Swellable microneedle-coupled light-addressable photoelectrochemical sensor for in-situ tracking of multiple pesticides pollution in vivo.

In vivo monitoring of multiple pesticide contamination is of great significance for evaluating the health risks of different pesticides, agricultural production safety, and ecological and environmental assessment. Here, we report a hydrogel microneedle array coupled light-addressable photoelectrochemical sensor for tracking multiple pesticide uptake and elimination in living animals and plants, holding three prominent merits: i) enables in-situ detection of in vivo pesticides, avoiding cumbersome and complex sample transportation and handling processes; ii) allows repeated in vivo sampling of the same organism, improving tracking test controllability and accuracy; iii) avoids lethal sampling, providing a better understanding of the pesticides fate in living organisms. The coupled sensor is mechanically robust for withstanding more than 0.35 N per needle and highly swellable (800 %) for timely extraction of sufficient in vivo solution for analysis. For proof-of-concept, it achieves in-situ detection of atrazine, acetamiprid, and carbendazim efficiently and quantitatively in artificial agarose skin models, mouse skin interstitial fluids, and plant leaves with little inflammatory reaction. This simple, highly integrated, minimally invasive, and high-throughput in vivo monitoring method is ideal for future field environmental monitoring and plant and animal disease diagnosis.

Spatiotemporal variation, fluxes and risk evaluation of neonicotinoid insecticides within the midsection of Yangtze River, China: An exploration as ecological protection threshold.

Neonicotinoid insecticides (NNIs) have attracted global concern due to its extensive use in agricultural activities and their potential risks to the animal and human health, however, there is limited knowledge on the regional traits and ecological risks of NNIs in the aquatic environments. We herein investigated the occurrence of NNIs within the midsection of Yangtze River in China, offering the inaugural comprehensive report on NNIs within this region. In this study, eleven NNIs were analyzed in 108 river water and sediment samples from three seasons (normal, dry and wet season). We detected a minimum of seven NNIs in the water and four NNIs in the sediment, with total concentrations ranging from 12.33 to 100.5 ng/L in water and 0.08-5.68 ng/g in sediment. The levels of NNIs in both river water and sediment were primarily influenced by the extent of agricultural activities. The estimated annual load of NNIs within the midsection of Yangtze River totaled 40.27 tons, April was a critical contamination period. Relative potency factor (RPF) analysis of the human exposure risk revealed that infants faced the greatest exposure risk, with an estimated daily intake of 11.27 ng kg-1∙bw∙d-1. We established the acute and chronic thresholds for aquatic organisms by employing the Species Sensitive Distribution (SSD) method (acute: 384.1 ng/L; chronic: 168.9 ng/L). Based on the findings from this study, 33% of the river water samples exceeded the chronic ecological risks thresholds, indicating the urgent need for intervention programs to guarantee the safety of the river for aquatic life in the Yangtze River Basin.

The fate and transport of neonicotinoid insecticides and their metabolites through municipal wastewater treatment plants in South China.

Neonicotinoid insecticides (NEOs) have gained widespread usage as the most prevalent class of insecticides globally and are frequently detected in the environment, posing potential risks to biodiversity and human health. Wastewater discharged from wastewater treatment plants (WWTPs) is a substantial source of environmental NEOs. However, research tracking NEO variations in different treatment units at the WWTPs after being treated by the treatment processes remains limited. Therefore, this study aimed to comprehensively investigate the fate of nine parent NEOs (p-NEOs) and five metabolites in two municipal WWTPs using distinct treatment processes. The mean concentrations of ∑NEOs in influent (effluent) for the UNITANK, anaerobic-anoxic-oxic (A2/O), and cyclic activated sludge system (CASS) processes were 189 ng/L (195 ng/L), 173 ng/L (177 ng/L), and 123 ng/L (138 ng/L), respectively. Dinotefuran, imidacloprid, thiamethoxam, acetamiprid, and clothianidin were the most abundant p-NEOs in the WWTPs. Conventional wastewater treatment processes were ineffective in removing NEOs from wastewater (-4.91% to -12.1%), particularly major p-NEOs. Moreover, the behavior of the NEOs in various treatment units was investigated. The results showed that biodegradation and sludge adsorption were the primary mechanisms responsible for eliminating NEO. An anoxic or anaerobic treatment unit can improve the removal efficiency of NEOs during biological treatment. However, the terminal treatment unit (chlorination disinfection tank) did not facilitate the removal of most of the NEOs. The estimated total amount of NEOs released from WWTPs to receiving waters in the Pearl River of South China totaled approximately 6.90-42.6 g/d. These findings provide new insights into the efficiency of different treatment processes for removing NEOs in current wastewater treatment systems.

Ag-coated tetrapod gold nanostars (Au@AgNSs) for acetamiprid determination in tea using SERS combined with microfluidics.

Acetamiprid is an organic and highly toxic compound. Despite being widely used as a pesticide agent on a large scale, acetamiprid poses numerous health risks to living organisms, particularly humans. Herein, a strategy for the detection of acetamiprid in tea employing surface-enhanced Raman scattering (SERS) technology incorporated with a microfluidic chip was developed. Significantly, a seed-mediated growth approach was utilized to engineer Ag-coated tetrapod gold nanostars (core-shell Au@AgNSs) with four sharp tips. The synthesized Au@AgNSs showed an enhancement factor of 7.2 × 106. Solid works was used to figure out the two-channel microfluidic chip featuring four circular split hybrid structures, and COMSOL (Software for Multiphysics Simulation) was utilized to model the fusion effect between the substrate (Au@AgNSs) and the sample (acetamiprid). For the first time, the core-shell Au@AgNSs and acetamiprid were fused in the microfluidic channel to facilitate the detection of acetamiprid using SERS. The outcomes pointed out that the standard curve correlation coefficient between SERS intensity (876 cm-1) and the concentration of acetamiprid in tea specimens was calculated as 0.991, while the limit of detection (LOD) was 0.048 ng mL-1, which is well below the minimum limit set by the European Union (10 ng mL-1). Thus, the developed technique combining SERS and microfluidics demonstrated high potential for the rapid and efficient detection of acetamiprid in tea.

