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Background: Between 1962 and 1975, a chlor-alkali plant in Canada discharged approximately 9 metric tons of mercury (Hg) into the Wabigoon River. Over the following decades, biomarkers of Hg exposure of persons from Grassy Narrows First Nation (Asubpeeschoseewagong Anishinabek), located downriver from the discharge, reflected Hg concentrations in fish. Hg exposure is known to target the calcarine fissure, resulting in visual field (VF) loss. Most studies and clinical reports focus solely on peripheral VF loss; little is known about the impact of Hg on the central and paracentral portions. The present study sought to characterize the patterns of VF loss with respect to past and current Hg., Methods: A 28-year hair-Hg (HHg) database, created from a 1970-97 government biomonitoring program, served to select study participants with ≥ 4 year-based HHg measurements (n = 81). Blood-Hg was assessed for current exposure. Light sensitivity thresholds across the VF were analyzed monocularly, using a Humphrey Field Analyzer (HFA). Following post-hoc exclusions, based on HFA interpretation indices, 65 participants were retained. Both eyes were combined for analyses (n = 130 eyes). Unsupervised hierarchical clustering of HFA plot data was used to identify patterns of VF loss. A series of mixed effects models (MEM) were performed to test the associations for current Hg exposure with respect to HFA interpretation indices and clusters, as well as for longitudinal past Hg exposure., Results: The clustering approach decomposed the light sensitivity deficits into 5 concentric clusters, with greatest loss in the peripheral clusters. No relation was observed between any of the cluster scores and current blood-Hg. VF deficits increased with past Hg exposure. Longitudinal MEM showed that HHg was significantly (p < 0.05) associated with all peripheral, paracentral, and central cluster scores, as well as with HFA interpretation indices., Conclusions: Past Hg exposure in Grassy Narrows First Nation was associated with present day VF loss. The cluster-based location-specific approach identified patterns of VF loss associated with long-term Hg exposure, in both the peripheral and the central areas. The functional implications of this type of visual loss should be investigated., (© 2024. The Author(s).)

Nitrosamines and semi-volatile organic compounds (SVOCs) are carcinogenic contaminants in water and biological matrices. Conventional analytical methods often struggle to detect trace concentrations due to poor extraction efficacies. This study presents a novel, low-cost, in-syringe-assisted fast extraction cum cleanup technique coupled with GC-FID for monitoring four nitrosamines and two SVOCs in drinking water and human urine samples to measure the contamination and exposure levels. This extraction protocol combines a novel green in-syringe liquid-liquid extraction step using dimethyl carbonate as the green extraction solvent, coupled with a semi-automated solid-phase extraction cleanup process. Then, the final extractant is analyzed using gas chromatography-flame ionization detection (GC-FID) for monitoring. The method demonstrated excellent linearity (R 2  > 0.998) between 1.5 and 500 ng mL⁻ 1 for all six target compounds. Detection limits ranged from 1.0 to 2.0 ng mL⁻ 1 . Extraction recoveries were between 87 and 105% for both urine samples and water samples. Intra-day and inter-day precision were below 9% RSD. The blue applicability grade index evaluation scored 70.0, indicating good practical applicability. The developed analytical protocol offers a sensitive, accurate, low-cost, rapid, and environmentally friendly method for simultaneously quantifying multiple nitrosamines and SVOCs in environmental and human samples. Its performance characteristics and sustainability metrics suggest the potential for broad application in monitoring and exposure studies., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Background: An increasing number of β 2 -adrenergic agonists are illicitly used for growth promoting and lean meat increasing in animal husbandry in recent years, but the development of analytical methods has lagged behind these emerging drugs., Results: Here, we designed and developed an ultrasound probe enhanced enzymatic hydrolysis reactor for quick separation and simultaneously quantification of 22 β 2 -adrenergic agonists in animal urine and livestock wastewater. Owing to the enhancement of the conventional enzymatic digestion through the ultrasound acoustic probe power, only 2 min was required for the comprehensively separation of β 2 -adrenergic agonists from the sample matrices, making it a much more desirable alternative tool for high-throughput investigation. The swine, bovine and sheep urines (n = 287), and livestock wastewater (n = 15) samples, collected from both the north and south China, were examined to demonstrate the feasibility and capability of the proposed approach. Six kinds of β 2 -adrenergic agonists (clenbuterol, salbutamol, ractopamine, terbutaline, clorprenaline and cimaterol) were found in animal urines, with concentrations ranged between 0.056 μg/L (terbutaline) and 5.79 μg/L (clenbuterol). Up to nine β 2 -adrenergic agonists were detected in wastewater samples, of which four were found in swine farms and nine in cattle/sheep farms, with concentration levels from 0.069 μg/L (tulobuterol) to 2470 μg/L (clenbuterol)., Significance: Interestingly, since β 2 -adrenergic agonists are usually considered to be abused mainly in the pig farms, our data indicate that both the detection frequencies and concentrations of these agonists in the ruminant farms were higher than the pig farms. Furthermore, the findings of this work indicated that there is a widespread occurrence of β 2 -adrenergic agonists in livestock farms, especially for clenbuterol and salbutamol, which may pose both food safety and potential ecological risks. We recommend that stricter controls should be adopted to prevent the illegally usage of these β 2 -adrenergic agonists in agricultural animals, especially ruminants, and they should also be removed before discharging to the environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A novel ferrofluid prepared from a hydrophobic deep eutectic solvent (DES) and Fe 3 O 4 @graphite composite materials was introduced as a green microextraction medium for the separation and enrichment of trace estrogens in real samples. It was found that the ferrofluid greatly improved the capacity and selectivity of target analytes, benefiting from the enrichment of both DES and Fe 3 O 4 @graphite composite materials. Using a combination of high-performance liquid chromatography-fluorescence detection (HPLC-FLD) and vortex-assisted liquid-liquid microextraction (VALLME), a new method was established for simultaneous rapid processing and accurate determination of three estrogens (estradiol [E2], estriol [E3], and ethinyl estradiol [EE2]) in environmental water and urine samples. Key parameters affecting the extraction efficiency were optimized using a single-factor approach and response surface methodology. Under optimal conditions, this method yielded a low limit of detection (1.01 ng L -1 , 3.03 ng L -1 , and 25.0 ng L -1 for EE2, E2, and E3, respectively), wide linear range (3-200,000 ng L -1 ), high enrichment factors (9.81-47.2), and satisfactory recovery (73.8-129.0%). Compared with traditional analytical techniques, this method avoids the use of volatile toxic organic extraction solvents and cumbersome phase separation operations., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

We developed a simple, paper-based device that enables sensitive detection by mass spectrometry (MS) without solid phase extraction or other sample preparation. Using glass fiber filter papers within a 3D printed holder, the device employs electrokinetic manipulations to stack, separate, and desalt charged molecules on paper prior to spray into the MS. Due to counter-balanced electroosmotic flow and electrophoresis, charged analytes stack on the paper and desalting occurs in minutes. One end of the paper strip was cut into a sharp point and positioned near the inlet of a MS. The stacked analyte bands move toward the paper tip with the EOF where they are ionized by paper spray. The device was applied to analysis of PFAS in tap water with sub part-per-trillion detection limits in less than ten minutes with no sample pretreatment. Analysis of opioids in urine also occurs in minutes. The crucial parameters to enable stacking, separation, and MS ionization of both positively and negatively charged analytes were determined and optimized. Experimental and computational modeling studies confirm the electrokinetic stacking and analyte transport mechanisms. On-paper separations were carried out by stacking analyte bands at different locations depending on their electrophoretic mobility, achieving baseline separation in some cases., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The combination of silica nanoparticles with fluorescent molecularly imprinted polymers (Si-FMIPs) prepared by a one-pot sol-gel synthesis method to act as chemical sensors for the selective and sensitive determination of captopril is described. Several analytical parameters were optimized, including reagent ratio, solvent, concentration of Si-FMIP solutions, and contact time. Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and the ninhydrin assay were used for characterization. The selectivity was evaluated against molecules belonging to other drug classes, such as fluoroquinolones, nonacid nonopioids, benzothiadiazine, alpha amino acids, and nitroimidazoles. Under optimized conditions, the Si-FMIP-based sensor exhibited a working range of 1-15 µM, with a limit of detection (LOD) of 0.7 µM, repeatability of 6.4% (n = 10), and suitable recovery values at three concentration levels (98.5% (1.5 µM), 99.9% (3.5 µM), and 99.2% (7.5 µM)) for wastewater samples. The sensor provided a working range of 0.5-15 µM for synthetic urine samples, with an LOD of 0.4 µM and a repeatability of 7.4% (n = 10) and recovery values of 93.7%, 92.9%, and 98.0% for 1.0 µM, 3.5 µM, and 10 µM, respectively. In conclusion, our single-vessel synthesis approach for Si-FMIPs proved to be highly effective for the selective determination of captopril in wastewater and synthetic urine samples., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

