A variety of antibiotics have been found in aquatic environments, but antibiotics in drinking water and their contribution to antibiotic exposure in human are not well-explored. For this, representative drinking water samples and 530 urine samples from schoolchildren were selected in Shanghai, and 21 common antibiotics (five macrolides, two β-lactams, three tetracyclines, four fluoquinolones, four sulfonamides, and three phenicols) were measured in water samples and urines by isotope dilution two-dimensional ultraperformance liquid chromatography coupled with high-resolution quadrupole time-of-flight mass spectrometry. Drinking water included 46 terminal tap water samples from different spots in the distribution system of the city, 45 bottled water samples from 14 common brands, and eight barreled water samples of different brands. Of 21 antibiotics, only florfenicol and thiamphenicol were found in tap water, with the median concentrations of 0.0089 ng/mL and 0.0064 ng/mL, respectively; only florfenicol was found in three bottled water samples from a same brand, with the concentrations ranging from 0.00060 to 0.0010 ng/mL; no antibiotics were found in barreled water. In contrast, besides florfenicol and thiamphenicol, an additional 17 antibiotics were detected in urine samples, and the total daily exposure doses and detection frequencies of florfenicol and thiamphenicol based on urine samples were significantly and substantially higher than their predicted daily exposure doses and detection frequencies from drinking water by Monte Carlo Simulation. These data indicated that drinking water was contaminated by some antibiotics in Shanghai, but played a limited role in antibiotic exposure of children.

We analyzed 13 metabolites of 9 phthalates in urine of 782 Chinese school children aged 8–11 years and estimated the daily intake for phthalates based on urinary metabolite levels. The daily intakes were compared with acceptable intake levels to calculate the hazard quotient (HQ) for single phthalate. Finally, the cumulative risk for each child was assessed by means of a hazard index (HI) which is the sum of HQs. Overall, 11 metabolites were found in at least 85% of the urine samples with the highest median concentration of 47.1 ng/mL (93.4 μg/g creatinine) for mono-n-butyl phthalate (MnBP). Monooctyl phthalate (MOP) and monoisononyl phthalate (MiNP) were not detectable. The cumulative risk assessment covering di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DnBP), di-isobutyl phthalate (DiBP), and butyl-benzyl phthalate (BBzP) demonstrated that 19.8% (volume model-based) and 40.3% (creatinine model-based) of the children exceeded 1 for the HI based on tolerable daily intake (TDI) values (considered as potential adverse antiandrogenic effect). Furthermore, at least 36% of the children from the manufacturing-intensive region had a HI higher than 1. The results indicate that Chinese children are widely exposed to phthalates and those from manufacturing-intensive regions are probably at a high risk of cumulative phthalate exposure.

To explore the antibiotic body burden of Chinese school children, total urinary concentrations (free and conjugated) of 18 representative antibiotics (5 macrolides, 2 β-lactams, 3 tetracyclines, 4 quinolones, and 4 sulfonamides) were measured by ultraperformance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry among 1064 school students recruited from 3 economically and geographically distinct areas in east China in 2013. All 18 antibiotics were detected in urine samples with the detection frequencies ranging from 0.4 to 19.6%. The antibiotics were detected in 58.3% of urine samples overall, and this detection frequency reached at 74.4% in one study site. Of them, 47.8% of the urine samples had a sum of mass concentration of all antibiotics between 0.1 (minimum) and 20.0 ng/mL, and 8 antibiotics had their concentrations of above 1000 ng/mL in some urine samples. Three veterinary antibiotics, 4 human antibiotics, and 11 human/veterinary antibiotics were found overall in 6.3, 19.9, and 49.4% of urine samples, respectively. The detection frequencies and concentration levels of antibiotics in urine samples differed by study areas. Concerning mixed exposures, a total of 137 combinations of antibiotics and 20 combinations of antibiotic categories were found overall. Two or more antibiotics or categories were concurrently detected in more than 20% of urine samples. On the basis of a usage analysis, contaminated food or environment might be relevant exposure sources for tetracyclines, quinolones, and sulfonamides.

