中国环境内分泌干扰物的污染现状分析

内分泌干扰物严重威胁着全球环境和生态健康,基于人为源内分泌干扰物的分类,分析了国内内分泌干扰物的污染现状,指出了目前研究工作的局限,提出了今后研究重点及污染控制的建议。     

金华市饮用水有机浓集物致突变性调查研究

分别在丰水期和枯水期对金华市自来水出厂水及婺江源水有机浓集物进行了致突变性研究，结果表明源水致变性较强，经氯化消毒后自来水有机物致变性增强，枯水期致变性高于丰水期。     

环境内分泌干扰物--邻苯二甲酸酯的研究

介绍了环境内分泌干扰物的生殖毒性，综述了不同环境样品中邻苯二甲酸酯类内分泌干扰物的前处理技术和分析测试技术，并指出环境中邻苯二甲酸酯的污染状况。     

纳滤去除水中的内分泌干扰物

采用陶氏DOW FILMTEC NF270芳香聚酰胺类复合纳滤膜处理水中内分泌干扰物——17α-乙炔雌二醇（EE2）,实验中分别考察了原液浓度、操作压力、pH值、Ca²⁺浓度及腐殖酸共存等不同条件下对EE2截留效果的影响。结果表明,NF270对于去除水中的EE2具有很好的效果,截留率可达到97.6%,而且,实验发现,原液浓度对EE2的截留效果影响较小;当操作压力为0.6 MPa时,膜对EE2的截留效果最好;而随着pH值和Ca²⁺浓度的增加,膜对EE2的截留率均呈上升趋势;而当腐殖酸存在时膜对EE2的截留率有明显提高,但同时也造成膜污染加剧和膜通量下降,特别是在EE2、腐殖酸和Ca²⁺共存时,膜污染更加严重。     

深圳河典型内分泌干扰物分布和季节变化规律研究

2011年6月至2012年5月在深圳河沿程采集水样,采用固相萃取一氮吹一衍生化的预处理方法和气相色谱/质谱联用法,对壬基酚(NP)、辛基酚(OP)、双酚A(BPA)、雌酮(E1)、雌二醇(E2)、17α-雌二醇(17α-E2)、雌三醇(E3)、雌炔醇(EE2)等8种内分泌干扰物(EDCs)在深圳河的浓度分布和时空变化规律进行了研究.同时通过主成分分析考察了EDCs与常规水质污染物的关系.结果表明,NP、BPA、E1、E3、EE2在深圳河各河段均有检出,而OP、17α-E2、E2的检出率均低于20％,EDCs主要来源是NP和BPA;深圳河旱季和雨季EDCs的浓度变化大,其中NP浓度表现出旱季高雨季低的规律,旱季浓度是雨季的1.74～5.63倍,但BPA和3种甾醇类雌激素的浓度呈现出了雨季高旱季低的相反变化规律,这应该与污水处理厂雨季污水溢流有关;通过主成分分析发现,BPA与DO存在明显的负相关关系,生物作用可能在BPA去除和甾醇类雌激素转化中起到了重要作用,具体机制还有待进一步研究.     

计算机模拟在环境内分泌干扰物研究中的应用

环境内分泌干扰物与受体蛋白质作用机制的研究,必须要得到蛋白质分子合理的三级结构,但是目前仍然难以通过实验得到大多数蛋白质的晶体结构。通过计算机同源模建的方法,得到结构合理的蛋白质三级结构,在蛋白质与配体分子结合的研究中,同样发挥了重要的作用。这些工具在认识蛋白质-配体结合引发的内分泌干扰效应中,能够发挥重要的作用。     

改性陶粒对水中内分泌干扰物的吸附去除

用CTMAB(十六烷三甲基溴化铵)对陶粒进行改性.实验研究了陶粒改性前后对5种内分泌干扰物EDCs(美托洛尔MTP、磺胺甲噁唑SMZ、卡马西平CBZ、对氯苯氧异丁酸CA、17α-乙炔基雌二醇EE2)的吸附特性.结果表明,CTMAB改性处理对陶粒的孔结构和表面性质都有影响,有效吸附的孔径所占比例和陶粒表面极性升高;室温条件下,EDCs初始浓度和吸附剂浓度均为1 mg/L时,实验用改性陶粒和陶粒达到吸附平衡的时间基本相同,均为5 min左右;改性陶粒能提高大部分EDCs的吸附量,5种内分泌干扰物混合物一起吸附时存在竞争,其中SMZ和MTP竞争力强,CA最弱;吸附机理包括表面物理吸附和分配作用.实验研究拟为改性陶粒应用于水中痕量污染物的处理提供理论依据,支撑保障饮用水处理达标的目的.     