In wastewater-based epidemiology (WBE), the selection of appropriate biomarkers presents a significant challenge. Recently, sulfated bisphenols have garnered attention as potential WBE biomarkers due to their increased stability in wastewater compared to glucuronide conjugates. This study aims to comprehensively assess the feasibility of employing sulfated BPA and BPS as WBE biomarkers by analyzing both WBE and human biomonitoring data. To conduct this research, wastewater samples were collected from six domestic wastewater treatment plants in Guangzhou, China, and urinary concentration of BPA and BPS were obtained from peer-reviewed literature. The results revealed that mean urinary concentrations of BPA and BPS, calculated using Monte Carlo simulations, significantly exceeded those reported in human biomonitoring studies. Furthermore, the per capita mass load ratio of sulfated BPA and BPS in human urine to the mass load in wastewater was found to be below 10 %. This outcome suggests that the excretion of BPA-S and BPS-S in urine does not make a substantial contribution to wastewater, hinting at the existence of other notable sources. Consequently, our study concludes that sulfated BPA-S and BPS-S are not suitable candidates as WBE biomarkers. This work provides a referenceable analytical framework for evaluating the feasibility of WBE biomarkers and emphasizes the necessity for caution when utilizing WBE to assess human exposure to chemicals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

This study investigated the degradation of clofibric acid (CFA), bezafibrate (BZF), and sulfamethoxazole (SMX) in synthetic human urine using a novel mesoporous iron powder-activated persulfate system (mFe-PS system), and identified the factors limiting their degradation in synthetic human urine. A kinetic model was established to expose the radical production in various reaction conditions, and experiments were conducted to verify the modeling results. In the phosphate-containing mFe-PS system, the 120 min removal efficiency of CFA decreased from 95.1% to 76.6% as the phosphate concentration increased from 0.32 to 6.45 mmol/L, but recovered to 90.5% when phosphate concentration increased to 16.10 mmol/L. Meanwhile, the increased concentration of phosphate from 0.32 to 16.10 mmol/L reduced the BZF degradation efficacy from 91.5% to 79.0%, whereas SMX removal improved from 37.3% to 62.9%. The mFe-PS system containing (bi)carbonate, from 4.20 to 166.70 mmol/L, reduced CFA and BZF removal efficiencies from 100% to 76.8% and 80.4%, respectively, and SMX from 83.5% to 56.7% within a 120-min reaction time. In addition, alkaline conditions (pH ≥ 8.0) inhibited CFA and BZF degradations, while nonacidic pH (pH ≥ 7.0) remarkably inhibited SMX degradation. Results of the kinetic model indicated the formation of phosphate (H 2 PO 4 · /HPO 4 ·- ) and/or carbonate radicals (CO 3 ·- ) could limit pharmaceutical removal. The transformation products (TPs) of the pharmaceuticals revealed more incompletely oxidized TPs occurred in the phosphate- and (bi)carbonate-containing mFe-PS systems, and indicated that H 2 PO 4 · /HPO 4 ·- mainly degraded pharmaceuticals via a benzene ring-opening reaction while CO 3 ·- preferentially oxidized pharmaceuticals via a hydroxylation reaction., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Increased values of arsenic in potable water in eastern Croatia has been a matter of scientific interest for the past two decades due to numerous health effects, including carcinogenic ones. This study investigated whether prolonged exposure to increased arsenic from water could be detectable through increased arsenic in urine, and whether it influenced the incidence of kidney and bladder cancer in Osijek-Baranja County. Inductively coupled plasma mass spectrometry (ICP-MS) was used for analysis of water samples from available water sources (wells, aqueducts). In addition, examinees from Osijek, Našice, Vladislavci, Čepin and Dalj gave their urine samples for analysis. Data on cancer incidence were obtained from the Institute for Public Health Registry and cumulative incidence of kidney and bladder cancer was calculated for the period between January 1, 2000 and December 31, 2018. Elevated arsenic concentration in drinking water was recorded in Vladislavci, Čepin and Osijek area with values above the allowed maximum according to the EU standards (10 µg L-1) and as a result, arsenic levels in urine of the inhabitants were also elevated. Cumulative incidence for bladder cancer showed correlation between increased arsenic in water and urine in the areas affected by increased arsenic in water. Epidemiologic data suggest a conclusion that elevated arsenic could be considered at least as a cofounding factor for urinary tract cancer., (Sestre Milosrdnice University Hospital.)

Herein, we synthesized a kind of magnetic covalent organic framework nanohybrids (NiFe 2 O 4 @COF), and integrated it with polydimethyl siloxane and silicone rubber curing agent for solid phase microextraction (SPME) fiber coating. The fiber coating demonstrated a porous and uniform surface with the BET specific surface of 169.7 m 2 g -1 . As for seven environmental analytes, the NiFe 2 O 4 @COF-based SPME fiber coating gave the higher extraction recoveries for triclosan (TCS) and methyltriclosn (MTCS) than those of fenpropathrin, bifenthrin, permethrin, fenvalerate and deltamethrin. Several operational parameters were rigorously optimized, such as extraction temperature, extraction time, thermal desorption time, solution pH and salt effect. Combined with the GC-ECD detection, the newly developed microextraction method supplied the wide linear range of 0.1-1000 µg L -1 with the correlation coefficients of > 0.9995. The limits of detection (LODs) and limits of quantitation (LOQs) reached as low as 1-7 ng L -1 and 3.3-23 ng L -1 , respectively. The intra-day and inter-day precisions in six replicates (n = 6 ) were < 3.55% and < 5.06%, respectively, and the fiber-to-fiber reproducibility (n = 3) was < 7.64%. To evaluate its feasibility in real samples, the fortified recoveries for TCS and MTCS, at low (0.2 µg L -1 ), middle (2.0 µg L -1 ) and high (20.0 µg L -1 ) levels, varied between 81.9% and 119.1% in tap, river and barreled waters as well as male, female and children urine samples. Especially, it is worth mentioning that the NiFe 2 O 4 @COF-based SPME coating fiber can be recycled for at least 150 times with nearly unchanged extraction efficiency. Moreover, the extraction recoveries by the as-fabricated fiber coating were much higher than those by three commercial fibers (PDMS, PDMS/DVB and PDMS/DVB/CAR). Overall, the NiFe 2 O 4 @COF-based SPME is a convenient, sensitive, efficient and "green" pretreatment method, thereby possessing important application prospects in trace monitoring of TCS-like pollutants in complex liquid matrices., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

A new analyte separation and preconcentration method for the trace determination of antidepressant drugs, Fluoxetine (FLU) and Citalopram (CIT) in urine and wastewaters, was developed based on HPLC-DAD analysis after magnetic solid phase extraction (MSPE). In the proposed method, FLU and CIT were retained on the newly synthetized magnetic sorbent (Fe 3 O 4 @PPy-GO) in the presence of buffer (pH 10.0) and then were desorbed into a lower volume of acetonitrile prior to the chromatographic determinations. Before HPLC analysis, all samples were filtered through a 0.45 µm PTFE filter. Experimental parameters such as interaction time, desorption solvent and volume, and pH were studied and optimized in order to establish the detection limit, linearity, enrichment factor and other analytical figures of merit under optimum operation conditions. In the developed method, FLU and CIT were analyzed by diode array detector at the corresponding maximum wavelengths of 227 and 238 nm, respectively, by using an isocratic elution of 60% pH 3.0 buffer, 30% acetonitrile, and 10% methanol. By using the optimum conditions, limit of detections for FLU and CIT were 1.58 and 1.43 ng mL -1 , respectively, while the limit of quantifications was 4.82 and 4.71 ng mL -1 , respectively. Relative standard deviations (RSD%) for triplicate analyses of model solutions containing 100 ng mL -1 target molecules were found to be less than 5.0 %. Finally, the method was successfully applied to urine (both simulated and real healthy human) and wastewater samples, and quantitative results were obtained in recovery experiments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

In 2014, in some parts of the water distribution system of the municipality of Pietrasanta (Tuscany, Italy), thallium (Tl) levels above the recommended limits were measured and some restrictions to water usage for drinking and food preparation were imposed. The study aimed to assess Tl exposure and possible health effects by means of a human biomonitoring survey. In the 2014-2016 time frame, 2154 urine and 254 hair samples were taken from different population groups and from a control group. The levels of Tl found in urine and hair were statistically higher in exposed groups than in controls and compared to the reference values for the general population. Concentrations in urine were significantly associated with the geographical origin of the sample, the consumption of drinking water and food grown in local gardens. A significant association was found between urine and hair. No positive associations were found between the Tl levels in hair or urine and several self-reported symptoms and health effects, except for sleep disturbance. The study indicates that the concentration of Tl in drinking water can be traced by urine analysis. Urine and hair have proven to be biological matrices that can be effectively used for the evaluation of Tl exposure. To date, the study represents the most extensive human biomonitoring campaign for the evaluation of the Tl exposure available at international level., Competing Interests: The authors have declared that no competing interests exist.

