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。     

Leaching characteristics of bisphenol A from epoxy-resin pavement materials

We investigated the leaching characteristics of bisphenol A (BPA) from two kinds of epoxy-resin pavement materials, one containing epoxy resins (EPs) and the other containing epoxy-acrylate resins (EPAs). Both samples contained residual BPA monomer, at levels of 9.0?µg?g^?1 for the EP resin sample and 4.4?µg?g^?1 for the EPA resin sample. These amounts were larger than amounts previously measured for polycarbonate samples. The amount of BPA leached from the samples increased with temperature. The leaching of BPA from EP was more strongly affected by temperature than the leaching from EPA. The pH also affected the amount of leached BPA. The maximum leached amount was observed under alkaline conditions (pH 10.8) for both sample types. The amounts of BPA that might leach from pavement materials during 1?h of heavy rain were estimated to be 0.9?µg?m^?2 for EP and 3.5?µg?m^?2 for EPA. Our results indicate that EPs disposed of in waste landfills without any treatment may be a source of BPA in leachate at landfill sites.     

Effects of bisphenol A on Gammarus fossarum and Lumbriculus variegatus in artificial indoor streams

The impact of bisphenol A (BPA) on Gammarus fossarum and Lumbriculus variegatus was studied in four artificial indoor streams (0, 5, 50 and 500?µg?L^?1 BPA, nominal) over 103 days in a pulse–dose exposure scenario (weekly BPA application). For G. fossarum populations at day 103, the proportions of juveniles and of breeding females from the highest BPA treatment were in tendency reduced. For individually exposed gammarid pairs an EC₁₀ of 17?µg?L^?1 BPA (nominal) for the proportion of reproductive females in the fourth brood was determined. During the first three broods, the largest brood size occurred at the highest BPA concentration, whereas in the fourth brood it decreased concentration-dependently (fourth brood EC₁₀?=?5?µg?L^?1 BPA, nominal). Effects on L. variegatus were a reduced population growth (103?d-EC₁₀ of 2?µg?L^?1 BPA, nominal) and an increase in dry weight and the number of segments in large, complete worms.     

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。     

Optimisation of bisphenol A removal from water using chemically modified pine bark and almond shell

The ability of pine bark and almond shells to remove bisphenol A (BPA) from aqueous solutions was evaluated. Samples of these traditional agro-forestry by-products were milled, sieved into different particle size fractions (0.10–0.15 and 1.5–2.0 mm) and submitted to two different types of treatment. Sorption experiments were conducted in a batch system at room temperature and natural pH. Sorption equilibrium was attained after 48 h for all systems under study. Bisphenol A was adsorbed more effectively on the smaller particles of the sorbents. Pine bark and almond shell pretreated with formaldehyde presented higher sorption efficiency (95%), followed by almond shell (87%) and pine bark (82%) washed with hot water. All the sorption isotherms were found to fit a Freundlich equation, with correlation coefficients (R ²) between 0.823 and 0.989. The sorption coefficient (K _F) ranged from 0.06 to 0.74 (mg^1?1/n ·L ^1/n ·g ^?1). These results indicate that utilisation of both materials as an alternative sorbent for the removal of bisphenol A from contaminated waters is promising because they are available in large amounts and have an acceptable cost–efficiency ratio when compared with traditional adsorbents.     

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。     

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.     

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.     

双酚A对青岛大扁藻的干扰效应

为了探讨双酚A(bisphenol A,BPA)对海洋微藻的生态毒性效应,实验选择了以青岛大扁藻(Platymonas helgolanidica)作为受试物种,设置6个实验浓度(即0、2、4、6、8、10 mg·L-1)对微藻进行了96 h暴露处理,测定了不同浓度暴露下对青岛大扁藻的生长以及抗氧化系统酶活性等指标。研究结果表明,BPA对青岛大扁藻的96h-EC50为9.32 mg·L-1,属高毒类污染物。青岛大扁藻经过BPA暴露处理后,细胞密度下降,细胞色素含量降低,并且呈现明显的剂量-效应关系;细胞抗氧化系统中超氧化物歧化酶(SOD)、抗坏血酸过氧化物酶(APX)、单脱氢抗坏血酸还原酶(MDHAR)、脱氢抗坏血酸还原酶(DHAR)、谷胱甘肽还原酶(GR)活性均受到干扰。     

