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Pentachlorophenol (PCP) is a ubiquitous environmental persistent organic pollutant and a Group 1 carcinogen. Human exposure level of PCP was reported to be relatively higher in China than in many other countries, because sodium pentachlorophenate was abused as molluscicide in China. PCP can induce oxidative stress; however, the relationship of PCP exposure with oxidative stress biomarkers (OSBs) in human beings has rarely been documented. In this study, 404 first-morning urine samples (including repeated samples in three days donated by 74 participants) were collected from 128 healthy adults (general population without occupational exposure to PCP) in autumn and winter of 2018, respectively, in Wuhan, central China. Urinary concentrations of PCP and three select OSBs [including 8-OHG (abbreviation of 8-hydroxy-guanosine), 8-OHdG (8-hydroxy-2'-deoxyguanosine), and 4-HNEMA (4-hydroxy-2-nonenal mercapturic acid), which reflect oxidative damage of RNA, DNA, and lipid, respectively] were determined. PCP was detectable in 100% of the urine samples (specific gravity-adjusted median concentration: 0.44 ng/mL; range: 0.02-14.2 ng/mL). Interday reproducibility of urinary PCP concentrations was excellent (intraclass correlation coefficient: 0.88) in three days. Significant differences in PCP concentrations were found among different age groups; the group of participants aged 20-45 y (median: 0.72 ng/mL) had higher concentrations than those in the elders (aged 45-60 y and 60 y). Spatial disparity was observed in autumn, and urban residents had higher PCP concentrations than rural residents (median: 0.60 vs. 0.31 ng/mL), whereas such disparity was not found in winter. There were no season-, sex-, or BMI-related differences between the corresponding subgroups. The urinary PCP concentrations were found to be associated with increases in 8-OHdG and 8-OHG rather than 4-HNEMA. An interquartile range increase in urinary PCP concentration was associated with a 23.5% (95% CI: 9.18-39.6) increase in 8-OHdG and a 21.3% (95% CI: 9.18-32.4) increase in 8-OHG, implied that PCP exposure at environmental relevant dose might be associated with nucleic acid oxidative damage in the general population. This pilot study reported associations between PCP exposure and OSBs in human beings. Future studies are needed to elucidate the mediating roles of OSBs in the association between PCP exposure and certain adverse health outcomes.

Bentazone is a widely used post-emergence herbicide, while no data was available on its concentrations in tap water from China and in urine among the general population. It was determined in the source (Wuhan section of the Yangtze River watershed), treated, and tap water (n = 20, 20, and 170, respectively) in different seasons (2019) in Wuhan, central China. Also, urine samples (n = 38) collected from healthy adults in Wuhan (September 2020) were analyzed to characterize its urinary concentration. Bentazone was detected in all the source and treated water samples. Its concentrations in the source water in July were higher than those in February (median: 17.9 ng/L vs. 2.86 ng/L) (p < 0.05). It cannot be removed efficiently (27.8–27.9%) by conventional drinking water treatment using NaClO, but it can be efficiently removed by using chlorine dioxide or ozone combined with activated carbon. Bentazone was frequently detected (detection frequency: 96.3%) in 160 tap water samples (underwent conventional treatment) (median: 1.95 ng/L, range

A comprehensive contamination profile of organophosphate esters (OPEs) in the Yangtze River in China has not yet been characterized. In this study, we investigated the occurrence, spatial variation, and seasonal difference of 18 selected OPEs in surface water samples of the Yangtze River mainstream. To characterize the contamination profile of the OPEs, we collected 144 Yangtze River water samples from 72 sampling sites in December 2020 and June 2021. Four alkyl-OPEs [trimethyl phosphate, triethyl phosphate (TEP), tributyl phosphate, and tris(2-butoxyethyl) phosphate (TBOEP)] and three halogenated OPEs [tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate] were the most frequently detected target compounds (95%). TCIPP (median: 34.6 ng/L), TEP (median: 26.2 ng/L), and TCEP (median: 17.9 ng/L) were the most abundant compounds, while the median values of the others were below 10 ng/L. Additionally, the concentrations of most OPEs gradually/dramatically increased from upstream to downstream Yangtze River. Notably, the median concentration of summed OPEs in Shanghai (415 ng/L; downstream) was approximately ten times higher than that in Qinghai (45.7 ng/L; upstream). Urban sampling sites had significantly or slightly higher concentrations of most OPEs than rural sampling sites. Moreover, the OPE concentrations in the river water differed between the winter and summer. The concentrations of summed OPEs (median: 117 vs. 106 ng/L), summed alkyl-OPEs (67.0 vs. 45.8 ng/L; p0.05), and summed aryl-OPEs (0.48 vs. 0.17 ng/L; p0.05) were slightly or significantly higher in December than those in June; nevertheless, summed halogenated OPEs were slightly higher in June (62.2 vs. 50.2 ng/L) than that in December. Compared with previously reported data for OPEs in other major rivers worldwide, the Yangtze River water had relatively lower concentrations of the OPEs than those in the rivers of developed countries and regions. Ecological risk assessment suggested that tris(2-ethylhexyl) phosphate and TCEP posed relatively high risks (RQ: 1.01 and 0.98, respectively) at the maximum concentration, and TBOEP posed a moderate risk (RQ: 0.25). This is the first study to comprehensively characterize the contamination profile of the Yangtze River by the OPEs.

