水体中双酚类物质的赋存现状及研究进展

双酚A(bisphenol A,BPA)是一种类雌激素物质,会对动物和人类造成不良的健康影响,由于近年来其使用在世界范围内受到限制,一些与BPA结构相似的双酚类物质(bisphenol analogues, BPs)作为替代品被越来越多地用作各种工商业产品中的添加剂和反应原料.相关研究表明,包括BPA在内的大多数BPs都是内分泌干扰物并具有细胞毒性、神经毒性、遗传毒性和生殖毒性.由于BPs的广泛生产和应用,其在各类环境水体中被普遍检出,其中BPA依然是环境中最主要的双酚类物质,同时双酚F和双酚S等双酚A的类似物的含量有着增加的趋势.本文介绍了BPs的结构与性质,分析了它们的应用情况和在水环境中可能的来源途径,综述了BPs在国内外地表水、污水和饮用水中的污染现状,同时提出了未来进一步研究BPs的重要性和方向.     

双酚A替代品与双酚A对非洲爪蛙急性毒性及其应激响应的比较

双酚F(bisphenol F, BPF)和双酚AF(bisphenol AF, BPAF)作为双酚A(bisphenol A, BPA)的替代品已被投入生产和使用,然而目前有关BPA替代品毒性的数据还很缺乏。本文从急性毒性和应激响应2个方面比较了BPF、BPAF与BPA对非洲爪蛙蝌蚪的毒性。结果表明,48 h的半致死浓度(LC_(50))顺序为BPF(11.01 mg·L~(-1))>BPA(7.54 mg·L~(-1))>BPAF(2.87 mg·L~(-1));对氧化应激水平的影响BPAF强于BPA,BPF与BPA相近;BPA和BPAF对热休克蛋白基因表达水平有影响,BPF没有影响。本研究提示,BPAF作为BPA的替代品,其毒性强于BPA,而BPF与BPA类似。     

双酚类化合物污染现状和内分泌干扰效应研究进展

双酚类化合物(bisphenols, BPs)是合成碳酸聚酯、环氧树脂和聚丙烯酸酯等高分子聚合物的主要原料,在商业制造中广泛使用。经过度排放污染环境,并能通过食物链放大作用在动物和人体内蓄积。已经在水体、底泥、室内灰尘、食品以及动物和人体内检测到双酚A(bisphenol A, BPA)及其替代品或衍生物等多种BPs。BPs对性激素、甲状腺素和神经内分泌系统具有干扰效应,能影响机体生殖功能、性腺发育、神经行为和激素依赖性疾病的发展,已经成为危害人体健康的风险因子。多种BPA替代品的内分泌干扰效应甚至比BPA更强,但缺乏全面的内分泌干扰效应评估数据和对作用机制的深入研究。本文对BPs种类来源、污染现状及其内分泌干扰效应进行综述。     

双酚A对鲤鱼急性和亚急性毒性的研究

以8月龄至1年龄的鲤鱼为实验对象,研究双酚A(BPA)对鲤鱼(CommonCarp)的急性毒性和双酚A在1/2LD50,1/3LD50,1/4LD50,1/6LD50亚急性浓度下,对鲤鱼肝、肾、鳃中过氧化氢酶(CAT)和超氧化物歧化酶(SOD)的影响.结果表明:双酚A24h,48h,96h的LC50值分别为4.46mg·l-1,4.30mg·l-1,4.25mg·l-1;亚急性毒性指标CAT和SOD对双酚A比较敏感,可作为双酚A污染环境的生物标志物.     

双酚A及其类似物对斑马鱼成鱼及胚胎的急性毒性

双酚B(BPB)、双酚F(BPF)、双酚AP(BPAP)、双酚AF(BPAF)、双酚Z(BPZ)、双酚P(BPP)和双酚S(BPS)作为双酚A(BPA)的替代品被广泛使用,但其毒性数据非常有限。将BPA、BPB、BPF、BPZ、BPP、BPAP、BPAF和BPS暴露于斑马鱼成鱼及胚胎,通过24、48、72和96 h死亡率等指标比较8种化合物的急性毒性。结果显示,双酚A及其类似物对斑马鱼成鱼及胚胎毒性具有线性相关性。根据GB 30000.28—2013《化学品分类和标签规范第28部分:对水生环境的危害》对受试物的急性水环境毒性的分级标准,判定BPP为毒性Ⅰ级,BPA、BPB、BPF、BPZ、BPAP和BPAF为毒性Ⅱ级,根据Verhaar分类方法,双酚A及其类似物属于麻醉致毒机制的化学品,其毒性大小与疏水基团相关。     

