determine the level of neonicotinoids present in flag leaves, pollen, and grain of rice. Thiamethoxam was applied as a seed treatment and foliar prior to flooding. Clothianidin was applied as a seed treatment and as a foliar at a preflood and postflood timing. Subsamples of flag leaves, pollen, and grain were analyzed for positive neonicotinoid detections and abundance. Thiamethoxam was detected in 8.9% of samples and clothianidin was detected in 1.4% of samples. For both thiamethoxam and clothianidin, more positive samples were observed in flag leaf samples than in pollen or grain. An average of 4.30 ng/g of thiamethoxam was detected in flag leaves from seed-applied thiamethoxam. An average of 1.25 ng/g of clothianidin was found in flag leaves from a preflood application of clothianidin. A survey of honey bees present in rice fields was conducted in Mississippi and Arkansas to determine the abundance of honey bees present in rice fields based on the time of day. Honey bee densities were low in rice, with less than 5% and 3% positive detections observed in Mississippi and Arkansas, respectively. More positive detections and higher densities of honey bees were observed for mid-day sampling than for morning or evening sampling.

First Detection of Thiamethoxam in a Free-Ranging Insectivorous Bird After its Agricultural Use Ban in Spain.

Neonicotinoids are insecticides used worldwide in phytosanitary and biocidal products and veterinary pharmaceuticals. Recently, some restrictions and bans have been imposed due to their adverse effects on nontarget invertebrates, including pollinators. Although they may have direct and indirect effects on wild vertebrates, few studies have assessed exposure to these compounds in wild birds, so our knowledge remains limited. In the present pilot study we have assessed the prevalence of seven neonicotinoid insecticides and some of their metabolites in whole blood samples from 19 European roller (Coracias garrulus) nestlings and five adult common kestrels (Falco tinnunculus) in an area treated with neonicotinoids to control the palm weevil (Rynchophorus ferrugineus) in southeastern Spain. One European roller nestling born in a palm tree was positive for thiamethoxam, with a concentration of 2.26 ng mL-1, but no residues of neonicotinoids or their metabolites were found in adult common kestrels. Future studies are needed to elucidate potential exposure to neonicotinoids at different times of the year. To our knowledge, this is the first report of the presence of thiamethoxam residues in whole blood of a wild bird species after its ban in Spain. Environ Toxicol Chem 2024;43:1836-1843. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Aptamer-based biosensors for the detection of neonicotinoid insecticides in environmental samples: A systematic review.

Neonicotinoids, sometimes abbreviated as neonics, represent a class of neuro-active insecticides with chemical similarities to nicotine. Neonicotinoids are the most widely adopted group of insecticides globally since their discovery in the late 1980s. Their physiochemical properties surpass those of previously established insecticides, contributing to their popularity in various sectors such as agriculture and wood treatment. The environmental impact of neonicotinoids, often overlooked, underscores the urgency to develop tools for their detection and understanding of their behavior. Conventional methods for pesticide detection have limitations. Chromatographic techniques are sensitive but expensive, generate waste, and require complex sample preparation. Bioassays lack specificity and accuracy, making them suitable as preliminary tests in conjunction with instrumental methods. Aptamer-based biosensor is recognized as an advantageous tool for neonicotinoids detection due to its rapid response, user-friendly nature, cost-effectiveness, and suitability for on-site detection. This comprehensive review represents the inaugural in-depth analysis of advancements in aptamer-based biosensors targeting neonicotinoids such as imidacloprid, thiamethoxam, clothianidin, acetamiprid, thiacloprid, nitenpyram, and dinotefuran. Additionally, the review offers valuable insights into the critical challenges requiring prompt attention for the successful transition from research to practical field applications.

Risk analysis for groundwater intakes based on the example of neonicotinoids.