Carbendazim (CBDZ) is the most widely used fungicide in China. It is ubiquitous in environment and can induce oxidative stress in mammals, while data on occurrence of its metabolite in human urine are scarce, and the relationship between CBDZ and oxidative stress biomarkers (OSBs) in young children has not been examined. The aim of this study was to measure the concentrations of methyl 5-hydroxy-2-benzimidazolecarbamate (5-HBC, the main metabolite of CBDZ in urine) in 390 urine samples collected from 130 healthy young ( 6.6 years old) children from Shenzhen and Wuhan, in south and central China, respectively, and to evaluate the associations of 5-HBC with three selected OSBs (4-HNEMA, 8-OHG, and 8-OHdG, for lipid, RNA, and DNA, respectively). 5-HBC was found in 99.2% of the urine samples at concentrations ranging from below the method detection limit ( 0.005 ng/mL) to 10.9 ng/mL (median: 0.11 ng/mL). Moderate inter-day reproducibility was found for specific gravity-adjusted 5-HBC concentrations (intraclass correlation coefficient: 0.50). The urinary 5-HBC concentrations were significantly and positively associated with 4-HNEMA (p 0.01). An interquartile range increase in urinary 5-HBC concentrations was associated with a 42.1% increase in 4-HNEMA, which implied that CBDZ exposure might be associated with lipid peroxidation in young children without occupational exposure. As far as we know, this pilot study is the first to report urinary 5-HBC and its associations with OSBs in children.

Arsenic in fine air particulate matter (PM2.5) has been identified as an important factor responsible for the morbidity of lung cancer, which has increased sharply in many regions of China. Some reports in China have shown that arsenic in the air exceeds the ambient air quality standard value, while long-term airborne arsenic concentrations in central China and human exposure via inhalation of PM–bound arsenic (inhalable airborne PM) have not been well characterized. In this study, 579 outdoor air PM2.5 samples from Wuhan, a typical city in central China, were collected from 2015 to 2017, and arsenic was measured by inductively coupled plasma-mass spectrometry. Personal exposure to PM-bound arsenic via inhalation and urinary arsenic concentration were also measured. The concentrations of arsenic in PM2.5 were in the range of 0.42–61.6 ng/m3 (mean 8.48 ng/m3). The average concentration of arsenic in 2015 (10.7 ng/m3) was higher than that in 2016 (6.81 ng/m3) and 2017 (8.18 ng/m3), exceeded the standard value. The arsenic concentrations in spring and winter were higher than those in summer and autumn. No significant differences (p > 0.05) were found among different sites. The daily intake of arsenic inhalation based on PM10 samples collected by personal samplers (median, 10.8 ng/m3) was estimated. Urban residents inhaled higher levels of PM-bound arsenic than rural residents. Daily intake of arsenic via inhalation accounted for a negligible part (

Arsenic can be easily enriched in air particulate matter and has been identified to be associated with many of diseases, including lung cancer. Tiered data regarding arsenic in ambient air particulate matter is limited in China, particularly data from small cities and rural areas. In this study, 918 outdoor air total suspended particulate samples were collected from 19 districts of 7 provinces in China (Hunan, Hubei, Hebei, Shanghai, Guangdong, Yunnan, and Shanxi) from January 2013 to September 2015. Results showed that arsenic concentrations fluctuated from 0.85 to 185 ng/m3 (geometric mean (GM): 11.7 ng/m3). The highest GM was observed in Hunan (20.5 ng/m3), followed by Hebei (18.8 ng/m3), Hubei (15.9 ng/m3), Shanxi (13.2 ng/m3), Yunnan (8.67 ng/m3), Guangdong (7.62 ng/m3), and Shanghai (6.34 ng/m3). All GMs exceeded the Chinese limit of 6 ng/m3 (annul average values in total suspended particulate matters) in ambient air. In general, winter and spring were characterized by higher arsenic concentrations in ambient air in comparison to summer and autumn. Rural areas in Hunan and Shanghai had higher levels of arsenic in air than their urban areas. The daily intake of arsenic through inhalation was estimated. Higher daily intake of arsenic through inhalation was observed in children in comparison to other age groups. Human exposure to arsenic via inhalation represented by daily intake was minor when compared with other pathways such as dietary intake; however, the potential adverse effects on sensitive and general populations in China require further study.

The inverse dynamic model and performance analysis of a new redundant parallel rehabilitation robot are presented in this paper. First, the kinematics of each part is analyzed based on a closed-loop vector chain method. Then, the dynamic model of each part is formulated based on the D'Alembert principle and Euler's equation. After that, the inverse dynamic formulation of the new redundant parallel robot is established by utilizing the principle of virtual work and the concept of linked Jacobian matrices. To validate the approach, dynamic simulations are implemented in ADAMS and MATLAB. The results demonstrate the correctness of this dynamic formulation. Then, the actuating forces are optimized by utilizing the weighted Moore-Penrose generalized inverse method, which determines the minimum norm of the least quadratic sum among the possible actuating force vectors. Finally, two novel dynamic performance indices are defined. The first index reflects the coupling effect of other neighboring limbs to the dominant limb; the second reflects the coupling effect of each neighboring limb to the dominant limb. The proposed approach can be used for the dynamic performance analysis in other types of redundant parallel robots and provides a reference for dynamic control strategies.