双酚A及其活性炭催化微波照射降解液对牛血清白蛋白的作用

采用UV-vis光谱和荧光光谱法研究双酚A(BPA)与牛血清白蛋白(BSA)的相互作用.结果显示,BPA的加入能使BSA肽链伸展,导致色氨酸,酪氨酸和苯丙氨酸等残基的芳杂环裸露,紫外光谱表现为明显的增色效应.在三个给定的温度(25℃,37℃和42℃)下,BPA对BSA的荧光猝灭方式均为静态猝灭,结合位点数(n)均为1,作用距离(r)均小于7 nm.BPA与BSA的相互作用是自发进行的,主要为疏水作用.同步荧光光谱表明,BPA对BSA的色氨酸残基微区的影响大于对酪氨酸残基微区的影响.酸度和离子强度的增加促进BPA与BSA的相互作用.另外,通过UV-vis光谱和高效液相色谱(HPLC)研究了活性炭催化微波照射下BPA的降解液对BSA的作用.结果表明,此法可有效地降解BPA,但其降解液仍然对BSA作用.而且即使经过较长时间(5.0 min)微波照射和多次稀释方式处理的BPA降解液仍然对BSA具有一定的作用.     

双酚A与其替代品对黑斑蛙急性毒性的比较

双酚F(BPF)和双酚S(BPS)作为双酚A(BPA)替代品广泛使用,然而有关BPF和BPS的毒性数据非常有限。采用系列浓度的BPA、BPF、BPS溶液,暴露黑斑蛙胚胎和蝌蚪96 h,通过半致死浓度(LC50)、最小生长抑制浓度(MCIG)和致畸率等指标比较3种化合物的急性毒性。结果显示:100 mg·L-1BPS未导致黑斑蛙胚胎及蝌蚪畸形和死亡。BPA和BPF对黑斑蛙胚胎的96h-LC50分别为7.68 mg·L-1和7.99 mg·L-1,MCIG分别为4.47 mg·L-1和4.77 mg·L-1,最大致畸率为33.33%;对蝌蚪的96 h-LC50分别为9.00 mg·L-1和9.52 mg·L-1。依据《化学农药环境安全评价准则》的毒性分级标准,判定BPA和BPF的毒性等级为中毒,BPS的毒性等级为低毒。表明BPF急性毒性与BPA相当,BPS急性毒性低于BPA。本研究数据可为BPF、BPS作为BPA替代品的生产和使用以及相应的环境管理提供毒理学参考。     

阳离子表面活性剂对沉积物及其主要组分吸附双酚A的影响

采用吸附实验、选择性萃取技术研究阳离子表面活性剂-十六烷基三甲基溴化铵(CTMAB)对表层沉积物(生物膜)吸附双酚A(BPA)的影响规律,及CTMAB不同加入条件下对表层沉积物(生物膜)选择性萃取(铁氧化物、锰氧化物、有机质)后的组分吸附BPA的影响.CTMAB对表层沉积物(生物膜)吸附BPA起到促进作用,且随着CTMAB浓度的增加,其促进作用增强;CTMAB掺杂顺序对表层沉积物吸附BPA的影响较小,但对生物膜吸附BPA的影响较大;CTMAB的引入导致BPA在选择性萃取后的表层沉积物(生物膜)组分上的吸附量显著增加,并且CTMAB对表层沉积物(生物膜)吸附BPA的促进作用远大于表层沉积物(生物膜)自身主要组分理化性质的影响.选择性萃取证明,阳离子表面活性剂的引入能降低BPA在水体环境中的迁移转化能力.     