Bone mineral density (BMD) changes were reported to be associated with excessive fluoride exposure and abnormal expression of RUNX2. However, whether the alteration of methylation status, a most commonly used marker for the alteration of gene expression in epidemiological investigation, of RUNX2 is associated with low-to-moderate fluoride exposure and BMD changes has not been reported. Our study aims to explore the role of RUNX2 promoter methylation in BMD changes induced by low-to-moderate fluoride exposure. A total of 1124 adults (413 men and 711 women) were recruited from Kaifeng City in 2017. We measured BMD using ultrasound bone densitometer. Concentrations of urinary fluoride (UF) were measured using ion-selective electrode, and the participants were grouped into control group (CG) and excessive fluoride group (EFG) according to the concentration of UF. We extracted DNA from fasting peripheral blood samples and then detected the promoter methylation levels of RUNX2 using quantitative methylation-specific PCR. Relationships between UF concentration, RUNX2 promoter methylation and BMD changes were analyzed using generalized linear model and logistic regression. Results showed in EFG (UF concentration > 1.6 mg/L), BMD was negatively correlated with UF concentration (β: -0.14; 95%CI: -0.26, -0.01) and RUNX2 promoter methylation (β: -0.13; 95%CI: -0.22, -0.03) in women. The methylation rate of RUNX2 promoter increased by 2.16% for each 1 mg/L increment in UF concentration of women in EFG (95%CI: 0.37, 3.96). No any significant associations between UF concentration, RUNX2 promoter methylation, and BMD were observed in the individuals in CG. Mediation analysis showed that RUNX2 promoter methylation mediated 18.2% (95% CI: 4.2%, 53.2%) of the association between UF concentration and BMD of women in EFG. In conclusion, excessive fluoride exposure (>1.6 mg/L) is associated with changes of BMD in women, and this association is mediated by RUNX2 promoter methylation., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Water quality improvement is the most efficient way to prevent arsenic exposure. After the cessation of arsenic ingestion, arsenic methylation capacity of the exposed population can change significantly. The factors associated with these changes remain poorly understood. Therefore, arsenic methylation capacity in a study cohort was estimated before and after water quality improvement in the present study. Results indicated that urinary content of the arsenic species in the study cohort significantly decreased after water quality improvement. In addition, the proportions of inorganic arsenic (%iAs) and monomethyl arsenic acid (%MMA) were significantly decreased, while proportions of dimethyl arsenic (%DMA) increased. The primary methylation index (PMI) and secondary methylation index (SMI) increased from 0.85 to 0.92 and 0.82 to 0.84, respectively. Arsenic species urinary content and arsenic methylation index varied slightly between the study cohort after water quality improvement and the control cohort. The rate of increase in PMI was higher than that in SMI. The study group aged 31-50 years had the highest increase in PMI. Logistic regression revealed that %DMA before water quality improvement was negatively associated with the increase in PMI, while %iAs were positively related, and %MMA were positively associated with the increase in SMI. It is concluded that urinary arsenic species content and arsenic methylation capacity increased to the levels of the control cohort after water quality improvement. An increase in primary arsenic methylation capacity may be a burden on the secondary arsenic methylation capacity. The main role of arsenic methylation capacity recovery may be the cessation of arsenic exposure.

Anticancer drugs have been detected in the aquatic environment, they have a potent mechanism of action and their consumption is expected to drastically increase in the future. Consequently, it is crucial to routinely monitor the occurrence of anticancer drugs and to develop effective treatment options to avoid their release into the environment. Prior to implementing a monitoring program, it is important to define which anticancer drugs are more prone to be found in the surface waters. In this study the consumption of anticancer drugs in the Lisbon region (Portugal), Belgium and Haryana state (India) were used to estimate the concentrations that can be expected in surface waters. Moreover, one important aspect is to define the major entry route of anticancer drugs in the aquatic environment: is it hospital or household effluents? The results disclosed in this study showed that in Belgium and Lisbon, 94 % of the total amount of anticancer drugs were delivered to outpatients, indicating that household effluents are the primary input source of these drugs and thus, upgrading the treatment in the domestic wastewater facilities should be the focus., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Dual-emission carbon dots were synthesized by one-pot hydrothermal pyrolysis of citric acid and polyethyleneimine in the presence of rhodamine B at 160 °C for 5 h. The carbon dots have an average diameter of 2.51 nm with rhodamine moiety on their surface. Two emission bands centered at 447 and 581 nm are exhibited in their fluorescence spectra excited at 360 nm, and the former is sensitive while the latter is insensitive to Hg 2+ and pH. Glutathione (GSH) can recover the fluorescence quenched by Hg 2+ . Therefore, the dual-emission carbon dots were developed as a fluorescent ratiometric probe employing the ratio of the two intensities at 447 and 581 nm (R I447/I581 ) as the signal for the determinations of pH, Hg 2+ , and GSH. In the range of 5.0-10.0, a good linear relationship between R I447/I581 and pH was built with a regression equation of R I447/I581  = 11.95-0.56 pH (R 2  = 0.998). In the range from 0.0 to 8.0 μM, an excellent linear relationship between R I447/I581 and the concentration of Hg 2+ was obtained with a calibration equation of R I447/I581  = 6.2317-0.4458c (R 2  = 0.995) and a limit of detection (LOD) of 0.24 μM. In the range from 1.0 to 10.0 μM, a linear equation, R I447/I581  = 1.9133-0.4157c (R 2  = 0.995), was calibrated between R I447/I581 and the concentration of glutathione with a LOD of 0.27 μM. The recoveries for the determinations of Hg 2+ and GSH in real samples were in the ranges of 94.6 to 103.8% and 94.3 to 104.2%, respectively. Graphical abstract Dual-emission carbon dots achieved by luminescence center modulation within one-pot synthesis for a fluorescent ratiometric probe of pH, Hg 2+ , and glutathione.

Thallium (TI) is one of the most toxic heavy metals and priority pollutant metals. The emerging TI environmental pollution worldwide has posed a great threat to human health. However, based on the World Health Organization (WHO), the risk and severity of adverse health effects of TI in the range of 5-500 μg/L are uncertain. Moreover, evidence regarding the adverse impacts of TI on children's health is still insufficient. Herein, we aim to investigate the early adverse effects of TI on children's health and provide references for the WHO to establish stricter safety limits of TI. From 2015 to 2019, urinary TI and many clinical laboratory parameters related to blood routine, hepatic, renal, myocardial, coagulation function and serum electrolyte were measured in six children aged 1-9 years. The urinary TI concentration ranged from 13.4 μg/L to 60.1 μg/L with a mean of 36.1 μg/L and a median of 34.8 μg/L in six children in 2015. Although only four children felt a little poor appetite, several laboratory abnormalities indicated early damage in liver, renal, and myocardial functions in all children in 2015. After treatment and following up for four years, although the children's TI concentration decreased below 5 μg/L, their liver and renal functions did not completely recover, and their myocardial function worsened. Results indicated that impaired liver, renal, and myocardial functions were closely associated with elevated urinary TI concentration in children. Considering the increasing use of TI in high-technology industries and emerging TI environmental-contamination zones worldwide, establishing stricter safety limits of TI and paying more attention to the adverse health effects of TI on children are urgently required. SUMMARY: We found that a relatively low concentration of thallium (13.4 μg/L to 60.1 μg/L) impaired liver, renal, and myocardial function in six children. After treatment and following up these children for four years, although their urinary TI concentration decreased below 5 μg/L, their liver and renal functions did not completely recover, and their myocardial function worsened., Competing Interests: Declaration of competing interest The authors declare they have no actual or potential competing financial interests., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The authors describe a novel electrochemical determination method for bisphenol A (BPA) based on the electrosynthesised Cu-BTC (H 3 BTC: trimesic acid) films. Using H 3 BTC as the ligand, Cu(NO 3 ) 2 as the precursor of copper ions, and triethylamine hydrochloride (Et 3 NHCl) as the probase source, Cu-BTC films were directly deposited on glassy carbon electrode (GCE) surface via cathodic electrochemical reduction under -1.30 V. Considering the electrocatalytic activity of metal center Cu 2+ , Cu-BTC films were applied to construct the electrochemical determination platform for BPA. Chronocoulometry and electrochemical impedance spectroscopy were used to study the signal enhancement mechanism. The determination conditions were optimized. As a result, a sensitive electrochemical method was constructed for BPA. The peak currents, best measured at voltage of 0.496 V vs. SCE (KCl saturated calomel reference electrode), increase linearly in the range from 5.0 to 2000 nM. The value of determination limit is 0.72 nM. The proposed method was successfully applied to determine BPA in spiked urine, spiked waste water samples and plastic products. The results were in good agreement with those obtained for the same samples by high-performance liquid chromatography (HPLC). Graphical abstract Schematics for the construction of electrochemical determination for bisphenol A.

