Human molybdenum exposure risk in industrial regions of China: New critical effect indicators and reference dose.

Evidence increasingly suggests molybdenum exposure at environmental levels is still associated with adverse human health, emphasizing the necessity to establish a more protective reference dose (RfD). Herein, we conducted a study measuring 15 urinary metals and 30 clinical health indicators in 2267 participants residing near chemical enterprises across 11 Chinese provinces to investigate their relationships. The kidney and cystatin-C emerged as the most sensitive organ and critical effect indicator of molybdenum exposure, respectively. Odds of cystatin-C-defined chronic kidney disease (CKD) in the highest quantile of molybdenum exposure significantly increased by 133.5% (odds ratio [OR]: 2.34, 95% CI: 1.78, 3.11) and 75.8% (OR: 1.76, 95% CI: 1.24, 2.49) before and after adjusting for urinary 14 metals, respectively. Intriguingly, cystatin-C significantly mediated 15.9-89.5% of molybdenum's impacts on liver and lung function, suggesting nephrotoxicity from molybdenum exposure may trigger hepatotoxicity and pulmonary toxicity. We derived a new RfD for molybdenum exposure (0.87 µg/kg-day) based on cystatin-C-defined estimated glomerular filtration rate by employing Bayesian Benchmark Dose modeling analysis. This RfD is significantly lower than current exposure guidance values (5-30 µg/kg-day). Remarkably, >90% of participants exceeded the new RfD, underscoring the significant health impacts of environmental molybdenum exposure on populations in industrial regions of China.

Probabilistic human health risk assessment of PCDD/Fs near municipal solid-waste incinerator using Monte Carlo analysis coupled with triangular fuzzy numbers.

PCDD/Fs are dioxins produced by waste incineration and pose risks to human health. We aimed to detail the health risks of airborne and soil PCDD/Fs near a municipal solid-waste incinerator (MSWI) for the surrounding population and develop a new model that improves upon existing methods. Thus, we conducted field sampling and then investigated a MSWI in the Pearl River Delta (2016-2018). Our results showed that the carcinogenic and non-carcinogenic risk values of PCDD/Fs exposed to residents in nearby areas were acceptable, with hazard index (HI) values lower than 1.0 and a total carcinogenic risk lower than 1.0E-6. Notably, the results raised concerns regarding higher non-carcinogenic risks in children than in adults. Comparative analysis of the frequency accumulation diagram, accumulated probability risk, and the absolute value of error (δ) between the 95% confidence interval (CI) and the 90% CI of the Monte Carlo stochastic simulation-triangular fuzzy number (MCSS-TFN) and the MCSS model, respectively, demonstrated that the MCSS-TFN exhibited less uncertainty than the MCSS model, regardless of the health risk value of PCDD/Fs in ambient air or in soil. This observation underscores the superiority of the MCSS-TFN model over other models in assessing the health risks associated with PCDD/Fs in situations with limited data. Our new method overcomes the limited dataset size and high uncertainty in assessing the health risks of dioxin substances, providing a more comprehensive understanding of their associated health risks than MCSS models.

Health risk assessment of trace metal(loid)s in agricultural soil using an integrated model combining soil-related and plants-accumulation exposures: A case study on Hainan Island, South China.

Traditional health risk assessment of trace metal(loid)s (TMs) in agricultural soil exclusively considers direct soil-related exposure and may underestimate the health risks they pose. In this study, the health risks of TMs were evaluated using an integrated model that combined soil-related and plant-accumulating exposures. A detailed investigation of common TMs (Cr, Pb, Cd, As, and Hg) coupled with probability risk analysis based on a Monte Carlo simulation was conducted on Hainan Island. Our results showed that, except for As, the non-carcinogenic risk (HI) and carcinogenic risk (CR) of the TMs were all within the acceptable ranges (HI < 1.0, and CR < 1E-06) for direct soil-related exposure to bio-accessible fractions and indirect exposure via plant accumulation (CR substantially lower than the warning threshold 1E-04). We identified crop food ingestion as the essential pathway for TM exposure and As as the critical toxic element in terms of risk control. Moreover, we determined that RfDo and SFo are the most suitable parameters for assessing As health risk severity. Our study demonstrated that the proposed integrated model combining soil-related and plant-accumulating exposures can avoid major health risk assessment deviations. The results obtained and the integrated model proposed in this study can facilitate future multi-pathway exposure research and could be the basis for determining agricultural soil quality criteria in tropical areas.

Why Do People Gain Belly Fat in Rural Areas? A Study of Urinary Metal(loid)s and Abdominal Obesity in China.