Fe-OH/UV-Vis体系中Cr(Ⅵ)还原和BPA降解的协同效应

研究了在250W金属卤化物灯(λ≥365nm)照射下,Fe(Ⅲ)-OH配合物同时光催化还原铬(Ⅵ)和氧化双酚A(BPA)的协同效应.结果表明:铬(Ⅵ)光还原和BPA光氧化相互促进,具有协同作用.在低pH值(2.5-4.0)时,光还原铬(Ⅵ)和光氧化BPA的初始速率较大;增加Fe(Ⅲ)的浓度,有利于铬(Ⅵ)光还原和BPA光氧化;铬(Ⅵ)的光还原率及BPA的降解率随其初始浓度的增加而快速减小.     

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。     

Occurrence of bisphenol A in surface and drinking waters and its physicochemical removal technologies

Bisphenol A (BPA), an endocrine disrupting compound, has caused wide public concerns due to its wide occurrence in environment and harmful effects. BPA has been detected in many surface waters and drinking water with the maximum concentrations up to tens of μg·L^-1. The physicochemical technology options in eliminating BPA can be divided into four categories: oxidation, advanced oxidation, adsorption and membrane filtration. Each removal option has its own limitation and merits in removing BPA. Oxidation and advanced oxidation generally can remove BPA efficiently while they also have some drawbacks, such as high cost, the generation of a variety of transformation products that are even more toxic than the parent compound and difficult to be mineralized. Only few advanced oxidation methods have been reported to be able to mineralize BPA completely. Therefore, it is important not only to identify the major initial transformation products but also to assess their estrogenic activity relative to the parent compounds when oxidation methods are employed to remove BPA. Without formation of harmful by-products, physical separation methods such as activated carbon adsorption and membrane processes are able to remove BPA in water effluents and thus have potential as BPA removal technologies. However, the necessary regeneration of activated carbon and the low BPA removal efficiency when the membrane became saturated may limit the application of activated carbon adsorption and membrane processes for BPA removal. Hybrid processes, e.g. combining adsorption and biologic process or combining membrane and oxidation process, which can achieve simultaneous physical separation and degradation of BPA, will be highly preferred in future.     

Electro-conductive crosslinked polyaniline/carbon nanotube nanofiltration membrane for electro-enhanced removal of bisphenol A

● A crosslinked polyaniline/carbon nanotube NF membrane was fabricated. ● Electro-assistance enhanced the removal rate of the NF membrane for bisphenol A. ● Intermittent voltage-assistance can achieve nearly 100% removal of bisphenol A. ● Membrane adsorption–electro-oxidation process is feasible for micropollutant removal. Nanofiltration (NF) has attracted increasing attention for wastewater treatment and potable water purification. However, the high-efficiency removal of micropollutants by NF membranes is a critical challenge. Owing to the adsorption and subsequent diffusion, some weakly charged or uncharged micropollutants, such as bisphenol A (BPA), can pass through NF membranes, resulting in low removal rates. Herein, an effective strategy is proposed to enhance the BPA removal efficiency of a crosslinked polyaniline/carbon nanotube NF membrane by coupling the membrane with electro-assistance. The membrane exhibited a 31.9% removal rate for 5 mg/L BPA with a permeance of 6.8 L/(m²·h·bar), while the removal rate was significantly improved to 98.1% after applying a voltage of 2.0 V to the membrane. Furthermore, when BPA coexisted with humic acid, the membrane maintained 94% removal of total organic carbon and nearly 100% removal of BPA at 2.0 V over the entire filtration period. Compared to continuous voltage applied to the membrane, an intermittent voltage (2.0 V for 0.5 h with an interval of 3.5 h) could achieve comparable BPA removal efficiency, because of the combined effect of membrane adsorption and subsequent electrochemical oxidation. Density functional theory calculations and BPA oxidation process analyses suggested that BPA was adsorbed by two main interactions: π–π and hydrogen-bond interactions. The adsorbed BPA was further electro-degraded into small organic acids or mineralized to CO₂ and H₂O. This work demonstrates that NF membranes coupled with electro-assistance are feasible for improving the removal of weakly charged or uncharged micropollutants.     

