Neonicotinoids (NEOs) have become the most widely used insecticides in the world. However, information on the NEO concentrations in tap water based on nationwide surveys is limited in China. In this study, the levels of six NEOs were measured in tap water samples collected from 38 cities in China. Across all sampling locations, the overall frequency of detection for at least one NEO was 100%, indicating that NEOs are ubiquitous in tap water from China. Imidacloprid was the most abundant NEO (median: 7.59 ng/L), followed by (in decreasing order) clothianidin (5.46 ng/L), dinotefuran (4.55 ng/L), thiamethoxam (4.50 ng/L), acetamiprid (2.72 ng/L), and thiacloprid (0.38 ng/L). Significantly positive correlations (r = 0.655–0.902, p < 0.001) among all pairs of NEOs were observed, which showed that the sources of NEOs in tap water were common or related. Across all sampling locations, regional differences in concentrations (ΣNEOs; sum of six NEOs varied from 0.79 ng/L to 415 ng/L) were observed within China, showing an increasing trend from northern to southern China. Although the estimated daily intake of NEOs were much lower than the reference dose, the potential health risk of NEOs via tap water consumption should raise more public concern considering the high detection rates of NEOs in tap water.

Soil contaminants can cause direct harm to lizards due to their regular swallowing of soil particles. As the world’s fastest growing insecticide with long half-life in soil, the endocrine disrupting effect of neonicotinoids on lizards deserves more attention. In this report, we assessed the endocrine disrupting effect of imidacloprid on Eremias argus during 28 days of continuous exposure. Among the imidacloprid and its metabolites, only the metabolite 6-chloropyridic acid had a significant accumulation in the gonads and was positively correlated with its blood concentration. Imidacloprid might cause endocrine disrupting effects on lizards in two ways. First, the desnitro metabolites of imidacloprid could accumulate in the brain, inhibited the secretion of gonadotropin-releasing hormone, and ultimately affected the feedback regulation of hypothalamic-pituitary-gonadal related hormones. Secondly, imidacloprid severely inhibited the gene expression of the corresponding enzymes in the gonadal anti-oxidative stress system, causing histological damage to the gonads and ultimately affecting gonadal function. Specifically, exposure to imidacloprid resulted in abnormal arrangement of spermatogenic epithelial epithelium, hyperplasia of epididymal wall, and oligospermia of male lizard. Meanwhile, gene expressions of cyp17, cyp19, and hsd17β were severely inhibited in the imidacloprid exposure group, consistent with decreased levels of testosterone and estradiol in plasma. Imidacloprid exposure could cause insufficient androgen secretion and less spermatogenesis in male lizards. The risk of imidacloprid exposure to female lizards was not as severe as that of male lizards, but it still inhibited the expression of cyp19 in the ovaries and led to a decrease in the synthesis of estradiol. This study firstly reported the endocrine disruption of imidacloprid to lizards, providing new data for limiting the use of neonicotinoids.

Little information is available about the occurrence of neonicotinoid insecticides in surface water and sediment of the metropolitan regions around the rivers in China. Here we investigate the residual level of neonicotinoids in the Guangzhou section of the Pearl River. At least one or two neonicotinoids was detected in each surface water and sediment, and the total amount of neonicotinoids (∑₅neonics) in surface water ranged from 92.6 to 321 ng/L with a geometric mean (GM) of 174 ng/L. Imidacloprid, thiamethoxam and acetamiprid were three frequently detected neonicotinoids (100%) from surface water. As for the sediment, total concentration was varied between 0.40 and 2.59 ng/g dw with a GM of 1.12 ng/g dw, and acetamiprid and thiacloprid were the common sediment neonicotinoids. Western and Front river-route of the Guangzhou section of the Pearl River suffered a higher neonicotinoids contamination than the Rear river-route, resulting from more effluents of WWTPs receiving, and intensive commercial and human activities. Level of residual neonicotinoids in surface water was significantly correlated with the water quality (p < 0.01), especially items of pH, DO and ORP, and nitrogen and phosphorus contaminants. Compared with reports about residual neonicotinoids in water and sediment previously, the metropolitan regions of the Guangzhou could be confronted with a moderate contamination and showed serious ecological threats (even heavier than the Pearl Rivers). Our results will provide valuable data for understanding of neonicotinoids contamination in the Pearl River Delta and be helpful for further assessing environmental risk of neonicotinoids.

