Exposure assessment of neonicotinoid insecticides and their metabolites in Chinese women during pregnancy: A longitudinal study.

Neonicotinoid insecticides (NNIs) are the most widely used insecticides globally and ubiquitous in the environment, which has led to widespread human exposure. However, studies on internal exposure levels of NNIs and their metabolites in pregnant women are scarce. In this study, we measured nine parent NNIs and ten main metabolites in 1224 urine samples donated by 408 pregnant women at three trimesters. In the urine samples, the unadjusted vs. specific gravity (SG) adjusted median concentrations and detection frequencies (DFs) of desmethyl-acetamiprid (DM-ACE; 1.01 vs. 1.08 ng/mL; DF: 99.7%), 5-hydroxy-imidacloprid (5-hydroxy-IMI; 0.54 vs. 0.56 ng/mL; 98.5%), imidacloprid-olefin (IMI-olefin; 0.41 vs. 0.44 ng/mL; 99.3%), and desnitro-imidacloprid (DN-IMI; 0.12 vs. 0.12 ng/mL; 90.4%) were higher than their corresponding parent NNIs, acetamiprid (ACE; <0.01 vs. <0.01 ng/mL; 26.4%) and imidacloprid (IMI; 0.04 vs. 0.04 ng/mL; 69.9%). The unadjusted and SG-adjusted median concentrations of clothianidin (CLO), thiamethoxam (THM), and desmethyl-clothianidin (DM-CLO) were 0.05 vs. 0.07, 0.05 vs. 0.06, and 0.04 vs. 0.05 ng/mL, with the DFs of 61.0%, 57.5%, and 75.7%, respectively. The cumulative exposure level, imidacloprid-equivalent total NNIs (IMIeq), was generated by the relative potency factor approach considering the toxic effects of NNIs and their metabolites. The unadjusted IMIeq varied from 0.17 ng/mL (SG-adjusted: 0.20) to 1969 ng/mL (SG-adjusted: 1817) with a median of 14.1 ng/mL (SG-adjusted: 14.1). A decreased trend was observed in urinary NNIs and their metabolites throughout the three trimesters. Maternal age, educational level, and household income were related to the concentrations of NNIs and their metabolites. DM-ACE, 5-hydroxy-IMI, and IMI-olefin were significantly lower in winter than in autumn; DN-IMI, THM, CLO, and DM-CLO were significantly higher in both summer and autumn than in winter. The maximum estimated daily intake of IMIeq [34.8 µg/kg-body weight (bw)/d] was lower than the chronic reference dose of IMI (57 µg/kg-bw/d) currently recommended by the United States Environmental Protection Agency. Human health risk of exposure to NNIs and their main metabolites warranted further studies.

A nationwide study of occurrence and exposure assessment of neonicotinoid insecticides and their metabolites in drinking water of China.

Neonicotinoid insecticides (NNIs) are the most extensively used insecticides worldwide, threatening ecosystem and human health. However, nationwide studies of NNIs and their metabolites in drinking water are limited. In order to characterize the contamination status of NNIs in drinking water throughout China, we collected 884 drinking water samples including 789 tap water and 95 groundwater samples from 32 provinces (covering seven regions of mainland China: south, central, east, north, northeast, northwest, and southwest) and Hong Kong. Ten NNIs and six of their main metabolites were determined in the water samples. The relative potency factor method was used to assess the cumulative concentrations of NNIs and their metabolites (imidacloprid-equivalent total NNIs, IMIeq) based on the chronic reference doses (cRfDs) of the NNIs or the toxic effects of the mataboilites. The IMIeq varied among the studied regions, with a median concentration of 24.5 ng/L and a maximum concentration of 8,622 ng/L. The predominant NNIs in drinking water were acetamiprid (ACE) and imidacloprid (IMI). Compared with tap water derived from groundwater, much higher concentrations of IMIeq and NNIs were found in tap water derived from surface water. Different concentrations and patterns of NNIs in drinking water were observed in different regions, provinces, and capital cities, mainly due to regional and provincial differences in crop types and volumes of pesticide usage. The concentrations of NNIs in the drinking water of provincial capitals and small/medium cities were higher than the concentrations in rural areas. The estimated daily intake (EDI) of IMIeq was at least two orders of magnitude lower than the cRfD of IMI, while the NNIs in 16 drinking water samples exceeded the acceptable value (100 ng/L) recommended by the European Union. This study provided a nationwide profile of the occurrence of NNIs and their metabolites in the drinking water of China and the associated potential cumulative human health risks, taking into account of the toxicity differences between NNIs and their metabolites.