垃圾渗滤液中典型内分泌干扰物质(EDCs)细胞毒性分析

垃圾渗滤液的人类健康风险评估日益受到人们重视,也成为研究热点。本文采用一种新型高级氧化技术UV-Fenton处理渗滤液,并用人体乳腺癌细胞(MCF-7)评估处理过程中渗滤液原液以及渗滤液中典型内分泌干扰物质(EDCs)的细胞毒性,对垃圾渗滤液中EDCs的细胞毒性和变化规律进行了研究。结果表明渗滤液中的邻苯二甲酸二丁酯(DBP)、双酚A(BPA)、壬基酚(NP)是产生细胞毒性的主要物质,其毒性大小为DBPBPANP。在同样的氧化降解过程中显示出不同毒性变化规律,通过GC-MS分析,结果显示UV-Fenton过程中产生了大量的中间产物,这也是引起毒性变化的主要原因。实验结果也说明垃圾渗滤液细胞毒性可以通过UV-Fenton过程有效去除。     

Degradation of endocrine disruptor bisphenol A in drinking water by ozone oxidation

The ozone oxidation of endocrine disruptor bisphenol A in drinking water was investigated. A stainless completely mixed reactor was employed to carry out the degradation experiments by means of a batch model. With an initial concentration of 11.0 mg/L, the removal efficiencies of BPA (bisphenol A) could be measured up to 70%, 82%, and 90% when the dosages of ozone were 1, 1.5, and 2 mg/L, respectively. The impacts on BPA degradation under the conditions of different ozone dosages, water background values, BPA initial concentrations, and ozone adding time were analyzed. The results showed that ozone dosage plays a dominant role during the process of BPA degradation, while the impact of the contact time could be ignored. UV wavelength scanning was used to confirm that the by-products were produced, which could be absorbed at UV254. The value of UV254 was observed to have changed during the ozonation process. Based on the change of UV254, it could be concluded that BPA is not completely degraded at low ozone dosage, while shorter adding time of total ozone dosage, high ozone dosage, and improvement of dissolved ozone concentration greatly contribute to the extent of BPA degradation. The effects of applied H₂O₂ dose in ozone oxidation of BPA were also examined in this study. The O₃-H₂O₂ processes proved to have similar effects on the degradation of BPA by ozone oxidation.     

Determination and occurrence of endocrine disrupting compounds,pharmaceuticals and personal care products in fish (Morone saxatilis)

Endocrine disrupting compounds (EDCs), pharmaceuticals and personal care products (PPCPs) have attracted much attention due to widespread contamination in aquatic environment. In this study, we determined 13 EDCs and PPCPs in fish blood, bile and muscle by using gas chromatography-mass spectrometry (GC-MS). The limits of quantitation (LOQ) were in the ranges of 0.23–2.54, 0.22–2.36 ng·mL⁻¹, and 0.24–2.57 ng·g⁻¹ dry weight (dw) for fish blood, bile and muscle, respectively. Recoveries of target compounds spiked into sample matrices and passed through the entire analytical procedure ranged from 65% to 95%, from 60% to 92% and from 62% to 91% for blood, bile and muscle, respectively. The methods were applied to the analysis of fish from a lake in California. Target compounds were relatively low in bile, and only bisphenol A (BPA) and diclofenac were measurable near the LOQ. Seven of 13 compounds were detected in blood, with total concentrations up to 39 ng·mL⁻¹. Only BPA was frequently found in muscle, with mean concentration of 7.26 ng·g⁻¹ dw. The estimated daily intake of BPA through fish consumption for U.S. resident was significantly lower than the tolerable daily intake recommended by the European Food Safety Authority. This study showed that the exposure to the bisphenol A from fish diet is unlikely to pose a health risk.     

