Fluorometric detection of copper and imidacloprid using nitrogen-doped graphitic carbon dots: A promising method for environmental monitoring.

Pesticides in environmental samples pose significant risks to ecosystems and human health since they require precise and efficient detection methods. Imidacloprid (IMI), a widely used neonicotinoid insecticide, exemplifies these hazards due to its potential toxicity. This study addresses the urgent need for improved monitoring of such contaminants by introducing a novel fluorometric method for detecting IMI using nitrogen-doped graphite carbon dots (N-GCDs). The sensor operates by quenching fluorescence through the interaction of Cu2+ ions with N-GCDs. Subsequently, IMI binds to the imidazole group, chelates with Cu2+, and restores the fluorescence of N-GCDs. This alternating fluorescence behavior allows for the accurate identification of both Cu2+ and IMI. The sensor exhibits linear detection ranges of 20-100 nM for Cu2+ and 10-140 µg/L for IMI, with detection limits of 18 nM and 1.2 µg/L, respectively. The high sensitivity of this sensor enables the detection of real-world samples, which underscores its potential for practical use in environmental monitoring and agricultural safety.

Spatiotemporal distribution, risk levels, and transport variations in neonicotinoids and fipronil and its metabolites cross a river-to-sea continuum.

Neonicotinoids (NEOs) and fipronil are widely used in pest control, but their spatiotemporal distribution and risk levels in the "river-estuary-bay" system remain unclear. Between 2018 and 2021, 148 water samples from rivers to inshore and offshore seawater in Laizhou Bay, China were collected to investigate the presence of eight NEOs and fipronil and its metabolites (FIPs). Significant seasonal variations in NEOs were observed under the influence of different cultivation practices and climatic conditions, with higher levels in the summer than in the spring. The average concentrations of total neonicotinoids (ΣNEOs) and ∑FIPs decreased from rivers (63.64 ng/L, 2.41 ng/L) to inshore (22.62 ng/L, 0.14 ng/L) and offshore (4.48 ng/L, 0.10 ng/L) seawater of Laizhou Bay. The average concentrations of ΣNEOs decreased by 85.3 % from 2018 to 2021. The predominant insecticides in the study area were acetamiprid, thiamethoxam, imidacloprid, and fipronil sulfone, with a gradual shift toward low-toxicity and environmentally friendly species over time. Influenced by agricultural intensity, ∑NEOs were mostly distributed in the Yellow River, Xiaoqing River, and their estuaries, where they pose chronic ecological risks. However, FIP exhibited high risk in certain rivers and sewage treatment plants owing to the use of animal repellents or landscape gardening insecticides. This study provides evidence of the transfer of NEOs and FIPs from rivers to the ocean and also clarifies their transition dynamics and changes in risk levels from rivers to oceans. Additionally, the study offers data support for identifying critical pesticide control areas.

Nitenpyram in tea: Eco-friendly detection methodology and residue behavior.

Studies on nitenpyram determination and behavior within tea remain limited despite its widespread use as a neonicotinoid. An organic-saving analytical approach tailored for the detection of nitenpyram in tea was established. Nitenpyram was extracted by boiling water and cleaned up by Cleanert PCX solid-phase. The average recoveries were 75.1-94.5 %, with relative standard deviations (RSDs) of 0.7-8.6 % for saving 34.5-88.6 % organic solvent. The limits of quantification (LOQs) were 0.002 mg·kg-1 in fresh tea shoots, 0.005 mg·kg-1 in made tea, and 0.001 mg·L-1 in tea brew, satisfying the current minimum Maximum Residue Limit (MRL). Nitenpyram dissipated rapidly with half-lives of 1.2-1.4 days at the recommended dosage (27 g a.i. ha-1) in two locations. Remarkably, 20-110 % of nitenpyram was leached out from made tea in different brewing modes. This work provides insights into nitenpyram's rational application in tea cultivation and offers considerations to institutions tasked with unestablished MRLs in tea.

Evaluating the Safety of Imidacloprid FS Seed Treatment Use in Potato Production: A Case Study from China.

