First Insight into Fetal Exposure to Legacy and Emerging Plasticizers Revealed by Infant Hair and Meconium: Occurrence, Biotransformation, and Accumulation.

Epidemiological studies have demonstrated the embryonic and developmental toxicity of plasticizers. Thus, understanding the in utero biotransformation and accumulation of plasticizers is essential to assessing their fate and potential toxicity in early life. In the present study, 311 infant hair samples and 271 paired meconium samples were collected at birth in Guangzhou, China, to characterize fetal exposure to legacy and emerging plasticizers and their metabolites. Results showed that most of the target plasticizers were detected in infant hair, with medians of 9.30, 27.6, and 0.145 ng/g for phthalate esters (PAEs), organic phosphate ester (OPEs), and alternative plasticizers (APs), and 1.44, 0.313, and 0.066 ng/g for the metabolites of PAEs, OPEs, and APs, respectively. Positive correlations between plasticizers and their corresponding primary metabolites, as well as correlations among the oxidative metabolites of bis(2-ethylhexyl) phthalate (DEHP) and 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH), were observed, indicating that infant hair retained the major phase-I metabolism of the target plasticizers. While no positive correlations were found in parent compounds or their primary metabolites between paired infant hair and meconium, significant positive correlations were observed among secondary oxidative metabolites of DEHP and DINCH in hair and meconium, suggesting that the primary metabolites in meconium come from hydrolysis of plasticizers in the fetus but most of the oxidative metabolites come from maternal-fetal transmission. The parent compound/metabolite ratios in infant hair showed a decreasing trend across pregnancy, suggesting in utero accumulation and deposition of plasticizers. To the best of our knowledge, this study is the first to report in utero exposure to both parent compounds and metabolites of plasticizers by using paired infant hair and meconium as noninvasive biomonitoring matrices and provides novel insights into the fetal biotransformation and accumulation of plasticizers across pregnancy.

Bioaccumulation and biotransformation of 1,2-bis (2,4,6-tribromophenoxyethane) (BTBPE) and 1,2-dibromo-4-(1,2-dibromoethyl)-cyclohexane (TBECH) in zebrafish (Danio rerio).

Despite the increasing production, use, and ubiquitous occurrence of novel brominated flame retardants (NBFRs), little information is available regarding their fate in aquatic organisms. In this study, the bioaccumulation and biotransformation of two typical NBFRs, i.e., 1,2-bis (2,4,6-tribromophenoxyethane) (BTBPE) and 1,2-dibromo-4-(1,2-dibromoethyl)-cyclohexane (TBECH), were investigated in tissues of zebrafish (Danio rerio) being administrated a dose of target chemicals through their diet. Linear accumulation was observed for both BTBPE and TBECH in the muscle, liver, gonads, and brain of zebrafish, and the elimination of BTBPE and TBECH in all tissues followed pseudo-first-order kinetics, with the fastest depuration rate occurring in the liver. BTBPE and TBECH showed low bioaccumulation potential in zebrafish, with biomagnification factors (BMFs) < 1 in all tissues. Individual tissues' function and lipid content are vital factors affecting the distribution of BTBPE and TBECH. Stereoselective accumulation of TBECH enantiomers was observed in zebrafish tissues, with first-eluting enantiomers, i.e. E1-α-TBECH and E1-ß-TBECH, preferentially accumulated. Additionally, the transformation products (TPs) in the zebrafish liver were comprehensively screened and identified using high-resolution mass spectrometry. Twelve TPs of BTBPE and eight TPs of TBECH were identified: biotransformation pathways involving ether cleavage, debromination, hydroxylation, and methoxylation reactions for BTBPE and hydroxylation, debromination, and oxidation processes for TBECH. Biotransformation is also a vital factor affecting the bioaccumulation potential of these two NBFRs, and the environmental impacts of NBFR TPs should be further investigated in future studies. The findings of this study provide a scientific basis for an accurate assessment of the ecological and environmental risks of BTBPE and TBECH.

Fetal exposure to organic contaminants revealed by infant hair: A preliminary study in south China.