Widespread exposure to herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) could have potential adverse health effects on pregnant women. However, related data are scarce. This study aimed to characterize 2,4-D exposure among three trimesters of pregnancy and to explore the relationship of 2,4-D with oxidative stress biomarkers [i.e., 8-hydroxy-2'-deoxyguanosine (8-OHdG), 8-hydroxy guanosine (8-OHG), and 4-hydroxy nonenal mercapturic acid (HNEMA)] in urine. The present study analyzed 3675 urine samples of 1225 women (across the three trimesters of pregnancy) in Wuhan, central China. 2,4-D was detectable in 97.4% of the urine samples. The median unadjusted concentration of 2,4-D was 0.12 ng/mL, and the corresponding concentration adjusted by urinary specific gravity (SG-adjusted) was 0.13 ng/mL. The intraclass correlation coefficient of 2,4-D (SG-adjusted concentrations) was 0.07 across the three trimesters. Significantly higher urinary levels of 2,4-D were found in samples from younger pregnant women/samples collected during winter. In addition, significantly positive association between urinary concentrations of oxidative stress biomarkers and 2,4-D were found in repeated analysis; an interquartile range increase in 2,4-D was significantly (p 0.001) associated with a 20.8% increase in 8-OHG, a 26.7% increase in 8-OHdG, and a 30.7% increase in HNEMA, respectively. Such associations were also found in trimester-specific analyses. This is the first time to quantify the urinary 2,4-D of pregnant women in China, and this study found significantly positive associations of 2,4-D with oxidative stress biomarkers. Further studies are needed to verify such associations and explore other potential adverse effects of 2,4-D exposure.

Pentachlorophenol (PCP) is ubiquitous and moderately persistent in the environment, and it is an identified human carcinogen. Previous animal experiments indicate that toxic mechanisms of PCP include oxidative stress. However, no epidemiological study has reported the association between PCP exposure and oxidative stress; such association in pregnant women, a vulnerable population, is of particular interest. This study aimed to characterize PCP concentrations in 2304 urine samples from 768 pregnant women, explore its determinants, and evaluate the associations between PCP exposure and three oxidative stress biomarkers across three trimesters. The median concentrations of PCP (100% detected) in the first, second, and third trimester were 0.61, 0.59, and 0.48 ng/mL, respectively, with a significant decrease trend. The intraclass correlation coefficient of specific gravity (SG)-adjusted PCP was 0.26, indicating high variability for PCP across the three trimesters. PCP concentrations were significantly higher in older, pre-pregnancy overweight, multiparous, high-income, and employed women during pregnancy. Urinary PCP was markedly lower in samples collected during spring compared to other seasons. Linear mixed effect models for repeated measures revealed that ln-transformed SG-adjusted PCP was significantly associated with increased 8-hydroxy-2'-deoxyguanosine (8-OHdG; percent change [%Δ] caused by each interquartile range increase of PCP: 46.2, 95% confidence interval [CI]: 40.2, 52.5) and 8-hydroxyguanosine (8-OHG;%Δ [95% CI]: 44.8 [40.1, 49.8]), but the positive association with 4-hydroxy2-nonenal-mercapturic acid (HNE-MA) was not significant. PCP was also positively associated with increased 8-OHdG and 8-OHG in each trimester using general linear models, and its associations with HNE-MA were only significant at T1 (%Δ [95% CI]: 19.1 [1.05, 40.3]) and T2 (%Δ [95% CI]: 12.6 [0.32, 26.3]). Our findings provide valuable information about PCP exposure characteristics during pregnancy and the potential effects of PCP exposure on oxidative stress in pregnant women.

Pentachlorophenol (PCP) is an endocrine-disrupting chemical that is ubiquitously found in the environment. Few studies have reported PCP exposure in pregnant women and its association with gestational diabetes mellitus (GDM). This nested case-control study aimed to determine the concentration of urinary PCP in early pregnancy and explore the association between PCP exposure and GDM risk. This study included 293 GDM cases and 586 non-GDM controls matched by fetal sex and maternal age from a birth cohort in Wuhan, China. PCP concentrations in spot urine samples collected between 8 and 16 weeks of gestation were measured by ultra-performance liquid chromatography-tandem mass spectrometry. Conditional logistic regression was used to assess the association between PCP exposure and the odds ratio of GDM. The median concentrations of specific gravity-adjusted PCP in controls and cases were 0.70 and 0.80 ng/mL, respectively, with no significant differences (P0.05). The multivariate-adjusted odds ratios (ORs) (95% confidence intervals) for GDM across quartiles of urinary PCP were 1 (reference), 1.63 (1.06-2.50), 1.70 (1.11-2.61), and 1.35 (0.87-2.08), respectively, showing a potential "inverted-U" shaped association. In addition, PCP levels and maternal age or fetal sex had significant interactions with GDM risk (both P for interaction0.05). Among older women and those carrying female fetuses, the ORs of GDM risk were higher. This study suggests that pregnant women in central China are widely exposed to PCP, and this is the first time to report that PCP exposure may increase the risk of GDM (with potential effect modifications by maternal age and fetal sex). The association observed is in agreement with PCP's "inverted-U" anti-estrogenic effect in vivo; thus, such an effect in humans at environmentally relevant doses should be studied further.