Obesity is prevalent in rural areas of China, and there are inconsistent findings regarding the association between metal(loid) exposure and the risk of obesity. Abdominal obesity (AOB), which reflects visceral fat abnormity, is a crucial factor in studying obesity-related diseases. We conducted a study measuring 20 urinary metal(loid)s, 13 health indicators, and the waist circumference (WC) in 1849 participants from 10 rural areas of China to investigate their relationships. In the single exposure models, we found that urinary chromium (Cr) was significantly associated with the odds of having AOB [adjusted odds ratio (OR) = 1.81 (95% confidence interval (CI): 1.24, 2.60)]. In the mixture exposure models, urinary Cr consistently emerged as the top contributor to AOB, while the overall effect of mixed metal(loid)s was positive toward the odds of having AOB [adjusted OR: 1.33 (95% CI: 1.00, 1.77)], as revealed from the quantile g-computation model. After adjusting for the effects of other metal(loid)s, we found that the elevation of apolipoprotein B and systolic blood pressure significantly mediated the association between urinary Cr and the odds of having AOB by 9.7 and 19.4%, respectively. Our results suggest that exposure to metal(loid)s is a key factor contributing to the prevalence of AOB and WC gain in rural areas of China.

Associations between trace level thallium and multiple health effects in rural areas: Chinese Exposure and Response Mapping Program (CERMP).

Thallium (Tl) is a cumulative high toxicant in the environment, but few studies have investigated the comprehensive health effects underlying chronic Tl exposure at trace levels. This study aims to evaluate the liver, kidney, lung and other potential health effects associated with chronic Tl exposure at trace levels in rural areas of China. Urinary Tl concentrations of 2883 adults from rural areas of 12 provinces in China were measured and 2363 participants were involved in the final analysis. Indicators of liver and kidney functions in the serum, as well as the lung function indicators, were determined in the participants. General linear regression and restricted cubic spline regression were combined to study the associations between urinary Tl and health indicators or outcomes. In this study, the detected rate of Tl in the urine of the participants was 97.28 %. When the urinary Tl concentration was ranged at the fourth quintile, the risk of having liver function disorder was 70 % higher [Odds ratio (OR) = 1.70 (95 % confidence intervals (CI): 1.30, 2.22)] in all the participants, whereas the farmers were more likely to have the disorder [OR = 2.08 (95 % CI: 1.49, 2.92)] than the non-farmers [OR = 1.20 (95 % CI: 0.77, 1.88)]. Nonlinear associations between most of the liver health indicators and urinary Tl were identified, of which serum bilirubin was strongly associated with the elevation of urinary Tl when its concentration was >0.40 µg/g creatinine. Besides, urinary Tl was negatively associated with lung health indicators. Our study proposes the safety re-assessment of the current exposure level of Tl in the environment, especially in rural areas of China.

Effects of organochlorine exposure on male reproductive disorders in an electronic waste area of South China.

Several studies suggest that organochlorine exposure can affect male reproductive functions, causing poor semen quality, endocrine disruption, or dysregulation of thyroid hormones. This study uses multiple linear regression (MLR) models to analyze the correlation between male reproductive functions and polychlorinated biphenyl (PCBs) congeners or p,p'-DDE levels in serum, semen, and indoor dust samples. Multiple comparisons were all adjusted using the false discovery rate (FDR). The results revealed that the PCB congener levels in seminal plasma were significantly associated with the quality parameters of human semen (i.e., sperm count, morphology, and motility) and thyroid hormones after adjusting for covariates, e.g., associations of the sperm concentration with levels of CB105 (ß = -0.323, 95% CI: -0.561, -0.085, p = 0.009), CB44 (ß = 0.585, 95% CI: 0.290, 0.880, p < 0.001), and CB66 (ß = -0.435, 95% CI: -0.728, -0.143, p = 0.004) in the seminal plasma were observed. Correlations between serum pollutants levels and the semen quality, reproductive hormones, or thyroid hormones were also observed. Moreover, our results demonstrate that the quantification of PCBs in seminal plasma can better describe male reproductive disorders than that in serum or dust. Organochlorine exposure measured in serum or dust, especially in seminal plasma, was associated with semen quality, as well as reproductive and thyroid hormones, thus suggesting that the impacts of persistent pollutants on male reproductive health require further investigation.

Excretion characteristics and tissue accumulation of tetrabromobisphenol-A in male rats after sub-chronic inhalation exposure.

