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.

Neonicotinoid insecticides in paddy fields: Dissipation dynamics, migration, and dietary risk.

Neonicotinoid insecticides (NNIs) have caused widespread contamination of multiple environmental media and posed a serious threat to ecosystem health by accidently injuring non-target species. This study collected samples of water, soil, and rice plant tissues in a water-soil-plant system of paddy fields after spaying imidacloprid (IMI), thiamethoxam (THM), and clothianidin (CLO) to analyze their distribution characteristics and migration procedures and to assess related dietary risks of rice consumption. In the paddy water, the concentrations of NNIs showed a dynamic change of increasing and then decreasing during about a month period, and the initial deposition of NNIs showed a trend of CLO (3.08 µg/L) > THM (2.74 µg/L) > IMI (0.97 µg/L). In paddy soil, the concentrations of the three NNIs ranged from 0.57 to 68.3 ng/g, with the highest residual concentration at 2 h after application, and the concentration trend was opposite to that in paddy water. The initial deposition amounts of IMI, THM, and CLO in the root system were 5.19, 3.02, and 5.24 µg/g, respectively, showing a gradual decrease over time. In the plant, the initial deposition amounts were 19.3, 9.36, and 52.6 µg/g for IMI, THM, and CLO, respectively, exhibiting concentration trends similar to those in the roots. Except for IMI in soil, the dissipation of the NNIs conformed to the first-order kinetic equation in paddy water, soil, and plant. The results of bioconcentration factors (BCFs) and translocation factor (TF) indicated that NNIs can be bi-directionally transported in plants through leaf absorption and root uptake. The risk of NNIs intake through rice consumption was low for all age groups, with a slightly higher risk of exposure in males than in females.

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.

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.

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.

Ubiquity of Amino Accelerators and Antioxidants in Road Dust from Multiple Land Types: Targeted and Nontargeted Analysis.

Amino accelerators and antioxidants (AAL/Os), as well as their degradation derivatives, are industrial additives of emerging concern due to their massive production and use (particularly in rubber tires), pervasiveness in the environment, and documented adverse effects. This study delineated their inter-regional variations in road dust collected from urban/suburb, agricultural, and forest areas, and screened for less-studied AAL/O analogues with high-resolution mass spectrometry. 1,3-Diphenylguanidine (DPG; median concentration: 121 ng/g) and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine quinone (6PPD-Q; 9.75 ng/g) are the most abundant congeners, constituting 69.7% and 41.4% of the total concentrations of AAL/Os (192 ng/g) and those of AAO transformation products (22.3 ng/g), respectively. The spatial distribution across the studied sites suggests evident human impacts, reflected by the pronounced urban signature and vehicle-originated pollution. Our nontargeted analysis of the most-contaminated road dust identified 16 AAL/O-related chemicals, many of which have received little investigation. Particularly, environmental and toxicological information remains extremely scarce for five out of the 10 most concerning compounds prioritized in terms of their dusty residues and toxicity including 1,2-diphenyl-3-cyclohexylguanidine (DPCG), N,N''-bis[2-(propan-2-yl)phenyl]guanidine (BPPG), and N-(4-anilinophenyl)formamide (PPD-CHO). Additionally, dicyclohexylamine (DChA), broadly applied as an antioxidant in automobile products, had an even greater median level than DPG. Therefore, future research on their health risks and (eco)toxic potential is of high importance.

Experimental evidence for clothianidin deposition in feathers of house sparrows after ingestion of sublethal doses treated seeds.