This work evaluated human exposure to bisphenol A (BPA) and its analogues based on human urinary excretion data and wastewater-based epidemiology (WBE). The results showed that the world's average human daily intake ranked from high to low is in order of bisphenol A (BPA), bisphenol F (BPF), bisphenol S (BPS), bisphenol P (BPP), bisphenol AP (BPAP), bisphenol B (BPB), bisphenol Z (BPZ), and bisphenol AF (BPAF), and their corresponding human daily intakes are 2.53, 0.68, 0.60, 0.41, 0.36, 0.29, 0.24, and 0.06 μg/p/day, respectively. BPA is clearly the dominant bisphenol for human exposure. However, the results also showed that humans have been widely exposed to BPA analogues as well. Many BPA analogues showed similar estrogenic activities to those of BPA; therefore, the adverse effects of BPA and its analogues on humans should be comprehensively evaluated. The nominal exposure levels obtained based on wastewater-based epidemiology ranked high to low are in order of BPA (513.73 μg/p/day), BPF (10.20 μg/p/day), BPS (5.21 μg/p/day), BPP (1.15 μg/p/day), BPZ (0.66 μg/p/day), BPB (0.61 μg/p/day), BPAF (0.58 μg/p/day), and BPAP (0.35 μg/p/day). The world's human average daily intakes of BPA and its analogues are only 0.5-47.9% of the intakes of their corresponding human nominal exposures. This study suggests that other sources rather human excretions are important origins in municipal wastewater, which indicates that the WBE method based on parent compounds is inappropriate for evaluations of human daily intakes of BPA and its analogues, neither for other industrial compounds that have multiple important sources. Three main important sources of BPA and its analogues in municipal wastewater are likely effluents of industrial wastewater, discharges of hospital wastewater, and landfill leachates. To decrease discharges of BPA and its analogues to the natural environment, any mixing of industrial and hospital wastewater as well as landfill leachates in municipal wastewater is not favorable.

Quelites are Mexican wild plants, reported as excellent sources of nutritional compounds such as amino acids (serine, glycine, and cysteine), minerals (Mg, Fe, and Zn), and phytochemicals, as phenolic acids (chlorogenic acid) and flavonoids (phloridzin and naringenin); on the other hand, high biological activity has been shown in these compounds. This work aimed to evaluate the effect of a supplementation with two endemic quelites of Mexico ( Chenopodium berlandieri L. and Portulaca Oleracea L.); in addition to supplementation, a nutritional intervention was performed; the biomarkers of hemoglobin (Hb), urinary malondialdehyde (UMDA), and urinary arsenic (UAs) were measured in adolescents exposed to arsenic. A clinical intervention study was conducted in 27 adolescents ages 11 to 12 years for 4 weeks. Weekly anthropometric and dietary evaluations were carried out, as well as the concentration of Hb; the UMDA and UAs were performed by plate-based colorimetric measurement and atomic absorption spectrophotometry with the hydrides generation system, respectively. The results showed that UMDA concentrations had a significant improvement in the supplemented group (SG) vs. control group (CG) (SG = 1.59 ± 0.89 µM/g creatinine vs. CG = 2.90 ± 0.56 µM/g creatinine) in the second week of intervention; on the other hand, the supplemented group showed an increase in Hb levels (15.12 ± 0.99 g/dL) in the same week; finally after the second week, an increase in UAs levels was observed significantly compared to the baseline value (Baseline: 56.85; Week 2: 2.02 µg/g creatinine). Therefore, the results show that the mixture of quelites (a rich source of phytochemicals and nutrients) improved hemoglobin and UMDA levels, and urinary arsenic excretion from the second week in the exposed population.

Novel molecularly imprinted polymer (MIP) for metformin was synthesized on the surface of magnetic multi-walled carbon nanotubes (MMWCNTs) as the support. Metformin was used as the template, methacrylic acid (MAA) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker and 2,2'-azoisobutyronitrile (AIBN) as the initiator. The synthesized composite was characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and Fourier transform infrared spectroscopy (FTIR). The surface molecularly imprinted composite was used for magnetic solid phase microextraction (MSPME) of metformin before its chemiluminescence (CL) determination and its capability was compared with non-imprinted polymer (NIP). The central composite design was used for optimization as well as consideration of possible interaction of effective variables on extraction. Under the optimized conditions, the developed method exhibited the linear dynamic range of 0.5-50.0 μg L -1 with a detection limit of 0.13 μg L -1 and enhancement factor of 195.3 for the preconcentration of 100 mL of the sample and 500 μL of an eluent. The intra- and inter-day relative standard deviations (RSD%) at 5.0 μg L -1 level of metformin (n = 6) were 3.7 and 4.9%, respectively. The maximum adsorption capacity of the sorbent was found to be 80.0 mg g -1 , the adsorption of metformin was endothermic and spontaneous and followed the Langmuir isotherm model. The adsorption kinetic was also found to be best fitted with the pseudo-second-order model. The designed method was successfully applied to the extraction and determination of metformin in biological fluids and water samples., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Benzophenones (BPs) and other ultra violet (UV) filters (UV-filters) are widely used in sunblock and other personal care products, raising concerns about their adverse health risks to human, especially for children. In the present study, BP-type UV-filters and other four widely used UV-filters were evaluated in the child urinary samples (4-6 years, n = 53), tap water and commercial distilled water in Hong Kong. The results suggested that the target chemicals are ubiquitous in the subject. BP1, BP2, BP3 and BP4 in children urine samples contributed closely to the overall children exposure of UV filters, with detection rates above 58% and geometric means ranging from 44.2 to 76.7 ng/mL. As a contrast, BP3 was the major substance found in the tap water and distilled bottle water, with detection rates of 100% and geometric means of 9.64 and 14.5 ng/L, respectively. There were some significant relationships between urinary UV filters and personal characteristics (BMI values, sex, income level, hand washing frequency, and body location usage), but the health risks associated with UV-filters in Hong Kong children might not be concerning. Only two children applied sun creams in this research, indicating that there were other sources to exposure these chemicals., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The aim of this study was to examine the effect of the secondary biological treatment plant effluent administration on the kidneys, urinary bladder, and testis of Wistar rats in relation to lead (Pb) and cadmium (Cd) accumulation, since such an effluent is used for irrigation of edible plants. Male Wistar rats, randomly assigned into 5 groups, were treated with domestic sewage effluent (DSE) for 24 months. Cadmium and lead concentrations in the DSE, rats' tissues, and urine were estimated by means of atomic spectroscopy. Lead was rapidly accumulated in high amounts in rats' kidney and to a lesser extent in the testis whereas Cd concentration was raised in all tissues examined. Deposition of Cd and Pd in the kidney of the rats resulted in profound damage over time. The results showed that long-term administration to DSE as drinking water exposes living organisms to urogenital stress related to heavy metal concentration and pH of the effluent.

Chloride widely exists in the environment and will cause serious interference for arsenic speciation analysis. The determination of four arsenic species including arsenite (As(III)), arsenate (As(V)), monomethylarsenate (MMA), and dimethylarsonate (DMA) in samples containing high concentrations of Cl - was carried out in this work by coupling of liquid chromatography (LC) with hydride generation atomic fluorescence spectrometry (HG-AFS). The interference of Cl - was successfully eliminated by coupling two anion-exchange chromatographic columns in series and eluting with 35.0 mmol L -1 (NH 4 ) 2 HPO 4 (pH = 6.00). A novel pre-treatment system was subsequently developed to realize on-line column switch and pre-reduction of As(V). The analysis time was shortened by an isocratic elution but programmed flow rate method, and the sensitivity of As(V) was also enhanced by the introduction of pre-reduction using the developed system. The proposed method can resist at least 10 g L -1  Cl - without any pre-treatment operations. Since LC-HG-AFS is low-cost and can be afforded or self-assembled by most labs, the developed method can be adopted as a routine analysis method for arsenic species in chloride-bearing samples, such as urine and seawater. Graphical abstract.

A microscale highly fluorescent Eu metal-organic framework (Eu-MOF) was synthesized with terephthalic acid and 1H-1,2,4-triazole-3,5-diamine by one-pot hydrothermal method. And it was characterized by scanning electron microscope, Fourier transform infrared spectroscopy, powder X-ray diffraction, fluorescence spectroscopy, thermogravimetric analysis, and energy dispersive X-ray mapping. The prepared Eu-MOF has high quantum yield of 30.99%, excellent water dispersibility, good fluorescence stability, and favorable thermal stability. Based on the distinctly different fluorescence responses of different emission, the prepared Eu-MOF was used as dual-mode visual sensor for the sensitive detection of berberine hydrochloride and tetracycline. The limits of detection are 78 nM and 17 nM, respectively. The sensing mechanism was also discussed. Moreover, a filter paper sensor has been designed for sensing tetracycline with a notable fluorescence color change from blue to red. The prepared Eu-MOF is promising to be developed as a multi-mode luminescent sensor for visual detection in biochemical analysis. Graphical abstract Illustration of the synthesis of Eu-MOF and its sensing applications for berberine hydrochloride and tetracycline.

