Ya-Xian Zhao

Diffusion of polybrominated diphenyl ether (PBDE) from an e-waste recycling area to the surrounding regions in Southeast China

Using Cinnamomum camphora (C. camphora) leaves as biomonitors, we investigated that the diffusion of polybrominated diphenyl ethers (PBDEs) from an e-waste recycling area to the surrounding regions. Variance in sigma(32)PBDEs concentrations (0.46-399.93 ng g(-1) dry weight) in the leaves showed that PBDEs from the e-waste recycling area diffused into the surrounding regions, and resulted in a halo of PBDEs contamination, at least 74 km in radius. The attenuation of sigma(32)PBDEs in the diffusing process fitted in log-linear regression. The difference in the attenuating slopes of linear equations among different directions can be explained by terrain and wind direction. The attenuation of PBDE congeners also fitted well in log-linear regression. The findings that similar attenuating slopes and characteristic travel distance among congeners suggest that the transport behavior of lower brominated congeners might not differ from that of higher brominated congeners in short-range scale.

Dual body burdens of polychlorinated biphenyls and polybrominated diphenyl ethers among local residents in an e-waste recycling region in Southeast China

E-waste recycling resulted in serious pollution of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Taizhou of Zhejiang Province, China. The aims of this study were to assess dual body burdens of the two pollutants and potential health risk for local residents. Blood samples were collected from two e-waste recycling sites, Luqiao (where PCBs-containing e-wastes were recycled) and Wenling (where PBDEs-containing e-wastes were recycled). The mean summation SigmaPCBs (CB-105, 118, 153, 183, and 180) and summation SigmaPBDEs (BDE-28, 47, 99, 100, 153, 154, 180, and 209) were 204.20 and 117.58 ng g(-1) lipid in the blood from Luqiao, respectively, while they were 83.80 and 357.44 ng g(-1) lipid from Wenling, respectively. The PCBs levels among Luqiao residents were comparable to the values reported for US populations, while the PBDEs levels among two study populations were higher than the values from US populations. This is the first report to present dual body burdens of PCBs and PBDEs at so high levels. Based on previous epidemiologic data, it is suggested that dual burdens of PCBs and PBDEs at so high levels might pose health risk for local residents. In addition, no correlation between PCBs or PBDEs concentrations and the ages of the volunteers was observed in the two populations, which was explained by similar exposure time. No correlation of PBDEs with PCBs concentrations suggested different pathways of human exposures to PCBs and PBDEs. Our findings have raised concern about human health risk of dual exposure to PCBs and PBDEs resulting from e-waste recycling.

Polybrominated diphenyl ethers (PBDEs) in aborted human fetuses and placental transfer during the first trimester of pregnancy.

Data on early human fetal exposure to polybrominated diphenyl ethers (PBDEs) is limited. However, early pregnancy, in particular the first trimester, is critical for fetal development. We investigated exposure to PBDEs and placental transfer during early pregnancy by analyzing PBDEs in paired aborted fetuses (n = 65), placentas (n = 65), and maternal blood samples (n = 31) at 10-13 weeks gestation, which were collected in a hospital near electronic wastes (e-wastes) recycling sites in Taizhou, China. Mean total PBDE (∑PBDE) concentrations were 4.46, 7.90, and 15.7 ng/g of lipid weight (lw) in the fetuses, placentas, and blood, respectively. The three matrices had roughly similar PBDE congener profiles, dominated by BDE-209, BDE-197, BDE-153, BDE-47, and BDE-28. Significant correlations were found between ∑PBDE concentrations in the paired matrices. Comparing the concentration ratios between the paired samples, we observed significantly higher fetus/blood and fetus/placenta ratios for BDE-28, BDE-99, and BDE-47 than for BDE-197, BDE-209, and BDE-153, while opposite results were found in placenta/blood ratios. Our results indicate that PBDEs can enter the fetus during the first trimester and low-brominated congeners cross the placenta more easily than high-brominated congeners, which tend to remain in the placenta. This phenomenon is consistent with findings at the end of pregnancy.