To elucidate the sorption affinity of biochars for neonicotinoid pesticides and the influence of biochar structure on sorption mechanisms therein, 24 biochar samples were obtained by pyrolyzing maize straw and pig manure at pyrolyzing temperatures (PTs) of 200–700 °C and by further deashing them using acids, and the sorption of three typical neonicotinoids, imidacloprid, clothianidin and thiacloprid on untreated and acid-deashed biochars were evaluated. All the biochar samples could efficiently adsorb the three neonicotinoids and multiple mechanisms were involved in sorption. With the increasing PTs, hydrophobic partition sorption increased, but had a declined contribution to the total sorption as revealed by a dual-mode model. Besides hydrophobic partition, specific interactions like cation-π electron donor acceptor (EDA) interactions (only for protonated IMI and CLO) and hydrogen bond and contributed much to the sorption on low-PT (≤500 °C) biochars, while the sorption on those high-PT (>500 °C) biochars mainly depended on pore-filling strengthened by cation-π and p/π-π EDA interactions. Thiacloprid showed stronger sorption on untreated biochars compared to imidacloprid and clothianidin, due to its greater ability to form hydrogen bond and hydrophobic interactions. Acid-deashing treatments increased the relative percentage contents of organic carbon, bulk O, aromaticity and O-containing functional groups, surface area and pore volume of biochars. The ash can bind neonicotinoids by specific interactions but played a negative role in the whole sorption on high-PT biochars by covering the inner sorption sites of organic moieties and blocking the micropores in biochars. The results acquired in the present study will help us to get deep insight in the comprehensive sorption mechanisms of polar pesticides on biochar and the effects of biochar structure.

Among the many factors responsible for the decline of bee populations are plant protection products such as neonicotinoids. In general, bees are exposed to not only one but mixtures of such chemicals. At environmental realistic concentrations neonicotinoids may display negative effects on the immune system, foraging activity, learning and memory formation of bees. Neonicotinoids induce alterations of gene transcripts such as nicotinic acetylcholine receptor (nAChR) subunits, vitellogenin, genes of the immune system and genes linked to memory formation. While previous studies focused on individual compounds, the effect of neonicotinoid mixtures in bees is poorly known. Here we investigated the effects of neonicotinoids acetamiprid, clothianidin, imidacloprid and thiamethoxam as single compounds, and binary mixtures thereof in honeybees. We determined transcriptional changes of nAChR subunits and vitellogenin in the brain of experimentally exposed honeybees after exposure up to 72 h. Exposure concentrations were selected on the basis of lowest effect concentrations of the single compounds. Transcriptional induction of nAChRs and vitellogenin was strongest for thiamethoxam, and weakest for acetamiprid. To a large extent, binary mixtures did not show additive transcriptional inductions but they were less than additive. Our data suggest that the joint transcriptional activity of neonicotinoids cannot be explained by concentration addition. The in vivo effects are not only governed by agonistic interaction with nAChRs alone, but are more complex as a result of interactions with other pathways as well. Further studies are needed to investigate the physiological joint effects of mixtures of neonicotinoids and other plant protection products on bees to better understand their joint effects.