Fetal exposure to multiple organic contaminants (OCs) is a public concern because of the adverse effects of OCs on early life development. Infant hair has the potential to be used as an alternative matrix to identify susceptible fetuses, owing to its reliability, sensitivity, and advantages associated with sampling, handling, and ethics. However, the applicability of infant hair for assessing in utero exposure to OCs is still limited. In this study, 57 infant hair samples were collected in Guangzhou, South China, to evaluate the levels and compositions of typical OCs in the fetus. Most of the target OCs were detected in infant hair, with medians of 144 µg/g, 17.7 µg/g, 192 ng/g, 46.9 ng/g, and 1.36 ng/g for phthalate esters (PAEs), alternative plasticizers (APs), organophosphorus flame retardants (OPFRs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs), respectively. Meanwhile, paired maternal hair (0-9 cm from the scalp) was collected to examine the associations between maternal and infant hair for individual compounds. Low-brominated PBDEs tended to deposit in infant hair, with median concentrations approximately two times higher than those in maternal samples. Levels of PBDEs and 4,4'-dichlorodiphenyldichloroethylene (p,p'-DDE) in paired maternal and infant hair showed strong positive correlations (p < 0.05), while most plasticizers (PAEs and APs) were poorly correlated between paired hair samples. Exposure sources were responsible for the variation in correlation between OC levels in the paired infant and maternal samples. Crude relationships between fetal exposure to OCs and birth size were examined using the Bayesian kernel machine regression (BKMR) model. BDE-28 was found to be adversely associated with the birth size. This study provides referential information for evaluating in utero exposure to OCs and their health risks based on infant hair.

Tissue-specific and stereoselective accumulation of Dechlorane Plus isomers in two predator fish in a laboratory feeding study.

The tissue-specific bioaccumulation of Dechlorane Plus (DP) isomers was investigated in two predator fish species (redtail catfish, RF; and oscar fish, OF) that were feeding on tiger barb (TB), which was exposed to syn-DP and anti-DP isomers. The biotransformation potential of DP isomers was examined by in vitro metabolism using fish liver microsomes. No difference in accumulation behaviors of DP isomers was observed between RF and OF, and the accumulation of both syn- and anti-DP isomers exhibiting a linear increase trend with the exposure time in all fish tissues. The assimilation efficiencies and depuration rates for syn-DP and anti-DP were determined to be the highest in the liver. Biomagnification factors (BMFs) for both syn-DP and anti-DP were higher than one in the serum and gastrointestinal tract of fish, whereas were less than one in the other tissues. The wet-weight concentrations of DP isomers in tissues were significantly correlated with the lipid contents in both fish species, indicating that the tissue distribution of DP isomers occurred through passive diffusion to the lipid compartments in vivo. Tissue-specific compositions of DP isomers were observed, with anti-DP selectively accumulating in the liver, gonad, serum, and gills, whilst syn-DP in the carcass and GI tract. However, after being normalized of all tissues, the fish showed no selective accumulation of DP isomers during the exposure period, and selective accumulation of syn-DP was observed during the depuration period. No potential DP metabolites were detected in the fish tissues and in vitro metabolism systems. The main cause of this stereoselective DP isomer accumulation could have been the selective excretion of anti-DP isomer through the fish feces.

[Liver and Kidney Function of E-waste Dismantling Workers and Potential Influencing Factors].

High levels of exposure to heavy metals and persistent organic pollutants (POPs) by e-waste dismantling workers has attracted increasing attention, but the health conditions of the workers are seldom reported. The liver and kidney functions of the workers were studied by comparing the blood indicators of the worker group with those of the control group. Moreover, factors affecting the liver and kidney functions, such as the sexuality, age, and working time, were identified using correlation analysis. The ratio of aspartate transaminase and alanine aminotransferase (AST/ALT) and the direct bilirubin (DBIL) of the workers were significantly lower than the control group but the abnormal rate of liver and kidney remained the same in both groups. The abnormal rates of liver and kidney were higher in men than in women. ALT, AST/ALT, and urea nitrogen (BUN) increased with age while creatinine (CREA) increased with working time. The factors of liver and kidney damage caused by POPs and DBIL can be used as the indicators of the damage caused by multi-factors.

Emission characteristics of toxic pollutants from an updraft fixed bed gasifier for disposing rural domestic solid waste.

