Tetrabromoethylcyclohexane affects gonadal differentiation and development in the frog Pelophylax nigromaculatus.

Tetrabromoethylcyclohexane (TBECH), an additive brominated flame retardant, has been shown to have an androgenic activity in vitro. In the present study, we aimed to investigate the effects of TBECH on gonadal differentiation and development in the frog Pelophylax nigromaculatus, an amphibian species sensitive to androgenic chemicals, and to assess the androgenic activity of TBECH in vivo. P. nigromaculatus tadpoles were exposed to TBECH (1, 10, 100nM) from Gosner stage 24 to complete metamorphosis, and to 5α-dihydrotestosterone (DHT) as a positive control. We found that 1nM DHT resulted in 100% males, while the sex ratio in the solvent control group was close to 1:1. In all the TBECH treatment groups, sexually ambiguous gonads based on gross morphology and intersexualities with testicular and ovarian histological structures were found, but no abnormality occurred in the solvent control. In the 1, 10, 100nM TBECH treatment groups, the female percentages were 52%, 31%, 17%, with 36%, 56%, 66% for males and 12%, 13%, 17% for abnormal sexes, respectively. X2-test revealed significant differences in sex ratios between the three TBECH groups and the solvent control group, and the sex ratios in the two higher concentration groups were male-biased. These observations show that TBECH has a masculinizing effect on gonadal differentiation and development in P. nigromaculatus, suggesting an androgenic activity of TBECH in vivo. To our knowledge, this is the first study demonstrating that TBECH could induce gonadal masculinization in an animal, which raises new concerns for reproductive risk of TBECH exposure.

Changes of polybrominated diphenyl ether concentrations in ducks with background exposure level and time.

To reveal what degree bioaccumulation of polybrominated diphenyl ethers (PBDEs) depends on exposure time and other factors, we conducted a semi-field experiment for a year (June 2008-June 2009) in a village in an e-waste recycling site in Taizhou, China. Approximately one hundred of juvenile ducks (Anas domestica Linnaeus) were entrusted to a villager. The ducks lived and forged in a PBDE-polluted pond from the late March to the end of November. Fish and mudsnails that were heavily polluted by PBDEs were main food. In cold days (from December to the middle March), the ducks lived in the villager' house, and mainly fed on paddy, which contained lower concentrations of PBDEs than fish and mudsnails. The female ducks were sampled for PBDE analysis every three months. We found that the ∑PBDE concentrations in duck liver, muscle, lung and brain fluctuated greatly with the changes of exposure levels that were determined by the environment and diets, but the ∑PBDE concentrations in fat tissue increased successively with time. Congener analysis demonstrated that the successive increase in the ∑PBDE concentrations with time in fat tissue was due to the successive increase in BDE-209, -183 and -153 concentrations, with large fluctuations of low brominated congeners. The results show that PBDE concentrations in liver, muscle, lung and brain tissues heavily depends on exposure levels rather than exposure time. In fat tissue, by contrast, PBDE concentrations (mainly high brominated congeners) slightly depends on exposure levels but heavily depend on time relative to other tissues, implying that high brominated congeners seem to have longer half-lives than low brominated congeners in fat tissue.

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.

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 compound's 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 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.

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.

Formation of PCDD/Fs from heating polyethylene with metal chlorides in the presence of air.

This paper investigated the effect of inorganic chlorine on the formation of PCDD/Fs from heating polyethylene (PE) in the presence of air. There was an increase in the formation of PCDD/Fs with an increasing amount of metal chlorides except NaCl, which was not observed to have any effects on the formation of PCDD/Fs without the presence of catalysts. Although the levels of PCDD/Fs formation in this study have no relevance to full scale municipal solid waste incineration, the results of the present experiments can aid understanding of the mechanisms of the formation of PCDD/Fs from heating PE in the presence of metal chlorides.

Phototransformation of polychlorinated dibenzo-p-dioxins from photolysis of pentachlorophenol on soils surface.

The phototransformation of polychlorinated dibenzo-p-dioxins (PCDDs) by photolysis of pentachlorophenol (PCP) on soil surface under irradiation of UV light in the laboratory has been investigated. Octachlorodibenzo-p-dioxin (OCDD) and heptachlorodibenzo-p-dioxin (H7CDD) were detected from the products of the photoreactions. The effects of soil types with different basic soil physicochemical properties were varied from silt loam, silt clay and clay soil on the formation of PCDDs by irradiation of PCP on soils surface. Fulvic acids can prevent phototransformation of PCDDs by photolysis of PCP on soil surface.