Determination of Steroid Estrogens in Wastewater Treatment Plant of A Controceptives Producing Factory

Steroid estrogens such as estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethynylestradiol (EE2) have been suspected to be the main contaminants, which can affect the endocrine system of animals. Many authors have investigated these chemicals in the domestic wastewater treatment plants (WTP). However, wastewater from industries producing steroid contraceptives has not got ample attention. From the environmental point of view, the four steroids are very significant because even very low concentrations (ng/L) can cause reproductive disturbances in human, livestock and wildlife. The main purpose of the present investigation was to develop an analytical method for the determination of the four steroid estrogens present in WTP of a pharmacy factory, mainly producing contraceptive medicine in Beijing, China. Analysis was performed by solid-phase extraction (SPE) system and liquid chromatography combined with tandem mass spectrometry (LC/MS/MS). The average recoveries from effluent samples ranged from 88% to 103% and the precision of the method ranged from 9% to 4%. Based on 0.5-L wastewater samples, the limit of quantification (LOQ) was determined at 0.7 ng/L for E1, 0.8 for E2, 0.9 ng/L for E3, and 0.5 ng/L for EE2 in influent, and 1.0 ng/L for E2 and EE2, and 2.0 ng/L for E1 and E3 in effluent. In the influent samples, average concentrations of 80, 85, 73 and 155 ng/L were determined for E1, E2, E3 and EE2, respectively, showing that they were removed in this WTP to the extent of 79, 73, 85 and 67%, respectively.     

A2O工艺中雌激素的行为变化和去除机理

研究了厌氧-缺氧-好氧(A2O)活性污泥工艺对生活污水中天然雌激素雌酮(Estrone,E1)、17β-雌二醇(17β-Estradiol,E2)以及17α-乙炔基雌二醇(17α-Ethynylestradiol,EE2)的去除性能。在对COD、N和P具有良好去除效果的前提下,对E1、E2和EE2的去除率可分别达到92.7%、100%和62.7%。通过对各反应单元内3种雌激素的物料平衡分析,表明A2O工艺对雌激素的去除主要发生在厌氧段和好氧段。以失活污泥作为对照组,好氧硝化过程中雌激素去除的小试实验发现,好氧过程中E1、E2的去除主要依靠生物降解作用,而EE2的去除则主要依赖于活性污泥对其的吸附作用。     

Development of a real-time immuno-PCR assay for the quantification of 17β-estradiol in water

A competitive real-time (RT) immuno-polymerase chain reaction (iPCR) (RT-iPCR) assay was developed for the sensitive quantification of 17β-estradiol in water. Using a universal iPCR method and polyclonal antibodies, 17β-estradiol was accurately quantified at concentrations ranging from 1 pg mL^?1 to 10 µg mL^?1. The RT-iPCR assay's limit of detection was 0.7 pg mL^?1. The RT-iPCR assay provided an 800-fold increase in sensitivity as well as an expanded working range compared with the corresponding enzyme-linked immunosorbent assay. Assay cross-reactivity to estrone and estriol, two structurally related estrogens, was below 8%. Water samples spiked with 17β-estradiol were analyzed by RT-iPCR to determine the assay's potential as a rapid screen for the monitoring of manure-borne estrogens in the environment. The assay showed recoveries of 82, 102 and 103% for Milli-Q, tap, and irrigation water, respectively, without requiring sample extraction or concentration prior to analysis.     

类固醇雌激素分析方法研究进展

类固醇雌激素因其对野生动物、人类健康及生态环境安全造成危害而受到全世界的普遍关注,并成为环境科学和生态毒理学研究的重点和热点之一.针对4种典型的类固醇雌激素(雌激素酮、17-β-雌二醇、雌三醇和17-α-乙炔基雌二醇),对其羟基和酮基衍生化技术、水和固体样品的前处理技术及仪器检测方法进行了综述,总结了类固醇雌激素分析方法的研究动态和进展.     

天然胶/公共网络/废胶粉互穿聚合物网络

通过互穿聚合物网络技术成功制备了天然橡胶/公共网络/废胶粉共轭三组分,并测定了力学性能和微观形态。结果表明:当A/B摩尔比为2/1、AB含量为4.5%、废胶粉粒径为60目、废胶粉含量为15%时,体系的力学性能最好,共轭三组分天然橡胶/公共网络/废胶粉体系的磨耗体积明显低于两组分天然橡胶/废胶粉体系的磨耗体积。界面共轭互穿改善了界面结合,可减少反复压缩过程中的相间摩擦生热和变形。     

基于平面波导型荧光免疫传感器的双酚A检测适用性研究

双酚A是一种环境内分泌干扰物,逐渐受到国内外广泛关注.平面波导型荧光免疫传感器可以对水样中存在的痕量双酚A进行快速高灵敏度检测.在最优检测条件下测得双酚A标准曲线的检出限为(0.04±0.007)μg·L-1,线性区间为0.16~22.40μg·L-1,半抑制浓度为(1.67±0.47)μg·L-1.加入0.5%的EDTA到样品溶液中可以削弱水体硬度的干扰,并在最优条件下测得4种实际水样的加标回收率在88%~111%之间,相对标准偏差小于15%,表明该方法可以运用于实际水样中双酚A的检测.     