Neonicotinoids are a class of broad-spectrum insecticides that are dominant in the world market. They are widely distributed in the environment. Understanding the sources, distribution, and fate of these contaminants is critical to mitigating their effects and maintaining the health of aquatic ecosystems. Contamination of surface and groundwater by neonicotinoids has become a widespread problem worldwide, requiring comprehensive action to accurately determine the mechanisms behind the migration of these pesticides, their properties, and their adverse effects on the environment. A new approach to risk analysis for groundwater intake contamination with emerging contaminants was proposed. It was conducted on the example of four neonicotinoids (acetamiprid, clothianidin, thiamethoxam, and imidacloprid) in relation to groundwater accessed by a hypothetical groundwater intake, based on data obtained in laboratory tests using a dynamic method (column experiments). The results of the risk analysis conducted have shown that in this case study the use of acetamiprid and thiamethoxam for agricultural purposes poses an acceptable risk, and does not pose a risk to the quality of groundwater extracted from the intake for food purposes. Consequently, it does not pose a risk to the health and life of humans and other organisms depending on that water. The opposite situation is observed for clothianidin and imidacloprid, which pose a higher risk of groundwater contamination. For higher maximum concentration of neonicotinoids used in the risk analysis, the concentration of clothianidin and imidacloprid in the groundwater intake significantly (from several to several hundred thousand times) exceeds the maximum permissible levels for drinking water (<0.1 µg/L). This risk exists even if the insecticides containing these pesticides are used according to the information sheet provided by the manufacturer (lower maximum concentration), which results in exceeding the maximum permissible levels for drinking water from several to several hundred times.

Greenhouse cultivation enhances pesticide bioaccumulation in cowpeas following repeated spraying.

Understanding pesticide residue patterns in crops is important for ensuring human health. However, data on residue accumulation and distribution in cowpeas grown in the greenhouse and open field are lacking. Our results suggest that acetamiprid, chlorantraniliprole, cyromazine, and thiamethoxam residues in greenhouse cowpeas were 1.03-15.32 times higher than those in open field cowpeas. Moreover, repeated spraying contributed to the accumulation of pesticide residues in cowpeas. Clothianidin, a thiamethoxam metabolite, was detected at 1.04-86.00 µg/kg in cowpeas. Pesticide residues in old cowpeas were higher than those in tender cowpeas, and the lower half of the plants had higher pesticide residues than did the upper half. Moreover, pesticide residues differed between the upper and lower halves of the same cowpea pod. Chronic and acute dietary risk assessments indicated that the human health risk was within acceptable levels of cowpea consumption. Given their high residue levels and potential accumulation, pesticides in cowpeas should be continuously assessed.

A study of the pesticide residues in rapeseeds in China: Levels, distribution and health risk assessment.

The aim of this survey was to evaluate the residue levels, distribution and exposure risk of the 38 most commonly used pesticides in rapeseed samples collected from the main production areas in China over a two-year period. The sampling area covered 12 provinces, including Guizhou, Shaanxi, Yunnan, Hunan, Jiangxi, Sichuan, Chongqing, Anhui, Henan, Hubei, Zhejiang, and Jiangsu provinces. The pesticide residues were determined using a QuEChERS (Quick Easy Cheap Effective Rugged and Safe) method coupled with gas chromatography-tandem mass spectrometry and liquid chromatography-tandem mass spectrometry. 8.4% of the rapeseed samples contained pesticides with a residue level ranging from 0.001 to 0.634 mg/kg. The detected analytes were imidacloprid, quizalofop-P-ethyl, thiamethoxam, paclobutrazol, prochloraz, tebuconazole, difenoconazole, s-metolachlor, carbofuran, and carbendazim. The concentrations of four analytes, including thiamethoxam, difenoconazole, carbendazim and prochloraz, exceeded the maximum residue level set by the Chinese government for rapeseed, with exceedance rates of 0.1%, 0.1%, 0.1%, and 1.1%, respectively. Based on the index of quality for residues (IqR) values, 91.6% of the total rapeseed samples had an IqR category of Excellent (IqR = 0). Only 1.5% of the tested samples were of inadequate quality. Furthermore, the assessment of chronic and acute exposure, as well as health risks associated with pesticide residues in rapeseed, was conducted for different age groups within the Chinese population, including adults (6-14 years), children (15-49 years), and the elderly (50-74 years). The results of this assessment indicated that pesticide residues in rapeseed cultivated in China are not expected to be of short- or long-term risks to the Chinese customers.

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.

Residual Pattern of Chlorantraniliprole, Thiamethoxam, Flubendiamide and Deltamethrin in Tomato Fruit and Soil.