China is the largest beekeeping and honey consumption country globally. Neonicotinoids in honey can pose adverse effects on honey bees and human, but data on neonicotinoids residues in honey and its health risk remain limited in China. A total of 94 honey samples were selected from Chinese market based on production region and sale volume in 2020. Eight neonicotinoids and four metabolites were determined by liquid chromatography coupled to mass spectrometry. Health risk of neonicotinoids in honey on honey bees and human was assessed by hazard quotient (HQ) and hazard index (HI). Neonicotinoids and their metabolites were overall detected in 97.9% of honey samples. Acetamiprid, thiamethoxam, and imidacloprid were top three dominant neonicotinoids in honey with the detection frequencies of 92.6%, 90.4%, and 73.4%, respectively. For honey bees, 78.7% of honey samples had a HI larger than one based on the safety threshold value of sublethal effects. Top three neonicotinoids with the highest percent proportion of HQ larger than one for honey bees were acetamiprid (43.6%), imidacloprid (31.9%), and thiamethoxam (24.5%) and their maximum HQs were 420, 210, and 41, respectively. Based on oral median lethal doses for honey bees, both HQ and HI were lower than one in all honey samples. For human, both HQ and HI were lower than one based on acceptable daily intakes in all honey samples. Neonicotinoids concentrations and detection frequencies in honey samples and its health risk varied with production region, commercial value of nectariferous plants, number of nectariferous plants, and sale price. The results suggested extensive residues of neonicotinoids in honey in Chinese market with a variation by the characteristics of honey. The residues were likely to affect the health of honey bees, but showed no detectable effect on human health.

Currently little is known of newer pesticide classes and their occurrence and persistence in recreational lakes. Therefore, the objectives of this study were to (1) assess average pesticide concentrations and loadings entering recreational lakes in three mixed land use watersheds throughout the growing season, (2) evaluate pesticide persistence longitudinally within the lakes, and (3) perform an ecotoxicity assessment. Six sampling campaigns were conducted at three lakes from April through October 2018 to measure the occurrence and persistence during pre, middle, and post growing season. Polar organic chemical integrative samplers (POCIS) were placed in streams near lake inlets and monthly samples were collected for analysis of twelve pesticides. Additional monthly grab water samples were taken at each POCIS location and at the midpoint and outlet of each lake. All pesticide samples were analyzed using liquid chromatography/tandem mass spectrometry (LC/MS/MS) and individual pesticide loading rates were determined. Occurrence and persistence of specific pesticides were significantly different between lakes in varying watershed land uses. Specifically, the recreational lake receiving predominately urban runoff had the highest load of pesticides, likely in the form of biocides, entering the waterbody. Concentrations of imidacloprid exceeded acute and chronic invertebrate levels for 11% and 61% of the sampling periods, respectively, with the recreational lake receiving predominately urban runoff having the most occurrences. Findings from this study are critical for preventing and mitigating potential effects of pesticides, specifically applied as biocides in urban landscapes, from entering and persisting in recreational lakes.

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.

We investigated the fates of seven neonicotinoids (NNIs) in full-scale drinking water treatment plants and assessed human exposure to NNIs through consuming drinking water. The total NNI concentrations in raw water and treated water samples from the drinking water treatment plants were 20.4–166 ng/L (median 118 ng/L) and 1.11–94.7 ng/L (median 20.4 ng/L), respectively. The dinotefuran (DIN) concentrations in raw water collected in different seasons were different, and the highest DIN concentration was found in summer. The drinking water treatment processes removed >91% of the NNIs except DIN and thiamethoxam (THIAM), for which the mean removal rates were 70% and 74%, respectively. The removal rates for all of the NNIs were higher for the granular activated carbon filtration process (mean 83.5%) than the other drinking water treatment plant processes (coagulation/sedimentation 22.3%, ozonation 29.2%). However, the removal rates in the granular activated carbon process were lower for DIN and THIAM (61.0% and 59.2%, respectively) than the other NNIs. Significant correlations were found between the NNI removal rates and physicochemical properties (solubility in water and log (octanol–water partition coefficient)). The estimated mean human exposure to NNIs in drinking water was 0.528 ng/(kg body weight d).