纳米二氧化钛(nTiO_2)与双酚A对斜生栅藻(Scenedes-mus obliquus)的联合毒性效应

纳米二氧化钛(n Ti O2)在被人们广泛使用的同时,其潜在的环境影响也受到越来越多的关注。为深入探讨n Ti O2与环境中现有污染物的相互作用及生物效应,以斜生栅藻(Scenedesmus obliquus)为受试生物,按照毒性单位法、相加指数法和混合毒性指数法,研究了n Ti O2与双酚A(BPA,一种常见的环境类雌激素)的联合毒性效应。结果显示,n Ti O2与BPA对S.obliquus生长的72 h半抑制浓度(EC50)分别为28.7 mg·L-1与1.81 mg·L-1。而n Ti O2与BPA共存时,在不同毒性比(4:1,3:1,2:1,1:1,1:2和1:3)下,其联合毒性作用(以BPA计)的72 h EC50值分别为2.198,1.58,1.153,0.428,0.306和0.189 mg·L-1。两者的联合毒性作用不仅仅是简单的相加,而是随着两者毒性比的变化,由拮抗作用转变为相加作用,继而转变为协同作用。这表明,n Ti O2进入环境后与现有污染物的毒性比(浓度比)可能是其联合毒性作用模式的一个重要影响因素。     

Effects of chronic bisphenol A exposure on hepatic antioxidant parameters in medaka (Oryzias latipes)

Bisphenol A (BPA), the plastic monomer and plasticizer with well-known endocrine-disrupting chemical properties, is widely present in the aquatic environment, but little is known regarding hepatic toxicity in fish. This study assessed the effects of chronic exposure to BPA on the antioxidant defense system of Japanese medaka liver. Fish were exposed to sub-lethal concentrations of BPA (0.1, 1, 10, 100, or 1000?µg?L^?1) for 60 days. Antioxidant parameters were determined and compared with controls. The results showed that the activities of catalase (CAT), superoxide dismutase, glutathione peroxidase, glutathione S-transferase, and the content of reduced glutathione were all induced at 10?µg?L^?1 BPA after 60 days. Further, hepatic CAT was sensitive to BPA at 1?µg?L^?1 concentration. In conclusion, CAT may serve as a potential early biomarker of BPA exposure in aquatic environment.     

Oxidative and genotoxic effects of bisphenol A on primary gill cell culture of Lake Van Fish (Alburnus tarichi Güldenstädt, 1814)

Lake Van is the largest lake in Turkey. The lake limits lifespan due to its high pH and brackish water. For this reason, only a single species of fish (Van Fish) is living in the lake that has been adapted to these conditions. In the present study, we investigated the total oxidant status (TOS), total antioxidant status (TAS), malondialdehyde (MDA) level and DNA damage effect of bisphenol A (BPA) (10^?7, 10^?6 and 10^?5?M) on primary gill cell culture of Van Fish for 24 and 48?h of incubation periods. TAS levels were not changed when compared to those of the control group, but TOS levels were decreased in both 24 and 48?h. The MDA level increased only at the highest concentration (10^?5) at the end of 12 and 24?h (p?.05). DNA damage increased only at the 10^?5?M concentration after 48?h. At the end of the experiment, BPA exposure caused lipid peroxidation and genotoxic effect. These results indicate that high levels of BPA exposure induced oxidative stress and DNA damage by time- and concentration-dependent fashion in the gill cell culture of Van Fish. Gill cell culture is a useful model for the rapid identification of the harmful effects of chemicals in the aquatic environment.     

Assessment of estrogenic chemicals using an estrogen receptor α (ERα)- and ERβ-mediated reporter gene assay in fish

In vitro reporter gene assays using vertebrate cell lines or yeast have been used for assessment of the estrogenic chemicals. However, estrogen receptor α (ERα)- and ERβ-mediated reporter gene system in fish has yet to be developed. In the present study, we developed an ERα- and ERβ-mediated reporter gene assay in fish and estimated estrogenic activities of 17β-estradiol (E2), p-nonylphenol (NP), bisphenol A (BPA), p,p′-DDE, and genistein (Gen) using the in vitro reporter assay. The activity was intensely induced by transfection with either ERα or ERβ expression plasmid under E2 or Gen administration, whereas it was significantly induced by transfection with ERα expression plasmid, but not with ERβ expression plasmid under NP administration. On the other hand, the activity was induced more intensely by transfection with ERα expression plasmid than ERβ expression plasmid under BPA or p,p′-DDE administration. These results indicate that there are obvious differences in the activity through ERα and ERβ among the estrogenic chemicals examined in vitro. Thus, the in vitro reporter assay provides an excellent system for elucidating the action mechanism of estrogenic chemicals in fishes. Physical and Chemical Impacts on Marine Organisms, a Bilateral Seminar Italy–Japan held in November 2004