Predicting EDC concentrations in a river mixing zone

The fate and transport of endocrine disrupting chemicals (EDCs) in ambient river waters is a major concern associated with effluents from municipal wastewater treatment plants (WWTPs). This paper presents a methodology for quantifying the spatial distribution of EDCs in a river mixing zone. The core of the technical analysis is based on a two-dimensional steady-state analytical model characterized by ambient turbulence in the receiving water. This model was first calibrated with mass transport data from field measurements for a conservative substance (electrical conductivity) and then used to predict aqueous-phase EDC concentrations throughout a WWTP mixing zone. To demonstrate the usefulness of this methodology for water quality management purposes, the modeling framework presented in this paper was used to determine a lumped in-stream attenuation rate constant (k_d = 3 d⁻¹) for 17β-estradiol under natural conditions. This rate constant likely accounts for the combined contributions of physical sorption, photolysis, microbial and chemical degradation, and the measured value is highly consistent with previously published results from bench-scale removal experiments.     

The arrival and discharge of conjugated estrogens from a range of different sewage treatment plants in the UK

The occurrence of free and conjugated estrogens was examined in a survey of eleven sewage treatment plants (STPs) and their discharge water in the United Kingdom using grab sampling. The STPs included trickling filter with and without tertiary treatment, and activated sludge with tertiary treatment. For three activated sludge plants both influent and effluent samples were compared. For a further 8 STPs only the effluent was examined. The estrone-3-sulphate, estradiol-3-sulphate and estriol-3-sulphate concentrations (up to 20 ng L⁻¹) were typically 5-fold that of the respective free estrogen concentration in the effluents. This represents a substantial additional ‘potential’ estrogen load arriving in the receiving waters. Estrone-3-glucuronide was found at 9 ng L⁻¹, estradiol-3-glucuronide at 7 ng L⁻¹, and estriol-3-glucuronide at 32 ng L⁻¹ in sewage influent. Except on one occasion, no glucuronide conjugates could be found in the effluent. The results suggest in most cases glucuronide conjugates will be completely transformed in sewage treatment whilst sulphate conjugates will only be partially removed.     

3种环境雌激素检测和筛选方法的比较

介绍了进行环境雌激素检测和筛选的3种方法:鱼类卵黄蛋白原诱导实验法、重组基因酵母检测法和酵母双杂交法,着重介绍了这3种方法的基本原理、具体操作、适用条件及应用现状.卵黄蛋白原诱导实验是根据正常雄性体内不会含有卵黄蛋白原,环境雌激素能刺激卵生动物肝细胞产生卵黄蛋白原,可通过测定动物体内合成的卵黄蛋白原含量来评价其活性.重组基因酵母法是根据环境雌激素能刺激转化酵母的报告基因表达,以表达的β-半乳糖苷酶的量为依据来判断雌激素活性的大小.酵母双杂交法是在重组基因酵母法的基础上,引入了辅激活蛋白,通过检测雌激素受体和辅激活蛋白之间的相互作用来评价环境雌激素的活性.这3种方法均具有灵敏、简便、快速、经济的优点,同时既可以定性检测又可以定量检测,是目前进行环境中雌激素类物质安全检测与监测的重要手段.     

Endocrine disruptors in the Leça River and nearby Porto Coast (NW Portugal): presence of estrogenic compounds and hypoxic conditions

The Leça River and two beaches close to the north and south margins of the estuary, nowadays an important seaport harbor, show signs of contamination. However, the chemical nature of that contamination is uncertain. Therefore, this study checked for the presence of 11 endocrine disrupting compounds (EDCs) of animal (17β-estradiol and estrone), pharmaceutical (17α-ethynylestradiol), and industrial (alkylphenols, alkylphenol ethoxylates, and bisphenol A) origins in water samples collected from six points at the river gradient and at two sites in the coastline (Atlantic Ocean). Along with the EDCs, evaluated by gas chromatography – mass spectroscopy (GC-MS) during spring, summer, and autumn, physico-chemical parameters were also assessed and particular attention was given to dissolved oxygen (DO) levels. Data showed the presence of high amounts of estrogens (up to 10?ng?L^?1 for estrone) and industrial compounds (up to 2?µg?L^?1 for the nonylphenol ethoxylates) at both river and seacoast. Along with this, clear signs of hypoxia were found in the river (DO??1 at several sampling sites). Taking into account these issues, it was concluded that there are local conditions for the occurrence of endocrine disruption in aquatic animals.     

