Occurrence of endocrine disruptor compounds in the estuary of the Iberian Douro River and nearby Porto Coast (NW Portugal)

Previous studies in the Douro River estuary, based on occasional sampling, showed the presence of several estrogenic disrupting chemicals (EDCs). In sequence, we hypothesized that such type of pollution was more likely an enduring issue than an occasional phenomenon, and that it may even affect recreational beaches in each side of the estuarine mouth. Thus to conclude about the continuous influx of EDCs, water samples were taken twice a day, once per a week, from March to May of 2009, at four sites within the estuary and at two sites in the coastline. After solid-phase extraction, the extracts were prepared for GC-MS analysis of 11 reference EDCs. These embraced natural and pharmaceutical estrogens (17β-estradiol, estrone and 17α-ethynylestradiol) and xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol, and their mono and diethoxylates and bisphenol A). Data showed the ubiquitous presence of potentially hazardous amounts of natural estrogens (particularly of estradiol, ca 5.5?ng?L^?1) and persistent organic pollutants such as nonylphenol mono (up to 550?ng?L^?1) and diethoxylate (up to 2000?ng?L^?1). It was concluded that the targeted area is continuously polluted by the assayed EDCs, and as a consequence, conditions exist for endocrine disturbance in the biota by chronic exposure to EDCs.     

Disposition of bisphenol A in pregnant mice and fetuses after a single and repeated oral administration

The risk assessment of bisphenol A (BPA) on the development of offspring of humans is an important issue. There have been some reports on the fate of BPA in rodents, but information on the BPA level in fetal organs essential for the extrapolation to humans is inadequate. In the present study, we investigated the distribution pattern of ¹⁴C-BPA-derived radioactivity in fetal tissues following administration of 10?mg/kg ¹⁴C-BPA to the pregnant mice. The radioactivity was rapidly transferred through placenta and distributed to all fetal organs including reproductive organs and brains in a similar level. The concentration declined slowly compared with dams. Analysis of metabolites in fetuses showed that a fraction of BPA was unexpectedly large compared to the maternal blood. There was no clear effect of the fetal position in a uterus to influence the radioactivity concentration in whole fetuses. The dose dependence of pharmacokinetics should be recognized to extrapolate the pharmacokinetic result from animal experiments at high doses to humans at low doses. Similar experiments were conducted with an addition of two doses, 1 and 100?mg/kg, respectively. The pharmacokinetics seemed to be linear between 1 and 10?mg/kg, although at 100?mg/kg BPA was absorbed slowly and the radioactivity concentrations in fetuses were much higher than expected based on the linear dose dependence. Repeated doses were administered to pregnant mice since humans are exposed to BPA chronically. Radioactivity level in most of the fetal tissues on repeated administration was higher than single administration.     

Cytotoxicity and cell membrane depolarization induced by aluminum oxide nanoparticles in human lung epithelial cells A549

The cytotoxicity of 13 and 22 nm aluminum oxide (Al₂O₃) nanoparticles was investigated in cultured human bronchoalveolar carcinoma-derived cells (A549) and compared with 20 nm CeO₂ and 40 nm TiO₂ nanoparticles as positive and negative control, respectively. Exposure to both Al₂O₃ nanoparticles for 24 h at 10 and 25 µg mL^?1 doses significantly decreased cell viability compared with control. However, the cytotoxicity of 13 and 22 nm Al₂O₃ nanoparticles had no difference at 5–25 µg mL^?1 dose range. The cytotoxicity of both Al₂O₃ nanoparticles were higher than negative control TiO₂ nanoparticles but lower than positive control CeO₂ nanoparticles (TiO₂ < Al₂O₃ < CeO₂). A real-time single cell imaging system was employed to study the cell membrane potential change caused by Al₂O₃ and CeO₂ nanoparticles using a membrane potential sensitive fluorescent probe DiBAC₄(3). Exposure to the 13 nm Al₂O₃ nanoparticles resulted in more significant depolarization than the 30 nm Al₂O₃ particles. On the other hand, the 20 nm CeO₂ particles, the most toxic, caused less significant depolarization than both the 13 and 22 nm Al₂O₃. Factors such as exposure duration, surface chemistry, and other mechanisms may contribute differently between cytotoxicity and membrane depolarization.     

双酚A对小鼠肝脏和肾脏细胞的氧化损伤

为探究双酚A(BPA)的氧化毒性,分别以剂量为20、40和80mg·kg~(-1)·d~(-1)的BPA对雄性昆明小鼠灌胃处理1周,并测定了小鼠体内活性氧自由基(ROS)水平、还原型谷胱甘肽(GSH)含量、丙二醛(MDA)含量和DNA-蛋白质交联系数(DPC)。与对照组相比,各BPA暴露组小鼠肝脏和肾脏细胞中的ROS生成量、MDA含量和DPC系数均升高,而GSH含量下降(P<0.05或P<0.01)。ROS生成量、GSH含量和DPC系数均显示出剂量-效应关系。研究表明,BPA可扰乱小鼠肝脏和肾脏细胞的氧化应激平衡,诱导细胞氧化损伤。     

改良剂对土壤-芦蒿系统中镉行为的影响

开展了硅肥、钙镁磷肥、石灰和骨炭粉等对镉污染土壤的固定修复研究,结果表明,施用固定剂后不同程度地缓解了芦蒿吸收Cd,其中硅肥和钙镁磷肥的效果最好,在1%的施用量下,两种固定剂可使芦蒿可食部位的Cd含量降低到卫生限量标准水平以下,而其它处理在本研究条件下未能使芦蒿Cd含量降低到安全范围,固定剂抑制芦蒿吸收Cd的效果从大到小的顺序依次为:硅肥≈钙镁磷肥＞石灰≈骨炭粉＞高炉渣≈钢渣,形态提取分析表明,施用固定剂处理使土壤Cd的水溶态、可交换态和碳酸盐结合态减少,而有机结合态和残渣态增加,说明促进Cd从有效态向缓效/迟效态转化是固定剂抑制芦蒿吸收Cd的重要机制.     