Arsenic intake from household drinking/cooking water and food may represent a significant exposure pathway to induce cancer and non-cancer health effects. This study is based on the human biomonitoring of 395 volunteers from 223 households with private water sources located in rural Punjab, Pakistan. This work has shown the relative contribution of water and staple food to arsenic intake and accumulation by multiple biological matrix measurements of inorganic and organic arsenic species, while accounting for potential confounders such as age, gender, occupation, and exposure duration of the study population. Multi-variable linear regression showed a strong significant relationship between total arsenic (tAs) intake from water and concentrations of tAs, inorganic arsenic (iAs), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) in urine and toenail samples. tAs intake from staple food (rice and wheat) also showed a strong significant relationship with hair tAs and iAs. The sole impact of staple food intake on biomarkers was assessed and a significant correlation was found with all of the urinary arsenic metabolites. Toenail was found to be the most valuable biomarker of past exposure to inorganic and organic arsenic species of dietary and metabolic origin.

Microcystins are potent hepatotoxins that have become a global health concern in recent years. Their actions in at-risk populations with pre-existing liver disease is unknown. We tested the hypothesis that the No Observed Adverse Effect Level (NOAEL) of Microcystin-LR (MC-LR) established in healthy mice would cause exacerbation of hepatic injury in a murine model (Lepr db /J) of Non-alcoholic Fatty Liver Disease (NAFLD). Ten-week-old male Lepr db /J mice were gavaged with 50 μg/kg, 100 μg/kg MC-LR or vehicle every 48 h for 4 weeks ( n = 15-17 mice/group). Early mortality was observed in both the 50 μg/kg (1/17, 6%), and 100 μg/kg (3/17, 18%) MC-LR exposed mice. MC-LR exposure resulted in significant increases in circulating alkaline phosphatase levels, and histopathological markers of hepatic injury as well as significant upregulation of genes associated with hepatotoxicity, necrosis, nongenotoxic hepatocarcinogenicity and oxidative stress response. In addition, we observed exposure dependent changes in protein phosphorylation sites in pathways involved in inflammation, immune function, and response to oxidative stress. These results demonstrate that exposure to MC-LR at levels that are below the NOAEL established in healthy animals results in significant exacerbation of hepatic injury that is accompanied by genetic and phosphoproteomic dysregulation in key signaling pathways in the livers of NAFLD mice.

Although phthalates (PAEs) are ubiquitous in drinking water, and phthalate monoesters (MPAEs) have been recognized as the bioactive metabolites of PAEs, little information is available regarding the occurrence of MPAEs in drinking water and the contributions of PAEs and MPAEs to human exposure. In this study, the concentrations of PAEs and MPAEs in 146 samples of drinking water collected from 24 cities throughout China were determined. The mean concentrations of dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), and di-2-ethylhexyl phthalate (DEHP) were 14.31 ± 26.28, 5.905 ± 11.57, 103.8 ± 310.5, 595.9 ± 1794, and 178.2 ± 422.0 ng/L, respectively. Monomethyl phthalate (MMP), monoethyl phthalate (MEP), monoisobutyl phthalate (MiBP), mono-n-butyl phthalate (MnBP), and mono-2-ethylhexyl phthalate (MEHP) were detected in drinking water for the first time, at mean concentrations of 12.1 ± 18.0, 2.4 ± 5.8, 11.3 ± 37.2, 36.3 ± 103, and 9.9 ± 18.0 ng/L, respectively. The geometric mean concentrations of MMP, MEP, MiBP, MnBP, and MEHP in urine samples collected from 1040 participants from 16 cities were 10.1, 19.3, 29.6, 47.3, and 3.63 μg/g creatinine, respectively. The concentrations of PAEs and MPAEs in drinking water and daily intakes (DIs) of PAEs from nine cities where drinking water and urine samples were simultaneously collected were used to estimate the contributions from drinking water. The percentages of DMP, DEP, DiBP, DnBP, and DEHP from drinking water accounted for DIs of 0.60%, 0.049%, 1.26%, 2.76%, and 0.56%, respectively. The percentages of MMP, MEP, MiBP, MnBP and MEHP via intake of drinking water accounted for urinary concentrations of 0.86%, 0.032%, 0.14%, 0.089%, and 0.045%, respectively., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Background: Arsenic exposure affects [Formula: see text] people worldwide, including [Formula: see text] in Bangladesh. Arsenic exposure increases the risk of cancer and other chronic diseases, and one potential mechanism of arsenic toxicity is epigenetic dysregulation., Objective: We assessed associations between arsenic exposure and genome-wide DNA methylation measured at baseline among 396 Bangladeshi adults participating in the Health Effects of Arsenic Longitudinal Study (HEALS) who were exposed by drinking naturally contaminated well water., Methods: Methylation in whole blood DNA was measured at [Formula: see text] using the Illumina InfiniumMethylationEPIC (EPIC) array. To assess associations between arsenic exposure and CpG methylation, we used linear regression models adjusted for covariates and surrogate variables (SVs) (capturing unknown technical and biologic factors). We attempted replication and conducted a meta-analysis using an independent dataset of [Formula: see text] from 400 Bangladeshi individuals with arsenical skin lesions., Results: We identified 34 CpGs associated with [Formula: see text] creatinine-adjusted urinary arsenic [[Formula: see text]]. Sixteen of these CpGs annotated to the [Formula: see text] array, and 10 associations were replicated ([Formula: see text]). The top two CpGs annotated upstream of the ABR gene (cg01912040, cg10003262 ). All urinary arsenic-associated CpGs were also associated with arsenic concentration measured in drinking water ([Formula: see text]). Meta-analysis ([Formula: see text] samples) identified 221 urinary arsenic-associated CpGs ([Formula: see text]). The arsenic-associated CpGs from the meta-analysis were enriched in non-CpG islands and shores ([Formula: see text]) and depleted in promoter regions ([Formula: see text]). Among the arsenic-associated CpGs ([Formula: see text]), we observed significant enrichment of genes annotating to the reactive oxygen species pathway, inflammatory response, and tumor necrosis factor [Formula: see text] ([Formula: see text]) signaling via nuclear factor kappa-B ([Formula: see text]) hallmarks ([Formula: see text])., Conclusions: The novel and replicable associations between arsenic exposure and DNA methylation at specific CpGs observed in this work suggest that epigenetic alterations should be further investigated as potential mediators in arsenic toxicity and as biomarkers of exposure and effect in exposed populations. https://doi.org/10.1289/EHP3849.

Blood trihalomethanes (THMs) and urinary haloacetic acids (HAAs) are the leading candidate biomarkers for disinfection byproduct (DBP) exposure. However, no studies have assessed the exposure profiles, temporal variability, and potential predictors of these biomarkers during pregnancy. Here we collected blood (n = 4304) and urine samples (n = 4165) from 1760 Chinese pregnant women during early, mid-, and late pregnancy, which were separately analyzed for 4 THMs and 2 HAAs. We calculated the intraclass correlation coefficients (ICCs) to assess the variability of these biomarkers and estimated their correlations with sociodemographic, water-use behavioral, dietary and sample collection factors using mixed models. The median concentrations of TCM, BDCM, Br-THMs [sum of BDCM, dibromochloromethane (DBCM), bromoform (TBM)], total THMs (TTHMs, sum of TCM and Br-THMs), DCAA and TCAA in the water distribution system were 4.2 μg/L, 1.7 μg/L, 2.9 μg/L, 7.1 μg/L, 3.4 μg/L and 8.2 μg/L, respectively. Chloroform (TCM), bromodichloromethane (BDCM), dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) were detected in > 75% of the biospecimens. Repeated measurements of blood TCM, BDCM, Br-THMs and TTHMs and urinary DCAA and TCAA uniformly exhibited high variability (ICCs = 0.01-0.13); the use of a single measurement to classify gestational average exposure resulted in a high degree of exposure misclassification. The sampling season was a strong predictor of all analyzed DBPs. Additionally, we detected a positive association of blood TCM and BDCM with household income, urinary DCAA with age, and urinary TCAA with tap water usage, education level and amount of tap water consumed. Inverse associations were found between blood BDCM and vegetable consumption, and between blood Br-THM and TTHM and time interval since the last bathing/showering. Afternoon samples had lower DCAA concentrations than did early morning samples. Our results indicate that blood THM and urinary HAA concentrations vary greatly over the course of pregnancy and are affected by sampling season, time of day of blood/urine collection, sociodemographic factors, recent water-use activities and dietary intake., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Cr(VI) has carcinogenic effects, so determination of trace amount of chromium in human body such as urine has a great deal of importance. In this work, a novel microextraction method was developed based on solidification of dispersed fine droplets (SDFD) of a low melting point deep eutectic solvent (DES), produced with the aid of sonication, for fast and efficient determination of Cr(VI) in urine samples. Cr(VI) contents of the human urine samples were first complexed using 1,5-diphenylcarbazone at pH ≈ 2.0 and then extracted by the method. A cloudy solution was achieved by the sonication of a microliter volume of a new water-immiscible DES consisting of benzyltriphenylphosphonium bromide (BTPPB) and phenol. Low freezing point of DES makes it possible to use simple, precise, and fast collection of the extraction phase by solidification and the subsequent centrifugation. Finally, the sedimented phase was diluted with methanol and analyzed by electrothermal atomic absorption spectrometry (ETAAS). The influences of the main factors on the efficiency of the procedure were investigated by a four-factor central composite design (CCD). Under the optimum conditions, the calibration curve was linear within the range of 10-1000 ng L -1 . The intra- and inter-day RSD% values of 2.6 and 4.7% were obtained at the concentration of 50.0 ng L -1 , respectively. The limits of detection (LOD) and quantification (LOQ) were calculated as 2.0 and 7.0 ng L -1 , respectively. Moreover, compared to the other approaches, the proposed method presented better or comparable analytical performance and provided accurate, precise, and reliable results for trace analysis of Cr(VI) in urine samples.