超高效液相色谱法对塑料玩具中16种环境雌激素的同时测定

含有环境雌激素的塑料玩具及儿童用品有可能被小孩放进口中,如果放置的时间足够长,就会导致雌激素的溶出量超过安全水平,危害儿童的肝脏和肾脏,也可引起儿童性早熟。采用超高效液相色谱法,对塑料玩具中16种环境雌激素类化合物进行检测,建立了超高效液相色谱法同时测定塑料玩具中16种环境雌激素的方法。采用超生萃取法进行提取,使用乙醇作为提取溶剂,在前处理过程中对样品进行无水硫酸钠脱水处理,使杂质显著降低;以乙腈-水为流动相,考察了5种具有不同选择性的UPLC色谱柱对16种环境雌激素的分离效果,结果表明,16种环境雌激素在ACQUITY UPLC BEH C18色谱柱上获得了最为理想的分离效果。该方法的回收率为93.6%～98.8%,RSD为0.5%～2.3%,检出限达0.11～0.76 ng。采用本方法对市售的28种儿童塑料玩具进行了检测,检出的环境雌激素有DEHP、DCHP、DMP、DNOP,其它未检出,其中DEHP、DCHP和DMP检出率相对较高,分别占32.8%、24.5%、19.5%,DNOP则最小,检出率为10.4%。此方法简便、易行、分离度较好,可作为测定塑料玩具中增塑剂环境雌激素类化合物的方法。     

Estrogenic Compounds Downstream From Three Small Cities in Eastern Nebraska: Occurrence and Biological Effect1

Abstract: Recent studies have detected estrogenic compounds in surface waters in North America and Europe. Furthermore, the presence of estrogenic compounds in surface waters has been attributed, in some cases, to the discharge of wastewater treatment plant (WWTP) effluent. The primary objective of the current study was to determine if WWTP effluent contributes estrogens to the surface waters of Nebraska. A second objective of this study was to determine if estrogens were found in concentrations sufficient enough to manifest feminizing effects on fish. These objectives were satisfied by deploying polar organic chemical integrative samplers (POCIS) and caged fathead minnows at eight field sites. Deployment sites included: three reference sites (Pawnee Creek, the Little Blue River, and the Middle Loup River), two sites upstream of the WWTPs at Grand Island and Columbus, and three sites downstream of the WWTPs at Grand Island, Columbus, and Hastings. Following the seven day deployments, POCIS extracts were analyzed for estrone, 17β‐estradiol, estriol and 17α‐ethinylestradiol using liquid chromatography tandem mass spectrometry (LC/MS/MS). 17β‐estradiol was detected in POCIS from six of the eight field sites with the greatest quantities recovered in POCIS deployed downstream from the Grand Island and Hastings WWTPs. Estrone was detected only in the POCIS deployed downstream from the Grand Island and Hastings WWTPs. Estrogenic effects were detected in caged minnows analyzed for the hepatic mRNA expression of two estrogen‐responsive genes, vitellogenin (vg1) and estrogen receptor α (ERα). Fish deployed at the site where the greatest quantities of estrogens were recovered (Hastings) had significantly higher expression of both vg1 and ERα than fish deployed at any of the other sites. These results confirm that WWTP effluent contributes biologically significant levels of estrogens to Nebraska surface waters.     