This study evaluated the residue behavior and dissipation dynamics of a new imidacloprid FS 600 seed treatment in potato cultivation systems in Shandong and Jilin, China. Sensitive and accurate UPLC-MS/MS methods were established to quantify imidacloprid residues in potatoes, potato plants, and soil. Results showed that imidacloprid dissipation followed a first-order kinetic model, with half-lives ranging from 6.9 to 26.7 days in plants and 19.8 to 28.9 days in soil. At harvest, the highest average residues in potatoes and soil were 0.778 mg/kg and 0.149 mg/kg, respectively. The dietary risk assessment indicated a chronic risk quotient (CRQ) of 39.73% for adults, indicating minimal risk to human consumers, while the ecological risk quotient (ERQ) and ecotoxicity exposure ratio (TER) revealed low to moderate toxicity to earthworms, warranting caution in the use of this formulation. This research provides valuable data for assessing the safety of imidacloprid FS seed treatment in potato cultivation.

A colloidal gold immunochromatographic method for rapid screening of imidacloprid residues in Chinese herbal medicines.

An imidacloprid colloidal gold immunochromatographic strip was developed in this work, and systematic analytical conditions were deeply investigated. The test strips were used for rapid screening of imidacloprid residues in Chinese herbal medicines. The performance of the colloidal gold test strips was investigated by using five selected Chinese herbal medicines (malt, Coix seed, lotus seed, dried ginger and honeysuckle). As a result, the developed imidacloprid colloidal gold immunochromatographic test strips could be used for rapid screening of imidacloprid residues in 60 kinds of different herbs (including 26 kinds of root/rhizome medicines, 20 kinds of seed/fruit/pericarp medicines, 11 kinds of flower/leaf/whole herb medicines, and 3 kinds of bark/aboveground issues of herb medicines), and the cut-off value was 50 µg/kg. The development of this method can achieve the goal of on-site, rapid and low-cost screening of imidacloprid residues in different herbs, which is of great significance for the quality assurance of herbs.

ZIF-8-wrapped AgNPs modified with ß-cyclodextrin for sensitive detection of thiacloprid and imidacloprid by SERS technology.

The high efficient surface-enhanced Raman scatterring (SERS) methods to detect thiacloprid and imidacloprid were established using ZIF-8-wrapped Ag nanoparticles (AgNPs) modified with ß-cyclodextrin (ß-CD). The substrate of ZIF-8/ß-CD@AgNPs was characterized by ultraviolet visible spectra (UV-vis), thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The interaction between the substrate and thiacloprid/imidacloprid was also explored. The optimum measurement conditions were obtained by response surface model based on single-factor experiments. Enhancement factors (EFs) of thiacloprid and imidacloprid were respectively 2.29 × 106 and 2.60 × 106. A good linearity between the scattering intensity and the concentration of thiacloprid/imidacloprid within 3-1000 nmol L-1/6-400 nmol L-1 was established. The interference experiments indicated that the methods had good selectivity. The SERS methods were successfully applied to detect thiacloprid and imidacloprid in several vegetables samples. The recoveries ranged from 95.5 % to 105 % (n = 5). The detection limits (LODs) (S/N = 3) for thiacloprid and imidacloprid were 1.50 and 0.83 nmol L-1, respectively.

Conjugated microporous polymer for solid-phase extraction of neonicotinoid insecticides from environmental water samples.

Conjugated microporous polymers (CMPs) have unique characteristics and have been used in a range of fascinating applications in separation sciences. In this study, a CMP, designated as CMP-1, was synthesized via the Sonogashira-Hagihara coupling reaction using 1,3,5-triphenylbenzene and 1,4-dibromobenzene as building blocks. CMP-1 features a large surface area, abundant micropore structures, and excellent stability, making it a promising solid-phase extraction adsorbent for the efficient enrichment of neonicotinoid insecticides (NEOs). Under the optimized conditions, CMP-1 was combined with high-performance liquid chromatography and diode array detection to enable the detection of NEOs with a wide linear range (0.5-200 µg·L-1), a low detection limit (0.26-0.58 µg·L-1), and acceptable precision. The developed method was applied to determine spiked NEOs in three types of environmental water samples, with recoveries of 73.7%-112.0% and relative standard deviations of 0.6%-9.4%.

A Tunable Threshold Colorimetric DNA Logic Gate for Intuitive Assessment of Chemical Contaminant Exceedance.