The aim of this research was to investigate circulating expression levels of three miRNAs (miR-126, miR-155, and miR-145) proposed as predictive CVD biomarkers in Mexican women exposed to inorganic arsenic via drinking water. Mean UAs concentration of 19.5 ± 14.0 μg/g creatinine was found after urine samples were analyzed (n = 105). Significant associations between UAs levels and serum expression levels of miR-155 (p < 0.05) and miR-126 (p < 0.05) were observed after adjustment for assessed co-variables. Alterations in the serum expression levels of miR-155 and miR-126 may be associated with the onset and development of cardiovascular diseases, hence miRNAs could be proposed as prognostic CVD biomarkers. Data found in this study are of concern and risk reduction plans are necessary for the assessed communities to prevent cardiovascular events in this population of women., (Copyright © 2019 Elsevier B.V. All rights reserved.)

An appropriate and precise identification of high-risk individuals to develop cardiovascular diseases (CVD) is of high importance to reduce these kinds of diseases, a major health concern worldwide. Therefore, the aim of this research was to evaluate prognostic CVD biomarkers in Mexican women exposed to inorganic arsenic via drinking water. Then, a cross-sectional study including 190 women was achieved. Urinary arsenic (UAs) levels were analyzed as exposure biomarker to that metalloid. While, plasma asymmetric dimethylarginine (ADMA), adipocyte fatty acid-binding protein (FABP4), adiponectin, and chemerin levels, hypertriglyceridemic waist (HW) phenotype, atherogenic index of plasma (AIP), and Framingham risk score (FRS) were assessed as prognostic CVD biomarkers. Mean UAs level detected in the evaluated urinary samples was 45.0 ± 40.0 μg/g creatinine. In addition, mean plasma ADMA, FABP4, chemerin and adiponectin levels were 0.68 µmol/L, 20.3 ng/mL, 12.5 μg/mL, and 255 ng/mL, correspondingly. Approximately, 54% of women participants displayed an HW phenotype. Regarding AIP and FRS values, 0.12 ± 0.15 and 7.50 ± 8.00 were found, respectively. Besides, strong and significant associations (p < 0.05) between UAs and AIP, ADMA, and FABP4 were distinguished. Also, after a multivariate analysis, the association between those variables persisted after adjustment for traditional risk factors of CVD. In conclusion, according to the results found in this research, the most sensible CVD biomarkers distinguished in this study were AIP, ADMA, and FABP4. Nevertheless, more studies are necessary to confirm the results found in this investigation., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Background: Disinfection by-products (DBPs) have been shown to be reproductive and developmental toxicity. However, few studies examine the effect of prenatal exposure to DBPs on fetal growth via ultrasound measures., Objective: To investigate the associations between maternal exposure to DBPs during late pregnancy and ultrasound measures of fetal growth., Methods: We included 332 pregnant women who presented to a hospital to wait for delivery in Wuhan, China. Ultrasound parameters of fetal growth including femur length (FL), head circumference (HC), abdominal circumference (AC) and biparietal diameter (BPD) were assessed. We measured maternal TCAA concentrations in first morning urine collected from late pregnancy as a biomarker of in utero DBP exposure levels. Multivariable linear regression models were used to examine the associations between maternal urinary TCAA concentrations during late pregnancy and ultrasound parameters of fetal growth., Results: We found that elevated maternal creatinine (Cr)-adjusted urinary TCAA levels had negative associations with BPD, HC and FL in boys but not in girls (P interaction = 0.04, 0.05 and 0.08, respectively). Male fetal BPD, HC and FL had decreases of 0.21 cm (95% CI: -0.35, -0.07; P for trend = 0.003), 0.46 cm (95% CI: -0.81, -0.10; P for trend = 0.01) and 0.17 cm (95% CI: -0.30, -0.04; P for trend = 0.01) for the highest vs. lowest tertile of Cr-adjusted urinary TCAA, respectively. These negative associations persisted for maternal Cr-adjusted urinary TCAA concentrations modeled as continuous variables., Conclusion: The results from our study suggest that maternal exposure to TCAA during late pregnancy may have adverse effects on male fetal growth., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Disinfected water is the major source of haloacetic acids (HAAs) in humans, but their inter- and intra-individual variability for exposure and risk assessment applications is under-researched. Thus, we measured HAAs in cross-sectional and longitudinal urine and water specimens from 17 individuals. Five regulated HAAs-mono, di, and trichloroacetic acid (MCAA, DCAA, and TCAA) and mono- and dibromoacetic acid (MBAA and DBAA)-and one unregulated HAA-bromochloroacetic acid (BCAA)-were measured. Urinary DCAA, MBAA, DBAA, and BCAA levels were always below the limits of detection (LOD). Measured levels and interindividual variability of urinary MCAA were higher than urinary TCAA. Longitudinal urinary specimens showed MCAA levels peaked in after-shower specimens, while TCAA levels remain unchanged. Correlation between urinary MCAA and TCAA was moderate but statistically significant. The prevalence of MCAA and TCAA in urine suggest they can be considered as biomarkers of HAA. Peak urinary MCAA in post-shower specimens suggest MCAA captures short-term exposure via dermal and/or inhalation, while urinary TCAA captures long-term exposure via ingestion. However, further research is warranted in a large pool of participants to test the reliability of MCAA as exposure biomarker., Competing Interests: The authors declare no conflicts of interest.