水中微量弱极性内分泌干扰物测定方法的研究

使用ENVITM Chrom P固相萃取小柱、双(三甲基硅烷基)三氟乙酰胺(BSTFA)衍生剂及气质联机,系统研究了水中弱极性内分泌干扰物(EDCs)的测定方法.通过正交试验,得到最佳固相萃取条件为:水样流速5 mL/min,洗脱剂为二氯甲烷,洗脱速率0.5 mL/min,洗脱剂体积6 mL.最佳衍生化条件为:BSTFA 100 μL,60 ℃,反应时间30 min.结果表明,双酚A、五氯酚、2,4-二氯苯酚、4-壬基酚、雌二醇、雌三醇、雌酮、炔雌二醇的回收率在82.4%～101.9%,检出限为0.01～0.06 μg/L.     

环境内分泌干扰物诱发小鼠睾丸细胞DNA损伤的研究

应用单细胞凝胶电泳技术技术，研究了烷基酚类化合物对离体小鼠睾丸细胞DNA的损伤作用。实验结果表明，9种烷基酚类化合物对小鼠睾丸细胞均能引起不同程度的DNA损伤，并呈现剂量效应关系，其高剂量组与对照组相比，均有极显著性差异（P＜0．01）。实验结果亦表明，其DNA的损伤程序与化学结构有一定的关系。     

Distribution and bioaccumulation of steroidal and phenolic endocrine disrupting chemicals in wild fish species from Dianchi Lake, China

The distribution and bioaccumulation of steroidal and phenolic endocrine disrupting chemicals (EDCs) were studied in various tissues of wild fish species from Dianchi Lake, China. In muscle tissue, 4-tert-octylphenol, 4-cumylphenol, 4-nonlyphenol and bisphenol A were detected in fish from each sampling site, with maximal concentrations of 4.6, 4.4, 18.9 and 83.5 ng/g dry weight (dw), respectively. Steroids (estrone, 17β-estradiol 17α-ethynylestradiol and estriol) were found at lower levels (<11.3 ng/g dw) and less frequently in muscle samples. The highest concentrations of steroids and phenols were found in liver, followed by those in gill and the lowest concentration was found in muscle. The field bioconcentration factors (BCFs) of phenols were calculated in fish species ranged from 18 to 97. Moreover, the measured tissue concentrations were utilized in order to estimate water concentration of steroids (4.4-18.0 ng/L). These results showed that steroidal and phenolic EDCs were likely ubiquitous contaminants in wild fish.     

Synthesis of core-shell magnetic molecular imprinted polymer by the surface RAFT polymerization for the fast and selective removal of endocrine disrupting chemicals from aqueous solutions

In this study, we present a general protocol for the making of surface-imprinted core-shell magnetic beads via reversible addition-fragmentation chain transfer (RAFT) polymerization using RAFT agent functionalized iron oxide nanoparticles as the chain transfer agent. The resulting composites were characterized by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) analysis, thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), and scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The surface-imprinted magnetic beads were demonstrated with a homogeneous polymer films (thickness of about 22 nm), spherical shape, and exhibited magnetic property (Ms = 0.41 mA m² g⁻¹) and thermal stability. Rebinding experiments were carried out to determine the specific binding capacity and selective recognition. The as-synthesized surface-imprinted core-shell magnetic beads showed outstanding affinity and selectivity towards bisphenol A over structurally related compounds, and easily reach the magnetic separation under an external magnetic field. In addition, the resulting composites reusability without obviously deterioration in performance was demonstrated at least five repeated cycles.     