Gasification has gained advantage as an effective way to dispose domestic solid waste in mountainous rural of China. However, its toxic emissions such as PCDD/Fs and heavy metals, as well as their potential environmental risks, were not well studied in engineering application. In this study, an updraft fixed bed gasifier was investigated by field sampling analysis. Results showed that low toxic emissions (dust, SO2, NOx, HCl, CO, H2S, NH3, PCDD/Fs and heavy metals) in the flue gas were achieved when the rural solid waste was used as feedstock. The mass distribution of heavy metals showed that 94.00% of Pb, 80.45% of Cu, 78.00% of Cd, 77.31% of Cr, and 76.25% of As were remained in residual, whereas 86.58% of Hg was found in flue gas. The content of PCDD/Fs in the flue gas was 0.103 ngI-TEQ·Nm-3, and the total emission factor of PCDD/Fs from the gasifier was 50.04 µgI-TEQ·t-waste-1, among which only 0.04 µgI-TEQ·t-waste-1 was found in the flue gas. The total output of PCDD/Fs was1.89 times as high as input, indicting the updraft fixed bed gasifier increased emission of PCDD/Fs during the treatment domestic solid waste. In addition, the distribution characteristics of PCDD/Fs congeners reflected that PCDD/Fs was mainly generated in the gasification process rather than the stage of flue gas cleaning, suggesting the importance to effectively control the generation of PCDD/Fs within the gasifier chamber in order to obtain a low PCDD/Fs emission level.

[Possible Sources of PCDD/Fs in Atmosphere of a Certain District in Guangdong].

This paper analyzed 17 polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs) by HRGC/HRMS in the flue gas of a certain municipal solid waste incinerator(MSWI) and its surrounding air and other possible sources in Guangdong. It discussed the feature of homologs and main toxic monomers in all samples. It also investigated the relationship among surrounding area, MSWI and possible sources using principle component analysis (PCA) and cluster analysis. The results showed that the concentration of PCDD/Fs was higher in the flue gas than the ambient air, moreover non-effect suffered by prevailing wind direction. The possible sources might be tyre factory and open burning based on spot survey. The concentration of PCDD/Fs was lower in tyre factory than upwind station, but higher at open burning spot than outdrop monitoring station. The analysis of homologs showed that OCDD, 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8-HpCDF were the main materials in the flue gas and air, meanwhile OCDF was also found in atmosphere. There was similar feature of 17 PCDD/Fs between surrounding monitoring station and tyre factory, and the same between flue gas and open burning. The further analysis showed that the linearly dependent coefficients of 1,2,3,7,8-PeCDD and 2,3,4,6,7,8-HxCDF were 0.95 and 0.75, respectively. It showed the strong correlation of two monomers in all ambient air samples. The PCA and cluster analysis showed that MSWI influenced the surrounding air, tyre factory had an impact on upwind station, and open burning had a lower effect on outdrop monitoring station.

[Internal Exposure Levels of PAHs of Primary School Students in Guangzhou].

In order to investigate the internal exposure levels of polycyclic aromatic hydrocarbons (PAHs) in primary school students of Guangzhou, the research collected urine of 78 and 86 primary school students from two primary schools in the summer of 2014, one school located in the ordinary residential area and the other in the industrial area. The contents of 10 kinds of OH-PAHs were tested by the rapid liquid chromatography coupled to triple quadruple tandem mass spectrometry. The results showed that the concentrations of total OH-PAHs in primary school students in the residential zone ranged from 0.83 µmol · mol⁻¹ to 80.63 µmol · mol⁻¹, while those in industrial area ranged from 1.06 µmol · mol⁻¹ to 72.47 µmol · mol⁻¹. The geometric average concentrations were 6.18 µmol · mol⁻¹ and 6.47 µmol · mol⁻¹, respectively, and there was no statistical significance between them (P > 0.05). Comparison of the exposure levels of different components of PAHs in the two areas found that all the OH-PAHs had no significant difference except for the levels of 1- OHP (P < 0.05). We should also pay attention to the higher exposure levels of PAHs in both areas when compared with other researches. In addition, the OH-PAHs in primary school students in the ordinary residential area had a good correlation between 0. 511 and 0.928 (P < 0.01), whereas there was no correlation between 1-OHP and 2-OHN, 1-OHN in the primary school students in the industrial area and other OH-PAHs had relatively weak correlation ranging from 0.338 to 0.855 (P < 0.01). This difference might indicate different pollution sources of PAHs in different functional areas, which was relatively single in the residential area, while the industrial area was polluted by multiple sources of industrial enterprises and logistics transportation emissions.

[Effect of meteorological factors on characteristics of PCDD/F pollution in Guangzhou].