In epidemiological studies, urinary biomonitoring is a valid approach to assess the association between environmental chemical exposure and children’s health. Many clinical biomarkers (e.g., endogenous metabolites) are also based on analysis of urine. Considering the variability in urinary output, urinary concentrations of chemicals are commonly adjusted by creatinine and specific gravity (SG). However, there is a lack of systematic evaluation of their appropriateness for children. Furthermore, urinary SG and creatinine excretion could be influenced by body mass index (BMI), but the effect of BMI status on the two correction factors is unknown. We measured SG and creatinine concentrations of repeated first morning urine samples collected from 243 primary school children (8–11 years) over 5 consecutive weekdays. Urinary SG presented a higher temporal consistency compared with creatinine. Urinary SG was associated with sex (p < 0.001), whereas sex (p =0.034) and BMI (p = 00.008) were associated with urinary creatinine levels. Inter-day collection time was not associated with SG or creatinine after excluding the effect of Monday as a confounder. When stratified by BMI status, none of the factors were associated with creatinine among the overweight and obese children.

Bisphenol A (BPA) is one of the highest production and consumption volume chemicals in the world. Although exposure of children to BPA has been studied in Western countries, little is known about its level in China. In this study, total BPA was measured in the morning urine samples of 666 school children aged 9–12 years from three regions in eastern China in 2012. A rapid and sensitive ultraperformance liquid chromatography (UPLC) tandem mass spectrometry (MS/MS) method was used for the measurement and urinary concentrations of BPA were presented as unadjusted (ng/ml), creatinine-adjusted (μg/g creatinine) and specific gravity (SG)-adjusted (ng/ml) forms. BPA was detected in 98.9% of urine samples with their unadjusted concentrations ranging from 0.1 to 326.0 ng/ml (LOD=0.06 ng/ml), indicating that the exposure of BPA was common for school children living in eastern China. The geometric mean and median of BPA was 1.11 ng/ml (creatinine-adjusted: 2.32 μg/g creatinine; SG-adjusted: 1.17 ng/ml) and 1.00 ng/ml (creatinine-adjusted: 2.22 μg/g creatinine; SG-adjusted: 1.07 ng/ml), respectively. The highest urinary BPA level was found in the age group of 12 years with GM concentration of 1.55 ng/ml, and it decreased with decreasing age (11 years: 1.18 ng/ml; 10 years: 1.05 ng/ml; and 9 years: 0.99 ng/ml), but there was a lack of consistency for age associated with BPA levels in three study areas. The estimated daily intake of BPA (0.023 μg/kg bw/day) was much lower than the tolerable daily and reference dose of 50 μg/kg bw/day recommended by either the European Food Safety Authority or the US Environment Protection Agency. There was no significant difference in urinary BPA concentrations between children who were overweight or obese and those with normal weight (P=0.26), whereas BPA daily intake was unexpectedly higher among normal-weight children (P=0.003). Compared with creatinine correction, the correction method of specific gravity is preferred to evaluate BPA exposure for children.

In this study, a method employing ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) was developed to simultaneously screen for 36 endocrine-disrupting chemicals (EDCs; e.g., estrogens, progestogens, phenols, and their metabolites) both in potable and river water. From the selected compounds, 21 target compounds, for which reference standards were available, were used as model compounds for method development and optimization. The other target compounds, for which reference standards were unavailable, were investigated in post-target analysis on the basis of their theoretical molecular masses. The solid-phase extraction and chromatographic separation steps were optimized. For this method, limits of detection for the target compounds were less than 0.72 ng L− 1, and the overall recoveries varied between 46% and 134% with relative standard deviations ranging from 7% to 35%. The mass errors between theoretical and experimental mass for all resulting precursor and characteristic fragment ions ranged from − 1.9 to 2.8 mDa. The method developed was successfully used to analyze the composition of potable and river water in Shanghai City; in addition, some compounds of interest (estriol, estrone, and bisphenol A) were identified accurately. Further, a post-target analysis was performed and an estrogen metabolite was hypothesized in the water samples due to the excellent sensitivity of the method in full-spectrum acquisition mode and the valuable accurate mass information in MS and tandem MS mode. Therefore, UPLC-Q-TOF-MS has proven to be a powerful technique for wide-scope screening and identification of relevant EDCs in environmental water sources.Highlights► A method for screening of estrogens, progestogens, phenols, and their metabolites in water using UPLC-Q-TOF-MS was developed. ► The mass errors between theoretical and experimental mass of all target compounds were less than 3mDa. ► Some target compounds were detected in the actual potable water and river water samples from Shanghai City in China. ► One estrogen metabolite was hypothesized by the post-target analysis in river water samples.