Widespread use of fungicides has raised the concern of exposure to them among the general population. However, there are extremely limited studies reporting the occurrence of fungicides in indoor dust in China. This study aimed to determine ten agricultural fungicides in indoor dust samples collected in three cities of China from 2016 to 2019, assess spatial and seasonal variations, and estimate the related exposure via dust ingestion. Six out of ten fungicides including difenoconazole, prochloraz, tebuconazole, tricyclazole, azoxystrobin, and pyraclostrobin were frequently detected in the dust samples (ranged 65.8-97.7%) and the concentrations of some fungicides showed a strong correlation with each other. Difenoconazole was the most abundant one among the selected fungicides. The highest level of the selected fungicides was observed in the indoor dust collected from Wuhan in summer 2019 (median cumulative concentration of the fungicides: 62.6 ng/g), while the relatively low concentrations of fungicides were found in the dust from Taiyuan (2.08 ng/g). Heavier fungicide contamination was observed in urban districts compared to that in rural districts. Seasonal variations in the fungicide residuals were also identified. The exposure assessment suggested that intake of the selected fungicides via dust ingestion was much lower than dietary intake reported in other studies. This study filled the data gap of fungicide residuals in the indoor dust in China and further studies are needed to identify the sources and determinants of indoor fungicide contamination.

N-Acetyl-4-aminophenol (NA4AP, paracetamol/acetaminophen), a widely used pharmaceutical, is ubiquitous in urine samples of general population, raising concern about human health risks; oxidative stress is considered to be a mechanism for its toxicities. N-Acetyl-2-aminophenol (NA2AP) is an isomer of NA4AP; until now, few studies characterized exposure characteristics of NA4AP and NA2AP in pregnant women. In this work, NA4AP and NA2AP concentrations in urine samples (n = 2124) collected at three different trimesters were measured to examine their internal body burden among Chinese pregnant women (n = 708) and their associations with three oxidative stress biomarkers (OSBs, 8-OHG, 8-OHdG, and HNE-MA). NA4AP was detected in 100% of the urine samples (median concentration: 7.96 ng/mL); NA2AP was detected in 94.9% of them (median: 3.05 ng/mL). The intraclass correlation coefficients of their concentrations across three trimesters were poor (0.4); correlations of NA4AP and NA2AP were weak (r: 0.15-0.23). Pregnant women who had higher household income or urine samples provided in summer (vs. winter) had higher concentrations of NA4AP. Pregnant women who had a college degree or above (vs. less than a high school education) had higher concentrations of NA2AP but urine samples provided in summer (vs. winter) had lower concentrations of NA2AP. The 95th percentile estimated daily intake of NA4AP (2,331 ng/kg-bw/d) based on averaged concentrations of the three trimesters was 40 times lower than the cRfD for NA4AP (2.33 vs. 93 μg/kg-bw/d). Urinary concentrations of NA4AP and NA2AP were associated with higher levels of the selected OSBs. For example, an interquartile range increase in NA4AP was associated with a 26.5% (95% CI: 23.6-29.6%) increase in 8-OHG, a 27.5% (95% CI: 23.8-31.3%) increase in 8-OHdG, and a 33.4% (95% CI: 24.7-42.7%) increase in HNE-MA (p0.05). This is the first study to measure their concentrations repeatedly over three trimesters, examine their exposure characteristics, and reveal their associations with the selected OSBs in pregnant women. Further studies are needed to identify non-intentional exposure sources of NA4AP, NA2AP, and another isomer of them (i.e., N-acetyl-3-aminophenol), as well as more health risks related to their exposure.

Although it is a probable human carcinogen, propylene oxide is widely applied in industry and daily life. However, data on neurodevelopmental effects of propylene oxide exposure among children are extremely limited. We aimed to determine the urinary concentrations of propylene oxide metabolite among school-aged children and evaluate the potential association of propylene oxide exposure with risk of dyslexia. A total of 355 dyslexic children and 390 controls were recruited from three cities (Jining, Wuhan, and Hangzhou) in China, between 2017 and 2020. Urinary N-acetyl-S-(2-hydroxypropyl)-L-cysteine (i.e., 2-hydroxypropyl mercapturic acid; 2-HPMA) was measured as the biomarker of propylene oxide exposure. The detection frequency of 2-HPMA was 100%. After adjusting for potential confounders, the odds ratio (OR) for dyslexia per 2-fold increase in urinary 2-HPMA was 1.19 [95% confidence interval (95% CI): 1.01, 1.40, P = 0.042]. Compared with the lowest quartile of urinary 2-HPMA concentrations, children with the highest quartile of 2-HPMA had a 1.63-fold (95% CI: 1.03, 2.56, P = 0.036) significantly increased risk of dyslexia, with a dose-response relationship (P-trend = 0.047). This study provides epidemiological data on the potential association between propylene oxide exposure and the risk of dyslexia in children. Further studies are warranted to confirm the findings and reveal the underlying biological mechanisms.