Bird feathers are commonly used to assess environmental contamination by chemical pollutants. However, although neonicotinoid insecticides are widely applied worldwide, feathers have rarely been used to survey the contamination by neonicotinoids in birds. To investigate whether clothianidin, one compound of the neonicotinoid class, is deposited into birds' feathers, we conducted an experiment with 56 wild male and female house sparrows dispatched in 7 aviaries. During this experiment, house sparrows were fed with certified organic seeds treated with clothianidin at an estimated concentration of 0.25 µg/g BW per day and per individual. We collected blood samples and plucked four tail feathers at the onset of the experiment to confirm that no birds were previously exposed to clothianidin. 35 days later, we collected blood samples and the newly grown feathers. Before exposure, a small number of birds showed very low clothianidin concentrations in plasma and feathers. After exposure, the plasma and the newly grown feathers of all birds contained clothianidin. Clothianidin concentrations in feathers were similar in both sexes, but the plasma of males contained clothianidin at higher concentrations than that of females. Our results confirm that ingested clothianidin transits in the plasma and is deposited in feathers during their growth. They also suggest substantial individual variation in the amounts of clothianidin transiting in the plasma and being deposited in feathers that may reflect variation in metabolism and/or access to food in relation to sex, social hierarchy and group dynamics. Whether increasing levels of exposure translate linearly or non-linearly (e.g. saturation process) into increasing clothianidin concentrations in bird plasma and feathers remains to be investigated. To conclude, these results confirm the relevance of using feathers to biomonitor the presence of neonicotinoids, but the relationship between the level of exposure and the concentrations found in feathers remains to be established.

Unique guanidine-conjugated catechins from the leaves of Alchornea rugosa and their autophagy modulating activity.

Natural guanidines, molecules that contain the guanidine moiety, are structurally unique and often exhibit potent biological activities. A phytochemical investigation of the leaves of Alchornea rugosa (Lour.) Müll.Arg. by MS/MS-based molecular networking revealed eight undescribed guanidine-flavanol conjugates named rugonines A-H. The chemical structures of the isolated compounds were comprehensively elucidated by NMR spectroscopy, HRESIMS, and circular dichroism (CD) analysis. All isolated compounds were tested for autophagosome formation in HEK293 cells stably expressing GFP-LC3. The results revealed that compounds rugonines D-G showed potential autophagy inhibitory activity.

Occurrence and risks of 23 tire additives and their transformation products in an urban water system.

Tire wear particles (TWPs) enter road surface with the friction between tires and road surfaces. Under the volatilization, leaching, and transformation action on TWPs by sunlight and rain, tire additives are released into urban water systems, such as surface rainfall runoff, wastewater treatment plants (WWTPs), receiving surface waters, and drinking water treatment plant (DWTP). In this study, we investigated the occurrence of 23 tire additives and their transformation products in the urban water system of the Pearl River Delta region, South China. Nineteen target compounds were detected in the surface runoff, with 1,3-Diphenylguanidine (DPG) showing highest maximum concentration of 58780 ng/L. Benzothiazole and its transformation products are detected at the frequency of 100 % with the total concentrations of 480-42160 ng/L. The antioxidant derivative N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-Q) was also detected up to 1562 ng/L, which was considerably higher than that of the parent compound 6PPD (the maximum concentration of 7.52 ng/L). Eleven and 8 compounds were detected in WWTPs influents and effluents, respectively, with removal rates of - 62-100 %. Seventeen compounds were detected in the receiving Zhujiang and Dongjiang rivers, while 9 compounds were detected in drinking water sources and DWTP samples. Road runoff, with total concentrations of target compounds up to 79200 ng/L, is suggested as the main non-point source for receiving rivers, while WWTPs effluents are the point sources due to incomplete removal of target compounds after accepting the initial runoff. 6PPD-Q and other 10 compounds displayed median to high ecological risks in surface waters, and the human daily intake of tire additives was estimated to be 2.63 × 10-8-3.16 × 10-5 mg/(kg d) via drinking water. This is the first report of the 6PPD-Q and 1,3-Diphenylurea levels in surface waters in China.

Time-concentration profiles of tire particle additives and transformation products under natural and artificial aging.

Tire and road wear particles (TRWP) are polymer-based microparticles that are emitted into the environment during tire usage. Growing efforts are currently being made to quantify these emissions, characterize the leachates and assess their environmental impact. This study aimed to investigate the effect of aging on TRWP composition. Cryomilled tire tread particles (CMTTP) and TRWP were exposed for different durations to three aging conditions: accelerated thermal and photochemical aging and natural outdoor aging. Particles were then extracted with cyclohexane/ethanol. The time-concentration profiles of 23 additives and transformation products present in these extracts were determined by UHPLC-HRMS. Several chemicals, such as N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6-PPD) or 1,3-diphenylguanidine (DPG), decayed exponentially under all aging conditions, with half-lives of a few days under artificial photoaging versus dozens of days under pure thermal aging at 60 °C. The natural aging profiles lie between those 2 laboratory aging conditions. Other chemicals, such as 6PPD-quinone, presented bell-shaped concentration profiles within CMTTP when particles were exposed to UV light. 6PPD-quinone reached a maximal concentration within a month under natural aging. For TRWP, the initial load of 6PPD-quinone had already reached a maximum prior to the aging experiments and decreased exponentially under natural aging with a half-life below one month. Pure thermal aging induced a significantly slower decay of 6PPD-quinone within TRWP (half-life of half a year), emphasizing a greater stability and persistence in environmental compartments without light. This study highlighted that the more readily accessible CMTTP could be considered a reasonable proxy of TRWP to investigate the fate of chemicals within rubber particles, at least from a qualitative standpoint. Overall, the concentrations of 20 of the evaluated chemicals decreased by >50 % within 50 days under natural aging.