Tetrabromobisphenol-A (TBBPA) is an emerging organic pollutant and a commonly used brominated flame retardant that has received much attention owing to its toxicity. Although TBBPA is ubiquitously detected in atmospheric particulate matter and dust, few studies have investigated the sub-chronic inhalation exposure to TBBPA. To further understand the excretion characteristics and tissue accumulation of TBBPA after inhalation exposure, we used the rat model to conduct a sub-chronic inhalation exposure study. Male rats were administered with different doses of aerosol TBBPA (12.9, 54.6, 121.6, and 455.0 mg/m3). TBBPA was found in the excretion (feces and urine) and all the target tissues (lung, liver, heart, thymus gland, spleen, testicles, muscles, kidneys, brain and serum). Feces were the main route of excretion, which contributed 19.18% to 72.54% (urine <0.10%). TBBPA excretion through feces following inhalation administration was much higher than that following oral and dermal exposure, thereby indicating lower bioavailability of TBBPA under inhalation exposure. Liver and serum showed higher levels of TBBPA compared with those of other tissues, thereby suggesting tissue-specific accumulation of TBBPA in rats. Owing to the relative non-invasiveness of serum sampling and greatest TBBPA concentration among the tissues, serum is a suitable matrix for estimation of TBBPA bioaccumulation after inhalation exposure.

Levels and congener profiles of halogenated persistent organic pollutants in human serum and semen at an e-waste area in South China.

Typical halogenated persistent organic pollutants (Hal-POPs), including polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), polychlorinated biphenyls (PCBs), and dichlorodiphenyltrichloroethane (DDT), are a group of ubiquitous organic pollutants with an endocrine disrupting effect. This study evaluated the accumulation and congener profiles of Hal-POPs in the bodies of men who live/work in areas of South China where electronic wastes are collected and managed, especially in their semen samples. The results show that the detection frequency and serum concentrations of Hal-POP congeners within the high-exposure group (HEG) were higher than those of the low-exposure group (LEG). Furthermore, an identical trend was observed for the seminal plasma concentrations of Hal-POPs. The distribution characteristics, such as their mean, median, and discrete values, of PBDE congeners in serum and semen samples from the same subjects were consistent with each other. However, the distribution characteristics of PCB congeners in serum samples were different from those in semen samples. BDE153 was one of the most abundant congeners found in the serum and semen samples; hence, it can be identified as an indicator PBDE congener. Further research is needed to explore the mechanism of Hal-POPs distribution in human semen and serum samples.

Male workers' exposure characteristics of ΣPCDD/F from a municipal solid waste incinerator in south China through hair analysis.

Human hair, flue gas and fly ash from a municipal solid waste incinerator (MSWI) in south China were collected and analyzed for polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF). The ΣPCDD/F level in hair from male workers were higher than those from residents. The Principal Component Analysis (PCA) suggested that ΣPCDD/F in flue gas is an external source of male workers' hair ΣPCDD/F. Results of daily intake of ΣPCDD/F by inhaling flue gas suggested that the inhalation exposure of ΣPCDD/F was at a slight health risk. For the male workers directly exposed to the MSWI power plant, ΣPCDD/F levels in their hair were significantly higher than those who were non-directly exposed. Moreover, a significantly positive relationship was obtained between ΣPCDD/F levels in male workers' hair and the working time. The result of correlation analysis suggested that 1,2,3,4,6,7,8-HpCDD and OCDD could be level indicator congeners to estimate ΣPCDD/F levels. In addition, 2,3,7,8-TCDD could be applied as TEQ indicator congener to characterize the hair of MSWI male workers.

Associations between PBDEs exposure from house dust and human semen quality at an e-waste areas in South China-A pilot study.

Previous studies have confirmed that house dust is one of the main sources of polybrominated diphenyl ethers (PBDEs) exposure, and also indicated that PBDEs might affect human semen quality. The aim of this study was to explore the association between PBDEs concentration in house dust and the semen quality of male resident. Results showed that the semen qualities of the residents living around the e-waste dismantling workshops for a long time (3-17years) at the e-waste areas in South China significantly decreased, and the DNA damage of sperms were aggravated. The adjusted correlation analysed by multiple linear regression model showed that the sperm concentration and count both had negative correlation with BDE47 level in semen (ß = -0.295, 95%CI: -0.553∼-0.036; ß = -0.400, 95%CI: -0.708∼-0.092, respectively). In addition, the sperm progressive motility [(A+B)%] and sperm viability both had negative correlation with BDE100 level in dust (ß = -0.360, 95%CI: -0.680∼-0.040; ß = -0.114, 95% CI: -0.203∼-0.025, respectively). And there were significant linear positive correlation between PBDE congener (e.g. BDE28, 47, 153) concentrations in dust and in paired semen samples (rs = 0.367-0.547, p < 0.05). This study suggested that exposure to PBDEs from house dust might have adverse effects on human semen quality. But the results need to be confirmed in further studies with a large-scale sampling, and find out more direct and convincing evidence.

The Comparative Safety of TNF Inhibitors in Ankylosing Spondylitis-a Meta-Analysis Update of 14 Randomized Controlled Trials.

