环境激素的种类及危害分析

环境激素（环境荷尔蒙和环境内分泌）干扰物质是一类具有高稳定性、难生物降解的持久性有机化合物,因其引起的环境污染问题受到广泛关注。本文系统地分析了环境激素类干扰物质的来源、种类及与生物体作用机制,并讨论了它们进入人体的途径以及对生物和人类的危害,通过调查国内环境激素污染问题,指出环境激素污染存在的广泛性,需要引起政府部门高度重视,进一步加强防治环境激素污染工作力度。     

Removal of steroid hormones from mariculture system using seaweed Caulerpa lentillifera

•Steroid hormones could be removed efficiently from mariculture system using seaweed; • Caulerpa lentillifera was the most efficient seaweed for removal of steroid hormones; • More than 90% of E₂ or EE₂ were removed within 12 h using Caulerpa lentillifera; • The removal included the rapid biosorption and the slow bio-accumulation; •The hormones and nutrients in mariculture wastewater could be simultaneously removed. The removal of steroid hormones from the mariculture system using seaweeds (Caulerpa lentillifera, Ulva pertusa, Gracilaria lemaneiformis, and Codium fragile) was investigated. The results illustrated that both 17β-estradiol (E₂) and 17α-ethinylestradiol (EE₂) could be removed by the seaweeds at different levels, and the Caulerpa lentillifera was the most efficient one. More than 90% of E₂ or EE₂ at concentration of 10 μg/L was removed by Caulerpa lentillifera within 12 h. Processes including initial quick biosorption, the following slow accumulation, and biodegradation might explain the removal mechanisms of E₂/EE₂ by Caulerpa lentillifera. E₂/EE₂ removal was positively related to the nutrient level and the initial concentration of steroid hormone. A significant linear relationship for E₂ and EE₂ existed between the initial pollutant concentration and the average removal rate. The highest removal kinetic constant (k) value was obtained at 30°C as 0.34 /h for E₂ and at 20°C as 0.28 /h for EE₂, demonstrating the promising application potential of Caulerpa lentillifera in the water purification of the industrialized mariculture system with relatively high water temperature. Simultaneous and efficient removal of E₂ and EE₂ by Caulerpa lentillifera was still achieved after 3 cycles in the pilot-scale experiment. The steroid hormones and nutrients in mariculture wastewater could also be simultaneously removed using Caulerpa lentillifera. These findings demonstrated that Caulerpa lentillifera was the promising seaweed for the removal of steroid hormones in mariculture systems.     

Spatial and Temporal Patterns of Endocrine Active Chemicals in Small Streams Indicate Differential Exposure to Aquatic Organisms

Alkylphenolic chemicals (APCs) and hormones were measured six times from February through October 2007 in three Minnesota streams receiving wastewater to identify spatial and temporal patterns in concentrations and in estrogen equivalency. Fish were collected once during the study to evaluate endpoints indicative of endocrine disruption. The most commonly detected APCs were 4‐tert‐octylphenol and 4‐nonylphenol and the most commonly detected hormones were estrone and androstenedione. Chemical concentrations were greatest for nonylphenol ethoxycarboxylates (NPECs) (5,000‐140,000 ng/l), followed by 4‐nonlylphenol and 4‐nonylphenolethoxylates (50‐880 ng/l), 4‐tert‐octylphenol and 4‐tert‐octylphenolethoxylates with concentrations as great as 130 ng/l, and hormones (0.1‐54 ng/l). Patterns in chemicals and estrogen equivalency indicated that wastewater effluent is a pathway of APCs and hormones to downstream locations in this study. However, upstream contributions can be equally or more important indicating alternative sources. This study indicates that aquatic organisms experience both spatially and temporally variable exposures in the number of compounds, total concentrations, and estrogenicity. This variability was evident in fish collected from the three rivers as no clear upstream to downstream pattern of endocrine disruption endpoints emerged.     