Fipronil (FP) is an emerging insecticide which could induce reproductive toxicity in male rats at very low dosage, but the occurrence of FP and its transformation products (FPs) in human seminal plasma and their impacts on human semen quality have not been documented. In this study, FPs including FP, fipronil desulfinyl (FP-DES), fipronil sulfone (FP-SFO), fipronil amide (FP-AM), and fipronil sulfide (FP-SFI), were measured in seminal plasma samples (n = 200), which were collected from Shijiazhuang, north China. The cumulative concentration of FPs (ΣFPs), in the seminal plasma samples ranged from 0.003 to 0.180 ng/mL (median: 0.043 ng/mL). FP-SFO was the major target analyte (median: 0.040 ng/mL), accounting for approximately 42.3-100.0% of the ΣFPs. Significantly higher exposure levels of FPs were found in the overweight or obese group (≥25 kg/m

Human beings are extensively and concurrently exposed to multiple volatile organic compounds (VOCs, including some Class I human carcinogens), which may induce oxidative stress in human body. Data on urinary metabolites of VOCs (mVOCs) among young children are limited. No studies have examined their inter-day variability of mVOCs and their associations with oxidative stress biomarkers (OSBs) using repeated urine samples from children. In this study, we measured twenty one mVOCs and three OSBs [8-hydroxy-2'-deoxyguanosine (8-OHdG; for DNA), 8-hydroxyguanosine (8-OHG; for RNA], and 4-hydroxy nonenal mercapturic acid (HNEMA; for lipid)] in 390 urine samples of 130 children (three samples on three consecutive days provided by each participant) aged 0-7 years from September 2018 to January 2019 in Shenzhen, south China, and Wuhan, central China. HPMMA (3-hydroxypropyl-1-methyl mercapturic acid/N-Acetyl-S-(3-hydroxypropyl-1-methyl)-l-cysteine), 3HPMA (3-hydroxypropyl mercapturic acid/N-Acetyl-S-(3-hydroxypropyl)-l-cysteine), and ATCA (2-aminothiazoline-4-carboxylic acid) had higher specific gravity-adjusted median concentrations (1 383, 286, and 273 μg/L, respectively) than the others. Intraclass correlation coefficients of mVOCs ranged from 0.29 to 0.71. After false-discovery rate (FDR, defined as FDR q-value0.05) adjustment, linear mixed-effects models revealed that 14 mVOCs were positively associated with 8-OHdG (β range: 0.09-0.37), 11 mVOCs were positively associated with 8-OHG (β range: 0.08-0.30), and 11 mVOCs were positively associated with HNEMA (β range: 0.21-0.70) in urine. Considering the weight of the mVOC index accounted for the associations, based on the weighted quantile sum regression model, parent compounds of DHBMA (3,4-dihydroxybutyl mercapturic acid/N-Acetyl-S-(3,4-dihydroxybutyl)-l-cysteine) and t,t-MA (trans,trans-muconic acid) should be listed as priority VOCs for management to mitigate health risks. For the first time, this study characterized the inter-day variability of urinary mVOCs and their associations with selected OSBs (8-OHdG, 8-OHG, and NHEMA) in young, healthy Chinese children.

Animal studies have revealed that exposure to neonicotinoid insecticides (NNIs) could compromise male reproductive function; however, related data on the occurrence of NNIs and their specific metabolites in human seminal plasma are scarce. To explore the potential effects of NNI exposure on male semen quality, we determined the concentrations of NNIs and some of their metabolites (collectively defined as mNNIs) in seminal plasma samples collected from men (n = 191) who visited a fertility clinic in Shijiazhuang, North China from 2018 to 2019. Associations between the mNNI concentrations and semen quality parameters were assessed using linear regression models, adjusting for important covariates. In the seminal plasma samples, desmethyl-acetamiprid (DM-ACE, detection frequency: 98.4%), imidacloprid-olefin (IMI-olefin, detection frequency: 86.5%), and desmethyl-clothianidin (DM-CLO, detection frequency: 70.8%) were frequently detected at median concentrations of 0.052, 0.003, and 0.007 ng/mL, respectively; meanwhile other compounds were detected at less than the method detection limits. In the single-mNNI models, the IMI-olefin concentration was associated with decreased progressive motility [IMI-olefin concentration: percent change (%Δ) = −17.0; 95% confidence interval (CI) = −30.3, −0.92; the highest tertile compared with the lowest tertile: %Δ = −21.1; 95% CI = −37.5, −0.23]. Similar results were found in the multiple-mNNIs models. No other inverse associations were found between the other mNNI concentrations and semen quality parameters. This is the first study to identify the occurrence of mNNIs in the seminal plasma and the potential associations of their concentrations with human semen quality parameters. These findings imply an inverse association between the IMI-olefin concentration and semen quality.

In this study, LaCoO3/Al2O3 (LCA) was utilized as a heterogeneous catalyst to activate peroxymonosulfate (PMS) to degrade atrazine (ATZ). The structural properties of the catalysts were characterized by SEM, EDS, XRD, XPS and TPD. The effects of some key parameters (i.e., loadings of LCA, ATZ concentration, catalyst dosage, PMS concentration, initial pH and coexisting ions) were optimized. In addition, under the optimal conditions of 100 mg/L 23LCA, 100 mg/L PMS and initial solution pH 6.8, the removal rate and mineralization efficiency of ATZ (5 mg/L) reached 100% and 30.8%, respectively. The superiority of the 23LCA/PMS system was verified by two controlled experiments. After three cycles of experiments, the degradation effect of ATZ was within an acceptable range. The degradation intermediates of ATZ were detected by UPLC-QTOF-MS/MS, and the possible degradation pathway of ATZ was proposed. In addition, the presence of SO4 − and HO was identified by quenching experiments and SO4 − was verified as the predominant radical. Finally, based on the comprehensive analysis, a reasonable reaction mechanism of the 23LCA/PMS system was proposed. In a word, these results indicate that LCA can act as a highly efficient heterogeneous catalyst to activate PMS to degrade ATZ in water.