Analyses of phenolic compounds occurring in olive oil mill wastewaters by GC–MS

Phenolic compounds in olive oil mill wastewaters were analysed by HRGC–MS after extracting the acidified solution with ethyl acetate and derivatization with N,O-bis(trimethylsilyl)trifluoroacetamide. Both simple and complex phenols were detected with the latter being the most abundant. 1,2-dihydroxybenzene (catechol), p-hydroxyphenyl ethanol (tyrosol), 3,4-dihydroxyphenyl ethanol (hydroxytyrosol) and 4-hydroxy-3-methoxyphenyl ethanol (homovanillyl alcohol) predominated among the simple phenols using a gas chromatograph coupled with a mass selective detector.     

Influence of 1,2,4,5-tetrazine derivatives on growth of bacterial consortium isolated from soil

This article presents the results of laboratory studies of the influence of tetrazine derivatives on the growth kinetic parameters of soil bacteria. 3,6-Dihydrazinotetrazine (DHTz), 3,6- bis(3,5-dimethylpyrazol-1-yl)-dihydro-1,2,4,5-tetrazine (DMPDHT) and N,N′-bis(1,2,4,5-tetrazine-6-(3,5-dimethylpirazylo))hydrazine (BDMPT) were applied. 3,6-Dihydrazinetetrazine had the largest influence on the growth of bacteria, reflected in a significant lengthening of the lag-phase and a decrease in the specific growth rate. Dehydrogenase activity was also determined in bacterial cultures exposed to tetrazine derivatives. Dehydrogenases remained active even at DHTz concentrations of 80 mg · L^?1, which completely inhibited bacterial growth. The compounds studied variously influence the kinetics of growth in the bacterial consortium; at the same time, they undergo biodegradation in soil by autochthonous microflora.     

The effects of bisphenol A on sex hormone levels of F0 female rats and F1 male rats during weaning period

The effects of bisphenol A (BPA) were examined on sex hormones of F1 generation male rats during weaning period. Female rats were exposed to BPA from day 0 after pregnancy to the weaning period at doses of 50, 100, or 200 mg kg^?1. The sex hormone levels of F1 generation male rats were determined. This study shows that F0 generation female rats fed with 200 mg kg^?1 BPA had a significantly higher serum prolactin (PRL) levels at the end of weaning. Significantly higher levels of serum estradiol (E₂) were also found in female rats fed 100 or 200 mg kg^?1 BPA. Serum levels of E₂ in F1 male generation rats were higher in treatment groups compared to control groups while serum testosterone (T) levels were lower. Follicle stimulating hormone (FSH) in F1 generation rats fed 200 mg kg^?1 was markedly decreased. The relative testicular weights were significantly less in 100 and 200 mg kg^?1 BPA groups. BPA was found to alter the sex hormone levels in F1 male rats during weaning period and thus disrupted endocrine functions.     

Removal of bisphenol a in soil by cyclodextrin derivatives

The apparent aqueous solubility of the endocrine disruptor in hydroxypropyl‐cyclodextrin (HP‐CD) solutions was investigated for evaluating the remediation of soil contamination and ground water pollution. The apparent solubility of bisphenol A (BPA) in water was significantly increased in HP‐CD solutions. The solubilization effect of HP‐CD's is caused by the formation of inclusion complexes of BPA and cyclodextrin. The relative aqueous‐phase concentration of BPA linearly increased with increasing HP‐CD concentration. The solubility of BPA increased in the order of the addition of HP‐a‐CD, HP‐7‐CD, and HP‐ß‐CD. However, it did not depend upon the degree of hydroxypropylation substitution. It is concluded that HP‐CD may be utilized for the remediation of soil contamination.     