TNF inhibitors have been used in ankylosing spondylitis (AS). The efficacy of TNF inhibitors was already evaluated by meta-analysis of randomized controlled trials (RCTs). However, the safety of TNF inhibitors is still unclear. Therefore, we aimed to evaluate and update the safety data from RCTs of TNF inhibitors in patients treated for AS. A systematic literature search was conducted from 1990 through May 31, 2016. All studies included were randomized, double-blind, controlled trials of patients with ankylosing spondylitis that evaluated adalimumab, certolizumab pegol, etanercept, golimumab, or infliximab treatment. The overall serious adverse events, the risk of serious infection events, and the risk of malignancy and discontinuation rates were abstracted, and risk estimates were calculated by Peto odds ratios (ORs). Fourteen randomized controlled trials involving 2032 subjects receiving TNF inhibitors and 1030 subjects receiving placebo and/or traditional disease-modifying anti-rheumatic drugs (DMARDs) were included. The overall serious adverse events (OR, 1.34; 95% CI, 0.87-2.05), the risk of serious infection events (OR, 1.59; 95% CI, 0.63-4.01), the risk of malignancy (OR, 0.98; 95% CI, 0.25-3.85), and discontinuation due to adverse events (OR, 1.55; 95% CI, 0.95-2.54) in patients treated with TNF inhibitors as a group were not significantly different from those treated with placebo in the control group. TNF inhibitors were generally safe for treatment of ankylosing spondylitis. These data may help guide clinical comparative decision making in the management of AS.

Synthesis of methoxy-substituted picenes: substitution position effect on their electronic and single-crystal structures.

A series of picenes having methoxy groups was synthesized through Pd-catalyzed Suzuki-Miyaura couplings or Wittig reaction/intramolecular cyclization sequences, and their physicochemical properties and single-crystal structures were evaluated. The substitution position effects between the outer 1,12-, 2,11-, and 4,9-position and the inner 3,10-position are quite different; the former showed the same electronic structure as that of picene, but the latter results in a HOMO geometry different from those of picene and other methoxy picenes. In addition, crystal structures of four types of methoxy-substituted picenes 4a-c,e strongly depend on their substitution position and number of methoxy groups, which dramatically changes the structures from the fully anisotropic 1D π-stacked structure to a unique 3D herringbone structure due to steric hindrance of methoxy groups. The calculations of transfer integrals based on their single-crystal structures reveal that the methoxy picenes have intermolecular overlaps less effective than that of the parent nonsubstituted picene. These results are attributed not only to the packing structure but also to electronic structures such as the HOMO distribution. The preliminary OFET of the representative 4c,e showed hole mobilities significantly lower than that of picene due to their less effective intermolecular overlaps, as predicted by the calculated transfer integrals.

Synthesis of substituted picenes through Pd-catalyzed cross-coupling reaction/annulation sequences and their physicochemical properties.

A novel and versatile synthetic method for picene derivatives is developed using the Pd-catalyzed intramolecular double cyclization of the corresponding 2,3-bis[(1Z)-2-phenylethenyl]-1,4-dichlorobenzenes, which are readily prepared by Suzuki-Miyaura cross-coupling reactions of polyhalobenzenes with (Z)-arylethenylboronates. The physical properties of the obtained picenes can be modified via introducing a variety of functional groups to the picene framework. All compounds are investigated by UV-vis and fluorescence spectroscopic measurements, CV, and DFT calculations as well as X-ray diffraction analysis.

[Occurrence and distribution of volatile organic compounds in conventional and advanced drinking water treatment processes].

A series of experiments were conducted to study the occurrence and distribution of volatile organic compounds (VOCs) in conventional and advanced drinking water treatment processes of 3 water treatment plants in Lianyungang City. Results showed that 30 compounds of 3 classes were detected from 67 kinds of VOCs in all the samples collected. The concentrations of carbonyl compounds, halogenated hydrocarbons and benzenes detected were in the ranges of 0.04-61.27, 0.02-35.61 and 0.07-2.33 microg x L(-1) respectively. Comparing the changes of different VOCs in three drinking water treatment plants, conventional chlorination process could effectively remove benzenes but meanwhile produced trihalomethanes (THMs). Additional advanced treatment ozonation-biological activated carbon process could decrease the formation of THMs during pre-chlorination but produced new risky contaminants like carbonyl compounds. The changes of VOCs in tap water were also investigated. It was found that carbonyl compounds produced by ozonation could be further transformed to THMs with residual chlorine. However, the health risks of all detected compounds in tap water were at a low level, except that the carcinogenic risk of crotonaldehydes (9.3 x 10(-5)-2.2 x 10(-4)) was slightly higher than the US EPA threshold (10(-6)-10(-4)).