Tomato, Lycopersicon esculentum L. is grown widely as an important day-to-day demand vegetable. The crop is attacked by various polyphagous insect pests like tomato fruit borer, stink bug, cabbage looper, flea beetle, aphids, whitefly, two-spotted spider mite, etc., and oligophagous insects like leaf-miner, five-spotted hawkmoth, etc. To combat the damage and yield loss, various chemical insecticides were sprayed on tomatoes under field conditions. The residual pattern of insecticides like chlorantraniliprole, thiamethoxam, flubendiamide, and deltamethrin residues was studied following applications of chlorantraniliprole 18.5% SC (Coragen) @ 30 g a.i./ha, thiamethoxam 25% WG (Actara) @ 50 g a.i./ha, flubendiamide 39.35 M/M SC (Fame) @ 48 g a.i./ha and deltamethrin 2.8% EC (Decis 100) @ 12.5 g a.i./ha using Reverse Phase High-Performance Liquid Chromatography (RP-HPLC). Fruit samples were collected at 0 (1 h after application), 1, 2, 3, 5, 7 days and at harvest time. All the residues of insecticides such as chlorantraniliprole (0.09 mg kg- 1), thiamethoxam (0.03 mg kg- 1), flubendiamide (0.02 mg kg- 1), and deltamethrin (0.01 mg kg- 1) were persisted up to 5th day. There were no residues found at harvest time. The residues of chlorantraniliprole and deltamethrin persisted up to 3rd day of spraying whereas the residues of flubendiamide and thiamethoxam were not detected on the same day in the soil.

Multivariate effect of inorganic wastewater matrix on the removal of pesticides by solar photo-Fenton.

An amount of works has reported the effect of wastewater matrix composition on pollutants removal by different AOPs. The biggest challenge is that each wastewater source has a challenging composition (organic and inorganic compounds, pollutants, etc.) and not only the concentration of all these species but also the interaction between them may affect the effectiveness of the studied process. This work has been carried out to evaluate the photo-degradation kinetics of six different pesticides (flutriafol, imidacloprid, myclobutanil, pirimicarb, thiamethoxam and triadimenol) by solar photo-Fenton (SPF) process at acidic pH. First, oxidant concentration (H2O2) was optimized with an actual WWTP effluent. Then, the process was validated with two different secondary and tertiary WWTP effluents, in which main intermediate transformation by-products were identified. Finally, the effect of the inorganic water matrix components (bicarbonate, chloride, sulphate, nitrate and phosphate) was evaluated by a multivariate analysis. Once H2O2 has been optimized at 30 mg L-1, the photo-degradation efficiency of pesticides in real wastewater samples was compared. DOC content of both secondary and tertiary WWTP effluents was dropped by 67%. The identification of the main intermediate transformation by-products (such as 1H-1,2,4-triazole, desmethyl-formamido pirimicarb, thiamethoxam urea, chloronicotinic acid and imidacloprid urea) was reviewed. Following, the multivariate analysis on pesticides photo-degradation, generally, predicted four significant effects in common for the studied pesticides: a positive effect (interaction bicarbonate/nitrate) and three negative ones (chloride, phosphate and the interaction chloride/sulphate); among others. In addition, optimum values of inorganic ion concentrations, to obtain an optimum desirability on studied pesticides removal by SPF at acidic pH, were also evaluated.

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.

Residue analysis and dietary risk assessment of thiamethoxam, flonicamid and their metabolites in cucumber under field conditions in China.

Thiamethoxam and flonicamid are two representative insecticides of neonicotinoids which are used to treat cucumber aphids, causing food safety and human health problems. A 60% thiamethoxam-flonicamid commercial mixture water dispersible granule (WDG) is being prepared for registering in China, so it is essential to investigate the residue levels of these neonicotinoids and their metabolites in cucumber and evaluate the dietary risks of these insecticides. We developed a modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method combined with high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) for the simultaneous determination of thiamethoxam and its metabolite clothianidin, flonicamid and its metabolites 4-trifluoromethylnicotinic acid (TFNA), 4-trifluoromethilnicotinamide (TFNA-AM), 4-(trifluoromethyl) nicotinol glycine (TFNG) in cucumber. Method validation indicated good selectivity, linearity (r ≥ 0.9996), accuracy (recoveries of 80-101%), precision (relative standard deviations (RSD) ≤ 9.1%), sensitivity (limits of detection (LOD), 0.28-1.44 × 10-3 mg/L; limits of quantification (LOQ), 0.01 mg/kg) and minor matrix effect (ME) ( ≤|± 5%|). In the terminal residue trials under good agricultural practice (GAP) conditions, the residue levels of six analytes in cucumber samples were ˂0.01-0.215 mg/kg after application trice with an interval of 7 days based on pre-harvest interval (PHI) of 3 days under the high recommended dosage of 54 g active ingredient/ha (g a.i./ha). Relevant toxicological, residual chemistry parameters and dietary consumption of the residents were applied to assess the potential risk of dietary exposure. The chronic and acute dietary exposure assessment risk quotient (RQ) values were less than 1. The above results indicated that the potential dietary intake risk of this formulation was negligible to consumers.