Current molecular logic gates are predominantly focused on the qualitative assessment of target presence, which has certain limitations in scenarios requiring quantitative assessment, such as chemical contaminant monitoring. To bridge this gap, we have developed a novel DNA logic gate featuring a tunable threshold, specifically tailored to the limits of contaminants. At the core of this logic gate is a DNA-gold nanoparticle (AuNP) hybrid film that incorporates aptamer sequences to selectively bind to acetamiprid (ACE) and atrazine (ATR). Upon interaction with these contaminants, the film degrades, releasing AuNPs that, in the presence of Hg2+, catalyze the oxidation of TMB, resulting in a visible blue coloration on test paper. This aptamer-enabled process effectively establishes an OR logic gate, with ACE and ATR as inputs and the appearance of blue color as the output. A key innovation of our system is its tunable input threshold. By adjusting the concentration of Hg2+, we can fine-tune the color mutation points to match the input threshold to predefined limits, such as Maximum Residue Limits (MRLs). This alignment allows semiquantitative assessment of contaminant levels, providing intuitive visual feedback of contaminant exceedance. Validation experiments with spiked samples confirm its accuracy and reliability by closely matching HPLC results. Therefore, our colorimetric DNA logic gate is emerging as a promising tool for easy and semiquantitative monitoring of chemical contaminants across diverse applications.

Unveiling the Contamination Patterns of Neonicotinoid Insecticides: Detection, Distribution, and Risk Assessment in Panax notoginseng across Plant Parts.

This study analyzed neonicotinoid insecticides (NEOs) and metabolite (m-NEOs) residues in 136 Panax notoginseng samples via ultra-performance liquid chromatography-tandem mass spectrometry. Imidacloprid was the most detected NEO (88.24% of samples), ranging from 1.50 to 2850 µg/kg. To the best of our knowledge, some novel NEOs were detected in P. notoginseng for the first time. NEO clustering patterns varied among plant parts, with higher contamination in leaves and flowers. Fourteen NEO/m-NEOs, including cycloxaprid and acetamiprid, showed site-specific behavior, indicating the possibility of using multiple NEOs simultaneously during planting, resulting in formation of distinct metabolites in different plant parts. Transfer rates in decoction and infusion ranged from 10.06 to 32.33%, reducing residues postprocessing. Dietary risk assessment showed low hazard quotients (HQa: 7.05 × 10-7 to 2.09 × 10-2; HQc: 3.74 × 10-7 to 2.38 × 10-3), but risk-ranking scores indicated potential hazards with imidacloprid and acetamiprid in flowers and leaves. The findings are expected to promote safety assessment and distribution research of NEOs in plants.

Residual distribution and risk assessment of neonicotinoids in urban green space soils of the pearl river delta, South China: A socioeconomic analysis.

Urban green spaces are the soil component in cities that interacts most closely with humans. This study investigated the residues of seven neonicotinoids (NEOs) in soils from urban green spaces within the Pearl River Delta (PRD) region and analyzed the correlation between the residue characteristics and the region's economic development. Notably, we introduced the Nemerow Index method, a comprehensive approach, to quantify the overall pollution level of NEOs in the soil of urban park green spaces and utilized this to assess the cumulative exposure probability risks for different populations in this scenario. We found that: (1) The soil of urban park green spaces exhibited varying degrees of NEOs contamination (Σ7NEOs: N.D.-137.31; 6.25 µg/kg), with imidacloprid and clothianidin constituting the highest proportions (89.46 % and 83.60 %); (2) The residual levels of NEOs in Children's Park were significantly higher than those in community parks within Guangzhou, with an average value of 13.30 µg/kg compared to 3.30 µg/kg; (3) The residual characteristics of NEOs exhibited a positive correlation with regional economic development; specifically, the per capita GDP well correlated with IMIRPF, a summation of seven NEOs in imidacloprid equivalents via relative potency factors (R2 =0.86). Regions with higher economic development typically exhibited elevated IMIRPF levels; (4) The fitted cumulative probability distributions for average daily exposure doses revealed that children's exposure was an order of magnitude higher than adults'. Despite this, the exposure risks for both groups remained within acceptable limits.

A close-looped DNAzyme walker with an available catalytic domain for electrochemiluminescent detection of acetamiprid.

Traditional DNA walkers face enormous challenges due to limited biostability and reaction kinetics. Herein, we designed a self-driven close-looped DNAzyme walker (cl-DW) with high structural biostability and catalytic activity that enabled rapid electrochemiluminescence (ECL) detection of pesticide residue acetamiprid. Specifically, cl-DW exhibited increasing ability to resist nuclease degradation with a 570-fold longer half-degradation time than that of the single-stranded DNAzyme walker (ss-DW) due to the protected DNA terminal. Furthermore, cl-DW achieved high catalytic activity with a 4.3-fold faster reaction kinetic than that of ss-DW due to the circularized nanostructure of an available catalytic domain. Consequently, we utilized cl-DW as a signal amplifier and tin-based sulfide (SnS2) nanoflowers as ECL emitters to construct an ECL aptasensor, which realized the sensitive detection of acetamiprid with a limit of detection of 0.85 nM. This work provides a reliable approach to exploring DNA walkers with high catalytic activity and better biostability for molecular monitoring.