In this study, the application of a mixture of organic solvents as a supported liquid membrane for improving the efficiency of the electromembrane extraction procedure was investigated. The extraction process was followed by high-performance liquid chromatography analysis of two model drugs (verapamil and riluzole). In this research, four organic solvents, including 1-heptanol, 1-octanol, 2-nitrophenyl octyl ether, and 2-ethyl hexanol, were selected as model solvents and different binary mixtures (v/v 2:1, 1:1 and 1:2) were used as the supported liquid membrane. The mixture of 2-ethyl hexanol and 1-otanol (v/v, 2:1) improved the extraction efficiency of model drugs by 1.5 to 12 times. It was found that extraction efficiency is greatly influenced by the level of electric current. In this study, for various mixtures of organic solvents, the electric current fluctuated between 50 and 2500 μA, and the highest extraction efficiencies were obtained with low and stable electric currents. Finally, the optimized extraction condition was validated and applied for the determination of model drugs in urine and wastewater samples., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study assessed the effects of polymorphic variants of gutathione-S-transferase and metallothioneins on profiles of urinary arsenic species. Drinking groundwater from Margarita and San Fernando, Colombia were analyzed and the lifetime average daily dose (LADD) of arsenic was determined. Specific surveys were applied to collect demographic information and other exposure factors. In addition, GSTT1-null, GSTM1-null, GSTP1-rs1695 and MT-2A-rs28366003 genetic polymorphisms were evaluated, either by direct PCR or PCR-RFLP. Urinary speciated arsenic concentrations were determined by HPLC-HG-AFS for species such as As III , As V , monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), and total urinary As (TuAs). Primary methylation index (PMI) and secondary methylation index (SMI) were also calculated as indicators of the metabolic capacity. Polymorphisms effects were tested using multivariate analysis, adjusted by potential confounders. The As concentrations in groundwater were on average 34.6 ± 24.7 μg/L greater than the WHO guideline for As (10 μg/L). There was a correlation between As concentrations in groundwater and TuAs (r = 0.59; p = 0.000). Urinary inorganic arsenic (%InAs) was associated with GSTP1, LADD, GSTP1*Age, GSTP1*alcohol consumption (r 2  = 0.43; likelihood-ratio test, p = 0.000). PMI was associated with sex (r 2  = 0.20; likelihood-ratio test, p = 0.007). GSTP1 (AG + GG) homozygotes/heterozygotes could increase urinary %InAs and decrease the PMI ratio in people exposed to low and high As from drinking groundwater. Therefore, the explanatory models showed the participation of some covariates that could influence the effects of the polymorphisms on these exposure biomarkers to As., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Prednisolone (PDNN) as an emergent micropollutant directly influences the regional ecological security. In this study, the degradation of PDNN by ultraviolet activated chlorine (UV/chlorine) oxidation process was comprehensively evaluated. The quenching experiment suggested that the PDNN degradation in UV/chlorine process was involved in the participation of hydroxyl radical (OH) and reactive chlorine species (RCS). Influence factors including chlorine dosage, pH, common anion and cation, fulvic acid (FA) on PDNN degradation via UV/chlorine process were investigated. A low chlorine (≤7.1 mg L -1 ) promoted the PDNN degradation, while a high chlorine dosage (>7.1 mg L -1 ) was adverse. The pH (4.0-10.0) showed negligible effect, while the investigated anions (Cl - , Br - , HCO 3 - and SO 4 2- ), NH 4 + and FA exerted negative impact on PDNN degradation. An efficient process to minimize pharmaceutical micropollutants was the disposal of human urine containing a high concentration of pharmaceutical and potential toxic metabolites. An inhibitory effect was observed in the synthetic urine (fresh urine and hydrolyzed urine). The intermediates/products were identified and the mechanism of PDNN degradation was proposed. PDNN gone through three degradation routes, involving the direct addition of α, β-unsaturated ketone at C 1 or C 5 , the photolysis of C 17 and H-abstraction of C 11 . The main reactive sites were further determined by comparison of the frontier orbitals calculation and the proposed mechanism. Based on the toxicological tests for PDNN degradation, TP396 (TP396-C 1 Cl and TP396-C 5 Cl) and TP414-2-1 (TP414-C 1 ClC 5 OH) exhibited much higher toxicity than PDNN, and prolonging reaction time was necessary to achieve PDNN detoxification., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The susceptibility of the kidneys to fluoride toxicity can largely be attributed to its anatomy and function. As the filtrate moves along the complex tubular structure of each nephron, it is concentrated in the proximal and distal tubules and collecting duct. It has been frequently observed that the children suffering from renal impairments also have some symptoms of dental and skeletal fluorosis. The findings suggest that fluoride somehow interferes with renal anatomy and physiology, which may lead to renal pathogenesis. The aim of this study was to evaluate the fluoride-associated nephrotoxicity. A total of 156 patients with childhood nephrotic syndrome were screened and it was observed that 32 of them had significantly high levels ( p ≤ 0.05) of fluoride in urine (4.01 ± 1.83 ppm) and serum (0.1 ± 0.013 ppm). On the basis of urinary fluoride concentration, patients were divided into two groups, namely group 1 (G-1) ( n = 32) containing normal urine fluoride (0.61 ± 0.17 ppm) and group 2 (G-2) ( n = 32) having high urine fluoride concentration (4.01 ± 1.83 ppm). Age-matched healthy subjects ( n = 33) having normal levels of urinary fluoride (0.56 ± 0.15 ppm) were included in the study as control (group 0 (G-0)). Kidney biopsies were taken from G-1 and G-2 only, who were subjected to ultrastructural (transmission electron microscopy) and apoptotic (terminal deoxynucleotidyl transferase deoxyuridine triphosphate nick end labeling) analysis. Various subcellular ultrastructural changes including nuclear disintegration, chromosome condensation, cytoplasmic ground substance lysis, and endoplasmic reticulum blebbing were observed. Increased levels of apoptosis were observed in high fluoride group (G-2) compared to normal fluoride group (G-1). Various degrees of fluoride-associated damages to the architecture of tubular epithelia, such as cell swelling and lysis, cytoplasmic vacuolation, nuclear condensation, apoptosis, and necrosis, were observed.

Lifestyle, food intake, and exposure to chemicals are potential risk factors for the development of calcium urolithiasis. Pb, Cd, and Hg have been proved to cause renal illness, and urinary tract stones might be caused by exposure to metals. Therefore, this study aimed to measure the concentration of metals in urinary tract stones and blood simultaneously in urolithiasis patients. Moreover, we intended to determine whether urinary tract stones can be regarded as a biomarker of exposure or an effect marker in a population with environmental exposure to metals. Thirty-five urolithiasis patients (case) and 34 healthy inhabitants (control) were recruited in this study. The contents of Pb, Cd, Cr, Cu, Ni, As, Zn, and Hg were determined in urinary stones and blood in the case and control groups. The most abundant metals were Zn and Cu in blood and Zn and Ni in urinary stones. Significantly higher levels of Zn, Ni, and As were found in calcium phosphate stones than in calcium oxalate or uric acid stones. The majority of metals were not present at consistent levels in both blood and urinary stones, except for Zn. Urinary stones might be explained as providing another metabolic pathway for metal contamination. Moreover, as the metals with the highest content in urinary stones were Ni and Zn, and Ni content was very much higher than in other countries, contamination by Ni should be further taken into consideration if there is any serious contamination in Taiwan.

Boric acid and sodium borates are currently classified as being toxic to reproduction under "Category 1B" with the hazard statement of "H360 FD" in the European CLP regulation. This has prompted studies on boron-mediated reprotoxic effects in male workers in boron mining areas and boric acid production plants. By contrast, studies on boron-mediated developmental effects in females are scarce. The present study was designed to fill this gap. Hundred and ninety nine females residing in Bandirma and Bigadic participated in this study investigating pregnancy outcomes. The participants constituted a study group covering blood boron from low (< 100 ng B/g blood, n = 143) to high (> 150 ng B/g blood, n = 27) concentrations. The mean blood boron concentration and the mean estimated daily boron exposure of the high exposure group was 274.58 (151.81-975.66) ng B/g blood and 24.67 (10.47-57.86) mg B/day, respectively. In spite of the high level of daily boron exposure, boron-mediated adverse effects on induced abortion, spontaneous abortion (miscarriage), stillbirth, infant death, neonatal death, early neonatal death, preterm birth, congenital anomalies, sex ratio and birth weight of newborns were not observed.

Fluoride (F) is a toxicant widely distributed in the environment. Experimental studies have shown kidney toxicity from F exposure. However, co-exposure to arsenic (As) has not been considered, and epidemiological information remains limited. We evaluated the association between F exposure and urinary kidney injury biomarkers and assessed As co-exposure interactions. A cross-sectional study was conducted in 239 adults (18-77 years old) from three communities in Chihuahua, Mexico. Exposure to F was assessed in urine and drinking water, and As in urine samples. We evaluated the urinary concentrations of albumin (ALB), cystatin-C (Cys-C), kidney injury molecule 1 (KIM-1), clusterin (CLU), osteopontin (OPN), and trefoil factor 3 (TFF-3). The estimated glomerular filtration rate (eGFR) was calculated using serum creatinine (Creat) levels. We observed a positive correlation between water and urine F concentrations (ρ = 0.7419, p < 0.0001), with median values of 1.5 mg/L and 2 μg/mL, respectively, suggesting that drinking water was the main source of F exposure. The geometric mean of urinary As was 18.55 ng/mL, approximately 39% of the urine samples had As concentrations above the human biomonitoring value (15 ng/mL). Multiple linear regression models demonstrated a positive association between urinary F and ALB (β = 0.56, p < 0.001), Cys-C (β = 0.022, p = 0.001), KIM-1 (β = 0.048, p = 0.008), OPN (β = 0.38, p = 0.041), and eGFR (β = 0.49, p = 0.03); however, CLU (β = 0.07, p = 0.100) and TFF-3 (β = 1.14, p = 0.115) did not show significant associations. No interaction with As exposure was observed. In conclusion, F exposure was related to the urinary excretion of early kidney injury biomarkers, supporting the hypothesis of the nephrotoxic role of F exposure., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Background: Mexico is included in the list of countries with concurrent arsenic and fluoride contamination in drinking water. Most of the studies have been carried out in the adult population and very few in the child population. Urinary arsenic and urinary fluoride levels have been accepted as good biomarkers of exposure dose. The Biomonitoring Equivalents (BE) values are useful tools for health assessment using human biomonitoring data in relation to the exposure guidance values, but BE information for children is limited., Methods: We conducted a systematic review of the reported levels of arsenic and fluoride in drinking water, urinary quantification of speciated arsenic (inorganic arsenic and its methylated metabolites), and urinary fluoride levels in child populations. For BE values, urinary arsenic and fluoride concentrations reported in Mexican child populations were revised discussing the influence of factors such as diet, use of dental products, sex, and metabolism., Results: Approximately 0.5 and 6 million Mexican children up to 14 years of age drink water with arsenic levels over 10 μg/L and fluoride over 1.5 mg/L, respectively. Moreover, 40% of localities with arsenic levels higher than 10 μg/L also present concurrent fluoride exposure higher than 1.5 mgF/L. BE values based in urinary arsenic of 15 μg/L and urinary fluoride of 1.2 mg/L for the environmentally exposed child population are suggested., Conclusions: An actual risk map of Mexican children exposed to high levels of arsenic, fluoride, and both arsenic and fluoride in drinking water was generated. Mexican normativity for maximum contaminant level for arsenic and fluoride in drinking water should be adjusted and enforced to preserve health. BE should be used in child populations to investigate exposure., Competing Interests: The authors have no competing interests to declare., (© 2018 The Author(s). This is an open-access article distributed under the terms of the Creative Commons Attribution 4.0 International License (CC-BY 4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. See http://creativecommons.org/licenses/by/4.0/.)