Bioaccumulation, maternal transfer and elimination of polybrominated diphenyl ethers in wild frogs

To investigate bioaccumulation, maternal transfer and elimination of polybrominated diphenyl ethers (PBDEs) in amphibians, we collected adult frogs (Rana limnocharis) from a rice field in an e-waste recycling site in China. We found that ∑PBDEs in the whole frogs and various tissues (brain, liver, testis and egg) ranged from 17.10 to 141.11 ng g(-1) wet weight. Various tissues exhibited a similar PBDE congener profile, which was characterized by intermediate brominated congeners (BDE-99 and BDE-153) as the largest contributors, with less lower brominated congeners (BDE-28 and BDE-47) and higher brominated congeners (BDE-209). The maternal transfer capacity of PBDEs declined with the increase in bromine numbers of PBDE congeners. We suggest that the bromine atom number (the molecular size, to some degree) might be a determining factor for the maternal transport of a PBDE congener rather than K(ow) (Octanol-Water partition coefficient), which expresses a compounds lipophilicity. ∑PBDEs concentrations in frogs decreased over time during a depuration period of 54 days when these wild frogs were brought to the lab from the e-waste recycling site. The half-life of ∑PBDEs was 35 days, with about 14 days for BDE-47, and 36 and 81 days for BDE-99 and BDE-153, respectively. The data shows that the elimination of PBDEs has no essential difference from aquatic and terrestrial species.

Determination of polybrominated diphenyl ethers in human semen

Some persistent organic pollutants (POPs) have been found in human semen but until this point it was unclear whether polybrominated diphenyl ethers (PBDEs) could be detected in human semen. In this study, PBDEs were found for the first time in human semen samples (n=101) from Taizhou, China. The concentrations of total PBDEs (∑PBDEs) varied from 15.8 to 86.8 pg/g ww (median=31.3 pg/g ww) and 53.2 to 121 pg/g ww (median=72.3 pg/g ww) in semen and blood samples, respectively. The ∑PBDE level in semen was about two times lower than in human blood, which was different in the distribution in the two matrices from other POPs. A correlation of ∑PBDE concentration was found between paired semen and in blood. The results suggest that semen could be used to detect PBDE burden in human body as a non-invasive matrix. In addition, the levels of BDE-209 and BDE-153, especially the latter, were much higher in blood than in semen, while the levels of BDE-28, BDE-47 and BDE-99 were comparable in the two matrices, suggesting that low brominated congeners could be more easily transferred to semen than high brominated congeners. Considering different toxicities among the PBDE congeners, it might be more significant to measure PBDEs in semen than in blood for evaluating male reproduction risks of PBDEs.

Tetrabromobisphenol A Disrupts Vertebrate Development via Thyroid Hormone Signaling Pathway in a Developmental Stage-Dependent Manner

Data concerning effects of tetrabromobisphenol A (TBBPA) on thyroid hormone (TH)-dependent vertebrate development have been limited, although TBBPA has been demonstrated in vitro to disrupt the TH signaling pathway at the transcriptional level. In this study, we investigated the effects of TBBPA on T3-induced and spontaneous Xenopus laevis metamorphosis, which share many similarities with TH-dependent development in higher vertebrates. In a 6-day T3-induced metamorphosis assay using premetamorphic tadpoles, 10-1000 nM TBBPA exhibited inhibitory effects on T3-induced expression of TH-response genes and morphological changes in a concentration-dependent manner, with a weak stimulatory action on tadpole development and TH-response gene expression in the absence of T3 induction. In a spontaneous metamorphosis assay, we further found that TBBPA promoted tadpole development from stage 51 to 56 (pre- and prometamorphic stages) but inhibited metamorphic development from stage 57 to 66 (metamorphic climax). These results strongly show that TBBPA, even at low concentrations, disrupts TH-dependent development in a developmental stage-dependent manner, i.e., TBBPA exhibits an antagonistic activity at the developmental stages when animals have high endogenous TH levels, whereas it acts as an agonist at the developmental stages when animals have low endogenous TH levels. Our study highlights the adverse influences of TBBPA on TH-dependent development in vertebrates.