Assessment of imidacloprid related exposure using imidacloprid-olefin and desnitro-imidacloprid: Neonicotinoid insecticides in human urine in Wuhan, China.

While neonicotinoid insecticides (NNIs) have been widely used worldwide, limited studies have measured specific metabolites of imidacloprid (IMI, the most commonly used NNI) in human urine. To better understand human exposure to NNIs, 10 parent compounds, and 6 of their metabolites were analyzed in 408 urine samples collected from 129 healthy adults in Wuhan, Central China, during autumn and winter of 2018. These specimens included repeated urine samples taken in 3 d from 75 volunteers. The urinary concentrations of desnitro-imidacloprid (DN-IMI), imidacloprid-olefin (IMI-olefin), and desmethyl-acetamiprid (DM-ACE) were higher (4-40 times) than those of their parent compounds (IMI and acetamiprid, ACE). DN-IMI and IMI-olefin accounted for 92% of the urinary Σ3IMI (the sum of IMI and its specific metabolites measured). Positive correlations (r) were observed between DN-IMI and IMI (0.50), IMI-olefin and IMI (0.75), and DM-ACE and ACE (0.53). Good to excellent inter-day reliabilities (unadjusted intraclass correlation coefficients) were observed for IMI-olefin (0.61) and DM-ACE (0.81), while moderate inter-day reliability was observed for DN-IMI (0.43). The urinary NNI concentrations were significantly higher in autumn than in winter, and higher in urban areas than in rural areas, while no significant gender or age-related differences were observed. To our knowledge, this is the first report on DN-IMI and IMI-olefin in human urine.

A nationwide study of the occurrence and distribution of atrazine and its degradates in tap water and groundwater in China: Assessment of human exposure potential.

Despite frequent detection of atrazine (ATZ) and its degradates (including hydroxyatrazine, ATZ-OH; deethylatrazine, DEA; deisopropylatrazine, DIA; and deethyldeisopropylatrazine, DACT) in a variety of water bodies, documentation of their occurrence and distribution in tap water in China is still scarce. A nationwide survey about ATZ and its degradates (ATZs) in tap water from 31 provinces in 7 regions of mainland China and Hong Kong was conducted during June 2019. At least one of the analytes was found in all the water samples (n = 884). The median sum concentrations of ATZs (ΣATZs) was 21.0 ng/L (range: 0.02 ng/L-3.04 µg/L). The predominant compounds of ATZs in tap water were ATZ and DEA, with a detection frequency of 99.5% and 98.0%, respectively, followed by ATZ-OH (87.3%), DACT (84.0%), and DIA (78.1%). Significant regional variations (p < 0.05) were found in the concentrations of ATZs in tap water, and the highest concentration of ΣATZs (median: 254 ng/L, range: 0.44 ng/L-3.04 µg/L) was found in Northeastern China, followed by Eastern (37.2 ng/L, 0.02-706 ng/L), Northern (30.2 ng/L, 0.04-317 ng/L), Central (29.3 ng/L, 0.04-256 ng/L), Southern (25.0 ng/L, 0.04-297 ng/L), Southwestern (17.2 ng/L, 0.02-388 ng/L), and Northwestern China (3.22 ng/L, 0.06-214 ng/L). The level of ΣATZs in groundwater from rural area of China was about 1/3 of that found in tap water. ATZs cannot be removed by boiling tap water. The highest estimated daily intake of ΣATZs (248 ng/kg-body weight/day) was found in the infant population of Changchun, Jilin, Northeastern China.