双酚A对斑马鱼成鱼肝脏功能基因转录调控的影响

运用实时定量即时聚合链式反应RT-PCR方法,研究了双酚A对斑马鱼成鱼肝脏的功能基因转录水平的影响。结果显示,28 d半静水暴露以后,FGF8A和STAU 2 表现出传统的正剂量—效应关系,CLDN 1和CALCA的表达为倒剂量—抑制效应关系,SP 4基因在15 μg·L^-1 双酚A时表现为显著抑制效应,但是在150 和1 500 μg·L^-1却表现为显著的诱导效应。 试验进一步探讨了这些表达异常的基因在双酚A干扰去除后能否自我调节和修复。结果显示,CLDN 1能恢复到正常表达水平,而其他4个基因在低剂量组却维持原来的高毒性作用水平甚至表现出更高的毒性作用。研究证明双酚A对斑马鱼成鱼肝脏的基因转录调控具有一定的非单调剂量—效应作用。     

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.     

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.     

双酚A类似物雌激素干扰效应的定量结构-活性关系模型

由于双酚A(BPA)具有内分泌干扰等毒性效应,有些国家已经开始限制其在部分工业品生产中使用。一些双酚A类似物因用于替代BPA而被大量使用。因其与双酚A具有相似的分子结构,双酚A类似物是否也具有内分泌干扰等毒性效应受到越来越多的关注。采用逐步多元线性回归(MLR)方法,构建了可预测双酚A类似物雌激素效应的定量结构-活性关系模型。模型的决定系数R~2=0.899,去一法交叉验证系数Q_(LOO)~2=0.868,Bootstrapping验证系数Q_(BOOT)~2=0.755,均方根误差RMSE=0.339,表明模型具有较好的拟合优度、稳健性;验证集决定系数Q_(EXT)~2=0.921,外部验证系数Q_(EXT)~2=0.810,均方根误差RMSE=0.638,表明模型具有较好的预测能力。采用欧几里德距离方法和Wil iams图表征了模型应用域,依据分子描述符对模型进行了机理解释,并用所建模型,填补了22种其他双酚A类似物缺失的雌激素干扰效应数据。     

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     

Epigenetic effect of long-term bisphenol A exposure on human breast adenocarcinoma cells

In this research, epigenetic effects of bisphenol A (BPA) on human breast cancer MCF-7 cells were analyzed. Genome-wide DNA methylation and gene expression were analyzed in MCF-7 cells exposed to BPA (10^?5 and 10^?6 mol/L for 5 weeks). No significant changes in the global level of 5-methyl-2′-deoxycytidine and 5-hydroxymethyl-2′-deoxycytidine were observed. DNA methylation profiling analysis indicated that BPA exposure resulted in the hypermethylation of FOXK2, LKB1, LMX1A and CUGBP2 and the hypomethylation of PTPRN2, TRIM27, BCAS3 and ZNF423. Decreased expression of apoptosis genes (P38 and BCL2L1) and increased expression of chemokine (Cxcl2 and ccl20) were detected. Changes of these genes were speculated to affect the ERα-related cell growth as well as cell apoptosis.     

Degradation of bisphenol A by photo-fenton processes

The photo-Fenton reactions, which could yield hydroxyl radicals via the catalytic degradation of H₂O₂ by Fe(II), were focused as one of the abiotic degradation processes of bisphenol A (BPA) in surface waters. At pH 6, in the presence of H₂O₂ only, 32% of BPA was degraded after 120?min of irradiation. However, 97% of BPA was degraded in the presence of both H₂O₂ and Fe(II). Without light irradiation, no BPA degradation was observed even in the presence of Fe(II) and H₂O₂. These results show that photo-Fenton processes are effective in the natural attenuation of BPA in surface water. In addition, the presence of humic acids (HAs), which were of more aliphatic nature, resulted in enhancing BPA degradation via the photo-Fenton processes. Therefore, HAs can be one of the important factors in enhancing the degradation of BPA in surface water via the photo-Fenton processes.