Determination of environmentally relevant exposure concentrations of polybrominated diphenyl ethers for in vitro toxicological studies

Toxicological studies at environmentally relevant concentrations are essential for understanding ecotoxic and health risks of pollutants such as polybrominated diphenyl ethers (PBDEs). However, no information is available on what exposure levels of PBDEs in vitro studies are environmentally relevant. We exposed MCF-7, HepG2, H295R and PC12 cells to BDE-47, and measured BDE-47 concentrations in the cells after exposure. We also used the percentile method to summarize literature data on environmental exposure levels of biotic tissues to PBDEs. The exposure concentration that resulted in a BDE-47 burden in cells close to the 90th percentile of PBDEs levels in tissues was assigned as the upper limit for the environmentally relevant concentration. Exposure to 1nM BDE-47 resulted in PBDEs burdens in MCF-7, HepG2 and H295R cells close to the 90th percentile but PBDEs burdens in PC12 cells were higher than the 90th percentile. In consideration of the high exposure levels in PBDE-polluted areas, we concluded that the highest environmentally relevant exposure concentration of PBDEs in culture media should be approximately 10nM for MCF-7, HepG2 and H295R cells, and<10nM for PC12 cells. These results provide an approximate reference for setting environmentally relevant exposure concentrations of PBDEs for studies in vitro.

Thyroid disruption by technical decabromodiphenyl ether (DE-83R) at low concentrations in Xenopus laevis.

Decabromodiphenyl ether (decaBDE), as a flame retardant, is widely produced and used. To study the thyroid disruption by technical decaBDE at low concentrations, Xenopus laevis tadpoles were exposed to technical decaBDE mixture DE-83R (1-1000 ng/L) in water from stage 46/47 (free swimming larvae, system of Nieuwkoop and Faber) to stage 62. DE-83R at concentration of 1000 ng/L significantly delayed the time to metamorphosis (presented by forelimb emergence, FLE). Histological examination showed that DE-83R at all tested concentrations caused histological alterations - multilayer follicular epithelial cell and markedly increased follicle size accompanied by partial colloid depletion and increase in the peripheral colloid vacuolation, in thyroid glands. All tested concentrations of DE-83R also induced a down-regulation of thyroid receptor mRNA expression. These results demonstrated that technical decaBDE disrupted the thyroid system in X. laevis tadpoles. Analysis of polybrominated diphenyl ethers (PBDEs) (sum of 39 congeners) in X. laevis indicated that mean concentrations of total PBDEs in X. laevis exposed to 1, 10, 100, 1000 ng/L were 11.0, 128.1, 412.1, 1400.2 ng/g wet weight, respectively. Considering that PBDEs burden ofX. laevis tadpoles was close to PBDEs levels in amphibians as reported in previous studies, our study has raised new concerns for thyroid disruption in amphibians of technical decaBDE at environmentally relevant concentrations.

Energy deposition by heavy ions: Additivity of kinetic and potential energy contributions in hillock formation on CaF2

Modification of surface and bulk properties of solids by irradiation with ion beams is a widely used technique with many applications in material science. In this study, we show that nano-hillocks on CaF2 crystal surfaces can be formed by individual impact of medium energy (3 and 5 MeV) highly charged ions (Xe22+ to Xe30+) as well as swift (kinetic energies between 12 and 58 MeV) heavy xenon ions. For very slow highly charged ions the appearance of hillocks is known to be linked to a threshold in potential energy (Ep) while for swift heavy ions a minimum electronic energy loss per unit length (Se) is necessary. With our results we bridge the gap between these two extreme cases and demonstrate, that with increasing energy deposition via Se the Ep-threshold for hillock production can be lowered substantially. Surprisingly, both mechanisms of energy deposition in the target surface seem to contribute in an additive way, which can be visualized in a phase diagram. We show that the inelastic thermal spike model, originally developed to describe such material modifications for swift heavy ions, can be extended to the case where both kinetic and potential energies are deposited into the surface.

Polybrominated diphenyl ether （PBDE） in blood from children （age 9–12） in Taizhou, China

Polybrominated diphenyl ethers (PBDEs) as ubiquitous persistent organic pollutants have attracted much attention in recent years. Exposure to PBDEs could induce a high health risk for children. The aim of this study was to investigate the PBDEs exposure of children (9-12 years) from Taizhou, China. Fifty-eight blood samples were collected in one school in a mountainous area in Taizhou. The concentrations of sigma9PBDEs (sum of BDE-28, -47, -99, -100, -153, -154, -183, -197 and -209) ranged from 2.66 to 33.9 ng/g lipid wet (lw) with a median of 7.22 ng/g lw. These concentrations were lower than those of children in USA, but close to European and Asian general population levels. The results showed that children in Taizhou countryside were at a low level of PBDEs exposure. The predominant congener was BDE-209, followed by BDE-28, -47, -197 and -153. High abundance of BDE-209 was consistent with the pollution background of PBDEs in China characterized by high brominated congeners as main pollutants.