Assessment of Endocrine‐Disrupting Chemicals Attenuation in a Coastal Plain Stream Prior to Wastewater Treatment Plant Closure

The U.S. Geological Survey is conducting a combined pre/post‐closure assessment at a long‐term wastewater treatment plant (WWTP) site at Fort Gordon near Augusta, Georgia. Here, we assess select endocrine‐active chemicals and benthic macroinvertebrate community structure prior to closure of the WWTP. Substantial downstream transport and limited instream attenuation of endocrine‐disrupting chemicals (EDCs) was observed in Spirit Creek over a 2.2‐km stream segment downstream of the WWTP outfall. A modest decline (less than 20% in all cases) in surface water detections was observed with increasing distance downstream of the WWTP and attributed to partitioning to the sediment. Estrogens detected in surface water in this study included estrone (E1), 17β‐estradiol (E2), and estriol (E3). The 5 ng/l and higher mean estrogen concentrations observed in downstream locations indicated that the potential for endocrine disruption was substantial. Concentrations of alkylphenol ethoxylate (APE) metabolite EDCs also remained statistically elevated above levels observed at the upstream control site. Wastewater‐derived pharmaceutical and APE metabolites were detected in the outflow of Spirit Lake, indicating the potential for EDC transport to aquatic ecosystems downstream of Fort Gordon. The results indicate substantial EDC occurrence, downstream transport, and persistence under continuous supply conditions and provide a baseline for a rare evaluation of ecosystem response to WWTP closure.     

Time-dependent effects of pentabrominated diphenyl ether (PBDE) on thyroid hormones and histology in rats

In order to examine the time-dependent effects of pentabrominated diphenyl ether (BDE-99) on thyroid hormones levels and histological structure in rats, 4-week-old SD rats were divided into 10 groups randomly, according to their body weight. Rats in treatment groups were orally gavaged with BDE-99 at the dose of 60 mg kg^?1 for 10, 15, 20, 30 or 40 days, while rats in control group received equal volume of corn oil. Serum levels of thyroxine (FT4), triiodothyronine (FT3), and thyroid stimulating hormone (TSH) were measured by radioimmunoassay. Sections of thyroids were dyed with hematoxylin-eosin (HE) to detect any pathologically alterations. In BDE-99 treated groups, on day 10, changes in serum levels of FT4, FT3 and TSH were not found. On days 15 and 20, serum levels of FT4 and FT3 decreased, accompanied by increased levels of TSH. On days 30 and 40, serum levels of these hormones returned to control values. As for alterations in histology, on day 15, follicular epithelium of the thyroid were found to proliferate into two layers in BDE-99 treated rats. On day 20, in focal areas the two-layer follicular epithelia were observed to continuously proliferate into 3–4 layers of follicular epithelium, called hyperplasia plaques. On days 30 and 40, solid buds and secondary follicles to solid buds were detected. The earliest alteration of thyroid hormones in treated SD rats occurred at the duration of 10–15 days, with corresponding histopathologic changes. As the exposure time increased, the serum level of hormones and histopathology altered accordingly in a time-dependent manner.     

十溴联苯醚（BDE-209）对成年大鼠甲状腺激素的影响

多溴联苯醚(PBDEs)是现代工业中广泛应用的溴系阻燃剂,PBDEs具有持久性有机卤素污染物(Organohalogen Contaminants,OHCs)和内分泌干扰物(Endocrine Disrupters,EDs)的化学物理特性.PBDEs的生物毒性也是国际上环境生态科学的关注热点.论文建立了十溴联苯醚(BDE-209)暴露剂量的成年大鼠模型,测定了不同暴露剂量的实验动物血清甲状腺激素(Thyroid hormones,THs)水平,初步研究了PBDEs污染物对生物体甲状腺激素的影响.BDE-209的量-效关系研究结果显示,TT4、FT4和TT3浓度均随着暴露剂量的提高而下降,这可能是BDE-209对甲状腺合成分泌T4、T3起到了抑制作用.不同BDE-209暴露剂量下,TT4~FT4以及TT4~TT3的正相关系数大于FT3~TT3以及FT3~FT4,这意味着BDE-209暴露对于T4从甲状腺激素转运结合蛋白(Transthyretin,TTR)的分离与脱碘过程影响不明显,而影响了结合态T3从TTR的分离过程以及FT4的脱碘过程,从而对甲状腺激素的平衡具有干扰效应.采用基准点分析法,研究了BDE-209对于甲状腺干扰相对效应的时间-效应关系,实验表明由于甲状腺的应激作用,对于毒物具有自我防御功能,BDE-209对甲状腺的干扰效应在5~8d后才有所显现,持续时间至少为14d.     