High-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was used to measure contents of 2, 3, 7, 8-polychlorinated dibenzo-p-dioxin and furan (PCDD/F) in ambient air in Guangzhou city, and its sources were traced and tracked preliminarily. Spatial and seasonal distributions, the correlation between PCDD/F concentrations and various kinds of meteorological factors were studied with emphasis, as well as the trajectory of air mass simulated by hybrid single-particle lagrangian integrated trajectory (HYSPLIT) model of the U. S. A Air Resources Laboratory, which will provide important basic data for understanding PCDD/F pollution levels in urban regions. The results show, PCDD/F concentrations in the industrial area are higher than others, and in spring, PCDD/F TEQs are the highest. Meteorological factors, like wind direction and speed, temperature, air pressure, relative humidity, precipitation all have influence on pollution levels of atmospheric PCDD/Fs. Temperature and wind speed has a negative correlation with the concentration, but it is not obvious. By the analysis of the backward trajectory of air mass, something are obtained that the trajectory extends mainly to northwest areas in autumn, and air masses from inland migrate slowly in winter, while they arrive at Guangzhou after passing southeast coast or sea.

[Concentrations, distribution characteristics and electron beam radiolysis degradation of PCDD/Fs in waste water from a paper mill].

Concentrations and distribution characteristics of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (2,3,7,8-PCDD/Fs) were analyzed in waste water from a paper mill. And concentrations of 2,3,7,8-PCDD/Fs in waste water before and after electron beam irradiation with different doses were compared. The feasibility, mechanism and rates of 2,3,7,8-PCDD/Fs degradation were discussed. The PCDD/Fs concentrations and corresponding I-TEQ (toxic equivalent quantity) values were 239 pg x L(-1) and 41.0 pg x L(-1), respectively, in the waste water. The concentrations of total 2,3,7,8-PCDD/Fs decreased after electron beam radiolysis at a dose of 30 kGy and 60 kGy with degradation rates of 5.27% and 23.6%, respectively.

[Uncertainty analysis of ecological risk assessment caused by heavy-metals deposition from MSWI emission].

The CALPUFF model was applied to simulate the ground-level atmospheric concentrations of Pb and Cd from municipal solid waste incineration (MSWI) plants, and the soil concentration model was used to estimate soil concentration increments after atmospheric deposition based on Monte Carlo simulation, then ecological risk assessment was conducted by the potential ecological risk index method. The results showed that the largest atmospheric concentrations of Pb and Cd were 5.59 x 109-3) microg x m(-3) and 5.57 x 10(-4) microg x m(-3), respectively, while the maxima of soil concentration incremental medium of Pb and Cd were 2.26 mg x kg(-1) and 0.21 mg x kg(-1), respectively; High risk areas were located next to the incinerators, Cd contributed the most to the ecological risk, and Pb was basically free of pollution risk; Higher ecological hazard level was predicted at the most polluted point in urban areas with a 55.30% probability, while in rural areas, the most polluted point was assessed to moderate ecological hazard level with a 72.92% probability. In addition, sensitivity analysis of calculation parameters in the soil concentration model was conducted, which showed the simulated results of urban and rural area were most sensitive to soil mix depth and dry deposition rate, respectively.

[Seasonal variation of concentrations and distribution characteristics of PCDD/Fs in atmosphere of an industrial area, Guangzhou].

Atmospheric concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were measured seasonally in an industrial area of Guangzhou City. And seasonal variation of concentrations and distribution characteristics of 2,3,7,8- PCDD/Fs was investigated. The PCDD/Fs concentrations and corresponding I-TEQ (toxic equivalent quantity) values were in the range of 2.33-75.4 pg x m(-3) (mean = 23.2 pg x m(-3)) and 0.229-10.7 pg x m(-3) (mean = 2.00 pg x m(-3)), respectively. The seasonal variation of PCDD/Fs concentrations was obvious, with the highest concentration was found in spring (37.8 pg x m(-3)) and the lowest in summer (13.5 pg x m(-3)). However, no obvious difference of concentrations was observed for autumn (22.3 pg x m(-3)) and winter (19.1 pg x m(-3)). The seasonal variation of I-TEQ values is as follows: spring (5.58 pg x m(-3)) > summer (1.06 pg x m(-3)) > autumn (0.839 pg x m(-3)) > winter (0.525 pg x m(-3)). The influences of monsoon and rainfall on the concentration of PCDD/Fs in atmosphere are discussed.