Neonicotinoid insecticides (NNIs) are extensively used insecticides worldwide, yet the data on NNIs residues in the Yangtze River, China is scarce. Occurrence and distribution of six NNIs and a metabolite (desmethyl-acetamiprid) in surface water were investigated in the central Yangtze River, China at 20 sites from March to July and September 2015. Acetamiprid (ACE), imidacloprid (IMI) and thiamethoxam (THM) were the most frequently detected NNIs and IMI had a highest median concentration of 4.37 ng/L, followed by ACE (2.50 ng/L), THM (1.10 ng/L), nitenpyram (NTP; 0.34 ng/L), clothianidin (CLO; 0.10 ng/L), and thiacloprid (THCP; 0.02 ng/L). Significantly higher concentrations and detection frequencies of NNIs were observed in the summer than in the spring, which may be explained by the heavier precipitation in summer. Spatial variation with higher levels among the lower sites than the upper sites may be related with the agriculture land use. NNI contamination presented a low risk to aquatic life according to the risk quotient method, while IMI had potential risk to aquatic life according to the threshold of IMI (8.3 ng/L) in freshwater recommended in Netherland. Using the relative potency factors method for chronic cumulative risk assessment for NNIs, potential exposure to NNIs through water ingestion are three orders of magnitude lower than the recommended relative chronic reference dose. Ongoing environmental monitoring of NNIs is needed due to the increase use of NNIs in China.

Increasing evidence suggests a potential role of endocrine disrupting chemicals (EDCs) in inducing gestational diabetes mellitus (GDM). However, as far as we know, no study has examined the associations between GDM and exposure to parabens, a kind of EDCs. In this study, we explored the association between urinary parabens of pregnant women and GDM and studied the modification effect of prepregnancy body mass index (BMI). Urine samples were collected from 696 pregnant women and parabens were measured, including four alkyl side chain substituted para-hydroxybenzoic acid ester, substituents varying from methyl to butyl (abbreviates as MeP, EtP, PrP and BuP), and benzyl substituted para-hydroxybenzoic acid ester (BzP). Logistic regression models adjusting for potential confounders were used to study the association of parabens and GDM in the overall population, and further stratified analysis by prepregnancy BMI categories was also performed. The detection rates for the five parabens in the urine samples were 97.70% (MeP), 71.26% (EtP), 96.55% (PrP), 15.80% (BuP) and 2.73% (BzP). No significant association was found between parabens and GDM among the overall population. However, significant non-linear associations of PrP and the summed estrogenic activity of parabens with GDM were found in the stratified analysis by prepregnancy BMI in the overweight/obese population, with adjusted odds ratios (aORs) of 3.47 (95% CI: 1.28, 9.42) and 2.87 (95% CI: 1.07, 7.73) for GDM in the second tertile of urinary PrP and the summed estrogen activity, respectively, when compared to the first tertile. Although no statistically significant association between parabens and GDM was found in the overall population, we found that among the overweight/obese pregnant women, who represent a subgroup more prone to GDM, moderately higher levels of PrP and summed estrogenic activity of parabens were significantly associated with an increasing GDM prevalence.

Fungicides are widely used in agriculture worldwide. However, data on the occurrence of fungicides in drinking water are scarce. This study aimed to determine the occurrence of 12 selected fungicides in drinking water, the removal efficiency of conventional water treatment processes for fungicides, and the risk of fungicide exposure. In this study, source water (February and July), treated water (February and July), and tap water samples (February, April, July, and October) were collected from Wuhan, central China, in 2019. Seven of the twelve selected fungicides were 100% detected in the three types of water samples; tricyclazole was found with the highest concentrations in the source water phase (median: 15.2 ng/L; range: 4.21–67.9 ng/L). The concentrations of the 12 selected fungicides remaining in the treated water samples (median proportion of the remaining content: 77.5%) revealed that most of the target analytes may not be removed efficiently by conventional water treatment processes, though they could be removed efficiently by advanced treatment. Higher concentrations of the fungicides were observed in samples collected in July (median: 38.7 ng/L; range: 12.5–85.8 ng/L), followed by those in October (median: 21.8 ng/L; range: 10.2–58.8 ng/L), February (median: 9.82 ng/L; range: 5.63–93.3 ng/L), and April (median: 7.13 ng/L; range: 6.23–91.1 ng/L). The health risk assessment implied that estimated daily intake of these fungicides through tap water ingestion might pose a low risk to consumers, though risk associated with infant exposure to the fungicides requires further attention. This study provides baseline data on the occurrence, removal efficiencies, and seasonal variations of the selected fungicides in tap water from central China.