Biotransformation of Barley Phenolamide by Mice and the Human Gut Microbiota and Quantitative Analysis of the Major Metabolites in Mice.

SCOPE: This study investigates the metabolism of p-coumaroylagmatine (pCAA), one of the phenolamides in barley, in mice, and by human gut microbiota, and measures the concentrations of its main metabolites in mice. METHODS AND RESULTS: Nine major metabolites are identified from fecal and urinary samples collected from pCAA treated mice via analysis of their LC chromatograms and tandem mass spectra compared to the commercial and synthesized standards. These nine metabolites are generated through four different biotransformation pathways: double bond reduction, amide bond hydrolyzation, cleavage of guanidine, and oxidation of guanidine. Furthermore, interindividual differences in the formation of dihydro-pCAA (M3), high and low metabolizers, are observed in human in vitro intestinal microbial conversion. Moreover, significant amount of pCAA is detected in mice (29.33 ± 1.58 µmol g-1 in feces and 2020.44 ± 130.07 µM in urine), and the concentrations of agmatine (M1) are increased to 177.6 times and 3.2 times in mouse feces and urine, respectively. CONCLUSION: This study demonstrates that pCAA is metabolized in mice and by human gut microbiota to generate potential bioactive metabolites through four major metabolic pathways. pCAA and its metabolites have the potential to be used as the exposure biomarkers to reflect the intake of whole grain barley.

6,8-(1,3-Diaminoguanidine) luteolin and its Cr complex show hypoglycemic activities and alter intestinal microbiota composition in type 2 diabetes mice.

Flavonoid compounds such as luteolin exhibit hypolipidemic effects, and there are few reports on the hypoglycemic activity of luteolin derivatives. In this research, 6,8-(1,3-diaminoguanidine) luteolin (DAGL) and its Cr complex (DAGL·Cr) were obtained as a result of structural modifications to luteolin, and the hypoglycemic activities and the composition of intestinal microbiota in T2DM mice were investigated. This study found that DAGL and DAGL·Cr could significantly restore body weight, FBG, OGTT, AUC, and GSP in T2DM mice. Moreover, the pancreatic islet function index and the biochemical indicators of serum and the liver were also significantly improved. The histopathological results also showed that DAGL and DAGL·Cr had a stronger repair ability in the liver and the pancreas. It was also revealed that the potential hypoglycemic mechanism of DAGL and DAGL·Cr was involved in the simultaneous regulation of PI3K/AKT-1/GSK-3ß/GLUT-4 and PI3K/AKT-1/mTOR/S6K1/IRS-1. Furthermore, DAGL and DAGL·Cr could also regulate the structure of the intestinal microbiota and increase the content of SCFA to relieve the symptoms of hyperglycemia in T2DM mice. This included a significant reduction in the ratio of Firmicutes and Bacteroidetes (F/B), and at the genus level, an increase in the relative abundance of Alistipe and Ruminiclostridium, and improvement in the content of SCFA in the feces of T2DM mice. In conclusion, in this study, DAGL and DAGL·Cr were found to improve hyperglycemia in T2DM mice by improving the pancreatic islet function index, regulating the biochemical indicators of serum and the liver, repairing damaged tissues, and regulating the PI3K/AKT-1 signaling pathway as well as reducing F/B, increasing the relative abundance of intestinal beneficial microbiota, and the content of SCFA in the feces. The hypoglycemic effect of DAGL·Cr on the body weight, serum IL-10, serum IL-6, and pancreatic islet function index was significantly better than that of DAGL.

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.

