Seed coating (‘seed treatment’) is the leading delivery method of neonicotinoid insecticides in major crops such as soybean, wheat, cotton and maize. However, this prophylactic use of neonicotinoids is widely discussed from the standpoint of environmental costs. Growing soybean plants from neonicotinoid-coated seeds in field, we demonstrate that soybean aphids (Aphis glycines) survived the treatment, and excreted honeydew containing neonicotinoids. Biochemical analyses demonstrated that honeydew excreted by the soybean aphid contained substantial concentrations of neonicotinoids even one month after sowing of the crop. Consuming this honeydew reduced the longevity of two biological control agents of the soybean aphid, the predatory midge Aphidoletes aphidimyza and the parasitic wasp Aphelinus certus. These results have important environmental and economic implications because honeydew is the main carbohydrate source for many beneficial insects in agricultural landscapes.

Neonicotinoid insecticides (NIIs) are extensively used worldwide and frequently detected in the environment. The human and ecological risks associated with the occurrence of NIIs in agricultural zones are of high importance. The present study highlights the regional occurrence and human exposure risks of NIIs in agricultural soil within the Pearl River Delta (PRD), South China. Six neonicotinoids, i.e., imidacloprid, clothianidin, acetamiprid, imidaclothiz, dinotefuran, and flonicamid, were measured in 351 soil samples from Zengcheng, a typical agricultural zone. The soil samples were categorized into three groups based on cultivated plants: vegetables, rice, and fruits. At least one of these neonicotinoid insecticides was detected in 95% of the soil samples. The levels of ∑₆NII (range (median)) were 0.26–390 (23), 0.26–280 (6.1), and 0.26–120 (5.0) ng g⁻¹ dry weight in soil samples from vegetable farms, rice paddies, and fruit farms, respectively. Neonicotinoids were detected more frequently and at statistically higher concentrations in vegetable farms than in both rice paddies and fruit farms. This is likely ascribed to higher application frequencies of NIIs in vegetable farms due to higher planting frequencies. The hazard index values for human exposure to NIIs in the agricultural soils were all below 1, suggesting negligible non-cancer risks. The current residual levels of NIIs in the soils could however pose sub-lethal or acute effects to non-target terrestrial organisms such as earthworms. The present study suggests that more information is needed regarding NIIs contamination in soils from agricultural regions of South China to ensure that human and ecological risk from exposure to these compounds can be fully addressed.

Neonicotinoid insecticides have posed a great threat to non-target organisms, yet the mechanisms underlying their toxicity are not well characterized. Major modes of action (MoAs) of imidacloprid were analyzed in an aquatic insect Chironomus dilutus. Lethal and sublethal outcomes were assessed in the midges after 96-h exposure to imidacloprid. Global transcriptomic profiles were determined using de novo RNA-sequencing to more holistically identify toxicity pathways. Transcriptional 10% biological potency values derived from ranked KEGG pathways and GO terms were 0.02 (0.01–0.08) (mean (95% confidence interval) and 0.05 (0.04–0.06) μg L⁻¹, respectively, which were more sensitive than those from phenotypic traits (10% lethal concentration: 0.44 (0.23–0.79) μg L⁻¹; 10% burrowing behavior concentration: 0.30 (0.22–0.43) μg L⁻¹). Major MoAs of imidacloprid in aquatic species were identified as follows: the activation of nicotinic acetylcholine receptors (nAChRs) induced by imidacloprid impaired organisms’ nerve system through calcium ion homeostasis imbalance and mitochondrial dysfunction, which posed oxidative stress and DNA damage and eventually caused death of organisms. The current investigation highlighted that imidacloprid affected C. dilutus at environmentally relevant concentrations, and elucidated toxicity pathways derived from gene alteration to individual outcomes, calling for more attention to toxicity of neonicotinoids to aquatic organisms.

Neonicotinoid insecticides (NNIs) had been detected in soil and surface water frequently because of extensive use worldwide, however, data regarding regional characteristics and potential influential factors of sediment were scarce. In the present study, eight NNIs were analyzed in 86 surface sediment samples from different regions (central cities, rural areas and suburbs) and land use types (construction land and crop land) in Jiangsu Province. NNIs were widespread in the sediments, with a mean value of 1.73 ± 0.89 ng g⁻¹ dry weight (dw) (ranged from 0.41 to 3.87 ng g⁻¹ dw). Imidaclothiz (IMIZ), dinotefuran (DIN) and nitenpyram (NIT) were the dominant compounds in the surface sediment, accounted for half of combined total. The results of regional distribution analysis show that NNIs were at higher concentrations in rural areas and crop land, while the residues of NNIs in lakes were more severe compare with rivers in Jiangsu Province. Region characteristics and land use types have an influence on residues of NNIs in surface sediment. Principal component analysis showed that residues of NNIs in surface sediment in Jiangsu Province mainly originated from protect grain crops (maize), fruit (apples, pears) and vegetables in agricultural systems. The residues of NNIs were found to be mostly concentrated in the northwest and northeast in Jiangsu Province, where were the area of intensive agriculture. To investigate the residues of NNIs, while identify the contributing factors, could provide a scientific basis for basic of region environment management and pollution control.