Polybrominated Diphenyl Ethers (PBDEs) in paired human hair and serum from e-waste recycling workers: source apportionment of hair PBDEs and relationship between hair and serum.

Human hair has been widely used as a bioindicator for human persistent organic pollutants (POPs) exposure, but studies on the sources of hair POPs and the relationship between hair and body burden are limited. This study analyzed the possible source apportionment of hair PBDEs and examined the relationship between PBDE concentrations in paired hair and serum from e-waste recycling workers. Using the ratio of BDE 99/47 and BDE 209/207 as indices, we calculated that only 15% of the highly brominated congeners (nona- and deca-BDE congeners) comes from exogenous (external) exposure for both female and male hair, but an average of 64% and 55% of the lower-brominated congeners (tetra- to penta-BDE congeners) come from exogenous exposure for female and male hair, respectively. The higher contribution of exogenous exposure for less-brominated congeners could be related to their relatively lower log KOW and higher volatility than higher-brominated congeners, which make them more readily to evaporate from dust and then to be adsorbed on hair. Higher hair PBDE levels and higher exogenous exposure of less-brominated congeners in females than in males can be attributed to a longer exogenous exposure time for females than males. Significant positive relationships were found in tri- to hepta-BDE congeners (BDE 28, 47, 66, 85, 100, 153, 154, and 183) (R = 0.36-0.55, p < 0.05) between hair and serum, but this relationship was not found for octa- to deca-BDE. Difference in the half-lives between highly brominated congeners and less-brominated congeners could be a reason. This result also implied that we should treat the results of correlation analyses between hair and other organs cautiously.

[Concentration, profile distribution and source identification of PCDD/Fs in environmental medium around a HSWI].

The concentration and profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the environmental air, soil and plant samples around a hospital solid waste incinerator (HSWI) in Northwest of China were determined by HRGC/HRMS, and the flue gas samples of the HSWI were also involved. The results showed that the average concentration (I-TEQ) of PCDD/Fs in the exhaust gas was 184 ng x m(-3), which seriously exceeds the emission standard (0.5 ng x m(-3)). And the average concentration of PCDD/ Fs was 7.30 pg x m(-3) in the ambient air samples, 52.5 pg x g(-1) in the soil samples, and 146 pg x g(-1) in the leaves samples. All of them were at quite high levels. The concentrations of PCDD/Fs in air samples of downwind were obviously higher than those of upwind. The concentration increased and then decreased with the increase of distance from the HSWI, and the highest concentration occurred at the distance of 700 m from the HSWI. The mass concentration (I-TEQ) proportional distributions of 2, 3, 7, 8 substitution toxic dioxins in downwind air and soil samples was similar to those in the exhaust gas samples. The analysis results of PCDD/Fs concentrations, profiles distributions and principal components all showed that the major source of PCDD/Fs in this area was from the HSWI flue gas emissions.

[Content analysis and assessment of polycyclic aromatic hydrocarbons in surface sediments from Beijiang River, China].

In the present study, 16 polycyclic aromatic hydrocarbons (PAHs) in the surface sediment from Beijiang River in China were quantitatively determined by GC/MS. The concentration of PAHs varied from 38.2 to 6470 ng x g(-1) dry weight, with average 1071 ng x g(-1), which was in moderate level compared with other rivers in Pear River Basin. The PAHs distribution in Bejiang River was obviously affected by point source emissions. The high PAHs concentrations of 6470 ng x g(-1) and 4 470 ng x g(-1) were found at the outfalls of Shaoye and the Shakou town, respectively, where PAHs probably derived from local mining/smelting and related industrial actives. The ecological risk of surface sediment in Beijiang River was assessed with the methods of sediment quality guidelines (SQGs), sediment quality standards (SQSs) and contamination factors (CFs) . The result shows that the adverse biological toxicity effect might occasionally happen in more than half of sampling stations. By comparison with the background area, the contamination degrees of PAHs in 20 sampling stations were at very high level, which should arrest the local governments' attentions. The highest ecological risk areas occurred at the outfalls of Shaoye and the Shakou town in which the ecological risks derived from PAHs were within between probable effect level (PEL) and frequent effect level (FEL). The future research was suggested mainly focusing on the status of benthos, sources of pollutants and ways to control pollution in high-risk areas.