Acetaminophen (AAP) is the most widely used over-the-counter analgesic in the world; it is also a metabolite of industrial chemical aniline. It may predispose individuals to oxidative stress. However, the exposure profile of AAP in the general population in China and the associations between AAP and oxidative stress biomarkers have scarcely been investigated. In this study, we determined the urinary concentrations of AAP and evaluated its associations with 8-hydroxy-guanosine (8-OHG) and 8-hydroxy-2'-deoxyguanosine (8-OHdG), the most widely used biomarkers of nucleoside oxidation affecting RNA and DNA, in 393 urine samples collected from 131 healthy children (0-6.6 y) on three consecutive days from Wuhan, central China, and Shenzhen, south China. AAP was found in all urine samples, suggesting that exposure to AAP was ubiquitous in young children in central and south China. The median concentration of specific gravity (SG)-adjusted AAP was 9.21 ng/mL (range: 1.11-1 453 ng/mL). Good inter-day reproducibility was observed for SG-adjusted AAP concentrations (intraclass correlation coefficient, 0.75). The SG-adjusted urinary 8-OHdG and 8-OHG concentrations were positively correlated with AAP (β = 0.08; 95% confidence interval [95% CI]: 0.02-0.13, and β = 0.10; 95% CI: 0.04-0.15, respectively). The data indicated that AAP exposure might be associated with oxidative DNA and RNA damage in the general population with unintentional exposure. To our knowledge, this is the first report of AAP exposure in young healthy children in central and south China. This is also the first study to evaluate the inter-day variations in urinary AAP concentrations and to explore the associations between AAP exposure and oxidative stress biomarkers in the general population.

Fipronil (FP) is widely used as a highly effective insecticide worldwide, thereby raising concern about environmental contamination and risk for human health. However, data on the occurrence of FP and its transformation products (FPs) in human blood and urine are limited. In this study, 39 pairs of serum, plasma, blood cells (BCs), and urine samples were collected from adults in Wuhan, central China (2020), in order to characterize the concentration profiles of FPs in different matrices. FPs were also determined in serum samples (n = 226, including 57, 56, 56, and 57 samples for Wuhan, Huangshi, Nanjing, and Zhenjiang, respectively) collected from four cities of China (2015) to characterize the exposure levels of FPs among the general population and potential spatial variations. Fipronil sulfone (FP-SFO) was 100% detectable in blood samples, and it was the predominant metabolite (accounting for 86-95% of the cumulative concentrations of FPs [ΣFPs]), with the median concentrations (ng/mL) of 0.17, 0.16, and 0.03 in serum (range: 0.07-1.53), plasma (range: 0.06-1.41), and BCs (range: 0.01-0.24), respectively. The compositional profiles of FPs in serum, plasma, and BCs were similar; very strong positive correlations were observed between different blood matrices for FP-SFO (r = 0.94-0.97, p < 0.01) but not between blood and urine. The median ΣFPs (ng/mL) in the serum (0.20; range: 0.09-1.56) and the plasma samples (0.19; range: 0.09-1.43) was higher than that in BCs samples (0.04; range: 0.01-0.24). In the urine samples, only the major metabolite FP-SFO was detectable in approximately 10% of the samples. Additionally, the highest median ΣFPs (ng/mL) in the serum samples was found in Nanjing (0.56; range: 0.13-1.88), followed by Wuhan (0.34; range: 0.06-1.02), Huangshi (0.10; range: 0.03-0.60), and Zhenjiang (0.08; range: 0.02-0.42). The level of ΣFPs seemed to increase with city sizes and urbanization scale, though further studies are needed to confirm the variations with larger sample size. The estimated daily intake of ΣFPs based on the median concentration of samples from Nanjing (18.5 ng/kg-bw/d) was higher than that of Wuhan (11.3), Huangshi (3.40), and Zhenjiang (2.80). Dietary intake should be the major exposure route for the general population, while water or indoor dust accounted for

Journal of water reuse and desalination (2021). doi:10.2166/wrd.2021.046, Published by IWA Publ., London

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

Previous studies implied that elevated exposure to parabens may result in increased oxidative stress. However, the association between exposure to paraben derivatives and oxidative stress biomarkers in children has been rarely studied. This study examined the associations between exposure to paraben derivatives and oxidative stress biomarkers in Chinese children. Nine targeted compounds of parabens and their derivatives including methyl paraben (MeP), ethyl paraben (EtP), propyl paraben (PrP), butyl paraben (BuP), p-hydrox4ybenzoic acid (p-HB), 3,4-dihydroxy benzoic acid (3,4-DHB), benzoic acid, methyl 3,4-dihydroxybenzoate (rOH-MeP), and ethyl 3,4-dihydroxybenzoate (rOH-EtP) were detected in urine collected from 139 children from South and Central China. Additionally, 8-hydroxy-2'-deoxyguanosine (8-OHdG), 8-hydroxyguanosine (8-OHG), and 4-hydroxy-2-nonenal mercapturic acid (HNE-MA) were measured as oxidative stress biomarkers. All targeted compounds (except for BuP) were frequently detected in urine (detection frequencies ranged 80.8%-100%). Linear mixed effects model revealed that all targeted compounds (with detection frequencies50%), except for EtP, were significantly associated with an increase in 8-OHdG. rOH-EtP was found to be significantly associated with 8-OHG (β = 0.12; 95% confidence interval [95% CI]: 0.08, 0.16) positively. In addition, PrP and benzoic acid were associated with elevated levels of HNE-MA. Weighted quantile sum regression revealed that co-exposure to the targeted compounds was positively associated with 8-OHdG (β = 0.17; 95% CI: 0.12, 0.22), 8-OHG (β = 0.14; 95% CI: 0.10, 0.18), and HNE-MA (β = 0.43; 95% CI: 0.27, 0.59); rOH-EtP and benzoic acid were the major contributors for the combined effects on oxidative stress of nucleic acids and lipid, respectively. Our findings provide new evidence for the effects of exposure to paraben derivatives on nucleic acid oxidative damage and lipid peroxidation in children.