Residual levels and dietary risk assessment of bifenthrin and dinotefuran and its major metabolites in open wheat field conditions.

To evaluate the residual levels of bifenthrin and dinotefuran, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) and high-performance liquid chromatography-tandem mass spectrometry method for simultaneous detection of bifenthrin and dinotefuran and its major metabolites in wheat was developed and validated. Dietary risk assessments were further performed based on the relevant residual data from 12 wheat fields, toxicology data and dietary patterns. In wheat grain and straw, the recoveries of all analytes ranged from 77 to 102% with the relative standard deviation <9.7% and the limit of quantitation 0.05 mg kg-1 . The highest terminal residue of bifenthrin in wheat grain was 0.069 mg kg-1 and dinotefuran was 0.34 mg kg-1 . Residual concentrations of bifenthrin and dinotefuran decreased to <0.05 and 0.15 mg kg-1 at 21 days (pre-harvest interval), respectively. The chronic risk quotient ranged from 6.4 to 62.7% and the acute risk quotient varied from 0.38 to 17.73%. The chronic and acute dietary risks caused by the terminal residues of the two insecticides were negligible for Chinese populations. The recommended pre-harvest interval was proposed to ensure safe wheat consumption. These data could provide a scientific reference to establish the Chinese maximum residue limit of dinotefuran in wheat.

Detecting Pesticide Dodine by Displacement of Fluorescent Acridine from Cucurbit[10]uril Macrocycle.

According to a simple guest-replacement fluorescence turn-on mechanism, we constructed a fluorescent probe system based on cucurbit[10]uril (Q[10]) and protonated acridine (AD) to detect the pesticide dodine (DD). Formation of a homoternary inclusion complex AD2@Q[10] in both aqueous solution and solid state was studied by means of 1H NMR spectroscopy and X-ray crystallography. Although AD can emit strong fluorescence in aqueous solution, the homoternary inclusion complex AD2@Q[10] does not exhibit any fluorescence. Upon the addition of the pesticide DD into the aqueous solution of AD2@Q[10], the AD molecules in the Q[10] cavity are displaced by the pesticide DD, and strong fluorescence recovers. The fluorescent probe system based on Q[10] and AD provided a wide determination of DD from 0 to 4.0 × 10-5 mol·L-1 with a low limit of detection of 1.827 × 10-6 mol·L-1. The guest-replacement fluorescence turn-on mechanism is also confirmed by 1H NMR spectroscopy. Further, the fluorescent probe can directly detect DD residues in real agricultural products, and obvious fluorescence signal was observed under UV irradiation.

A three-year large scale study on the risk of honey bee colony exposure to blooming sunflowers grown from seeds treated with thiamethoxam and clothianidin neonicotinoids.

Despite the restriction of the use of neonicotinoids in the EU, including thiamethoxam and clothianidin, the debate over their risk on honey bees has not been fully settled. This study presents results of a three-year study working with 180 honey bee colonies in ten replicates. Colonies were sorted into three treatments (60 colonies per treatment) exposed to sunflower blooms grown from seeds treated with thiamethoxam, clothianidin and a non-treated control. Each colony was assessed at six moments: one before to exposition to sunflower, two during the exposition (short-time risk), two after exposition (medium-time risk) and one after wintering (long-time risk). The health and development of the colonies were assessed by monitoring adult bee population, brood development, status of the queen, food reserves and survival. No significant difference among treatments when raw data was considered. However, when evolution from initial status of the colony was evaluated, a significant difference was observed from the first week of exposure to sunflower blooms. In this period, the number of adult bees and the amount of brood were slightly lower in the bee hives exposed to neonicotinoids, although such differences disappeared in subsequent evaluations. The concentration of residues in samples of beebread and adult bees was at the level of ng·g-1. Magnitude of the effect of the treatment factor on the variability of colony health and development related parameters was low. The most important factor was the hive, followed by the replicate and year, and to a lesser extent the initial strength of the colonies.

Determination of Neonicotinoid Pesticides in Propolis with Liquid Chromatography Coupled to Tandem Mass Spectrometry.