Neonicotinoid insecticides in a large-scale agricultural basin system-Use, emission, transportation, and their contributions to the ecological risks in the Pearl River Basin, China.

Neonicotinoid pollution has increased rapidly and globally in recent years, posing significant risks to agricultural areas. Quantifying use and emission, transport and fate of these contaminants, and risks is critical for proper management of neonicotinoids in river basin. This study elucidates use and emissions of neonicotinoid pesticides in a typical large-scale agriculture basin of China, the Pearl River Basin, as well as the resulting agricultural non-point source pollution and related ecological risks using market surveys, data analysis, and the Soil and Water Assessment Tool. Neonicotinoid use in the basin was estimated at 1361 t in 2019, of which 83.1 % was used in agriculture. After application, approximately 99.1 t neonicotinoids were transported to the Pearl River, accounting for 7.2 % of the total applied. Estimated aquatic concentrations of neonicotinoids showed three seasonal peaks. Several distinct groups of neonicotinoid chemicals can be observed in the Pearl River, as estimated by the model. An estimated 3.9 % of the neonicotinoids used were transported to the South China Sea. Based on the present risk assessment result, several neonicotinoids posed risks to aquatic organism. Therefore, the use of alternative products and/or reduced use is deemed necessary. This study provides novel insights into the fate and ecological risks of neonicotinoid insecticides in large-scale watersheds, and underscores the need for greater efficiency of use and extensive environmental monitoring.

Sampling-rate calibration vs. equilibrium calibration for in vivo solid-phase microextraction: Analysis of neonicotinoids in bananas.

In vivo solid-phase microextraction (in vivo SPME) is an emerging fascinating sample pretreatment technique, but its quantitative correction method is different from the traditional correction methods, which has become a bottleneck limiting its development. At present, the sampling-rate calibration and equilibrium calibration are mainly used, however, their characteristics and applicability are not clear. In this study, the sampling-rate calibration and equilibrium calibration were evaluated in the case of the determination of neonicotinoids in bananas by in vivo SPME. The factors that affect the sampling rate (Rs), such as the matrix states, sampling durations, and individual differences were studied, and they all had impacts on Rs. Conversely, the equilibrium distribution coefficient (Kfs) remained constant after extraction equilibrium and the individual differences were smaller. The highest accuracy and precision were achieved by equilibrium calibration, and the relative recoveries were in the range of 83.2 %-104.3 % with the relative standard deviations below 8.1 % compared to a standard QuEChERS-based method. The lower limits of quantification for 4 neonicotinoids in bananas were below 5 ng g-1, lower than the standard method and the maximum residue levels in China and the European Union. This work clarifies the characteristics, rules and performance of the sampling-rate calibration and equilibrium calibration, which is of crucial importance for the development and application of in vivo SPME. The developed method is convenient, sensitive, and accurate for the determination of pesticide residues, which is of great significance to guide the safe use of pesticides in the field and prevent products with excessive pesticide residues from entering the market.

Exposure of pregnant women to neonicotinoids in Wenzhou City, East China: A biomonitoring study.

BACKGROUND: China produces and consumes a large amount of neonicotinoids. A non-negligible exposure to neonicotinoids might occur for Chinese pregnant women, but relevant data remain limited. OBJECTIVE: To investigate the exposure to neonicotinoids by urinary biomonitoring in pregnant women from Wenzhou City, East China. METHODS: We selected 432 pregnant women in Wenzhou City in 2022. A total of eight parent neonicotinoids and four metabolites were determined in single spot urine by liquid chromatography coupled to mass spectrometry. Basic characteristics, physical activity, pre-pregnant body mass index, and intake of drinking water and food were investigated by the questionnaire. Health risk was assessed by hazard quotient (HQ) and hazard index (HI) based on human safety thresholds derived from different health endpoints. RESULTS: Neonicotinoids and their metabolites in urine had a detection frequency between 0 % and 80.1 %. At least one neonicotinoid or metabolite was detected in 93.5 % of urine samples. Except for clothianidin (51.2 %) and N-desmethyl-acetamiprid (80.1 %), the detection frequencies of other neonicotinoids and metabolites ranged from 0 % to 43.8 %. The summed concentrations of all neonicotinoids and their metabolites ranged from < LOD to 222.83 µg/g creatinine with the median concentration of 2.58 µg/g creatinine. Maternal age, educational level, occupation, household income, screen time, and pre-pregnant body mass index were associated with detection frequencies or concentrations of neonicotinoids and their metabolites. Pregnant women with higher consumption frequencies of wheat, fresh vegetable, shellfish, fresh milk, and powdered milk had higher detection frequencies of neonicotinoids and their metabolites. Both HQ and HI were less than one. CONCLUSIONS: Overall, pregnant women in Wenzhou City showed a notable frequency of exposure to at least one neonicotinoid, although the exposure frequency for each specific neonicotinoid was generally low. Several food items derived from plants and animals were potential exposure sources. A low health risk was found based on current safety thresholds.

