Feasibility of sulfated BPA and BPS as wastewater-based epidemiology biomarkers: Insights from wastewater and reported human urine analysis.

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.

A solid-phase microextraction fiber coating based on magnetic covalent organic framework for highly efficient extraction of triclosan and methyltriclosan in environmental water and human urine samples.

Herein, we synthesized a kind of magnetic covalent organic framework nanohybrids (NiFe2O4@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 m2 g-1. As for seven environmental analytes, the NiFe2O4@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 NiFe2O4@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 NiFe2O4@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.

Sensitive determination of Fluoxetine and Citalopram antidepressants in urine and wastewater samples by liquid chromatography coupled with photodiode array detector.

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 (Fe3O4@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.

Human biomonitoring to assess exposure to thallium following the contamination of drinking water.

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.

Association between low-to-moderate fluoride exposure and bone mineral density in Chinese adults: Non-negligible role of RUNX2 promoter methylation.

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 (ß: -0.14; 95%CI: -0.26, -0.01) and RUNX2 promoter methylation (ß: -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.

Dual-emission carbon dots achieved by luminescence center modulation within one-pot synthesis for a fluorescent ratiometric probe of pH, Hg2+, and glutathione.

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 Hg2+ and pH. Glutathione (GSH) can recover the fluorescence quenched by Hg2+. 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 (RI447/I581) as the signal for the determinations of pH, Hg2+, and GSH. In the range of 5.0-10.0, a good linear relationship between RI447/I581 and pH was built with a regression equation of RI447/I581 = 11.95-0.56 pH (R2 = 0.998). In the range from 0.0 to 8.0 µM, an excellent linear relationship between RI447/I581 and the concentration of Hg2+ was obtained with a calibration equation of RI447/I581 = 6.2317-0.4458c (R2 = 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, RI447/I581 = 1.9133-0.4157c (R2 = 0.995), was calibrated between RI447/I581 and the concentration of glutathione with a LOD of 0.27 µM. The recoveries for the determinations of Hg2+ 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, Hg2+, and glutathione.

Predicted concentrations of anticancer drugs in the aquatic environment: What should we monitor and where should we treat?

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.

Changes in urinary arsenic species and methylation capacity in original arsenic exposure cohort after water quality improvement.

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.

Cathodic electrodeposited Cu-BTC MOFs assembled from Cu(II) and trimesic acid for electrochemical determination of bisphenol A.

The authors describe a novel electrochemical determination method for bisphenol A (BPA) based on the electrosynthesised Cu-BTC (H3BTC: trimesic acid) films. Using H3BTC as the ligand, Cu(NO3)2 as the precursor of copper ions, and triethylamine hydrochloride (Et3NHCl) 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 Cu2+, 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.

Human exposure of bisphenol A and its analogues: understandings from human urinary excretion data and wastewater-based epidemiology.

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.

Thallium exposure at low concentration leads to early damage on multiple organs in children: A case study followed-up for four years.

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.

Assessment of YAP gene polymorphisms and arsenic interaction in Mexican women with breast cancer.

The identification of gene-environment interactions related to breast cancer reveals the biological and molecular mechanisms underlying the disease and allows the distinction of women at high risk from women at lower risk, which could decrease the morbimortality of this neoplasm. The current study evaluated the association between polymorphisms rs1820453 and rs11225161 of the Yes-associated protein (YAP) gene in women with breast cancer exposed to arsenic (As) through drinking water. In total, 182 women were assessed for the frequency of YAP rs1820453 and rs11225161 polymorphisms and As urinary levels. The results demonstrated a positive and significant association between breast cancer and smoking, type of drinking water, and levels of AsIII , AsV and inorganic As (iAs) but not the YAP gene polymorphisms evaluated. In conclusion, our data showed that the source of drinking water and AsV and iAs urinary levels increased the risk for breast cancer, but no interactions between YAP gene polymorphisms and As urinary levels were found.

Ultra violet filters in the urine of preschool children and drinking water.

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.

Effects of secondary biological treatment plant effluent administration, as drinking water, to rats' urogenital system in relation to cadmium and lead accumulation.

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.

Speciation analysis of arsenic in samples containing high concentrations of chloride by LC-HG-AFS.

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 (NH4)2HPO4 (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.

Surface molecularly imprinted polymer on magnetic multi-walled carbon nanotubes for selective recognition and preconcentration of metformin in biological fluids prior to its sensitive chemiluminescence determination: Central composite design optimization.

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.

Chronic Low Dose Oral Exposure to Microcystin-LR Exacerbates Hepatic Injury in a Murine Model of Non-Alcoholic Fatty Liver Disease.

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 (Leprdb/J) of Non-alcoholic Fatty Liver Disease (NAFLD). Ten-week-old male Leprdb/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.

A highly fluorescent lanthanide metal-organic framework as dual-mode visual sensor for berberine hydrochloride and tetracycline.

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.

Association of Arsenic Exposure with Whole Blood DNA Methylation: An Epigenome-Wide Study of Bangladeshi Adults.

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.

Contribution of phthalates and phthalate monoesters from drinking water to daily intakes for the general population.

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 ±â€¯26.28, 5.905 ±â€¯11.57, 103.8 ±â€¯310.5, 595.9 ±â€¯1794, and 178.2 ±â€¯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 ±â€¯18.0, 2.4 ±â€¯5.8, 11.3 ±â€¯37.2, 36.3 ±â€¯103, and 9.9 ±â€¯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.