Background: Multiple epidemiological studies exist for some of the well-studied health endpoints associated with inorganic arsenic (iAs) exposure; however, results are usually expressed in terms of different exposure/dose metrics. Physiologically based pharmacokinetic (PBPK) models may be used to obtain a common exposure metric for application in dose-response meta-analysis., Objective: A previously published PBPK model for inorganic arsenic (iAs) was evaluated using data sets for arsenic-exposed populations from Bangladesh and the United States., Methods: The first data set was provided by the Health Effects of Arsenic Longitudinal Study cohort in Bangladesh. The second data set was provided by a study conducted in Churchill County, Nevada, USA. The PBPK model consisted of submodels describing the absorption, distribution, metabolism and excretion (ADME) of iAs and its metabolites monomethylarsenic (MMA) and dimethylarsenic (DMA) acids. The model was used to estimate total arsenic levels in urine in response to oral ingestion of iAs. To compare predictions of the PBPK model against observations, urinary arsenic concentration and creatinine-adjusted urinary arsenic concentration were simulated. As part of the evaluation, both water and dietary intakes of arsenic were estimated and used to generate the associated urine concentrations of the chemical in exposed populations., Results: When arsenic intake from water alone was considered, the results of the PBPK model underpredicted urinary arsenic concentrations for individuals with low levels of arsenic in drinking water and slightly overpredicted urinary arsenic concentrations in individuals with higher levels of arsenic in drinking water. When population-specific estimates of dietary intakes of iAs were included in exposures, the predictive value of the PBPK model was markedly improved, particularly at lower levels of arsenic intake., Conclusions: Evaluations of this PBPK model illustrate its adequacy and usefulness for oral exposure reconstructions in human health risk assessment, particularly in individuals who are exposed to relatively low levels of arsenic in water or food. https://doi.org/10.1289/EHP3096.

Inorganic arsenic (iAs) exposure increases risk of several diseases, including cancer. Some nutrients such as flavonoids enhance glutathione activity, which in turn play a key role in iAs elimination. Our objective was to explore whether dietary non-soy flavonoids are associated with iAs metabolism. We hypothesized that the intake of flavonoids belonging to the following groups, flavan-3-ols, flavone, flavonol, flavanone, and anthocyanidin, is positively associated with urinary dimethylarsinic acid (DMA), which is the most soluble iAs metabolite excreted. We performed a cross-sectional study that included 1027 women living in an arsenic-contaminated area of northern Mexico. Flavonoid intake was estimated using a validated food frequency questionnaire. Concentration of urinary iAs and its metabolites (monomethylarsonic acid and DMA) were determined by high performance liquid chromatography ICP-MS. Results showed positive significant associations between DMA and the flavonoid groups flava-3-ols (β= 0.0112) and flavones (β= 0.0144), as well as the individual intake of apigenin (β= 0.0115), luteolin (β= 0.0138), and eriodictyol (β= 0.0026). Our findings suggest that certain non-soy flavonoids may improve iAs elimination; however, there is still very limited information available regarding the consumption of flavonoids and iAs metabolism., (Copyright © 2018 Elsevier Inc. All rights reserved.)

This article presents a monolithic extraction unit with integrated stirring using carbon nanohorns and methacrylate-based compounds as monomers. The hybrid monolithic material was prepared by thermal polymerization at 70 °C for 24 h, and was applied for the extraction of UV-filters from waters and human urine samples. To achieve the integrated stirring unit, the monolith was grown over an ironware. Variables dealing with the polymerization mixture composition and the microextraction procedure were studied in depth. The resulting hybrid monolithic polymer was also characterized by scanning electron microscopy (SEM) and nitrogen intrusion porosimetry. The target analytes were quantified by UPLC-DAD, and the limits of detection were between 1 and 10 μg/L. The precision of the method (inter extraction units) expressed as relative standard deviation ranged from 5.4% and 7.9%. Also, relative recoveries values of the analyte spiked to swimming pool water and urine samples varied in the interval 72-124 and 71-114%, respectively., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this study, we have developed a facile method for preparation of highly fluorescent Au nanoclusters (AuNCs) using 11-mercaptoundecanoic acid (MUA) as both the reducing and stabilizing agent. The as-prepared MUA functionalized AuNCs (MUA-AuNCs) have good water solubility, excellent photostability, and strong fluorescence emission at 610 nm with a quantum yield of 7.28% in water. The fluorescence of MUA-AuNCs was first quenched by copper ions through electron transfer, subsequently caused obvious restoration by competitive effect after adding penicillamine, making it a potential fluorescent sensor for penicillamine with a detection limit of 0.08 μM. Furthermore, the newly designed fluorescence "on-off-on" assay was explored for the measurement of penicillamine in complex real water and urine samples with satisfactory results.

The Eastern Mediterranean and the Middle Eastern regions are both understudied in terms of possible environmental health risks for their populations. Water scarcity and desalination treatment provide the general population of countries from these regions (e.g., Kuwait and Cyprus) with unique tap water characteristics. This study investigated the association between external (tap water and 24 h personal air samples) and internal (urine) THM exposure metrics that reflected information about THM-related habits and activities collected using questionnaires and time activity diaries. The study population comprised of young females residing in either Kuwait (n=13) or Cyprus (n=22). First morning urine voids were collected on 2 consecutive days. Urinary creatinine-adjusted total THM (TTHM) levels were higher in Kuwait (median (interquartile range): 1044 (814, 1270) ng/g) than in Cyprus (691 (510, 919) ng/g, P<0.05). Median personal air TTHM levels in Kuwait (1.4 (0.7, 1.7) μg/m 3 ) were higher than those in Cyprus (0.9 (0.5, 1.4) μg/m 3 ), but did not reach statistical significance (P=0.17). Median tap water TTHM in Kuwait (6.7 (5.4, 11.6) μg/l) did not correlate with urinary or air THM and they were lower than those in Cyprus (29.5 (20.1, 48.0) μg/l; P<0.01). Despite that tap water did not contain chloroform (TCM), TCM was detected in both air and urine samples in Kuwait, suggesting other TCM exposure sources, such as household cleaning activities. Total duration of activities and mopping were significantly correlated with air and urine THM in Kuwait, as reported in the time activity diary. Personal air and urine exposure metrics were correlated in Kuwait (TTHM ρ=0.62, P<0.05), but not in Cyprus (TTHM ρ=-0.32, P>0.05). Time-activity diaries and urinary THM seemed to be useful measures of THM exposures in Kuwait. Coupling both external with internal exposure metrics could find use in population health studies towards further refining the association between environmental exposures and health outcomes.

Urine used as a biomarker was collected and compared between two groups of participants: (1) a groundwater-drinking group and (2) a non-groundwater-drinking group in intensively agricultural areas in Ubon Ratchathani province, Thailand. The statistical relationship with the metal concentration in shallow groundwater wells was established with urine data. According to the groundwater data, the health risk assessment results for four metals appeared to be higher for participants who drank groundwater than for the other group. The carcinogenic risk and non-carcinogenic risk of arsenic (As) were found in 25.86 and 31.03% of participants, respectively. For lead (Pb), 13.79% of the participants had a non-carcinogenic risk. Moreover, 30 of the 58 participants in the groundwater-drinking group had As urine higher than the standard, and 26, 2 and 9 of the 58 participants had above-standard levels for cadmium (Cd), Pb and mercury (Hg) in urine, respectively. Both the risk assessment and biomarker level of groundwater-drinking participants were higher than in the other group. The results showed an average drinking rate of approximately 4.21 ± 2.73 L/day, which is twice as high as the standard. Interestingly, the As levels in the groundwater correlated with those in the urine of the groundwater-drinking participants, but not in the non-groundwater-drinking participants, as well as with the As-related cancer and non-carcinogenic risks. The hazard index (HI) of the 100 participants ranged from 0.00 to 25.86, with an average of 1.51 ± 3.63 higher than the acceptable level, revealing that 28 people appeared to have non-carcinogenic risk levels (24 and 4 people for groundwater-drinking participants and non-groundwater-drinking participants, respectively). Finally, the associated factors of heavy metals in urine were the drinking water source, body weight, smoking, sex and use of personal protective equipment.