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

Dust abraded from thiamethoxam-treated seed during sowing: Refining the risk assessment for native bees in Brazil.

During sowing using pneumatic machinery, dust may be abraded from pesticide-treated seed and contaminate adjacent bee-attractive off-crop areas. This study quantified the risk to native bees of dust released during sowing of Brazilian crop seeds treated with a thiamethoxam formulation (Cruiser 350FS). To address toxicity to native bees, adult acute contact LD50 data for thiamethoxam were collated from the literature, a species sensitivity distribution generated, and the HD5 calculated. The LD50 HD5 was used to refine the default safety factor applied to the honeybee acute contact LD50 from 10 to 5.45 for thiamethoxam. Crop-specific abraded dust data (Heubach dust and Heubach AI) were generated for seeds treated with Cruiser 350FS sourced from on-farm and industrial facilities. The mean Heubach dust levels was ranked as cotton = maize > sunflower = soybean > drybean. There was no correlation between the measured residues of thiamethoxam (Heubach AI) and those estimated in dust based on the thiamethoxam content of Cruiser 350FS. A hazard quotient (HQ) for each crop (based on application rate, the default dust deposition factor, and the honeybee contact LD50/10) identified risks during sowing for all crops. Refinement of the application rate with the measured 90th percentile Heubach dust (assuming 100% thiamethoxam) resulted in sowing of industrially treated soybean and on-farm treated cotton being identified as risks. Further refinement using either the measured 90th percentile Heubach AI or the acute contact LD50 (HD5 ) resulted in sowing of all crops treated with Cruiser 350FS as being identified as low risk. Similar high quality seed treatment should be demonstrated for other formulations containing insecticides with high toxicity to bees. Data on dust drift from machinery and crops more representative of those in Brazil may allow further refinement of the default dust deposition value of 17% used in this study. Integr Environ Assess Manag 2023;19:1361-1373. © 2023 SETAC.

Modified QuEChERS Method for Extracting Thiamethoxam and Imidacloprid from Stingless Bees: Development, Application, and Green Metrics.

In the present study, a method for the determination of residues of the neonicotinoid insecticides thiamethoxam and imidacloprid in the stingless bee Melipona scutellaris Latreille (1811) was optimized through a factorial design, tested using green metrics, and then applied to exposed bees. It combines the extraction with a modified quick, easy, cheap, effective, rugged, and safe method and the determination by liquid chromatography-tandem mass spectrometry analysis. Different parameters such as the mass of the sample, dispersive sorbents, and elution solvents were assessed. Method validation parameters were checked and include sensitivity, specificity, and linearity. The limit of quantification of 0.0025 µg g-1 was obtained for both insecticides, where accuracy was 94%-100% with satisfactory intraday and interday precisions (relative standard deviation <10%). The qualified method was applied to orally and topically exposed bee samples, and the results indicated that it is suitable for the determination and quantification of neonicotinoid pesticide residues in this species. Moreover, green analytical metrics like the National Environmental Methods Index, Eco Scale score, high-performance liquid chromatography with an environmental assessment tool (HPLC-EAT), waste generation, and amount of sample were compared with methods described in the literature involving neonicotinoid analysis in honeybees. As a result, the present study displayed the highest Eco Scale score and HPLC-EAT score and the second smallest amount of sample and waste generated. Thus, the method meets green analytical metrics more than other methods. In this sense, besides the application, the multicriteria decision analysis tool employed suggests that this is a good option as a green analytical method. Environ Toxicol Chem 2022;41:2365-2374. © 2022 SETAC.

Ethanol-ammonium sulfate system based modified quick, easy, cheap, effective, rugged, and safe method for the determination of four neonicotinoid pesticide and metabolite residues in two canned fruits.