Neonicotinoids pollution poses a serious threat to aquatic ecosystems. However, there is currently little knowledge about how neonicotinoids are transferred from the agricultural environment to the aquatic environment. Here, we conducted in situ high-frequency monitoring of neonicotinoids in soil-water systems along the hydrological flow path during rainfall to explore the horizontal and vertical transport mechanisms of neonicotinoids. The collected samples included 240 surface runoff, 128 subsurface runoff, 60 eroded sediment, 120 soil and 144 soil solution, which were used to analyse neonicotinoids concentrations. Surface runoff, subsurface runoff and eroded sediment were the three main paths for the horizontal migration of neonicotinoids. In the CK (citrus orchards without grass cover) and grass-covered citrus orchards, there are 15.89% and 2.29% of the applied neonicotinoids were transported with surface runoff, respectively. While in the CK and grass-covered citrus orchards, there are only 1.23% and 0.19% of the applied neonicotinoids were transported with eroded sediment and subsurface runoff. Although the amount of neonicotinoids lost along with eroded sediment was small, the concentration of neonicotinoids in eroded sediment was two orders of magnitude higher than the concentration of neonicotinoids in sediments of the surface water. Meanwhile, neonicotinoids migrated vertically in soil due to water infiltration. In the CK and grass-covered citrus orchards, there are 57.64% and 24.36% of the applied neonicotinoids were retained in soil and soil solution, respectively, and their concentration decreased as soil depth increased. Another noteworthy phenomenon is that more neonicotinoids migrated to deeper soil layers under grass cover compared with no grass cover because grass roots promoted the formation of cracks and vertical preferential flow. Our results are expected to improve the accuracy of neonicotinoids pollution prediction by considering migration paths, including surface and subsurface runoff and eroded sediment.

The recently recognized adverse environmental and toxic effects of neonicotinoid insecticides (NNIs) on non-target organisms are alarming. A comprehensive design, screening, and regulatory system was developed to generate NNI derivatives and mutant receptors with selective-ecotoxicological effects to overcome such adverse effects. For ligand design, taking ACE-09 derivative as an example, the toxicity on non-target animals (aboveground: bees; underground: earthworms), plant absorption, and soil absorption decreased by 4.80% and 13.7%, 10.0%, and 121%, while the toxicity on target animals (aboveground: aphids; underground: B. odoriphagas), plant metabolism, and soil degradation increased by 70.2% and 51.7%, 5.08%, and 8.28%. For receptor modification, the ability of mutants to absorb ACE-09 derivative decreased by 31.0%, while the ability of mutants to metabolize ACE-09 derivative increased by 28.0% in scenario 2 (mainly plant selectivity); the ability of mutants to degrade ACE-09 derivative increased by 11.6% in scenario 3 (mainly soil selectivity). The above results indicated that the selective-ecotoxicological effects of ligand design and receptor modification were both improved. Additionally, the combined effects of the ACE-09 derivative on plant absorption and metabolic mutants improved by 31.1% and 31.4% in scenario 2, respectively, while the effect on microbial degradation mutant improved by 14.9%, indicating that there was a synergistic effect between ligand design and receptor modification. Finally, based on the interaction between the ACE-09 derivative and mutants, the optimal environmental factors that improved the selectivity of their ecotoxicological effects were determined. For example, alternate application of nitrogen and phosphorus fertilizers effectively reduced the oxidative damage to plants caused by NNI residues. The novel ligand-receptor joint modification method, combined with the regulation of environmental factors under multiple scenarios, can biochemically address the ecotoxicological concern and highlight the harmful effects of pesticides on the environment and non-target organisms.

Municipal sewage treatment plants (STPs) have been regarded as an important source of organic contaminants in aquatic environment. To assess the impact of STPs on occurrence and toxicity of STP-associated contaminants in receiving waterways, a novel passive sampler modified from polar organic chemical integrative sampler (m-POCIS) was deployed at the inlet and outlet of a STP and several upstream and downstream sites along a river receiving STP effluent in Guangzhou, China. Eighty-seven contaminants were analyzed in m-POCIS extracts, along with toxicity evaluation using zebrafish embryos. Polycyclic musks were the predominant contaminants in both STP and urban waterways, and antibiotics and current-use pesticides (e.g., neonicotinoids, fiproles) were also ubiquitous. The m-POCIS extracts from downstream sites caused significant deformity in embryos, yet the toxicity could not be explained by the measured contaminants, implying the presence of nontarget stressors. Sewage treatment process substantially reduced embryo deformity, chemical oxygen demand, and contamination levels of some contaminants; however, concentrations of neonicotinoids and fiproles increased after STP treatment, possibly due to the release of chemicals from perturbed sludge. Source identification showed that most of the contaminants found in urban waterways were originated from nonpoint runoff, while cosmetics factories and hospitals were likely point sources for musks and antibiotics, respectively. Although the observed embryo toxicity could not be well explained by target contaminants, the present study showed a promising future of using passive samplers to evaluate chemical occurrence and aquatic toxicity concurrently. Zebrafish embryo toxicity significantly decreased after sewage treatment, but higher toxicity was observed for downstream samples, demonstrating that urban runoff may produce detrimental effects to aquatic life, particularly in rainy season. These results highlight the relevance of monitoring nonpoint source pollution along with boosting municipal sewage treatment infrastructure.