There is increasing evidence suggesting that Bisphenol A (BPA), one of the highest volume chemicals produced worldwide, can interfere with the body’s natural weight control mechanisms to promote obesity. However, epidemiological studies for this are limited, especially for children.A cross-sectional study was conducted to investigate the association between BPA exposure and body mass index (BMI) in school children. Three primary and three middle schools were randomly selected from 26 primary and 30 middle candidate schools in Changning District of Shanghai City in China. According to the BMI-based criteria by age and sex for screening of overweight or obese children, we randomly chose 20 obese, 10 overweight, and 30 normal weight children aged 8-15 years of age from each selected school. First morning urine was collected and total urine BPA concentrations were determined by ultra-performance liquid chromatography tandem mass spectrometry. Multiple linear regression analysis was conducted to examine the association of urine BPA concentrations and daily intake estimates with BMI.BPA was detected in 84.9% of urine samples with a geometric mean of 0.45 ng/mL. The daily intake estimates ranged from 0.03 μg/day to 1.96 μg/day with a geometric mean of 0.37 μg/day. The average urine BPA concentrations and daily intake estimates were similar for boys and girls, but significantly higher in older children than younger ones, and showed an increasing trend with BMI. Multiple linear regression analyses showed that urine BPA concentrations were significantly associated with increasing BMI values in all subjects after adjustment for age and sex and the results were similar before and after corrected by urine specific gravity. When stratified by age or sex, the associations remained significant in females and in those 8-11 years of age before corrected by specific gravity. Similar results were shown for the association between BMI and daily intake estimates.There is a possibility that BPA exposure increases BMI in school children. Given the cross-sectional nature of this study, longitudinal studies are warranted to confirm BPA exposure as a contributor to increased BMI in children.

A rapid, sensitive, and specific method has been developed and validated for the simultaneous analysis of nine estrogens in milk powder, including estriol, β-estradiol, a-estradiol, equilin, 17a-ethinylestradiol, estrone, diethylstilbestrol, dienestrol, and hexestrol using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). The milk powder was dissolved in water, the estrogens were extracted with acetonitrile using ultrasonication, and the fat in the extracted solution was removed by liquid-liquid extraction with n-hexane. Then, the estrogens were purified using a NH2-containing solid-phase extraction cartridge, separated on a Waters ACQUITY UPLC HSS T3 column (100 mm × 2.1 mm × 1.8 μm), and analyzed both qualitatively and quantitatively by UPLC-Q-TOF-MS. The overall analysis time of the proposed method was 13 minutes, and the linear range was between 0.001–0.5 mg L−1, with a correlation coefficient greater than 0.993. The limits of detection for the compounds were 0.11–0.30 μg kg−1, and the limits of quantification were within the range 0.37–1.0 μg kg−1. The mass errors between the theoretical and experimental masses obtained for the deprotonated molecules of the nine estrogens and the internal standard (β-estradiol-d3) were between −1.0 and 0.9 mDa. At the spiked levels of 1, 2, 10, and 100 μg kg−1, the average recoveries ranged from 61% to 137%, with relative standard deviations ranging between 1.0% and 22.6%, as determined by the matrix-matched internal-standard method. The results showed that the proposed method was suitable for the multiresidue detection of estrogens in milk powder and was successfully applied to the detection of estrogens in seven real milk powder samples.