High serum S-equol content in red clover fed ewes: the classical endocrine disruptor is a single enantiomer

An expedient high performance liquid chromatography (HPLC) method was developed for the quantitative analysis of environmental estrogenic isoflavonoids, particularly (S)-equol, in red clover fed ewes. We report here the phytoestrogen analysis of red clover silage and the serum of ewes fed with this feed. Ewes received daily 10.5 g of formononetin on average from red clover silage. In the serum samples a major part of formononetin had been metabolised to equol (average 7.7 μg ml⁻¹). According to chiral HPLC analysis, the equol present in the serum of ewes was solely of the (S)-form. We also demonstrate the presence of the metabolite O-demethylangolensin (O-DMA) in ovine serum.     

根系分泌物调控对人工湿地去除雌激素的影响

通过在所构建的3组垂直流人工湿地(CW1、CW2、CW3)中添加不同ρ(DOC)(0、14、28 mg/L,DOC为溶解性有机碳)的美人蕉根系浸出液来模拟根系分泌物浓度变化,考察其对2种SEs(steroidal estrogens,类固醇雌激素)去除效果的影响. 结果表明:①虽然根系浸出液和根系分泌物中的ρ(DOC)存在差异,但二者成分比例类似,均含有多种小分子化合物(如氨基酸、多糖、有机酸、脂肪酸、醇、烷等),并且甘油含量均为最高. ②各组湿地对SEs的去除率表现为CW2>CW3≈CW1,CW2对E1(Estrone,雌酮)、EE2(17α-Ethinylestradiol,17α-乙炔基雌二醇)的去除率最高可分别达到86.9%、72.7%. ③各组湿地全细菌和AOB(ammonia oxidizing bacteria, 氨氧化细菌)平均密度大小表现为CW3>CW2>CW1,NOB(nitrite oxidation bacteria, 亚硝酸氧化细菌)平均密度大小表现为CW2>CW3>CW1,DNB(denitrifying bacteria, 反硝化细菌)平均密度大小表现为CW3>CW1≈CW2,各组湿地基质上生物膜的脱氢酶活性表现为CW2>CW1>CW3.研究显示,适量添加根系浸出液有利于SEs的去除,但根系浸出液中ρ(DOC)过高,可能会对植物根系和特定根系微生物(如NOB)的生长造成毒害作用,并抑制微生物活性,从而影响SEs的去除效果.      

胜利油田区水体中环境雌激素生态风险评估

为了评价胜利油田石油开采对水体中雌激素生态风险。首先,检测胜利油田区26个样品中盐度、总氮、总磷、余氯、COD、石油烃类物质含量6个常规水质指标,结果发现水体中总氮及COD的含量均值达到5.2mg/L及64mg/L,这表明该区域有机污染物及富营养化程度比较严重。其次,利用人雌激素受体基因酵母干粉法检测了样品中环境雌激素含量,结果分析发现不同采样点间的雌激素污染水平不同,雌激素含量与水质指标间无显著相关性。样品中雌激素含量范围0.046-0.072ng/L,均值为0.062ng/L,雌激素水平相对较低,这证实胜利油田水体存在环境雌激素生态风险值也较低。     

雌激素受体作为壬基酚的主要作用靶点导致机体免疫毒性

雌激素作为一类重要的性腺类固醇化学信使,已经被证实能够直接调节机体免疫反应,因此,一些具有拟雌激素特性的环境内分泌干扰物(endocrine disruptors,EDs),会通过影响雌激素相关信号通路对免疫系统产生干扰作用。壬基酚(nonylphenol,NP)作为典型的环境内分泌干扰物,已有大量的文献报道其通过拟雌激素特性或干扰雌激素的合成、分泌、转运以及与靶点的结合,破坏机体生殖功能以及神经-免疫-内分泌系统,影响整体生理平衡与稳定。近年来,NP对免疫系统的干扰作用逐渐引起重视,研究发现,NP暴露会引起小鼠免疫器官及免疫细胞的发育异常,并且会导致新生小鼠肝毒性,肝脏细胞内炎性因子TNF-α、IL-1β分泌增加。除NP作为配体干扰雌激素信号通路外,尚未发现其他明确的分子机制解释NP造成的免疫毒性。本综述主要结合近年来相关的实验结果,总结了NP对免疫系统的潜在影响及其可能的分子机制。