Enhanced detection of acetamiprid via a gold nanoparticle-based colorimetric aptasensor integrated with a hybridization chain reaction.

This study presents a novel colorimetric aptasensor, which seamlessly integrates gold nanoparticles (AuNPs) with the amplification potential of the hybridization chain reaction (HCR) for enhanced detection of acetamiprid. The aptamer, hybridized with a partially complementary strand that is covalently linked to AuNPs, serves as the recognition element for acetamiprid. The free end sequence of the aptamer, distal from the AuNP surface, functions as the initiating strand for the HCR, triggering the amplification process. In the absence of acetamiprid, the HCR efficiently occurs, conferring robust salt tolerance to the AuNPs and maintaining their characteristic red coloration. However, in the presence of acetamiprid, the aptamer preferentially binds to its target, disrupting the double-stranded structure and leading to the dissociation of the aptamer from the AuNPs. This dissociation results in a decrease in the HCR product, subsequently diminishing the salt tolerance of AuNPs and triggering a colorimetric transition from red to gray. This integration enhances sensitivity to 3.14 nM. Additionally, carbon quantum dots (CQDs) transduce colorimetric signals to fluorescent ones, further boosting the sensitivity to 0.24 nM. The aptasensor exhibits excellent selectivity and robustness. Real-world testing on tomato, peach, and lettuce shows recoveries of 98.50% to 100.36% with low standard deviations, validating its utility for pesticide residue analysis and food safety. This study provides a powerful tool for rapid and accurate pesticide detection, crucial for food safety.

Temporal and spatial trends of imidacloprid-related hazards in France.

Neonicotinoids are the top-selling insecticides worldwide. Because of their method of use, mainly to coat seeds, neonicotinoids have been found to widely contaminate the environment. Their high toxicity has been shown to be a major concern in terms of impact on biodiversity, and the use of these insecticides has been associated with population declines of species in different countries. Despite the widespread recognition of the risk of neonicotinoids to biodiversity, their temporal and spatial use remains poorly known in many countries. Yet this information is essential to address the potential impacts of these pesticides on biodiversity and to inform measures to establish protected areas or biodiversity restoration. The present study relied a large publicly available dataset to characterise the temporal and spatial use in France of imidacloprid, the most widely used neonicotinoid worldwide, as well as analysed water contamination surveys between 2005 and 2022 to assess the contamination of the environment. The results show that imidacloprid was the main neonicotinoid used in France over the study period. This use was spatially structured, with higher use in northern and western France, particularly related to cereal and beet crops area. The water contamination survey indicated that imidacloprid has widely contaminated the environment and consequently increased the risk to biodiversity, especially in counties crossed by the Loire, Seine and Vilaine rivers. This risk increased between 2005 and 2018 due to the higher use of imidacloprid and decreased sharply after 2018 due to its ban, although it was reauthorized by derogation for sugar beet in 2021. This study is the first assessment of imidacloprid pressure on biodiversity in France and shows the spatial and temporal correlation between agricultural practices and the freshwater contamination level. These results will help to identify priority areas for mitigation and restoration measures.

Novel cross-linkable fluorescent probe with oriented antibody to enhance lateral immunoassay strip for the detection of acetamiprid.