Studies have shown that the mixture toxicity of compounds with similar modes of action (MOAs) is usually predicted by the concentration addition (CA) model. However, due to the lack of toxicological information on compounds, more evidence is needed to determine whether the above conclusion is generally applicable. In general, the same type of compounds with similar chemical structures have similar MOAs, so whether the toxicities of the mixture of these compounds are additive needs to be further studied. In this paper, three types of pesticides with similar chemical structures (three organophosphoruses, two carbamates and two neonicotinoids) that may have similar MOAs were selected and five binary mixture systems were constructed. For each system, five mixture rays with different concentration ratios were designed by the direct equipartition ray design (EquRay) method. The mortality of Caenorhabditis elegans was regarded as the endpoint for the toxicity exposure to single pesticides and binary mixtures. The combined toxicities were evaluated simultaneously using the CA model, isobologram and combination index. The structural similarity of the same type of pesticides was quantitatively analyzed according to the MACCS molecular fingerprint and the slope of dose-response curve at pEC₅₀. The results show that the toxicities of neonicotinoid mixtures and carbamate mixtures are almost antagonistic. The entire mixture system of dichlorvos and dimethoate produced synergism, and four of the five mixture rays of dimethoate and methamidophos induced antagonism, while among the mixture rays of dichlorvos and methamidophos, different concentrations showed different interaction types. The results of structural similarity analysis show that the size of structural similarity showed a certain quantitative relationship with the toxicity interaction of mixtures, that is, the structural similarity of the same type of pesticides may show an additive action in a certain range.

In developing countries, urban areas may be at greater risk of pesticide exposure compared to semi-urban agricultural regions. To investigate this, concentrations of selected pesticides were measured in 81 human milk samples collected in urban Kolkata and semi-urban Nadia in West Bengal, India. Three classes of pesticides were investigated – legacy organochlorines and emerging pyrethroids and neonicotinoids. The average concentration of the majority of the chemicals (DDT, its metabolites, HCH isomers, bifenthrin, endosulfan), showed a clear urban > semi-urban trend. Compared with previous measurements in other Indian cities and developing nations, current HCH and DDT concentrations in urban Kolkata were high. These chemicals were detected in 100% of the samples in both the urban and the semi-urban region. Also in both regions, the Estimated Daily Intake of DDTs, HCHs, aldrin, dieldrin and the pyrethroid bifenthrin for breastfed infants exceeded the Tolerable Daily Intake in a number of samples. Three pyrethroids were detected in human milk samples in India for the first time. This indicates a shift in the usage pattern of pesticides in India from organochlorines to pyrethroids. These findings may be used to drive targeted regulation of pesticides in developing countries with similar histories of pesticide use.

Guadipyr, which combines neonicotinoid and semicarbazone functional groups in one molecule, exhibits good activity on several pests and high acute and chronic toxicity to silkworms (Bombyx mori). In this report, the effects of low-dose guadipyr on the midgut microbiota and immune system of silkworms were studied. Results showed that the structure and richness of the midgut microbiota of silkworms were altered after being treated with 5.25 mg/L (1/10 of LC₅₀) of guadipyr. The abundance of Pseudomonas was evidently increased, whereas Curvibacter was substantially reduced, which might be related to the growth and immunity of silkworms. The expression of key genes in the Toll, IMD, and JAK/STAT pathways, which ultimately led to the downregulation of antimicrobial peptide genes (AMPs), such as CecA, Defensin1, Leb, and glv2, was reduced upon guadipyr exposure. Simultaneously, the suppression of steroid hormone 20-hydroxyecdysone receptor and response genes, such as BR-C Z4, was detected in the exposed groups. The decreased expression of these immune regulatory pathway-related and 20-hydroxyecdysone signal pathway-related genes indicated that the immune system of silkworms was affected by low-dose guadipyr. Our results revealed the negative effects of guadipyr on silkworms and highlighted the unneglectable toxicity of low-dose guadipyr to this economic insect. Given the risk, it is necessary to control the application of guadipyr in or around the mulberry fields.