Peroxidase-mediated removal of endocrine disrupting compound mixtures from water

Several classes of oxidative enzymes have shown promise for efficient removal of endocrine disrupting compounds (EDCs) that are resistant to conventional wastewater treatments. Although the kinetics of reactions between individual EDCs and selected oxidative enzymes are well documented in the literature, there has been little investigation of reactions with EDC mixtures. This makes it impossible to predict how enzyme-mediated treatment systems will perform since wastewater effluents generally contain multiple EDCs. This paper reports pseudo-first order rate constants for a model oxidative enzyme, horseradish peroxidase (HRP), during single-substrate (k₁) and mixed-substrate (k_1-MIX) reactions. Measured values are compared with literature values of three Michaelis-Menten parameters: half-saturation constant (K_M), enzyme turnover number (k_CAT), and the ratio k_CAT/K_M. Published reports had suggested that each of these could be correlated with HRP reactivity towards EDCs in mixtures, and empirical results from this study show that K_M can be used to predict the sequence of EDC removal reactions within a particular mixture. We also observed that k_1-MIX values were generally greater than k₁ values and that compounds exhibiting greatest estrogenic toxicities reacted most rapidly in a given mixture. Finally, because K_M may be tedious to measure for every EDC of interest, we have constructed a quantitative structure-activity relationship (QSAR) model to predict these values. This model predicts K_M quite accurately (R² = 89%) based on two molecular characteristics: molecular volume and hydration energy. Its accuracy makes this QSAR a useful tool for predicting which EDCs will be removed most efficiently during enzyme treatment of EDC mixtures.     

Rapid resolution liquid chromatography-tandem mass spectrometry method for the determination of endocrine disrupting chemicals (EDCs), pharmaceuticals and personal care products (PPCPs) in wastewater irrigated soils

A multiresidue analytical method was developed for the determination of 9 endocrine disrupting chemicals (EDCs) and 19 pharmaceuticals and personal care products (PPCPs) including acidic and neutral pharmaceuticals in water and soil samples using rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS). Solid phase extraction (SPE), and ultrasonic extraction combined with silica gel purification were applied as pretreatment methods for water and soil samples, respectively. The extracts of the EDCs and PPCPs in water and soil samples were then analyzed by RRLC-MS/MS in electrospray ionization (ESI) mode in three independent runs. The chromatographic mobile phases consisted of Milli-Q water and acetonitrile for EDCs and neutral pharmaceuticals, and Milli-Q water containing 0.01 % acetic acid (v/v) and acetonitrile: methanol (1:1, v/v) for acidic pharmaceuticals at a flow rate of 0.3 mL/min. Most of the target compounds exhibited signal suppression due to matrix effects. Measures taken to reduce matrix effects included use of isotope-labeled internal standards, and application of matrix-match calibration curves in the RRLC-MS/MS analyses. The limits of quantitation ranged between 0.15 and 14.08 ng/L for water samples and between 0.06 and 10.64 ng/g for solid samples. The recoveries for the target analytes ranged from 62 to 208 % in water samples and 43 to 177 % in solid samples, with majority of the target compounds having recoveries ranging between 70–120 %. Precision, expressed as the relative standard deviation (RSD), was obtained less than 7.6 and 20.5 % for repeatability and reproducibility, respectively. The established method was successfully applied to the water and soil samples from four irrigated plots in Guangzhou. Six compounds namely bisphenol-A, 4-nonylphenol, triclosan, triclocarban, salicylic acid and clofibric acid were detected in the soils.     

Combining passive samplers and biomonitors to evaluate endocrine disrupting compounds in a wastewater treatment plant by LC/MS/MS and bioassay analyses

Two types of integrative sampling approaches (passive samplers and biomonitors) were tested for their sampling characteristics of selected endocrine disrupting compounds (EDCs). Chemical analyses (LC/MS/MS) were used to determine the amounts of five EDCs (nonylphenol, bisphenol A, estrone, 17β-estradiol and 17α-ethinylestradiol) in polar organic chemical integrative samplers (POCIS) and freshwater mussels (Unio pictorum); both had been deployed in the influent and effluent of a municipal wastewater treatment plant (WWTP) in Genoa, Italy. Estrogenicity of the POCIS samples was assessed using the yeast estrogen screen (YES). Estradiol equivalent values derived from the bioassay showed a positive correlation with estradiol equivalents calculated from chemical analyses data. As expected, the amount of estrogens and EEQ values in the effluent were lower than those in the influent. Passive sampling proved to be the preferred method for assessing the presence of these compounds since employing mussels had several disadvantages both in sampling efficiency and sample analyses.