扩展细胞色素P4502A6对大位阻底物的适应性

细胞色素P450酶(P450)的分子改造及其催化的生物转化是当前的两个研究热点.本研究以扩展P450 2A6的底物适应性为目标,通过尝试对P450 2A6酶进行N-端修饰提高表达量、筛选随机突变库以及点突变改变活性位点重要氨基酸残基等手段,在两个随机突变体中未筛选到功能突变体,但通过点突变重要氨基酸残基获得了新的突变体P450 2A6 (N297Q/I300A).该突变体具有比野生型和已报道的其它突变体更广泛的底物适应性,能够催化氧化大位阻底物6-苄氧基吲哚(6-OBzl-indole)生成蓝绿色物质.该物质经质谱测定为靛蓝类二聚体化合物.实验表明,其中两个氨基酸残基的变化都是关键突变,此结果与最新的P450 2A6突变体晶体结构研究相符.计算机模拟显示,I300A突变导致活性口袋在铁卟啉环的垂直和水平方向都增大,使其能接纳在两个方向都有位阻的底物;而297位的天冬酰胺是一个功能保守的残基,N297Q的变化可能与氢键等弱作用有关.图4表1参29     

珠江口地区水体中双酚A污染及其与环境因子的关系

采用固相微萃取、气-质联用方法,调查了珠江口地区鱼塘、河流及入海口表层水中双酚A(BPA)的污染特征, 分析了BPA残留水平与环境因子的关系.结果显示:珠江口地区鱼塘、横门水道、入海口表层水中BPA均值分别为1.19、1.41和2.06 μg·L-1.相关分析表明水体中BPA残留量与pH值显著相关(P<0.05).根据EC/PNEC(环境中某一污染物的残留水平与该污染物生态风险阈值之比)指标判断,目前珠江口地区表层水中BPA残留水平不会产生生态风险.     

泥法A／O生物脱氮工艺处理腈纶废水和炼油废水

采用泥法Ａ／Ｏ生物脱氮工艺处理腈纶废水和炼油废水,出水中ＣＯＤ〈１００ｍｇ／Ｌ,ＮＨ３－Ｎ〈１５ｍｇ／Ｌ。但进水中油〉２０ｍｇ／Ｌ,ＮＨ３－Ｎ〉７００ｍｇ／Ｌ或ＳＣＮ＾－〉７０ｍｇ／Ｌ时,将对系统产生不良影响。本文介绍了１年来的运行情况,探讨了系统受影响的原因,并提出了改进建议。     

Effects of Al3+ on pollutant removal and extracellular polymeric substances (EPS) under anaerobic,anoxic and oxic conditions

The highest removal efficiencies of COD and TN were achieved under 10 mg/L of Al³⁺. The highest TP removal efficiency occurred under 30 mg/L of Al³⁺. EPS, PS and PN concentrations increased with the addition of Al³⁺. Sludge properties significantly changed with the addition of Al³⁺. Aluminum ions produced by aluminum mining, electrolytic industry and aluminum-based coagulants can enter wastewater treatment plants and interact with activated sludge. They can subsequently contribute to the removal of suspended solids and affect activated sludge flocculation, as well as nitrogen and phosphorus removal. In this study, the effects of Al³⁺ on pollutant removal, sludge flocculation and the composition and structure of extracellular polymeric substances (EPS) were investigated under anaerobic, anoxic and oxic conditions. Results demonstrated that the highest chemical oxygen demand (COD) and total nitrogen (TN) removal efficiencies were detected for an Al³⁺ concentration of 10 mg/L. In addition, the maximal dehydrogenase activity and sludge flocculation were also observed at this level of Al³⁺. The highest removal efficiency of total phosphorus (TP) was achieved at an Al³⁺ concentration of 30 mg/L. The flocculability of sludge in the anoxic zone was consistently higher than that in the anaerobic and oxic zones. The addition of Al³⁺ promoted the secretion of EPS. Tryptophan-like fluorescence peaks were detected in each EPS layer in the absence of Al³⁺. At the Al³⁺ concentration of 10 mg/L, fulvic acid and tryptophan fluorescence peaks began to appear, while the majority of protein species and the highest microbial activity were also detected. Low Al³⁺ concentrations (<10 mg/L) could promote the removal efficiencies of COD and TN, yet excessive Al³⁺ levels (>10 mg/L) weakened microbial activity. Higher Al³⁺ concentrations (>30 mg/L) also inhibited the release of phosphorus in the anaerobic zone by reacting with PO₄^3-.