Exposure to organophosphate (OP) insecticides has been found to be related to neurodevelopmental disorders in children. However, no study has examined the association between OP insecticide exposure and the risk of dyslexia among children. We aimed to explore the association between OP insecticide exposure, indicated by urinary dialkylphosphate metabolites (DAPs), and the risk of dyslexia among Chinese Han children from three cities. A total of 845 children (422 dyslexics and 423 non-dyslexics) from Tongji Reading Environment and Dyslexia research program were included in the current case-control study. We measured six DAPs in urine samples, collected from November 2017 to December 2020. Logistic regression models were used to estimate odds ratios (ORs) for the association between DAPs and dyslexia risk, adjusting for potential confounders. The detection frequencies of DAPs were above 97.5%, except for diethyldithiophosphate (DEDTP) and dimethyldithiophosphate (DMDTP). Diethyl phosphate metabolites (DEs) were significantly associated with the risk of dyslexia. Compared with the lowest quartile, the adjusted ORs of dyslexia risk for the highest quartile of urinary diethylthiophosphate (DETP) and diethylphosphate (DEP) were 1.82 (1.04, 3.20) and 1.85 (1.08, 3.17). In addition, the adjusted ORs for dyslexia per 10-fold of urinary DEP, DETP, and ∑DEs concentration were 1.87 (1.12, 3.13), 1.55 (1.03, 2.35), and 1.91 (1.13, 3.21), respectively. Analyses stratified by gender indicated that such associations were more significant among boys. This study suggested that exposure to OP insecticides may be related to dyslexia among Chinese Han children from the three studied cities. However, our results should be interpreted with caution because of the case-control design and the fact that only one-spot urine sample was collected from the children. More studies with children living in China are necessary concerning the relatively high levels of urinary OP metabolites in our study.

Herbicide 2,4-Dichlorophenoxyacetic acid (2,4-D) and its analogues are widely used in agriculture. Although the occurrence of 2,4-D in urine has been widely reported in North America, it has scarcely been investigated in China, especially in young children. In addition, both in vivo and in vitro studies have shown that high-level 2,4-D exposure is associated with oxidative stress, but their association in a general sensitive population has rarely been evaluated. In this study, 2,4-D and its analogues were measured in 417 urine samples collected from 139 children aged 0–7 during the non-peak season of pesticide application in Wuhan, central China, and Shenzhen, south China. Each of them provided three samples in three consecutive days. An oxidative stress biomarker, 8-hydroxy-2-deoxyguanosine (8-OHdG), was also measured. The geometric mean (GM) of unconjugated urinary 2,4-D concentration was 0.10 μg/L (corrected by urinary specific gravity, SG-corrected). After β-glucuronidase hydrolysis, the GM of SG-corrected urinary 2,4-D was 0.15 μg/L, and the detection frequency was 100%. Moderate inter-day reproducibility was found within individuals, with an intraclass correlation coefficient of 0.68 for SG-corrected urinary deconjugated 2,4-D. The GM of estimated daily intake of 2,4-D was 6.05 ng/kg-bw/day. A significant positive correlation was found between urinary 2,4-D and 8-OHdG, whereas no association was found after SG-correction. This is the first study to characterize the occurrence of urinary 2,4-D, its inter-day reliability, and its association with urinary 8-OHdG in young children from 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.

Studies on the occurrence of emerging pesticides in surface and drinking water in Vietnam are limited. In this study, lake water (n = 7), river water (n = 1), tap water (n = 46), and bottled water (n = 3) collected from Hanoi and other four provinces in northern Vietnam were analyzed for selected pesticides (including insecticides such as neonicotinoids, fipronil, and chlorpyrifos; fungicide carbendazim; herbicides such as atrazine, terbuthylazine, simazine, 2,4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, and bentazon) and some of their degradates by liquid chromatography-tandem mass spectrometry. Carbendazim (median: 86.7 ng/L) and triazines (49.3 ng/L) were the major pesticides found in lake water samples, followed by neonicotinoids and their degradation products (15.1 ng/L), chlorpyrifos and its degradate (13.4 ng/L), fipronil and its degradates (3.76 ng/L), chlorophenoxy acid herbicides (2.10 ng/L), and bentazon (0.62 ng/L). Triazines (164 ng/L) were the major pesticides in river water. Higher concentrations (median: 39.3 ng/L; range: 1.20–127) of selected pesticides were found in tap water from Hanoi than those from four other provinces studied (5.49 ng/L; 4.73–66.8 ng/L). Bottled water samples collected from Hanoi contained lower concentrations of pesticide residues (median: 3.54 ng/L, range: 2.18–8.09) than those of tap water samples. The calculated risks from pesticide exposure through ingestion of tap water by the general populations were low. However, fipronil concentrations in lake water exceeded the benchmark value recommended for freshwater in the United States or the Netherlands. Degradation of acetamiprid into desmethyl-acetamiprid was found in lake water.