基于响应面法优化污水中雌酮的固相萃取条件

为提高污水样品中雌酮(E1)的固相萃取回收率,应用响应面法(RSM)对影响固相萃取的关键参数进行了优化,建立了固相萃取回收率的二次多项式模型,分析了模型有效性和因子交互作用,确定了最佳固相萃取条件;并对实际污水处理厂进、出水样品中的E1进行了固相萃取和浓度检测。结果表明,影响E1固相萃取回收率的因素重要性依次为:洗脱体积>进样速率>洗脱速率。最佳固相萃取条件为:洗脱体积11.15 mL;进样速率10.62mL/min;洗脱速率4.15 mL/min;在此条件下,预测回收率最大可达81.82%。分别采用SBR、氧化沟和A2/O工艺的3座污水处理厂进水E1浓度分别为36.8⁸9.0、24.189.0、24.1²8.4和27.828.4和27.8⁵8.1 ng/L,对应去除率分别为62.8%58.1 ng/L,对应去除率分别为62.8%⁷7.0%、49.3%77.0%、49.3%⁶3.6%和56.1%63.6%和56.1%⁷4.9%。3种污水处理工艺对E1均有一定的去除能力,但出水中残余E1仍远超过预测无效应浓度。     

我国直辖市畜禽养殖排放类固醇激素特征及其潜在污染风险

通过对北京、天津、重庆及上海4个直辖市畜禽养殖的统计分析,借鉴英美等发达国家的相关研究,估算了各直辖市畜禽养殖业类固醇雌激素和雄激素的年排放量,并初步探讨了各市单位耕地面积的类固醇雌激素承载量及类固醇雌激素对地表水体的潜在污染风险.结果表明,4个直辖中,重庆市的雌激素和雄激素年排放量处于4个直辖市之首,2008年两类激素的排放量分别达到1283.0和136.1 kg.北京和上海市类固醇激素总排放量均较10年前有所减少,尤其是上海市,10年间类固醇激素排放量减少了1/3.相反,天津市和重庆市的畜禽养殖业类固醇激素排放量却在增长.北京市单位耕地面积畜禽粪便类固醇雌激素的承载量最大,且明显增大,2008年达到839.1 mg·hm-2,是1998年的1.5倍.根据英国环保署(Environment Agency,United Kingdom)建议的最低可观测效应浓度10 ng·L-1,北京市和天津市的畜禽养殖排泄物有可能对当地地表水系统产生生态危害.在3种类固醇雌激素中,雌酮的排放对耕地承载的贡献最大.因此,各直辖市尤其是北京市和天津市亟需加强规模化养殖业管理,加强畜禽养殖业排污中类固醇激素的去除,保障城市的耕地及地表水生态安全.     

再生水中微量有毒有害污染物的初步筛查

采用气相色谱质谱联用(GC-MS)、电感耦合等离子体质谱(ICP-MS)等方法对5个污水处理厂再生水中的162种微量有毒有害污染物进行了评价。在各种污染物中,酚类、酞酸酯、类固醇激素和金属类物质被检出。酚类物质的质量浓度为0.01~148 ng/L,符合地表水环境质量标准,但三氯生、双酚A仍存在一定的生态风险;酞酸酯类物质的质量浓度为0.1~0.45μg/L,符合地表水环境质量标准;类固醇激素的质量浓度为0.5~30 ng/L,具有内分泌干扰效应,需优先控制;金属类物质的质量浓度为1~27μg/L,满足污水排放标准和地表水环境质量标准。     

结合态雌激素的检测方法及污染现状

结合态雌激素是天然雌激素物质的一种重要赋存形态,在环境中可水解为自由态,产生内分泌干扰效应,因此具有潜在的环境风险,并且会影响天然雌激素污染调查和毒性评估的准确性.本文详细探讨了结合态雌激素特定的化学结构对其检测、转化及环境风险等方面的影响,对比分析了目前常用的几类检测方法的优缺点,并初步总结了其在污水处理设施和环境水体中的污染浓度及归趋,以期为我国开展相关研究工作提供参考.