As the pesticide and its metabolite residues in processed fruits could become a significant route of human exposure. The work presented herein focuses on developing a feasible quick, easy, cheap, effective, rugged, and safe method with improved extraction and cleanup system for the determination of imidacloprid, acetamiprid, thiamethoxam, and clothianidin (a metabolite of thiamethoxam) in canned fruits. The low toxic solvent ethanol was used to extract the analytes, and ammonium sulfate was used to promote phase separation. Moreover, the carboxylated multi-walled carbon nanotube acted as the clean-up sorbent for the removal of high solubility impurities. The proposed method was validated with fortified real samples at different concentration levels (20-200 µg/kg). Recoveries obtained from three spiked levels (20, 50, and 200 µg/kg) ranged from 74.9 to 86.4% with relative standard deviations of the intra-day and inter-day in the range of 0.8-5.5 and 2.0-7.1%, respectively. The limits of detection ranged from 0.2 to 0.5 and 0.2 to 0.6 µg/kg for orange and peach, respectively. The results demonstrated that the proposed method could be considered appropriate, and comparatively lower toxic for the analysis of neonicotinoid pesticide residues in canned fruit.

Dissipation Behavior and Acute Dietary Risk Assessment of Thiamethoxam and Its Metabolite Clothianidin on Spinach.

Thiamethoxam and its metabolite clothianidin residues pose a potential threat to human health. This study aims to investigate the residue behavior and acute dietary risk assessment of thiamethoxam and clothianidin on spinach. Thiamethoxam and clothianidin were extracted using a quick, easy, cheap, effective, rugged, safe (QuEChERS) method and analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). At spike levels from 0.01 to 5 mg kg−1, the average recoveries of both analytes were in the range of 94.5−105.5%, with relative standard deviations (RSDs) of 3.8−10.9%. The dissipation behavior of thiamethoxam followed first-order kinetics, with half-lives of ≤1.6 days. Clothianidin appeared readily as a plant metabolite with highest level exhibited during 3 to 5 days after application. Temperature and light may be two main factors for degradation of thiamethoxam. Besides, acute risk assessment of thiamethoxam and clothianidin was evaluated with risk quotients (RQs) <100%, which suggested a low health risk for all consumer groups of Chinese residents.

The fate of thiamethoxam and its main metabolite clothianidin in peaches and the wine-making process.

Thiamethoxam is widely used to control a large number of insect pests of peach crops. Understanding the fate of thiamethoxam and its main metabolite clothianidin in field peach, during storage, and in the processing of peach wine is of vital importance for food safety. The thiamethoxam and clothianidin were separated and determined by high-performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). Field and storage results showed that the half-lives of thiamethoxam were 4.9-5.5 and 10.3-15.8 days, respectively. The processing factors (PFs) of all the wine-making procedures were less than 1, and the PFs of the overall process ranged from 0.10 to 0.47. The highest elimination rate was obtained for thiamethoxam and clothianidin during the fermentation process. The results from this study could understand the dissipation kinetics and residual levels of thiamethoxam and clothianidin in peach, and also help to accurately assess their risks in the raw and wine-making process.

Fate of thiamethoxam from treated seeds in mesocosms and response of aquatic invertebrate communities.

Thiamethoxam is a neonicotinoid insecticide widely applied in the Canadian Prairies. It has been detected in surface waters of agro-ecosystems, including wetlands, but the potential effects on non-target invertebrate communities in these wetlands have not been well characterized. In an effort to understand better the fate of thiamethoxam in wetlands and the response of invertebrates (zooplankton and emergent insects), model systems were used to mimic wetland flooding into planted fields. Outdoor mesocosms were treated with a single application of thiamethoxam-treated canola seeds at three treatment levels based on a recommended seeding rate (i.e., 6 kg/ha; 1×, 10×, and 100× seeding rate) and monitored over ten weeks. The mean half-life of thiamethoxam in the water column was 6.2 d. There was no ecologically meaningful impact on zooplankton abundances or community structure among treatments. Statistically significant differences were observed in aquatic insect abundance between control mesocosms and the two greatest thiamethoxam treatments (10× and 100× seeding rate). The observed results indicate exposure to thiamethoxam at environmentally relevant concentrations likely does not represent a significant ecological risk to abundance and community structure of wetland zooplankton and emergent insects.