Raman silent region - based method for detection of pesticides with cyano group.

Based on the fact that not all chemical substances possess good Raman signals, this article focuses on the Raman silent region signals of pesticides with cyano group. Under the optimized conditions of methanol-water (1:1, v/v) as the solvent, irradiation at 302 nm light source for 20 min, and the use of 0.5 mol/L KI as the aggregating agent, Surface-enhanced Raman spectroscopy (SERS) method for azoxystrobin detection was developed by the Raman silent region signal of 2230 cm-1, and verified by detecting the spiked grapes with different concentrations of azoxystrobin. Other four pesticides with cyano group also could be identified at the peak of 2180 cm-1, 2205 cm-1, 2125 cm-1, and 2130 cm-1 for acetamiprid, phoxim, thiacloprid and cymoxanil, respectively. When azoxystrobin or acetamiprid was mixed respectively with chlorpyrifos without cyano group, their SERS signals in the Raman silent region of chlorpyrifos were not interfered, while mixed with cymoxanil in different ratios (1:4, 1:1 and 4:1), respectively, each two pesticides with cyano group could be distinguished by the changes in the Raman silent region. In further, four pesticides with or without cyano group were mixed together in 1:1:1:1 (acetamiprid, cymoxanil, azoxystrobin chlorpyrifos), and each pesticide still could be identified even at 0.5 mg/L. The results showed that the SERS method combined with UV irradiation may provide a new way to monitor the pesticides with C≡N performance in the Raman silent region without interference from the food matrix.

Development of aptamer surface-enhanced Raman spectroscopy sensor based on Fe3O4@Pt and Au@Ag nanoparticles for the determination of acetamiprid.

As a common chlorinated nicotinic pesticide with high insecticidal activity, acetamiprid has been widely used for pest control. However, the irrational use of acetamiprid will pollute the environment and thus affect human health. Therefore, it is crucial to develop a simple, highly sensitive, and rapid method for acetamiprid residue detection. In this study, the capture probe (Fe3O4@Pt-Aptamer) was connected with the signal probe (Au@DTNB@Ag CS-cDNA) to form an assembly with multiple SERS-enhanced effects. Combined with magnetic separation technology, a SERS sensor with high sensitivity and stability was constructed to detect acetamiprid residue. Based on the optimal conditions, the SERS intensity measured at 1333 cm-1 is in relation to the concentration of acetamiprid in the range 2.25 × 10-9-2.25 × 10-5 M, and the calculated limit of detection (LOD) was 2.87 × 10-10 M. There was no cross-reactivity with thiacloprid, clothianidin, nitenpyram, imidacloprid, and chlorpyrifos, indicating that this method has good sensitivity and specificity. Finally, the method was applied to the detection of acetamiprid in cucumber samples, and the average recoveries were 94.19-103.58%, with RSD < 2.32%. The sensor can be used to analyse real samples with fast detection speed, high sensitivity, and high selectivity.

Exposure of Male Farmers and Nonfarmers to Neonicotinoid Pesticides in the South-West and Littoral Regions of Cameroon: A Comparative Study.

Pesticides, especially the newly developed neonicotinoids, are increasingly used in many countries around the world, including Cameroon, to control pests involved in crop destruction or disease transmission. Unfortunately, the pesticides also pose tremendous environmental problems because a predominant amount of their residues enter environmental matrices to affect other nontargeted species including humans. This therefore calls for continuous biomonitoring of these insecticides in human populations. The present study sought to assess the neonicotinoid insecticide exposures in two agrarian regions of Cameroon, the South-West region and Littoral region. The study involved 188 men, including 125 farmers and 63 nonfarmers. Spot urine samples were obtained from these subjects and subjected to liquid chromatographic-tandem mass spectrometric analysis for concentrations of neonicotinoid compounds, including acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, nitenpyram, thiamethoxam, and N-dm-acetamiprid. Neonicotinoid compounds were detected in all study participants, and residues of all the screened pesticides were detected among participants. N-dm-Acetamiprid and imidacloprid were the most prevalent among the subjects (100.0% and 93.1%, respectively), whereas nitenpyram was less common (3.2%). The median values of imidacloprid and total urinary neonicotinoid concentrations were elevated among farmers (0.258 vs. 0.126 µg/L and 0.829 vs. 0.312 µg/L, respectively). Altogether the findings showed that both the farmer and nonfarmer study populations of Cameroon were exposed to multiple residues of neonicotinoids, with relatively higher levels of pesticides generally recorded among farmers. Although exposure levels of the neonicotinoids were generally lower than their respective reference doses, these results warrant further research on the health risk evaluation of multiple residues of the pesticides and reinforcement of control measures to minimize the exposure risks, especially among farmers. Environ Toxicol Chem 2024;43:952-964. © 2024 SETAC.

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.

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.

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.

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.

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%.

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.

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.

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.