In this study, a method was developed for the determination of five neonicotinoid pesticides (acetamiprid, clothianidin, imidacloprid, thiacloprid, and thiamethoxam) in propolis. Two sample preparation methods were tested: solid-phase extraction and the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The identities of analytes were confirmed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the selected reaction monitoring mode. Solid-phase extraction resulted in cleaner extracts; therefore, the SPE-LC-MS/MS method was validated according to the SANTE protocol in triplicate at two spiking levels (10 ng/g and 50 ng/g). The average recoveries of analytes ranged from 61% to 101%, except for clothianidin (10-20%). The LOD ranged from 0.2 ng/g to 4.4 ng/g, whereas the LOQ was in the range of 0.8 ng/g-14.7 ng/g. In order to compensate for the matrix effect, matrix-matched calibration was used. Good accuracy (relative error: 1.9-10.4%) and good linearity (R2 > 0.991) were obtained for all compounds. The optimised method was applied to 30 samples: 18 raw propolis and 12 ethanol tinctures. Acetamiprid, imidacloprid, and thiacloprid were detectable in seven samples but were still below the LOQ. This study is the first to report the determination of several neonicotinoid residues in propolis.

Fugitive Dust During Planting of Canola with an Air Seeder as a Source of Environmental Contamination for Pesticides Applied on Seed: A Case Study.

The dispersion of clothianidin from treated seeds was studied in a commercial winter canola field. During planting, using a John Deere 1890 single disk air seeder, a proportion, an estimated 14.2 ± 2.9% (mean ± standard error), of the clothianidin that was applied to the seed escaped into the atmosphere from the seeder's exhaust. We suggest that this source of environmental contamination may be the main contributor that explains the off-target detection of neonicotinoid residues in soils and water near canola plantings better than movement from seed after it is placed in the soil, which is often proposed in the literature. Environ Toxicol Chem 2020;39:2420-2423. © 2020 SETAC.

Capillary liquid chromatography as an effective method for the determination of seven neonicotinoid residues in honey samples.

A new analytical method based on capillary liquid chromatography with diode array detection has been developed for the simultaneous quantification of seven neonicotinoid insecticides commercially available (imidacloprid, thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram, and dinotefuran) in honey samples. The separation was achieved in a Zorbax XDB-C18 column (150 × 0.5 mm id, 5 µm), with a mobile phase consisting of ultrapure water (solvent A) and acetonitrile (solvent B) at a flow rate of 10 µL/min. Capillary column was thermostated at 25°C during the analysis and 254 or 270 nm was established as detection wavelength, depending on the analyte. Furthermore, full loop injection mode (8 µL) was selected, using water as injection solvent. Finally, the optimized method was applied to the analysis of neonicotinoid residues in honey of different floral origins using dispersive liquid-liquid microextraction as sample treatment. Variables affecting the extraction efficiency were optimized, choosing methanol and dichloromethane as dispersive and extraction solvents, respectively. The method was characterized in terms of linearity ( R 2 ≥ 0.9948), repeatability, reproducibility (relative standard deviation below 4.5 and 6.3% respectively), and recoveries (≥80.5%). Detection and quantification limits were lower than 6.6 and 22.0 µg/kg for the studied analytes, respectively.

Properties of Polyhexamethylene Guanidine (PHMG) Associated with Fatal Lung Injury in Korea.

The use of humidifier disinfectant (HD) has been determined to be associated with lung injuries (HDLI) in Korea. Although HD brands containing polyhexamethylene guanidine (PHMG) oligomers have been found to cause more HDLI compared to brands containing other disinfectants, the physicochemical properties of PHMG have been poorly defined. We aimed to quantify the PHMG dissolved in HD brands, characterize the number-average (Mn) and weight-average (Mw) molecular masses, and identify the polymerization degree of PHMG. Analysis of the PHMG oligomers was performed using a matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOF MS) operated in positive-ion reflectron mode. Eight brands of HD containing PHMG were identified. The PHMG concentrations in these brands ranged from 160 to 37,200 ppm (mean = 3100.9 ppm). Concentration was a significant variable among and within HD brands. The degree of PHMG oligomerization fell within the range of two to four. The averages of Mn and Mw were 517.2 g/mol (range: 422-613 g/mol) and 537.3 g/mol (range: 441.0-678.0 g/mol), respectively. Based on the average molecular weight and the degree of polymerization, the PHMG examined here could be regarded as oligomers, which may be associated with the highest proportion of HDLI being caused by PHMG.