BSA体系中2,4-D和阿特拉津对性激素的干扰机理

在2,4-D和阿特拉津以及天然性激素(雌二醇、睾酮)中加入牛血清白蛋白(BSA),通过紫外吸收峰的变化、温度与体系荧光强度的关系、以及计算扩散碰撞猝灭常数Kq等方法确定2,4-D和阿特拉津均可以发生类似天然性激素和BSA间的基态络合.并通过双倒数公式计算出各自二元体系的结合常数.2,4-D、阿特拉津、雌二醇、睾酮与BSA的结合常数(K)均在104数量级,可以认为2,4-D和阿特拉津具有与天然性激素相近的对BSA结合能力,并可通过竞争占据结合位点的方式干扰正常性激素与BSA的结合.     

环境激素与人类健康

探讨了环境激素的来源、分类、特性和分布,尤其是分析了环境激素对人类健康的危害,指出化学内分泌干扰物通过干扰激素和发育,正在改变着人类的未来.建议政府和全社会的共同努力,来制止环境激素的蔓延与影响.     

Formation of multiple trimethylsilyl derivatives in the derivatization of 17α-ethinylestradiol with BSTFA or MSTFA followed by gas chromatography-mass spectrometry determination

N,O-bis(trimethylsily)trifluoroacetamide (BSTFA) and N-methyl-N(trimethylsily) trifluoroacetamide (MSTFA) are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone (E1) and 17(-ethinylestradiol (EE2). In this study, three trimethylsilyl (TMS) steroid derivatives, mono-and di-trimethylsilyl EE2 and mono-trimethylsilyl E1, were observed during the derivatization of EE2 with BSTFA or MSTFA and/or GC separation. Factors influencing the production of multiple TMS derivatives and their relative abundance were examined. It was found that both methanol and bisphenol A competed with estrogenic esteroids when reacting with silylation reagents, and thus affected the formation of TMS derivatives and their relative abundance in the derivatization products. Methanol was found to be more reactive than bisphenol A with the BSTFA reagent. None of the three solvents tested in this study could prevent the generation of multiple TMS derivatives during the derivatization of EE2 with BSTFA, followed by GC analysis. A similar result was observed using MSTFA as the derivative reagent followed by GC analysis. Thus, the suitability of BSTFA or MSTFA as the derivatization reagent for the determination of E1 and EE2 by GC-MS, under the conditions reported here, is questionable. This problem can be solved by adding trimethylsilylimidaz (TMSI) in the BSTFA reagent as recommended, and the performance of the method has been proved in this study.     

The impact of behavioral and physiological maternal effects on offspring sex ratio in the common snapping turtle,<Emphasis Type="Italic"> Chelydra serpentina</Emphasis>

Theory suggests that maternal effects are especially important in organisms with environmentally-sensitive sex-determining mechanisms. However, there is no substantive body of empirical evidence to confirm this conjecture. We integrated field and laboratory studies to jointly evaluate the significance of behavioral (nest-site choice) and physiological (yolk hormone allocation) maternal effects on offspring sex ratio in the common snapping turtle (Chelydra serpentina), a species with temperature-dependent sex determination (TSD). Of the 16 microhabitat variables measured, only three (south, east, and total overstory vegetation cover) were significantly correlated with nest temperature: cooler nests were located under more vegetation cover. In turn, these microhabitat predictors of nest temperature, and nest temperature itself, may influence nest sex ratio: shadier, cooler nests were more likely to produce a higher proportion of male offspring than less shady, warmer nests. Analysis of eggs from these same nests incubated in a common garden design in the laboratory revealed that clutch sex ratio was unaffected by levels of yolk estradiol, yolk testosterone, or their interaction. Examination of both behavioral and physiological maternal effects revealed no concordant impact on offspring sex ratio. However, eggs from nests that produced male-biased sex ratios in the field yielded higher proportions of males under constant-temperature conditions in the laboratory. Our study confirms the importance of behavioral maternal effects in nature on offspring sex ratios in species with TSD, while also revealing the potential presence of a predisposition for sex-ratio production underlying TSD in this system.Communicated by S. Krackow