Time-resolved fluorescent lateral immunoassay strip (TRFLIS) is a reliable and rapid method for detecting acetamiprid. However, its sensitivity is often affected by the structural patterns and stability of the fluorescent probe. Researchers have shown significant interests in using goat anti-mouse IgG (GaMIgG) which is indirectly bound to time-resolved fluorescent microsphere (TRFM) and antibody. This allowed for oriented modification of the antibody. However, the stability of fluorescent probe in this binding mode remained unexplored. Herein, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride was innovatively used as a cross-linking agent to enhance the binding of antibody to GaMIgG, which improved the stability of the fluorescent probe. Under optimal working conditions, this strategy exhibited a wide linear response range of 5-700 ng/mL. Its limit of detection (LOD) was 0.62 ng/mL, the visual LOD was 5 ng/mL, and the limit of quantification (LOQ) of 2.06 ng/mL. Additionally, under tomato matrix, leek matrix and Chinese cabbage matrix, the linear response ranges were 5-400, 5-300, and 5-700 ng/mL, with LODs of 0.16, 0.60, and 0.41 ng/mL, with LOQs of 0.53, 2.01 and 1.37 ng/mL, respectively. In conclusion, this strategy effectively reduced the dosage of acetamiprid antibody compared with TRFM directly linking acetamiprid antibody, and greatly increased the sensitivity of TRFLIS. Meanwhile, it demonstrated outstanding specificity and accuracy in acetamiprid detection and had been successfully applied to vegetable samples. This method enables rapid and accurate detection of large-volume samples by combining qualitative and quantitative methods. As such, it has great potential in the development of low-cost and high-performance immunochromatographic platforms.

In vivo tracing of cyromazine and three neonicotinoids in cowpea under field conditions by solid-phase microextraction combined with ultra-performance liquid chromatography-tandem mass spectrometry.

BACKGROUND: Excessive pesticide residues in agricultural products could accumulate in organisms through the food chain, causing potential harm to human health. The investigation of dissipation kinetics and residues of pesticides in crops is crucial for the scientific application of pesticides and the mitigation of their adverse effects on human health. In vivo solid-phase microextraction (in vivo SPME) has unique advantages, but the research on field plants is still lacking and the quantitative correction methods need to be further developed. RESULTS: A method combining in vivo solid-phase microextraction with ultra-performance liquid chromatography-tandem mass spectrometry (in vivo SPME-UPLC-MS/MS) was developed to monitor the presence of acetamiprid, cyromazine, thiamethoxam and imidacloprid in cowpea fruits grown in the field. The sampling rates (Rs) were determined using both in vitro SPME in homogenized cowpea samples and in vivo SPME in intact cowpea fruit samples. The in vivo-Rs values were significantly higher than the in vitro-Rs for the same analyte, which were used for in vivo SPME correction. The accuracy of this method was confirmed by comparison with a QuEChERS-based approach and subsequently applied to trace pesticide residues in field-grown cowpea fruits. The residual concentrations of each pesticide positively correlated with application doses. After 7 days of application at two different doses, all of the pesticides had residual concentrations below China's maximum residue limits. Both experimental data and predictions indicated that a safe preharvest interval for these pesticides is 7 days; however, if the European Union standards are to be met, a safe preharvest interval for cyromazine should be at least 13 days. SIGNIFICANCE: This study highlights the advantages of in vivo SPME for simultaneous analysis and tracking of multiple pesticides in crops under field conditions. This technique is environmentally friendly, minimally invasive, highly sensitive, accurate, rapid, user-friendly, cost-effective, and capable of providing precise and timely data for long-term pesticide surveillance. Consequently, it furnishes valuable insights to guide the safe utilization of pesticides in agricultural production.

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.

Characterization of near-field temporal and spatial variations of pesticide residues using honeybee specimens as bio-sensing matrices.

This study was prompted by recent reports of the ubiquity of neonicotinoids (neonics) in environment and the likelihood of exposures and health hazards to non-target organisms. We aimed to quantify neonics levels in time- and location-match pollen and nectar samples foraged by honeybees (Apis mellifera) and characterized the temporal and spatial variations using a relative potency factor method to determine the total neonic levels, expressed as the imidacloprid-adjusted total neonics, IMIRPF (ng/g). Six pairs of pollen and nectar samples, a total of twelve samples, were collected from each of the thirty-two experimental hives during the active foraging months of March, April, and June and analyzed for eight neonics. We found 59% and 64% of pollen and nectar contained at least one neonic, respectively. Among those neonic-detected pollen and nectar samples, 45% and 77% of them contained more than one neonic, respectively. Imidacloprid and acetamiprid in pollen and clothianidin and thiamethoxam in nectar accounted for 60% and 83% detection, respectively. The highest 3-month average of IMIRPF in pollen (6.56 ng/g) and nectar (11.19 ng/g) were detected in a location with the predominant production of citrus fruit. The temporal and spatial variations of IMIRPF levels demonstrated the robustness of using paired pollen and nectar data as the bio-sensing matrices to facilitate the assessment of near-field exposure to total neonics and the delineation of risks.