中国地表饮用水水源地有机类内分泌干扰物污染现况分析

有机类内分泌干扰物(EDCs)是一类对人类和生物内分泌系统产生干扰,并可造成其紊乱的特殊外来物质,对人类和生物健康有极大的危害.以与人类生活密切相关的地表饮用水水源地中的有机类EDCs为研究重点,对中国目前地表饮用水水源地EDCs污染状况、污染物种类及其来源及可能的污染途径进行了评述.目前,中国各地区地表饮用水水源地均有有机类EDCs检出.其中以有机氯农药六六六及其异构体、DDT及其代谢产物和多氯联苯检出率最高,且某些地区检测浓度相当高,主要来源是农药使用和污水排放.国内外对地表饮用水水源地EDCs突发污染事件的研究均较少,应引起高度重视.     

Selective removal of 2,4-dichlorophenol from contaminated water using non-covalent imprinted microspheres

A molecularly imprinted polymer (MIP) for selective removal of 2,4-dichlorophenol (2,4-DCP) in water was prepared as microspheres by the reverse microemulsion polymerization method based on the non-covalent interactions between 2,4-DCP, oleic acid, and divinylbenzene in acetonitrile. Microspheres have been characterized by Fourier transform infrared spectrometer (FTIR) and energy dispersive X-ray spectrometer (EDS) studies with evidence of 2,4-DCP linkage in polymer particles and scanning electron microscopy (SEM) to study their morphological properties. The proper adsorption and selective recognition ability of the MIP were studied by an equilibrium-adsorption method. The MIP showed outstanding affinity towards 2,4-DCP in aqueous solution and the optimum pH value for binding has been found around the neutral range. The molecular recognition of 2,4-DCP was analyzed in detail by using molecular modeling software. In addition, by investigating the variation in the adsorption ability of the MIP, it clearly showed excellent reproducibility.     

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。     

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.     

Selective removal of diclofenac from contaminated water using molecularly imprinted polymer microspheres

A molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using diclofenac (DFC) as a template. Binding characteristics of the MIP were evaluated using equilibrium binding experiments. Compared to the non-imprinted polymer (NIP), the MIP showed an outstanding affinity towards DFC in an aqueous solution with a binding site capacity (Q_max) of 324.8 mg/g and a dissociation constant (K_d) of 3.99 mg/L. The feasibility of removing DFC from natural water by the MIP was demonstrated by using river water spiked with DFC. Effects of pH and humic acid on the selectivity and adsorption capacity of MIP were evaluated in detail. MIP had better selectivity and higher adsorption efficiency for DFC as compared to that of powdered activated carbon (PAC). In addition, MIP reusability was demonstrated for at least 12 repeated cycles without significant loss in performance, which is a definite advantage over single-use activated carbon.     

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.     

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.     

Effects of activated carbon types and service life on removal of endocrine disrupting chemicals: amitrol, nonylphenol, and bisphenol-A

Removal performances of endocrine disrupting chemicals (EDC) such as amitrol, nonylphenol, and bisphenol-A were evaluated in this study using granular activated carbon (GAC) adsorption. This study found that GAC adsorption was effective in removal of EDCs with high K_ow value. Nonylphenol and bisphenol-A were effectively adsorbed onto all carbons (including the used carbons) tested in this study. As indicated by K_ow value, nonylphenol was more effectively adsorbed than bisphenol-A. The coal-based carbon was found more effective than other carbons in the adsorption of nonylphenol and bisphenol-A due to its larger pore volume. The adsorption capacity reduced with the operation year, and the extent of the reduction was different depending upon the carbon type and the operation year. Amitrol was effectively removed by biological degradation, but was poorly adsorbed. Since the microbes residing at the used carbons already accustomed to amitrol, the used carbons removed amitrol better than the virgin carbons. Although the coal-based carbon showed the best removal performance of amitrol, GAC adsorption could not be recommended for amitrol removal because considerable portion of incoming amitrol (9–87%) passed through GAC adsorption column. According to this study, pore volume mainly influenced the adsorption capacity, but the surface charge was also important due to electrical interaction. The adsorption parameters for nonylphenol and bisphenol-A provided by this study could be valuable when GAC adsorption was considered to handle an accidental spill of nonylphenol and bisphenol-A.     

Post-irradiation physicochemical features of polymer composite for the removal of Co(II) and Nd(III) from aqueous solutions

Environmental Science and Pollution Research - The scientific impact of this work is the protection of the environment from hazardous pollutants. Gamma irradiation was employed for the preparation...     

Synthesis of piperazine functionalized magnetic sporopollenin: a new organic-inorganic hybrid material for the removal of lead(II) and arsenic(III) from aqueous solution

Environmental Science and Pollution Research - The present work describes the successful functionalization/magnetization of bio-polymeric spores of Lycopodium clavatum (sporopollenin) with...